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EP1177082A1 - Procede et appareil d'elaboration de composites - Google Patents

Procede et appareil d'elaboration de composites

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Publication number
EP1177082A1
EP1177082A1 EP98958677A EP98958677A EP1177082A1 EP 1177082 A1 EP1177082 A1 EP 1177082A1 EP 98958677 A EP98958677 A EP 98958677A EP 98958677 A EP98958677 A EP 98958677A EP 1177082 A1 EP1177082 A1 EP 1177082A1
Authority
EP
European Patent Office
Prior art keywords
primary
phase
condensable gas
free
solidifiable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98958677A
Other languages
German (de)
English (en)
Inventor
H. Victor Vidaurre
L. Jorge Dufeu
G. Wilfredo Bendek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vidaurre-Miller Francisca
Original Assignee
Vidaurre-Miller Francisca
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Vidaurre-Miller Francisca filed Critical Vidaurre-Miller Francisca
Priority claimed from PCT/US1998/024862 external-priority patent/WO2000030821A1/fr
Publication of EP1177082A1 publication Critical patent/EP1177082A1/fr
Withdrawn legal-status Critical Current

Links

Definitions

  • the present invention relates to gas occlusion-free and void-free, two-primary phase, solidifiable compounds, and derived void-free solidified composite materials, and more particularly to gas occlusion-free and void-free polymeric solidifiable compounds and derived void-free solidified composites, including methods and apparatus for producing same.
  • primary solid phase is defined herein as one or more distinct solid substances each physically homogeneous, in solid state, which serves primarily as material reinforcement upon solidification of the primary liquid phase.
  • primary solidifiable liquid phase is defined herein as one or more distinct liquid substances, each physically homogeneous, in liquid state, capable of solidifying to constitute a solid continuous material matrix that binds the primary solid phase at ambient temperatures.
  • compound is defined as the unsolidified state of a composite.
  • composite is defined here as any solid primary phase mixed with any primary solidifiable liquid phase, forming a monolithic two-phase solid state material upon solidification of the liquid primary phase.
  • voids are defined herein as filled or unfilled spaces, within interstices of a packed primary solid phase or surface pores in solid constituents. Voids are further defined as gas phase occlusions within a primary liquid phase originating from entrainment and/or adsorption of air, water vapor and other gases within the interstices of the solids in the primary solid phase, within the primary solidifiable liquid phase or within the multiphase, mixed unsolidified state of the two phases.
  • voids as defined above, specifically excludes intermolecular and atomic spaces, which are natural unfilled spaces in matter. Furthermore, the scale of physical measurement of voids herein is about one micron (10 "6 m) or more.
  • the process leading to the production of a polymeric composite involves mixing a generic primary solid phase with a polymeric resin system, thereby constituting a two-phase unsolidified compound.
  • the polymeric resin in the mixed unsolidified state is made to solidify, or harden, in an appropriate forming device, such as a mold or a die, yielding a formed, solid composite with the shape, or configuration, of the forming device.
  • the role of the polymeric liquid resin system in polymeric composites is to provide an essential binding matrix to the primary solid phase upon solidification. Initially, its low viscosity provides an adequate liquid medium for mixing with the solids of the primary solid phase. Upon solidification, the resin matrix provides a continuous solid phase that enables the composite to behave monolithically as a single solid material body.
  • Resin systems in polymeric composites are further classified as either thermoplastic, which soften when heated and may be shaped or reshaped while in a semifluid state or thermosetting, which are generally low viscosity liquids that solidify through chemical cross-linking.
  • the most common resin systems in polymeric composites are thermosetting, and the most predominant thermosetting resin is unsaturated polyester.
  • Other thermosetting resins include epoxies, vinylesters, phenolics and urethanes.
  • Certain thermosetting polymer resin systems consist of solid polymer particles dissolved in a low viscosity liquid and solvent monomer, for example, an unsaturated polyester dissolved in monostyrene.
  • the monomer plays the dual role of providing a solvent medium for the distribution of the polymer resin, and also has the ability to react with the polymer into a final solid state.
  • thermosetting resin systems are made to harden or solidify into a permanent shape by an irreversible chemical reaction known as curing or cross-linking, in which linear polymer chains and monomer chains in the liquid resin system are joined, or reacted, together to form complex, highly rigid, three- dimensional solid structures.
  • This reaction requires anaerobic conditions; i.e., the liquid resin system will not harden in the presence of air.
  • O 2 is known to have an inhibitory effect on the polymerization/solidification process.
  • water which is known to diffuse into liquid thermosetting resin systems, significantly impairs the cross linking solidification reaction.
  • thermosets are generally brittle. Thus, thermosets are rarely used without some form of solid reinforcement. However, high resistance to weight ratio, ability to solidify at ambient temperatures and retain their shape and properties at somewhat elevated temperature as, well as good creep resistance and corrosion resistance properties, give thermoset resin systems significant advantages over thermoplastics. These advantages essentially are the reasons for their preference in the developmental history of polymeric composites.
  • the role played by the solids in the primary solid phase matrix of polymeric composites is one of structural reinforcement.
  • the choice of geometrical shape of the solid phase constituents is a function of the intended reinforcement requirement of the particular polymeric composite in terms of the type of predominant stresses from externally applied forces that are to be resisted.
  • the geometrical shape of the solid reinforcement generally can be of two generic classes: 1 ) filament shaped, or fiber and 2) granular/spherical shaped, or aggregate-type solid material.
  • the fiber reinforced polymeric composites are intended for predominantly tensional, mechanical resistance applications, whereas the aggregate reinforced polymeric composites are intended for predominantly compressional, mechanical resistance applications.
  • FRPs Fiber Reinforced Polymers
  • the most common fibers used in the present art are glass, graphite, ceramic and polymeric fibers.
  • this generic class includes polymeric composite materials such as “Glass Reinforced Plastics” (GRP), produced by open, manual or spray, lay up methods, pultrusion, filament winding, etc. or by enclosed methods such as “Resin Transfer Molding” (RTM), Seeman Composites Resin Infusion Manufacturing Process (SCRIMP), etc.
  • GRP Glass Reinforced Plastics
  • RTM Resin Transfer Molding
  • SCRIMP Seeman Composites Resin Infusion Manufacturing Process
  • FRP composites produced by enclosed methods are based on polymeric compound materials, such as "Bulk Molding Compound” (BMC), “Sheet Molding Compound” (SMC), “Thick Molding Compound” (TMC), etc.
  • BMC Bind Molding Compound
  • SMC Sheet Molding Compound
  • TMC Thiick Molding Compound
  • Solid aggregate materials mixed with thermosetting polymeric resin (resins) matrices comprise the generic class of polymeric composites known as cast polymer products, polymer concretes, polymer mortars or polymer grouts.
  • siliceous aggregates are widely used in the production of polymer concretes due to their mechanical, dielectric and chemical resistance properties, as well as for their abundance and low cost.
  • thermosetting polymeric composites offer inherent advantages over traditional materials (metals, cement concrete, wood, ceramics and natural inorganic materials), including energy efficiency, high strength-to-weight ratio, design flexibility, parts consolidation, corrosion resistance, high dielectric and thermal properties, excellent appearance, low maintenance and extended service life.
  • a vast array of thermosetting polymeric composite products are currently available worldwide in over 50,000 successful applications developed over the past 45 years.
  • Well over 95% of the U.S. production is dedicated to fiber reinforced polymeric composites, and the industry's shipments and growth are tracked under nine major market segments totaling over 3.2 billion pounds per year.
