Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/40—Shaping or impregnating by compression not applied
  • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
  • B29C70/44—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
  • B29K2995/0017—Heat stable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0063—Density
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
  • B29L2031/3097—Cosmonautical vehicles; Rockets

Definitions

• the present invention relates to low density composite articles, and in particular to low density rocket nozzle components.
• the present invention further relates to a process for making the low density composite rocket nozzle components.
• Pre-preg materials generally include fabric and/or fiber that has/have been pre-impregnated with resin, typically a phenolic resin.
• resin typically a phenolic resin.
• the fabric or fiber is referred to as the reinforcement of the composite while the resin is called the composite matrix or matrix formulation.
• pre-preg a standard density or low density material
• pre-pregs for fabricating standard density composite rocket nozzle components include the reinforcement, matrix formulation, and appropriate fillers.
• carbon having substantially the same density as the carbon fiber is selected as the filler.
• Carbon or graphite fibers can be rayon, polyacrylonitrile ("PAN”) or pitch-based materials.
• PAN polyacrylonitrile
• Glass and silica composite pre-pregs utilize silica fillers when fillers are used.
• hollow spheres such as described in U.S. Patent No. 4,268,320, U.S. Patent No. 4,294,750, or U.S. Patent No. 4,621 ,024, are introduced into the pre-preg formulation as the filler.
• the effective densities of these hollow spheres typically range from 0.2 g/ml to 0.5 g/ml.
• an elastomer is added to the resin mix to maintain a more even dispersion of the hollow spheres during pre-impregnation of the fiber/fiber reinforcement.
• the cost of the conventional low density composite material can be 50 to 100 percent higher than that of the standard density version of the material.
• hollow spheres and elastomer in the pre- preg formulation also results in a composite having an across ply tensile strength as low as one tenth that of standard density material.
• the lower across ply tensile strength of LDCs significantly increases the likelihood of the LDC rocket nozzle components experiences ply lifting, wedge outs and other failure phenomena.
• LDCs used in exit cone environments can exhibit ply lift. The tendency of these materials to exhibit these failure modes must be addressed and accommodated by nozzle design. Such accommodation typically involves making the components thicker to improve margins of safety; however, the added thickness of the components partially offsets the weight advantage, i.e., the lower density, that LDC materials have over standard density materials.
• One predominantly used process for the fabrication of conventional so-called standard density nozzle components involves applying material to a mandrel such as by tape wrapping; ply by ply applying and debulking of pre-preg at very high pressures and temperatures to soften the resin, immediately followed by cooling; and autoclaving or hydroclaving curing, such as by pressurized curing at 200 to 1000 psig.
• the material is applied to the mandrel in such a way as to achieve 80 to 95 percent of the material debulk (compaction) required in the final component.
• Currently practiced processes can require a pressure greater than 800 psig to 2400 psig, to achieve desired debulking. Final debulking is achieved during the pressurized cure.
• This process provides a cured composite specific gravity (SpG) in carbon/graphite phenolic components of 1.40 to 1.60 glass phenolic components of 1.95 to 2.05 and silica phenolic components of 1.70 to 1.80 (g/ml).
• the conventional pre-pregs are designed to be used at elevated (high) pressures and temperatures to produce fully densified composites.
• the present process achieves the aforementioned objects while enabling the practitioner to avoid the need to use a specially designed pre-preg to fabricate low density composite articles, including rocket nozzle components.
• FIG. 1 are flow charts comparing a process for preparing conventional "standard density” composite articles, the present process for preparing low density composite articles, and an industry standard process for preparing low density composite articles;
• FIG. 2 is a diagrammatical view of a tape wrapping process suitable for practicing an embodiment of the present invention
• FIG. 3 is a schematic showing a press debulking step practiced in accordance with another embodiment of the present invention.
• FIG. 4A is a cross sectional view of a forty pound charge motor having propellant loaded therein.
• FIG. 4B is a sectional sliced side view of a forty pound charge rocket motor ("FPC") which is useful for testing nozzle materials; and
• FIG. 4C is a graph showing the relationship of time and pressure.
• FIG. 5 is a side view of a platen press showing the vacuum bag and bleeder material.
• FIG. 6 is a table summarizing results obtained with composites.
• FIG. 7 is bar graph reporting total heat affected depths of forty pound charge (FPC) motor 45° blast tube sections.
• FIG. 8 is bar graph reporting total heat affected depths of forty pound charge (FPC) motor 30° blast tube sections.
• FIG. 9. is a bar graph reporting some normalized erosion rates of aft exit cone section test specimens.