  • Aggregate polymeric composites are widely used as cast materials for bath tubs, shower stalls, kitchen sinks and counters, flooring and decorative panels in construction. Cast polymer concrete products find use in specialized niche industrial applications, where the combination of high structural strength, corrosion and dielectric resistance is required.
  • polymeric composites Key common and inherent characteristics of polymeric composites include: 1) the composites are all heterogeneous and most are anisotropic; 2) the composites generally exhibit considerable variability in their properties compared to metals; this variability is directly related to the volume of the respective fractions of the two phases, i.e., the primary liquid phase versus the primary solid phase; and 3) the composites follow a general "rule of mixtures," in which a property of the composite is equal to the sum of solid and resin matrix properties weighted by their respective volume fractions.
  • the rule of mixtures is not valid for most properties in fiber reinforced polymeric composites, except for longitudinal extensional modulus.
  • the correlation of properties determined by the "rule of mixtures" is reasonably valid for many properties and supports the art of solid filler additives, commonly used to enhance desired properties in the composite, and/or mitigate the effects of undesired properties.
  • Heterogeneity in a two-phase polymeric composite material refers to certain properties that vary from point-to-point throughout the mass of the material. In a random selection of a point inside the material, properties can be very different, depending on whether the chosen point falls in the polymeric matrix or in the solid component . While it is true that generally all composite materials are heterogeneous at the micron level, the degree of heterogeneity is generally more pronounced in fiber polymeric composites.
  • thermosetting polymeric composites properties depend on the combination of several factors, such as the properties of the constituents, the form of the fiber reinforcement used (continuous fibers, woven fibers, chopped fibers, etc.), fiber volume fraction, length, distribution and orientation, bond strength between the phases, and void content.
  • strength and hardness characteristics of FRPs with continuous length fibers depend strongly on fiber orientation, spatial distribution and the variability of the properties of the specific fiber chosen. As it is impossible to position each fiber individually in the mix, the variability of the properties of the material is inevitable.
  • BMC bulk molding compounds
  • SMC sheet molding compounds
  • Anisotropy is another characteristic common to thermosetting polymeric composites, and is generally more pronounced in fiber polymeric composites than in aggregate polymeric composites.
  • An anisotropic material is one whose properties vary with direction. In the case of FRPs with straight, parallel and continuous fibers, the strength of the material is significantly stronger and stiffer in the direction parallel to the fibers than in the transverse direction.
  • Reinforcing fibers used in fiber polymeric composites are man-made in continuous processes yielding fine filaments that are quite brittle, and generally consisting of diameters ranging from 2 to 13 microns. Filaments are normally in bundles of several strands as rovings or woven into fabrics. Glass fibers are the oldest, cheapest and most widely used. They have generally good chemical resistance, are noncombustible and do not adsorb water, although generally they adsorb humidity from air in atmospheric conditions. Their tensile strength-to-weight ratios are relatively high, with elastic moduli in the range of those of aluminum alloys. The internal structure of glass fibers is amorphous, i.e., noncrystaline, and are generally considered isotropic.
  • Reinforcing aggregates used in aggregate polymeric composites are natural occurring inorganic materials that require processing to remove undesirable contaminants, such as clays, iron oxides, etc. This processing involves mechanically sieving the granules, separating them by sizes, and drying them within 0.1% humidity by weight to assure compatibility with the resin systems. Humidity strongly affects interfacial bonding of the resin with a dramatic drop in compression and flexure strengths. Geological origin, impurity levels, particle size distribution, and particle shape all affect uniformity and homogeneity of dispersion of the aggregates in the liquid resin system. These factors influence, in turn, interfacial bond strength and void content. For high corrosion resistance, thoroughly washed and dried, high silica content aggregates are generally used.
  • Voids are a major factor significantly contributing to property variation within a polymeric composite. Voids tend to reduce the integrity of the material and its mechanical and dielectric strengths, cause optical defects and lower the chemical resistance.
  • any open space or volume in the surface of solid matter, or the interstices of fractured packed solids, exposed to atmosphere are subject to atmospheric air pressure, which will instantaneously fill these spaces with air.
  • solid silica is fragmented and packed, as in the case of silica aggregates for polymeric concretes, or when filaments of molten silica glass are packed together to form glass fiber, as in the case of fiberglass
  • the mass of the fragmented packed aggregates or packed filaments exhibit an "apparent or bulk density" which is significantly lower than the respective unfragmented or unfilamented specific density of the respective original solid materials.
  • silica has a specific density of 2.65 g/cnr whereas the same silica fragmented into small diameter particles, approximately from say 100 microns up to say 6 mm, has a "bulk” density of only 1.6 g/cnv .
  • This "bulk density” indicates that the silica particles of irregular geometries in contact with each other, as when packed in a heap, leave random dimensional interstices or spaces - voids that are filled with air.
  • polymeric composites Since the formulations of polymeric composites are normally gravimetric, or by weight of bulk solids and liquid fractions, and furthermore, since the entrapped air is of negligible weight, its presence is not recognized gravimetrically.
  • the properties of polymeric composites are related primarily to volumes of the constituent solid and liquid phase fractions, which, of course, include whatever volumes are actually occupied by air and water vapor entrapped in void spaces of fragmented or filamented solids.
  • the air, water vapor and other gases entrained in the voids of the solids add an important contribution to the total volume of the mixed compound material when the original solids are mixed with the liquid polymeric resin system.
  • voids in a solid composite material interferes with its integrity because voids randomly interrupt the continuity, not only of the primary solidified liquid phase, but more importantly, also the continuity of the interfacial bond between the primary phases. Void sizes, number, distribution, and especially , locations are all critical because voids determine singular points of discontinuity within the phases of the material. These discontinuities compromise the composite's integrity, strength, and further, lead to the initiation of failures due to the localized stress concentration points they create. Moreover, if these voids in the mixed unsolidified state are filled with air and water vapor, O 2 in air will cause an inhibitory effect on the polymerization reaction of the resin.
  • Water particularly in liquid state, can be even more detrimental than O 2 to the polymerization reaction and to solidification.
  • the removal of air, water vapor and other gases from the primary liquid resin system can result in more complete polymerization/solidification of the resin, thereby producing a material with greater strength and integrity.
  • the gaseous phase is brought into the mixture entrained by the solids and/or by the liquid resin system and gets dispersed into the mixed unsolidified state. Therefore , in order to allow complete wet-out of the solids by the liquid resin system, some mechanism for removal of the gaseous phase is required. This is generally accomplished by degassing thin films of the mix under vacuum, which allows the occluded gas bubbles within the thin section to move towards its external surface. Moreover, these external surfaces are maintained at a lower pressure than the thin mass itself, thus facilitating evacuation by vacuum.
  • vacuum in a fiber polymeric composite made in a typical RTM or SCRIMP process does diminish entrapped air within the closed mold, or system, and from the glass fiber materials. Also gas vapors from the constituents of the resin system or from entrained air can be diminished by the application of vacuum, as evidenced by the reduction of visible occlusions in the solidified two-phase material.
  • vacuum applied to the thin sections of aggregate polymeric compounds in mixed state especially in conjunction with mechanical vibration, which allows entrained air to be dislodged, and with air release additives that reduce interfacial tension, diminishes the total entrapped air and gases, and consequently, substantially diminishes occlusions/voids in the solidified two-phase material.
  • Polymeric resin system materials cost is one of the major factors affecting overall composite costs. Efforts to decrease resin system cost for increased composites competitiveness in market penetration have been generally frustrated because associated increases in solid content generally worsen rather than improve mechanical, physical and chemical properties, while significantly increasing production difficulty.
  • the present invention comprises a method for producing at least a two primary phase compound that is substantially free of air and other gases by separately treating the solid primary phase and the liquid primary phase prior to bringing the two phases into contact.