• FIG. 10 is a table reporting a comparison of tag end properties with FPC billet performance.
• FIG. 11 is a table of results from testing of composite materials.
• FIG. 12 is a graph showing a comparison of average across-ply thermal expansion as a function of temperature (10°F/sec).
• FIG. 13 is a bar graph of a comparison of ultimate torsional shear strength of modified materials.
• FIG. 14 is bar graph of a comparison of fill permeability of modified composite materials.
• FIG. 15 is a bar graph of a comparison of open porosity of modified composite materials.
• FIG. 16 is a bar graph of fill thermal expansion maximum peak height of modified materials.
• UF means unfilled.
• VC means vacuum cured according to the present invention.
• NARC HRPF means standard density composite made using a pre-preg MX-4926 from Flberite.
• a LDR designation, such as in Figure 7, means specially formulated pre-preg designed for use in fabricating a conventional low density composite having microballoon fillers.
• the designation PC means a post-cure step.
• the present process concerns the production of composite reinforced products, particularly rocket nozzle type components.
• Our novel rocket nozzle components have lower density compared to corresponding industry standard density composite reinforced rocket nozzle components.
• Our rocket nozzle components remarkably exhibit erosion resistance and charring which are similar to the high density products prepared using an industry standard practice.
• our process offers a reduction in the weight penalty and the retention of desirable erosion and charring properties in finished rocket nozzle components.
• our process comprises (a) forming a compacted pre-preg into a desired configuration under a pre-determined level of compaction which is less than the compaction (pressure) applied in the conventional process; (b) curing the formed pre-preg at a selected temperature and pressure, wherein the pressure can be vacuum or less than about atmospheric pressure (e.g., about 14 Ibs/sq. inch at sea level); and (c) obtaining the cured product, such as a low density rocket nozzle component.
• the pre-pregs are partially debulked, and, in general may be debulked less than 80%, more particularly they are debulked to less than about 50%. Therefore, although the terms debulked or debulking may be used in describing our inventions, it should be understood that we mean partially debulked, e.g. less than 80% preferably less than 50% debulked.
• the forming and curing are conducted at sufficiently low pressures to permit the formation of voids in the resulting component, the voids being formed from volatiles evolving during the curing.
• the resulting cured product has a lower density than standard density products, even when the cured product of the present invention is formed from a composition substantially or completely free of low density fillers, such as hollow spheres ("microballoons"), and elastomers.
• the cured articles prepared in accordance with the present invention have a specific gravity which is lower than standard density composite rocket nozzle.
• a suitable carbon phenolic resin based pre-preg a lower density
• the cured articles of the present invention also exhibit across ply tensile strengths which may be greater than, or at least near to, those observed with well-prepared composites from standard density pre-pregs.
• the composite rocket nozzles of our invention can have an across ply tensile strength of about 1800 to about 3000 psig, and more particularly can be readily prepared to have across ply tensile strengths of 1800 to 2200 psig.
• the above-mentioned (a) can be performed by winding a suitable pre-preg material about a mandrel using a tape wrap process as shown in FIG. 2.
• a pre-preg material or tape to be wrapped is in rolled form about a reel or spool 10. The tape is unwound from spool 10 and passed between a roller 11 and a mandrel 12.
• the mandrel 12 rotates clockwise and the roller 11 rotates counterclockwise as the tape to be wrapped about the mandrel 11 is fed therebetween.
• Each of the roller 11 and the mandrel 12 has a longitudinal axis; the longitudinal axes of the roller 11 and mandrel 12 are situated in parallel relationship with respect to each other.
• the pre-preg tape is heated, such as by a hot air source, as it crosses over the roller 11 in order to soften the tape.
• the hot air can be supplied to the tape at a temperature in the range of about 350 to about 900 °F, but in present practice a temperature in the range of about 350 to 550°F has proven sufficient.
• the pressure is applied to the tape at the interface of the roller 11 and the mandrel 12 debulks the tape as it wraps onto mandrel 12.
• the pressure applied by the roller 11 and the mandrel 12 is generally less than about half (50%) of the lowest pressure recommended by pre-preg vendors (100 to 300 pounds per inch of tape width) and about 50 pounds per inch of tape width is exemplary of such a lower pressure.
• the tape is cooled and preferably hardened as the tape is wrapped about the mandrel 12. As shown in FIG. 2, carbon dioxide (or other coolant) from a liquid holding tank is applied to the wrapped tape as the tape wraps about the mandrel 12. This cools and hardens the wrapped tape about the mandrel whereby a wrapped billet is formed.