  • Treatment of the two phases entails washing the primary solid phase with a condensable gas, so as to substantially remove and replace the solid phase's void contents; and separately degassing the primary solidifiable liquid phase by conventional means.
  • the primary solid phase (whose voids are substantially filled with the condensable gas) and the primary solidifiable liquid phase are combined in a mixing step, and the condensable gas is condensed or liquefied in the mixed state.
  • the resulting void- free, solidifiable compound thus comprises at least a solid phase and a solidifiable liquid phase.
  • the solid primary phase may consist of either particulate or fibrous materials or combinations of both.
  • the primary solidifiable liquid phase may consist of a thermoplastic polymeric resin system, a thermosetting polymeric resin system, a combination of both systems, or an inorganic binding system. Further, both the washing and mixing steps may be carried out in a batch or continuous mode, or in a combination batch-continuous mode. Additionally, the two primary phase solidifiable compound having a gas phase composed substantially of the condensable gas may be stored for later use.
  • the present invention also includes two primary phase solidifiable compounds made in accordance with the inventive method, as well as substantially void free polymeric composites formed from the solidifiable compounds.
  • the condensable gas that is used to wash the primary solid phase in the inventive method may be condensed prior to or at solidification of the two phase compound, and may be partially or completely condensed in the mixed state.
  • Void-free composites made from the inventive method are especially useful as electrical insulators.
  • the present invention also includes an apparatus for continuous production of the substantially void-free, two primary phase solidifiable compound.
  • the apparatus is comprised of an enclosed container for the primary solid phase, and a means for producing vacuum within the enclosed container; a mixing device that is in communication with the enclosed container, and that is used both to combine the separately treated primary solid phase and the primary solidifiable liquid phase, and at least partially, to condense the condensable gas.
  • the apparatus also comprises a condensable gas inlet in the initial region of the mixing device, so that the condensable gas flows continuously within the enclosed container in a direction counter to the flow of the primary solid phase; and a primary solidifiable liquid phase inlet located downstream of the condensable gas inlet within the mixing device.
  • the apparatus contains a port for discharging the mixed, and substantially air-free, solidifiable compound.
  • the discharge port may consist of an airtight, expandable spout that allows for intermittent discharge of discrete amounts of the air-free compound while the mixing device continues to run.
  • the invention includes an apparatus for batch production of a two primary phase solidifiable compound that is substantially free of air and other gases and voids.
  • the apparatus is comprised of a closed revolving chamber for containing and mixing the primary solid phase, the primary solidifiable liquid phase, and the condensable gas phase; a means for applying vacuum and pressure within the chamber; one or more ports for discharging the chamber contents; and fixed or detachable molds that are attached to the discharge ports and are used to form the solidified composite.
  • the apparatus may also rotate about a transverse axis to aid in material handling.
  • the invention encompasses an apparatus for batch production of a substantially void-free solidifiable polymer concrete material.
  • the apparatus is comprised of an enclosed mixing chamber, an enclosed molding chamber, and an enclosed conduit that provides for communication of the mixing chamber with the molding chamber. Moreover, the apparatus can be rotated in a vertical plane about an axis perpendicular to the longitudinal axis of the apparatus. This allows the contents of the mixing chamber to flow by gravity into the molding chamber.
  • the apparatus may also provide a means for rotation about its longitudinal axis to mix the polymer concrete components.
  • the apparatus may also contain a material holding hopper that can be interchanged with the molding chamber. This hopper is equipped with an intermittent dispensing device that provides for discharge of discrete and metered amounts of the solidifiable polymer concrete material.
  • the invention includes an apparatus for continuously de-airing fiber rovings with a condensable gas prior to mixing with a degassed primary liquid.
  • the apparatus comprises a vacuum chamber and a number of parallel, cylindrical rollers that are mounted within the vacuum chamber.
  • fiber rovings are introduced into the vacuum chamber through an entrance port located in the top end of the vacuum chamber, pass over the conveying rollers, and leave the vacuum chamber through an exit port located in the bottom end of the vacuum chamber. Sealing means are provided at the entrance and exit ports to help maintain vacuum within the chamber.
  • Condensable gas is introduced into the vacuum chamber through a feed port located near the exit port, flows upward in a direction counter to the direction of the fiber rovings, and exits the vacuum chamber, along with entrained air and other non-condensable gases, through a vacuum port located near the entrance port.
  • Internal seals force the condensable gas to pass through the fiber rovings in the gap formed between each conveying roller.
  • the vacuum chamber can be split along its length into a front shell and a back shell.
  • FIGURE 1 is a schematic diagram illustrating the generic method of the present invention for processing a generic void-free, gas occlusion-free two primary phase solidifiable compound material.
  • FIGURE 2 is an illustration of some of the forms of voids.
  • FIGURE 3 is a schematic representation of another application of the present method in which a void-free polymer concrete composite material is produced by a batch mix and molding method.
  • FIGURE 4 is a schematic representation of yet another application of the present method in which a void-free polymer concrete compound is produced by a conventional continuous mixing method, and where a polymer concrete composite is produced by a mixer to storage to mold method.
  • FIGURE 5 is a schematic representation of still another application of the present method in which a void-free fiber reinforced polymer composite is produced by a Resin Transfer Molding (RTM) method.
  • RTM Resin Transfer Molding
  • FIGURE 6 is a schematic diagram of an apparatus of the present invention, used in this case to produce a batch mixed polymer concrete material, as illustrated in FIGURE 3.
  • FIGURE 7 is a schematic diagram of another apparatus of the present invention used, in this case, to continuously produce a void-free polymer concrete material, as illustrated in FIGURE 4.
  • FIGURE 7a is a perspective view of an apparatus for continuously de-airing fiber rovings.
  • FIGURE 7b is a cross-sectional view of an apparatus for continuously de-airing fiber rovings.
  • FIGURE 8 is a schematic representation of an electric insulator machined from a void-free polymer concrete composite material produced according to FIGURE 3.
  • the present invention relates to methods, materials and apparatus used to produce a variety of void-free materials. These void-free materials, and the methods and apparatus for producing same are also detailed herein.
  • the generic void-free method can be used to produce any two primary phase solidifiable compound and composite.
  • a key step in this inventive method is to replace the pre-existing entrained or entrapped gases with a selected "condensable gas” as defined herein.
  • the "condensable gas” utilized in the present invention is defined herein as one or more substances that at normal ambient temperature and up to 50 atmosphere of absolute pressure, exists as a liquid.
  • the purpose of the condensable gas in the invention is to displace and replace air, water vapor and other gases present within the voids and interstices of the primary solid phase.
  • Non-condensable gases are defined herein as air, water vapor and other gases, which originally exist as gases filling the voids, and subsequently, are replaced by a selected condensable gas.
  • a “non-condensable gas” is any gas other than the selected condensable gas used to replace the pre-existing gases, or displaced gases, in the system.
  • the present invention is an environmentally safe generic process of universal application to fabricate all types of two primary phase solidifiable compounds and composites, comprising a primary phase of reinforcing solid mixed with a primary of solidifiable liquid binder phase. It is applicable to the production of void-free polymeric composites in general. In particular, the method is applicable where the solidification mechanism of the primary solidifiable liquid phase involves solidification of its entire liquid phase. Additionally, the method is particularly applicable where thermosetting polymeric resin matrices are used as the primary solidifiable liquid phase.
  • the generic method leading to void-free and gas occlusion compounds involves three essential stages in the production process. These stages are applicable to any method of production to yield a wide variety of compounds and composites.