• (b) involves curing the formed pre- preg at a selected temperature and pressure.
• the pressure can and can be vacuum or up to less than about atmospheric pressure.
• the wrapped billet can be vacuum bagged using a vapor impermeable vacuum bag, such as a nylon vacuum bag, sealed with vacuum putty.
• a suitably thick or suitably layered bleeder material is used so that any resin bleed from the curing material does not clog vacuum lines or to avoid (if not minimize) adversely affect the vacuum bag itself.
• a bleeder material may comprise, for instance, at least one layer of perforated film; at least two layers of cotton mop; or at least two layers of bleeder material, such as a polyester bleeder material (about 10 oz or about 16 oz./sq. yard of polyester bleeder material).
• the vacuum bagged material is then cured using a selected maximum vacuum.
• the vacuum provides the only pressure applied during the curing, and low pressures on the order of sub-atmospheric up to about, preferably less than, atmospheric can be used, such as a vacuum equivalent of about 12.5 psia to less than about 14.7 psia, although the pressure selected will depend on the prevalent atmospheric pressure. Still lower pressures can also be used.
• the low pressure vacuum can, for instance, be in a range of from about 12.5 psia to about 14 psia, and more particularly in a range of from about 12.5 psia to about 12.7 psia.
• the cure pressure is adjusted to maintain or provide the desired cured component density.
• the cure pressures can range, for instance, from 12.5 psia to about 150 psig, but generally a lower upper pressure is preferred, such as up to about 50 psig.
• a suitable applied low cure pressure can be achieved by vacuum bagging the component by adapting the methodology per standard procedure for cure, but in which a vacuum is pulled throughout the cure cycle.
• thermal cycling it is possible to use thermal cycling to cure the pre-preg.
• various temperatures or temperatures and residence times are selected to ensure the satisfactory curing of the composite article fabricated in accordance with the process of the present invention.
• An exemplary, non-limiting temperature cycle that can be practiced in accordance with an embodiment of the present invention involves a thermal cycle in which the pre-preg is heated and cooled in cycles which change on the order of about 1 °F per minute.
• a three-stage temperature cycle can be used, although other-staged temperature cycling can be used within the scope of the invention.
• the thermal cycling can be programmed to have a first hold at about 180°F for a residence time of about 1.25-1.5 hours, a second hold at about 220° F for a comparable residence time as the first hold, and a third hold at a temperature in a range of from about 310°F to about 320°F for about 60 or more minutes for each inch of component wall thickness.
• the residence time at a holding temperature will be a function of process variables, such as the thickness of the material to be cured.
• suitable curing cyclings, including both residence times and cure temperatures is within the purview of those skilled in the art and can be determined without undue experimentation when done in reference to the instant disclosure.
• a further post-cure step can, if desired, be conducted.
• press debulking in a mold can be employed as an alternative to tape wrapping for performing step (a).
• a ply or stack of plies 31 is placed in a platen press for debulking.
• the platen mold comprises a first platen 30 and a second platen 32 pre-heated to a temperature of about 130°F to about 150°F before the ply or stack of plies 31 are placed in the mold.
• a pressure F is applied to urge platen 30 to close to compact a ply or stack of plies of curable pre-preg 31 on second platen 32.
• Stops 33 are set to restrict the travel of platen 30 and to achieve the selected debulked thickness.
• the platens 30 and 32 remain closed to the stops and the temperature is held at about 130 to 150°F for a sufficient amount of time to allow the ply layers to stabilize, equilibrate, at the pressure and come to a relatively even temperature.
• the partial set achieved with the partially de-bulked plies is not a cured set, e.g. by preference the de-bulked plies are not thermoset.
• the residence time of the ply or plies 31 in the closed platen mold is about 20 to 30 minutes when most rocket nozzle components are being fabricated, and particularly when the about 30 to 40 pre-preg plies are being used.
• Flat panels can be prepared using the platen mold process step to de-bulk the pre-preg. For instance, for a 0 degree ply angle flat panel, ply stacks can be de-bulked to stops (see FIG. 3) to achieve the pre-selected ply thickness. Ply thicknesses can vary, but plies of 20 to 22 mils can be facilely prepared. In general, de-bulked ply stacks are less than about 1 inch thick (less than 2.54 centimeters), such as, for example, 0.80 inch thick perpendicular to the ply. For billets other than flat panel lay up, it may be desired to use different ply angles.
• a 45 degree ply angle can be used in a closed cylindrical mold, with angled end plugs, inside of the press.