  • Stage 1- Washing the primary solid phase with a condensable gas, in the gas or liquid state, and in parallel de-airing/degassing the primary solidifiable liquid phase.
  • Stage 2- Mixing the above two primary phases, air-free, and in presence of a condensable gas phase.
  • Stage 3- Condensing of the above condensable gas phase within the mixed state compound.
  • FIGURE 1 shows a schematic of the generic process used to produce a generic non-condensable gas occlusion free and void-free two-primary phase solidifiable compound as disclosed in the present invention.
  • the initial steps 1 and 2 consist of separating the primary solid and liquid phase for the purpose of independently removing air, water vapor and other gases entrained in each phase prior to mixing.
  • each primary phase contains entrained non-condensable gases, which in the case of the primary solid phase, are removed by the inventive method.
  • Stage I An important step in the process is 5, shown in FIGURE 1, where the primary phase solids are de-aired/degassed by total replacement with a condensable gas 4.
  • This step 5 is significant to produce a non-condensable gas occlusion free and void-free compound because it permits the complete replacement of air/gases by washing the solids with a condensable gas chosen to adequately work within the parameters of conventional fabrication processes.
  • the addition of this step to the overall void-free method recognizes the fact that it is essentially impossible to completely degas solids, or mixtures of solids and liquids, using conventional techniques with or without the application of vacuum.
  • the present invention replaces air, water vapor and other non-condensable gases entrained in the solid with a condensable gas that can be liquefied within the mixed unsolidified state compound in the range of temperatures and pressures in which the production processes are carried out.
  • the condensable gas utilized when liquified, would be reacted within the primary solidifiable liquid phase prior to, or at, solidification to form a solid void-free composite in a subsequent step.
  • the displaced air with associated water vapor and other gases can be removed by vacuum together with the stream of condensable gas.
  • the condensable gas in filling the voids in the solids as the air associated with water vapor and other gases are being removed, and the condensable gas is also simultaneously being fed into the primary solid phase, as seen in 4.
  • the condensable gas as a liquid state substance is vaporized to its gas state by some appropriate combination of pressure and temperature.
  • the preferred vaporization conditions are at ambient temperature together with sufficient vacuum for vaporization.
  • the preferred choice of a condensable gas is one that in its condensed liquid state would be capable of further reaction with the primary solidifiable liquid phase upon its solidification.
  • Class I uses one or more liquid substances contained in, or forming part of, the solidifiable liquid system as sources of condensable gas to wash the primary solid phase.
  • Class LI uses one or more liquid substances, other than those forming part of the solidifiable liquid system, as a source of condensable gas to wash the primary solid phase.
  • Class LI the liquid substances are functionally equivalent to those contained in Class I, in that Class LI liquids are also capable of reacting in the solidification, or curing, process.
  • Class LLI substances do not utilize a reactive or functionally equivalent fluid substance as a source of the condensable gas, but instead uses one or more fluids that are either soluble or insoluble in the solidifiable liquid system process conditions.
  • the primary solidifiable liquid phase is an unsaturated polyester
  • styrene monomer would serve as a Class I condensable gas.
  • other ethenic polymerization monomers could serve as Class J condensable gases, including, acrylamide, methyl acrylate, methyl methacrylate, vinyl acetate and the like.
  • suitable Class LLI condensable gases would be organic solvents having normal boiling points between about 50°C and 100°C, including acetone, methanol, ethanol, isopropanol, acetonitrile. and the like.
  • Preparation of the substance to be used as condensable gas in the invention can be done by methods generally known in the art, which include evaporation of the gasifiable liquid into a condensable gas with subsequent feeding of the gas thus produced into a gas replacement chamber 5.
  • evaporation of the gasifiable liquid may take place outside of the gas-replacement chamber, and then fed into the gas replacement chamber 5.
  • evaporation of the condensable gas can take place within the gas replacement process chamber 5.
  • one or more of the liquid substances from within the solidifiable liquid system can be selectively evaporated from it and fed into the gas replacement process chamber 5.
  • evaporation into a condensable gas using an appropriate temperature and pressure, can take place outside the gas replacement process and fed into it at elevated temperature, so that it is made to condense inside the gas replacement process chamber at process temperature and then subsequently re-evaporated within chamber 5 by a combination of pressure and temperature.
  • the present invention requires that the primary liquid phase 2 be degassed by conventional vacuum methods, preferably thin film vacuum methods. This step allows removal of the entrapped air, water vapor or other gases within this primary phase.
  • the de-airing/degassing of the primary liquid phase takes place in a degasifying process chamber 6.
  • Reference numeral 7 illustrates that the air, water vapor or other gases entrained in the primary liquid phase are removed by the application of thin film vacuum methods which are generally more effective.
  • Reference numeral 8 and 9, shown in FIGURE 1 represents that the two primary phases having been separately treated to remove entrained air, water vapor and other non- condensable gases, and now, being de-aired/degassed by conventional methods in the case of the liquid phase, and condensable gas-replaced by washing with condensable gas in the case of the primary solid phase, can proceed to be mixed to form a non-condensable gas free, void-free solidifiable compound.
  • Reference numeral 10 represents the air-free mixing processes into which each pretreated primary phase is contacted to begin the mixing process of what is now a primary solid phase, a primary solidifiable liquid phase and a condensable gas system, to yield a mixed state non-condensable gas occlusion free and void-free solidifiable compound.
  • the mixing step 10 must be conducted only in air- free conditions and with the presence of the condensable gas in the gaseous phase.
  • the condensable gas in the mixing chamber may or may not be uniformly dispersed in the solidifiable liquid phase.
  • An optional step can be performed at this point to disperse the condensable gas more homogeneously within the solidifiable liquid phase. This optional step can be accomplished by applying vibration or mechanical work to the mixed state compound. Additionally, if elimination of excess condensable gas is desired. as it might in batch mixing process, vacuum and mechanical work can be applied at this point to achieve this end.
  • the next step is significant to the overall void-free process and production of the non-condensable gas occlusion free and void-free compound to yield a final void-free composite material.
  • This step involves condensation of the condensable gas preferably within a condensation chamber 12, as shown in FIGURE 1. Later, at the time of forming and hardening of the compound, pressure and/or heat can be applied to form a final solid composite.
  • This essential step 12 takes the condensable gas to its corresponding liquid state at process temperature by application of pressure 13, or by some appropriate combination of temperature and pressure.
  • the solidifiable compound may be vibrated or mechanically worked upon, as illustrated in 14, so that the condensed gas, now in liquid state, may be dispersed within the liquid phase of the mixture, thus allowing penetration of the liquid phase into interstices and voids on the surfaces of the solids.
  • Reference numeral 16 represents the end product of the generic process, yielding a non- condensable gas occlusion free, and void-free, two primary phase solidifiable compound that can now be immediately hardened or stored for future solidification.
  • the typical prior art degassing processes shift all attempts of gas removal to the wet mixing stage of the two primary phases.
  • the non-condensable gases naturally present in the mixing process become dispersed throughout the mixed state compound mass, making vacuum degassing at this stage ineffective and inefficient.
  • the prior art procedure is considerably more difficult and less effective in high viscosity systems.
  • gas phase removal becomes virtually impossible in cases where the resulting mixture viscosity of the mixed state of the solid and liquid phases is significantly increased by their addition.
  • the gas occlusions will remain in the mixed state solidifiable compound, and thus, will irremediably appear as voids in the final solid composite.
  • voids or unfilled spaces within the solidified liquid phase may be generated by one or more constituents materials of the mixed state gas occlusion free solidifiable compound, or during subsequent storage, handling and processing.
  • Such voids in the solidified composite are not caused by non-condensable gas filled voids or unfilled resin voids pre-existing in the mixed state gas occlusion free solidifiable compound, and thus the invention remains valid.