• the de-bulked plies as stated above, have a thickness of less than about 1.0 inch perpendicular to the ply.
• De-bulking can be achieved by warming the plies and the mold to a suitable temperature, generally above 100°F, such as about 130°F to about 150°F, while applying pressure to close the press to stops. The de-bulked plies are allowed to cool while the press remains closed to the stops. After de-bulking, the ply stacks are stacked together. Flat panels can be free standing and angle lay ups can be contained within the mold. The ply stacks are vacuum bagged and cured to a temperature cycle as described above. The platen mold with configured (shaped) pre-composite
• uncured de-bulked, shaped uncured article can, if desired, be autoclaved or placed in an oven for curing.
• debulk application pressures can be varied from just a few psig to less than about 800 psig.
• the pressures may generally be in a range of 240 psig to about 40 psig.
• the present process uses lower pressures.
• the present process is atypical and contrary to a vendor recommended procedure for using a standard density pre-preg.
• tape wrap or compaction pressures are selected in combination with cure pressures that allow voids to form based on the vapor pressure of the constituents of the resin.
• the pressure for applying the pre-preg to the mandrel is backed off sufficiently until the selected ply spacing is achieved.
• the debulked billet can be vacuum bagged and cured, whereby the applied vacuum results in atmospheric pressure being applied to the billet, providing across ply pressure that results in a cured component having an across ply tensile strength that is greater than the across ply tensile strengths achieved in pre-pregs which were specially designed by vendors to result in low density composite components.
• the use of the vacuum bag technique offers the further related advantage that volatiles evolving in the cure are capable of growing into voids in the curing material which further reduces the density of the component. As a consequence a conventional standard density material can now be used to produce a low density composite component.
• Panels fabricated according to the present process using a standard density grade carbon phenolic indicate that a cured bulk density as low as 1.0 to 1.15 grams per cubic centimeter can be produced.
• the same material, processed to typical, vendor recommended process parameters which are the norm in the industry results in a composite component having a bulk density of 1.45 to 1.49 grams per cubic centimeter.
• the present process can produce cured products from filled pre-pregs which have a lower density than a corresponding product prepared according to industry standard.
• a silica-filled phenolic pre-preg was processed to a cured article having a density of 1.53 g/ml using the present process whereas like material processed using the industry standard process had a density of 1.75 g/ml.
• a glass-filed pre-preg was likewise processed to a cured product having a lower density (1.81 g/ml) verses 2.0 g/ml for a conventionally prepared article.
• Suitable pre-preg materials are generally characterized by a reinforcement (fibers, cloth, tape) to which is impregnated with a thermosetting resin.
• Suitable reinforcement can comprise wide variety of fibers or filaments known in the art. These fibers and filaments include, but are not limited to, glass fibers, boron filaments, boron nitride, silicon carbide, graphite (carbon) filaments and high modulus organic filaments, particularly organic filaments of the nylon, polyethylene, and aramid type. Examples of high modulus organic filaments include, but are not limited to, poly(benzothiazoles) and poly(aromatic amides) which are commonly referred to simply as "aramids". Aramids include poly (benzamides) and family of materials sold by E. I. DuPont under the trademark KEVLAR.
• thermosetting resins include, for example, phenolic resins, and epoxy resins (especially those based on diglycidyl ethers of bisphenol A are employed).
• epoxy resins especially those based on diglycidyl ethers of bisphenol A are employed.
• bis- maleimide resins, polyurethanes, polyesters, and the like, and any combination thereof may also be employed as the base resin or a component thereof.
• a phenolic resin matrix resin for the pre-preg is used.
• Suitable commercially available curable phenolic resins are SC-I008 (Borden) and 91 -LD phenolic resin (Stuart -Ironsides).
• Epoxy-based pre-pregs are not preferred for rocket motor nozzle components.
• a suitable pre-preg is, in general, pliable to enable it to be wrapped. Pliability is generally observed prior to debulking, and curing.
• the pre-preg materials can, if desired, include filler materials. Suitable filler materials include silica, carbon powder and others known to those skilled in the art. Filler materials can serve more than one function. For instance, some fillers, including powdered alumina trihydrate or antimony oxide, may also provide some flame resistance, or other characteristics to the final cured products, but are nonetheless fillers.
• the present process does not require, and preferably avoids the use of hollow microspheres (and elastomers) in order to produce a low density composite article.
• pre-preg materials are suitable for use herein.
• a carbon cloth impregnated with a curable phenolic resin can be used.
• the carbon cloth can be rayon-based, polyacrylonitrile (PAN) based, or pitch-based.