  • the primary solidifiable liquid phase is a polymeric resin system generally exhibiting typical viscosities at normal process temperatures. These viscosities determine a behavior of the gaseous phase that require further description.
  • Gaseous phase occlusions are suspended in the polymeric resin system occurring naturally as discrete spherical volumes maintained by a pressure and surface tension equilibrium that is established between the liquid and gas phases. Also, gaseous phase occlusions may occur as amorphous thin layer gas filled voids of large surface to volume ratio, lodged in the interstices within fibers or formed around closely packed aggregates in the primary solid phase upon mixing with the polymer resin system, particularly in compounds having high volume fraction of solids.
  • the voids in the primary solid phase may release some of the entrained gaseous phase into the primary liquid phase, where it may join other entrained gases found in the primary liquid phase.
  • Mechanical work applied to the mixed state of the two primary phases containing entrained third gaseous phase will generally help the release of the gaseous phase lodged in voids of the primary solid phase into the primary liquid phase and also help disperse the gaseous phase within the liquid phase. Mechanical dispersion of the gaseous phase can also increase the surface to volume ratio of the gas occlusions.
  • Some gas occlusions get broken down into smaller spherical sizes, while others may adopt other than spherical shapes, generally of high surface relative to their initial volume, such as the amorphous thin layers voids described above. Gases filling these amorphous, thin layer voids are completely entrapped in the interstices within fibers or within packed fibers or aggregates by the surrounding primary liquid phase, forming localized and enclosed micro-gaseous phase systems separating the two primary phases in mixed state at discrete locations. Moreover, the volumes of localized, enclosed micro-gaseous phase systems will be determined by a pressure equilibrium existing between the gaseous phase systems internal pressure and the surrounding liquid phase at a given process temperature.
  • FIGURE 2 provides an illustration of some typical void forms in solid primary phases, prior to mixing. Voids can be viewed as spaces between the interstices of packed solids of a primary phase, prior to mixing, as shown in 21 in aggregates, and as shown in 22 in fibers.
  • the amorphous, high surface to volume voids, in the form of thin layers of gas adsorbed on the surface of solid in the mixed state are shown in 23 in an aggregate/resin system, and in 24 in a unidirectional and random oriented fiber/resin systems.
  • Reference numeral 25 illustrates the typical natural spherical gas bubble shape upon mixing of the primary phases.
  • the above characterized voids shown in 23, 24 and 25 are formed typically in the mixed state and will be retained in the final composite material upon solidification, if no effort is made for their removal.
  • Voids remain one of the major unrecognized source of problems fiber reinforced organic polymeric composites face today.
  • amorphous thin gas layers randomly located constitute a barrier intercepting contact of the fiber and liquid phases, and thus significantly affect proper resin wet out . More particularly, this barrier discretely interrupts the continuity of interfacial bonding.
  • a non- condensable gas occlusion-free and void-free material is defined as a two primary phase solidifiable polymer compound when in substantially the liquid state, and as a void-free composite when in the solid state.
  • Polymer composites made in accordance with present invention exhibit no gas occlusion voids, in the size range of one micron visually detected under 1250x magnification in any random cross-section sample of at least 400 mm". It is significant to point out that just one void of one micron diameter in a 1 mm" area represents less than 1 part per million .
  • voids could still affect fiber wet out by the resin, if they are very numerous and in the form of very thin gas layers. Such voids would still significantly interrupt interfacial boding, and thus, affect mechanical properties. Notwithstanding, a method capable of achieving void freeness could still be expected to generally increase significantly the longitudinal and transverse elongation moduli and associated strengths, and particularly transverse strength properties.
  • void-free polymer concrete composites made with the formulation of one of the examples in the invention do not exhibit oscilloscopically discernible partial discharges in prototype insulators when subjected to high voltages, at least below 90-100KV, while only very modest partial discharges would be seen starting above this range.
  • Optimized aggregate and resin formulations of dielectric polymer concrete composites can significantly increase the above-threshold of partial discharge initiation and the overall dielectric strength of void-free aggregate polymeric composites.
  • the generic method of the invention for producing two primary phase void-free/gas occlusion free unsolidified compounds can be applied to specific present art fabrication processes.
  • the generic method can be most effective in the manufacture of thermosetting polymeric compounds and composites where the primary solid phase materials, (are either packed fibers in fiber reinforced polymer composites or granular aggregates in aggregate reinforced polymer composites).
  • Such composites and compounds generally exhibit low bulk densities indicating large amounts of entrained air and other gases in the solids.
  • Tables 1 and 2, and the accompanying legend further illustrate how the generic method can be applied to produce two primary phase, thermosetting polymeric compounds and composites, combining the void free method with conventional mixing and forming processes (batch mixing, continuous mixing or combinations of both).
  • the void free method can be used to fabricate a vast array of thermosetting polymeric composites where the reinforcing solids in the primary solid phase can be either fiber or aggregates, or a combination of both, and where the primary liquid phase can be any thermosetting polymer resin system and monomer, either extended or not with filler solid materials intended to modify the properties of the binding resin matrices.
  • the generic method can be used in batch mixing and forming processes. Moreover, using the inventive method, these batch fabrication processes can be used to produce an array of void- free and gas occlusion free compounds and composites.
  • the choice of matrix reinforcement for the batch processes can be selected from either the fiber or aggregate class of solids. The legend, seen below, gives an explanation for each of the numbers contained in Table 1.
  • Stage 5 Solid composite final forming and curing under absolute pressure at least equal to vapor pressure of condensable gas at specified maximum process temperatures
  • Process 5.3 Process' own pressure Final Characterization-Formed solid composite product free from air and gas occlusions, voids.
  • the generic method can be used in continuous mixing processes.
  • the forming protocol can be either batch or continuous.
  • these continuous fabrication processes can be used to produce an array of void-free and occlusion free compounds and composites.
  • the choice of matrix reinforcement for the batch processes can be selected from either the fiber or aggregate class of solids. The legend above gives an explanation for each of the numbers contained in Table 2.
  • FIGURES 3-5 illustrate how both thermosetting polymer concrete composites and fiber reinforced thermosetting polymer composites can be produced from the generic method of the present invention with two additional successive processing stages that take the characterized non- condensable gas occlusion free and void-free compound to final void-free polymeric composite.
  • FIGURES 3-5 Detailed descriptions of preferred embodiments illustrating the application of the generic inventive method to the production of two-primary phase, void-free compounds and composites are shown in FIGURES 3-5.
  • FIGURES 3 and 4 are examples of void-free polymer concrete composites
  • FIGURE 5 is an example of a void-free fiber reinforced polymer composite produced by Resin Transfer Molding (RTM). Additionally, these figures show flow charts of specific fabrication methods applied in each of the successive three stages described in the inventive generic production method, followed by up to two additional successive stages required to yield the respective final void-free polymeric composites.
  • RTM Resin Transfer Molding
  • the generic method is likewise applicable to paints and gel coats, which are used as barriers to protect the external surfaces of reinforced polymer composites and polymer concrete.
  • Gel coats are polymeric compounds (solidifiable liquids) filled with thixotropic solids (pyrogenic or fumed silicas, for example) and are known in the industry to contain a significant amount of voids due to entrained air. Because these large and numerous voids are unsightly, gel coats are heavily pigmented to mask their presence.
  • PC composite sample in FIGURE 3 is made by batch processes in four successive stages to yield a non-condensable gas occlusion free and void-free solid polymer concrete material. The description of these stages is as follows per FIGURE 3 and as specified in Table 3.
  • Stage I Elimination of air water vapor and other gases from the primary solid phase in parallel with degassing of the primary solidifiable polymer liquid phase
  • the two primary phases are generally processed prior to their mixing, with each phase being degassed separately by a different method. These two degassed phases are then brought together and mixed under air free conditions.
  • the key objectives in the method are: 1) to completely eliminate air with associated water vapor and traces of any other gases by displacing them, and, thereby, filling the voids of the primary solid phase materials with a condensable gas prior to mixing, and 2) in a separate process, to eliminate air and traces of other gases from the liquid resin system by degassing the liquid under high vacuum using conventional thin film methods prior to mixing.
  • the two air free phases can then be mixed under air free conditions where the only gas present is the condensable gas used to wash the solid materials.
  • Air and associated water vapor and other gases which fill or are entrained in dry reinforcing materials, used in this batch mixing example, are eliminated by placing the solids inside a vessel connected to a vacuum source while using the apparatus illustrated in FIGURE 6.
  • Condensable gas in the liquid state at ambient temperature and atmospheric pressure is fed into the inclined vessel.
  • the amount of condensable gas in the liquid state is dosed so that at least twice the void volume of the vessel and void volume in the packed aggregates will be occupied by the condensable gas upon its evaporation.
  • Evaporation of the condensable gas in the liquid state is initiated by applying a vacuum to the closed vessel, preferably with the vessel and contents at rest, and with a stream of condensable gas rising from the bottom surface of the vessel upward through the packed solids to the upper vacuum port. This vacuum is pulled until the entire liquid content has evaporated and then the vacuum port is closed.
  • the chosen condensable gas will thus have completely displaced and replaced the entrained air, water vapor, and other gases in the voids of the solids and in the free volume of the vessel.
  • the vessel can be heated externally in order to maintain the initial system temperature to compensate for the heat intake of the endothermic evaporation process of the condensable gas and also to ensure the condensable gas remains in gaseous state.
  • the gas process conditions at the end of evaporation of the condensable gas must be maintained so that external air is prevented from contaminating the contents of solids soaked with condensable gas in gaseous state, and more importantly, to prevent reversion of the condensable gas replacement in the solids by external air.
  • the degassified solidified liquid resin phase is then fed into the closed vessel to begin batch mixing with the solids soaked with condensable gas. Air, water vapor, and other gases dispersed in the liquid thermosetting resin system are likewise also eliminated prior to mixing in a separate process by using any conventional, effective, thin film vacuum degassing process.
  • the resin system is a second source of potentially large volumes of air and other gases that would be incorporated into the two primary phase mixed compound if, as in prior art, no step is performed to ensure their complete removal.
  • the two air-free phases are then mixed under air free conditions in the closed mixer at process temperature and a suitable condensable gas vaporization pressure.
  • the only gas present is the condensable gas used previously to wash the solid materials.
  • mixing occurs in an atmosphere of the condensable gas.
  • the mixing process of the two primary phases takes place in a medium where the third phase, i.e., the gas phase has been rendered free of air by condensable gas replacement per the invention.
  • the third phase consists of a condensable gas phase, instead of air, water vapor and other gases.
  • the condensable gas is randomly dispersed throughout the viscous liquid phase by the mixing of the phases.
  • the gas phase is in the form of discrete spheres or bubbles suspended in the liquid phase or entrapped in the interstices within the primary solid phase.
  • the two primary phase polymeric compound as shown in FIGURE 6, is poured into the mold section of the vessel maintaining the mixing process conditions.
  • the mold is attached to , and forming part of, the mixing chamber in the vessel, and by pivoting the assembly, the contents in the mixing chamber are gravity fed into the mold cavity.
  • the accommodation of the two phase mixed compound in the mold is completed by mechanical vibration to pack the two phase mixed compound tightly to the shape of the mold, thus ensuring all corners are filled, and at the same time, dispersing the condensed gas droplets into the solidifiable liquid system.
  • the process pressure is made at least equal to, or preferably higher than the condensable gas vapor pressure at the process temperature.
  • This enables the absolute pressure at any point within the mixed state compound mass to be at, or above, the condensable gas vapor pressure, thus ensuring all dispersed condensable gas bubbles will condense, and all voids thereby, will be filled with liquid resin.
  • the condensable gas phase is totally condensed. Sufficient time is allowed for the condensed gas in the liquid state to fill voids throughout the mixed state compound, yielding a void-free polymer concrete compound.
  • the void-free polymeric concrete compound is allowed to solidify in the mold.
  • the void-free solid polymer concrete composite part is removed from the mold.
  • Table 3 this polymer concrete example has been produced according to the four stage method described herein The particular formulation of the phases, choice of the condensable gas, and process parameters were adjusted to produce a void-free dielectric class polymer concrete composite meeting the visual count void-free criteria and the electrical partial discharge criteria indicated in the invention herein, and illustrated in Figure 8.
  • the final composite is also a readily machineable material suitable for mass production of a high voltage electric current insulator, as illustrated in Figure 8.
  • Table 3 reveals the material specification and process parameters used to yield a void-free and occlusion free polymer concrete material.
  • the specific application of the generic method used to produce the example material given in Table 3 is illustrated in FIGURE 3.
  • FIGURE 4 illustrates a continuous mixing process in five successive stage to yield a void-free polymer concrete composite material, including an optional storage stage between the characterized two phase non-condensable gas occlusion free and void-free polymer concrete compound and the final solid void-free polymer concrete composite.
  • the two primary phases are generally processed as in Stage I above. However, as this embodiment is produced in a continuous process, there are differences in the condensable gas washing method.
  • the solids with entrained air, water vapor, or other gases are first gravity fed continuously under ambient conditions into a closed vertical solid loading hopper, and through a rotary seal valve located on the top of the hopper that prevents external air from entering and breaking vacuum.
  • Vacuum in the loading hopper reduces the volume of entrained air and other gases in the solids and prepares the primary solid phase for gravity discharge through a lower seal valve into a vertical condensable gas replacement column, which is also under vacuum.
  • the gas replacement column has a lower discharge through the shroud into the internal screw chamber of a conventional, continuous screw type, two primary phase solid/liquid mixing machine.
  • Condensable gas which is evaporated externally and fed through valves in the shroud of the continuous mixing machine first soaks the solids inside the screw chamber, and then streams upward towards the upper zone of the gas replacer column, soaking, in counter-current, the downward traveling solids of the primary solid phase.
  • Continuous feed of de-aired solids for mixing is produced by the rotation of the mixing screw which advances the de-aired solids forward, where they are soaked in condensable gas, and allowing continuous gravity feed of processed solids from the filled gas replacement column.
  • the primary liquid polymeric resin phase is degassed free from air and other gases in a separate process using any conventional, effective, thin film degassing process. ii. Stage II and Stage HI-Air free mixing of the two primary phases, and subsequent condensation
  • Air free continuous mixing process in the screw type machine is accomplished by screw rotation which advances forward the primary phase solids soaked in condensable gas and by feeding the degassed solidifiable liquid phase into the screw shroud. Mixing is followed by pressurized condensation of the condensable gas and densification of the mixed state compound in the screw type mixing machine. These steps are represented by successive adjacent zones, as illustrated in FIGURE 7.
  • the two phase void-free unsolidified compound characterized in the generic method of invention is discharged from the continuous mixing machine through a collapsible rubber spout choked by adjustable springs set to close down when the machine looses process speed, or to shut when stopped.
  • the spout allows essential air-free continuous discharge as it prevents atmosphere air from penetrating inside the screw and shroud of the machine discharge port.
  • the rubber spout is sized to suit the machine speed or capacity, compound characteristics, and other process parameters.