• PAN polyacrylonitrile
• These types of pre-pregs include the industry standard density pre-pregs such as MX-4926 (28-38% resin, 8-16% filler, the remainder including cloth reinforcement) which is a rayon based carbon phenolic pre-preg from Fiberite.
• Other suitable materials from Fiberite include PAN-based pre- pregs, such as those sold under the designations MX-4946 or MX- 4920 which both used a T300 fiber/yarn which is a vendor designation for a yarn having a modulus of 300 million.
• T type fiber/yarn products
• These materials can include a filler, and generally include carbon powder filler.
• Graphite cloth phenolics can be used.
• the graphite fiber can be rayon, PAN or pitch based.
• Suitable commercially available graphite pre-pregs include Fiberite products sold under the designations MXG-175 (graphite which is rayon based) and MX-4961 (graphite which is PAN based).
• Glass cloth pre-pregs include a glass fiber reinforced phenolic resin such as MXB-6001 from Fiberite.
• Silica fiber reinforced phenolic resin such as a product from Fiberite known as MX-2600, can be used.
• the fabric weave can be different between suitable pre-pregs.
• Table HS stands for harness satin weave, e.g. 8HS means 8 harness satin weave, etc., whereas a simple weave pattern comprises one over, one under, one over.
• PAN materials designations 3K, 6K and 12K refer, respectively, 3000, 6000 and 12,000 filaments in a single yarn used in the pre-preg.
• LD low density
• LDR rubber modified low density
• C carbon black
• MB microbailoons
• HS harness satin weave
• NBR norbutyldiene rubber
• T-300 AMOCO T-300 PAN-based carbon fibers
• the materials with MB, microbailoons may be used, but are not preferred because the composites produced therewith do not exhibit the overall balance of favorable properties for composites produced using standard density pre- pregs according to the present invention.
• the present invention does not require the use of the conventional specially formulated pre-pregs for low density.
• these low density pre-pregs include a low density carbon cloth phenolic, such as one in which the resin is filled with microballoons/microspheres, carbon filler and optionally an elastomer additive, such as MX-4926 LDC (rayon based carbon fiber) from Fiberite
• MX-4926 LDC rayon based carbon fiber
• MXS-385LD low density glass fiber reinforced phenolic resin loaded (filled) with microballoons/microspheres
• a low density silica cloth phenolic filled with microballoons/microspheres is known, and may also have an elastomer-modified resin, such as the specially formulated low density pre-preg known as MX-2600LD from Fiberite.
• Final cured and shaped products producible by the preset process include rocket nozzle components.
• the present process can also be used to manufacture composite panels.
• a standard density carbon-fiber cloth impregnated with a curable phenolic resin can be used to prepare a panel having, when cured, a bulk density of 1.0 g/ml to 1.15 g/ml.
• This type of panel is more cost-effective than a panel or, for instance, other part, such as an aft exit cone, for a C4 missile.
• Rocket motor components include, among others, blast tubes (aft, mid and/or forward); nozzle throats; exit cones; and such components as depicted in FIG. 17.
• blast tubes aft, mid and/or forward
• nozzle throats nozzle throats
• exit cones exit cones
• FIG. 17 ply properties of the composite material can be tailored by adjusting the pressure used in the initial compaction step and pressure used in the cure step. Such adjustments are techniques that, when viewed in reference to this disclosure, would be within the purview of the skilled artisan without undue experimentation.
• the data show that orders of magnitude improvement in tensile strength and significant improvement in erosion resistance are attainable with composite rocket nozzle components prepared according to the present process.
• One of the unexpected beneficial attributes is the over 400% improvement in across ply tensile strength with the present low density composite products compared to the conventional low density composite products.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Composite Materials (AREA)
• Mechanical Engineering (AREA)
• Moulding By Coating Moulds (AREA)
• Casting Or Compression Moulding Of Plastics Or The Like (AREA)

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Citations (8)

• 1998
  • 1998-06-04 JP JP50280999A patent/JP4392863B2/ja not_active Expired - Fee Related
  • 1998-06-04 EP EP98926235A patent/EP1009623B1/en not_active Expired - Lifetime
  • 1998-06-04 AU AU78118/98A patent/AU7811898A/en not_active Abandoned
  • 1998-06-04 WO PCT/US1998/011414 patent/WO1998055288A1/en not_active Ceased
• 2006
  • 2006-09-06 JP JP2006241199A patent/JP4476260B2/ja not_active Expired - Lifetime

Patent Citations (8)

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