  • Void-free compound packaging for storage is done using collapsed, air free, flexible material packaging containers of desired shape and dimension, which are attached onto the discharge spout of the continuous mixing machine to successively receive the void- free solidifiable polymer concrete compound. Pressure exerted by the rotation of the mixing screw will force the compound out of the discharge port of the machine into the collapsible rubber spring loaded spout, which is forced to remain open by the moving void-free material pressing against the set pressure of the closing springs. In this way, the compound is loaded into the collapsed flexible container attached to the spout. As an individual container is filled, a proximity signal mechanism increases the closing spring tension, collapsing the rubber spout shut while the mixing machine continues to run.
  • the volume of compound discharged expands the rubber body of the shut spout, which now acts as a compound accumulator, increasing its original volume.
  • the compound filled container is externally detached from the rubber spout and a new empty collapsed, air free, flexible container is re-attached on the spout to begin a new cycle.
  • the high tension level of the springs is then signaled to start releasing back to the normal setting.
  • the accumulated volume of void-free compound in the rubber spout thus begins to force itself out of the spout and into the new empty collapsed flexible container, as the spout spring tension becomes released to allow material discharge.
  • the containers filled with void-free unsolidified compound are sealed and the placed into a conventional autoclave, to harden in the shape of the containers at adequate combinations of pressure, temperature and time.
  • the flexible container with unsolidified compound can be subsequently shaped by placing the sealed container and contents into a two or more part sectional mold, in which, by a combination of pressure and temperature the void-free unsolidified compound will harden into a solid, void-free, shaped polymer concrete composite.
  • the filled flexible containers are sealed and placed in storage at reduced temperature, preferably in the range of +20°C to-20°C, for up to 6 months depending on the characteristics of the solidification substances incorporated in the liquid resin system.
  • FIGURE 5 illustrates a batch mix and forming processing by the inventive method in four successive stages to yield a void-free, solid, fiber reinforced polymer composite material in laminar shape, formed by Resin Transfer Method (RTM).
  • RTM Resin Transfer Method
  • vacuum is applied in the fiberglass solids in the mold before mixing with the resin.
  • the fiber is first washed with a stream of condensable gas through the same resin injection ports (particularly in SCRIMP), and the condensable gas is injected or infused while the system is still under vacuum. The process is continued until condensable gas is detected at the vacuum exhaust ports. Under these conditions the condensable gas stream will have adequately replaced all entrained air, traces of water vapor in the fibers, and other gases that may have been entrained by the solids.
  • the generic process offers an additional alternative which consists of cutting the vacuum flow, but retaining vacuum presence in the system.
  • This step is followed by pressure injected, outside evaporated, condensable gas at an elevated temperature, above the system's temperature, generally in a range of up to 4- 40 C above ambient temperature.
  • This gas injection is continued until the gas pressure in the outside evaporator, at the constant above ambient temperature selected, is in equilibrium with the internal pressure of the system.
  • This step is maintained until the amount of liquid in the external gas evaporation chamber has been evaporated.
  • the additional external condensable gas at higher temperature that has been introduced will thereby elevate the temperature of the fiber solids and, thus, is able to reach the mold corners and other difficult spots because of its higher pressure.
  • the condensable gas is able to disperse some of the original entrained air, water vapor and other non-condensable gases that may not have been totally removed.
  • the temperature of the condensable gas drops by giving off its heat to the colder solids, it will partially condense until pressures are in equilibrium.
  • vacuum is reestablished in the system and the condensable gas that has condensed will re-evaporate at each condensation spot and stream out under the vacuum, entraining the remaining air, water vapor and other gases.
  • the solids are now air-free, water vapor-free and soaked with condensable gas.
  • the reinforcing solid in Example 2, is a laminar fiberglass mat which is placed inside a close mold.
  • the same mold will serve, in this case, as a degassing device, mixing device, condensation device and solidification/molding device.
  • the mold Upon placement of the fiberglass mat, the mold is closed and evacuated while a condensable gas, preferably evaporated externally from a gasifiable liquid, is fed into the closed mold under vacuum for a sufficient time to completely soak the fiber glass mat and to displace all entrained air and other gases in the fiber glass solid.
  • O 2 presence in the exhaust ports of the mold can be monitored with an O 2 , sensor.
  • the processed primary fiber glass phase is now air-free, soaked with condensable gas, and ready for mixing with a separately degassed primary liquid polymer resin phase.
  • Liquid phase degassing is done by conventional thin film technology as disclosed in prior art. ii. Stage H-Air free mixing of the two air free primary phases
  • Stage II, air-free, two-primary phase mixing begins by infusing (SCRIMP) or injecting (RTM) the degassed primary liquid resin system under vacuum in the system. It is particularly important that the resin system is degassed and air-free. Once the liquid resin has been introduced filling the mold and soaking the solid phase, condensable gas in the system will be occluded in the mix.
  • Liquid polymer resin is injected under positive pressure per conventional RTM technology through conveniently located ports and distribution channels into the mold, until the liquid resin emerges from the separate vacuum exhaust ports. At this point both the vacuum and resin ports are closed and left closed until the beginning of the condensable gas condensation.
  • condensation of the condensable gas typically Stage in may have already occurred in Stage ⁇ , under the pressure of the resin injection. This is more likely in cases such as the straight forward laminar shape of the mold used in Example 2, and detailed in Table 4. However, in more complex shapes, and/or pieces with variable sections, it is preferred to place the closed mold with contents in a pressure chamber and pressurize the system to an adequate pressure for a sufficient time to achieve a void-free fiber reinforced polymer compound of the quality level required per conventional RTM technology.
  • the characterized compound invention condition will have been reached when:
  • Table 4 reveals the material specifications and process parameters to yield a void- free and occlusion free fiber reinforced polymer (FRP) material.
  • FRP fiber reinforced polymer
  • Special care may be necessary during the primary liquid phase degassing step to produce a void-free composite made from either a sheet molding compound (SMC) or a bulk molding compound (BMC) or pultrusions.
  • SMC sheet molding compound
  • BMC bulk molding compound
  • pultrusions a void-free composite made from either a sheet molding compound (SMC) or a bulk molding compound (BMC) or pultrusions.
  • conventional methods can be used to degas the primary liquid phase.
  • thin-film vacuum degassing of the thermosetting resin is generally sufficient to produce a void-free fiber or aggregate- reinforced composite.
  • solidification or cross-linking occurs at elevated temperature and pressure, as with composites made from a SMC, a BMC or pultrusions, physical and chemical changes within the void-free compound may lead to the formation of voids in the composite.
  • Voids in a composite made from a substantially void free solidifiable compound results from gassing that may occur during the solidification and/or forming (compression molding) steps. Gassing may occur for many reasons.
  • a component of the solidifiable compound may decompose at the high temperatures and pressures involved in compression molding.
  • granular aluminum trihydrate is often used as a filler in SMC and BMC formulations, but may begin to liberate water and decompose at 180°C and 1 bar.
  • compound constituents may react at elevated temperature and pressure producing unwanted gas. It is well known, for example, that calcium carbonate (a common filler) can react with acidic groups in unsaturated polyester resins forming CO2-
  • Gas may be formed in other ways.
  • the liquid resin system may contain dissolved gases that remain in solution when degassed under vacuum using conventional methods. These gases are liberated when the resin is exposed to high vacuum or when, at moderate vacuum, the resin is heated to high temperature; the presence of solids appears to increase gas production as well. In some cases, even the liquid monomer in a polyester resin system or the condensed washing gas may vaporize when the solidifiable compound is cured at sufficiently high temperatures, but without sufficient pressure.
  • the liquid phase should be degassed prior to mixing under the following conditions to help prevent voids or gas occlusions in the composite.
  • the primary liquid phase need only be degassed at ambient temperature under a vacuum of about 200 mm Hg. Furthermore, if the compound is cured at ambient pressure or up to about 8 bar and at a temperature between about 50°C and about 80°C, the primary liquid phase should be thin- film degassed at ambient temperature under a vacuum of about 50 mm Hg or less.
  • degassing should first be carried out at an appropriate temperature in a stripping processors at high vacuum levels but lower than the resin solvent monomer vapor pressure of the primary liquid phase, followed by compression at the same appropriate temperature and vacuum between about 100 mm Hg and 200 mm Hg, in order to condense immediately the resin solvent monomer.
  • a standard striping column designed for the above degassing conditions may be used.
  • the descriptions detailed above illustrate the many facets and applications of the generic void-free method in composite technology and production.
  • the inventive method can be utilized to produce a vast array of void-free polymeric compounds and composites.
  • a polymer concrete sample and a fiber reinforced polymer composite sample free of gas occlusions and voids has been produced and detailed herein.
  • FIGURE 6 illustrates a preferred embodiment of the apparatus for batch replacement of air, water vapor, or other gases normally contained within the interstices, spaces or voids of the primary solid phase at ambient temperature and pressure, by a condensable gas prior to batch mixing with a solidifiable liquid phase to yield, a two- primary phase solidifiable polymer concrete compound free from non-condensable gas occlusions.
  • the compound is poured from the mixer into a mold in air-free and non- condensable gas free environment.
  • the apparatus When the solidifiable compound is in the mold, the apparatus is pressurized to condense the condensable gas in the compound already in the mold, and optionally, can be solidified in the mold to produce a gas occlusion free and void-free composite formed in the shape or configuration of the mold.
  • the apparatus 30 shown in FIGURES 6A and 6B include mixing chamber 31 with a mold 32 attached to it.
  • the apparatus 30 has 2 operating positions : for mixing (FIGURE 6a) and for pouring the solidifiable mixed compound into the mold (FIGURE 6b).
  • the primary solid phase is placed in the mixing chamber 31 , preferably with a Class I gasifiable liquid.
  • Vacuum is applied through the vacuum inlet port 33 and the entire assembly is rotated mechanically about its longitudinal axis as indicated at 34 for 1 to 2 minutes with vacuum shut off.
  • the contents of solids and gasifiable liquid are washed thoroughly together. This allows the gasifiable liquid to completely wet out the solids and to begin an evaporation process.
  • the resulting condensable gases evaporated from the liquid to replace the air, water vapor associated with air, or other gases in the solids.
  • the system is stopped for 1 or 2 minutes and vacuum reestablished to evacuate the air, water vapor associated with air or other gases entrained in the condensable gas.
  • the wash cycle is repeated, preferably at least four times, without addition of condensable gas. Upon completion of the washing stage, the primary solid phase will have all its voids filled with condensable gas.
  • this step is accomplished by rotation of the apparatus 30 until the attached mold 32 is in the bottom position. Once the solidifiable mixed state compound is lodged in the mold, at rest, a thin film of liquid resin is formed over the top exposed surface after a short period of vibration (depending on the size and shape of the mold of) 1 or more minutes with the vibration device 39.
  • Pressure in the apparatus 30 is increased by allowing pure CO 2 gas to enter into the apparatus through inlet port 35.
  • This pressurizing gas is at atmospheric pressure or preferably at an absolute pressure at least equal to 2 times the condensable gas vapor pressure at the process temperature.
  • the CO 2 gas environment maintains the system air free and eliminates presence of O 2 from outside air to ensure optimal solidification of the primary solidifiable liquid phase in the compound.
  • the pressure of the CO 2 is exerted on the mold contents through the thin barrier layer of resin on its upper exposed surface, which is sufficient to prevent CO gas dispersion into the material in the mold, yet its pressure will condense the condensable gas within the solidifiable mixed state compound in the mold , and further maintenance of CO 2 gas pressurized condition for at least 1 minute will ensure the solidifiable liquid phase will enter all voids in the compound.
  • the two primary phase solidifiable compound in mixed state in the mold 32 will have reached the characterized condition of freedom from non-condensable gas occlusions and voids.
  • the mixed state compound is left to solidify in the mold 32 under positive CO 2 absolute pressure conditions.
  • the mold 32 is removable as indicated by the bolted joint 36 and bolt fasteners 37. This allows the compound to be cured in the mold 32 off-line while a new, empty mold is reattached to the apparatus 30 so that compound production can be expedited.
  • the mixer 31 is demountable at a similar bolted joint 38 to allow maintenance and repair, and also to allow attachment of other mixing chambers 31 of differing capacities and geometrical shapes, or allow attachment of a hopper equipped with a conventional air tight auger screw type discharge device in place of mold 32, to intermittently discharge discrete metered amounts of gas occlusion free solidifiable compound from the apparatus into external molds.
  • FIGURE 7 illustrates a preferred embodiment of an apparatus 40 for continuous void-free production of polymer concrete.
  • the apparatus 40 can be used in a method of production involving the replacement of air, water vapor or other gases normally contained within the interstices, spaces or voids of the primary solid phase at ambient temperature and pressure, by a condensable gas prior to continuously mixing with a solidifiable polymer concrete compound free from non-condensable gas occlusion and voids.
  • the apparatus 40 includes a condensable gas displacement/replacement counter- current column 46 with an upper zone vacuum chamber 26.
  • a controlled vacuum condition is maintained to exhaust air, vapors and gases, normally entrained in the primary solid phase which are continuously displaced/replaced by a stream of condensable gas.
  • a lower discharge zone 27 is connected at one end to the column 46 and to the shroud 49 of a continuous screw type mixing apparatus 28.
  • Inlets 48 for the condensable gas are provided in the shroud 49 to flood with the condensable gas the discharge zone 27 of the column 46 and the adjacent volume inside the shroud where processed solids are discharged.
  • Condensable gas horizontal deflector baffles 47 are provided inside the column wall to effectively distribute the upward stream of condensable gas, traveling towards the upper zone vacuum chamber 26, with the primary solid phase falling by gravity in the column. This counter flow of condensable gas produces a washing effect which displaces and replaces entrained air and other gaseous substances in the primary solid phase by the condensable gas.
  • Oxygen sensing devices 62 are provided in the column 46 at different levels to monitor the presence of air and to ensure no oxygen is detectable in the lower discharge zone 27 or in the flooded shroud zone 49 of the continuous mixing apparatus 40. This monitoring is achieved by means of a gas control and feedback system 30. If oxygen is detected by the monitors 62, the control system 30 appropriately adjusts the level of condensable gas entering the inlets 48.
  • a vibrating device 60 with vibration control mechanism is attached externally to the column wall to avoid agglomeration and promote free flow of the primary solid phase, and also to ensure its continuous gravity downward travel.
  • Flexible connections 63 are provided at the upper and lower extremes of the column
  • the receiving hopper 43 is provided with rotating seal valves 42 and 45 located at its upper inlet port 41 and at its lower discharge port to provide passage, under vacuum, of the primary solid phase from atmospheric conditions into the controlled vacuum gas displacer column 46.
  • the upper inlet port seal valve 42 of the hopper 43 is connected to the external supply of primary solid phase at open atmospheric conditions and prevents breaking vacuum inside the receiving hopper 43.
  • the vacuum chamber 44 in the hopper 43 is provided with vacuum to also assist in the reduction of the amounts of entrained gases and vapors in the incoming primary solid phase as it continuously passes through the hopper 43, so upon its discharge into the upper zone 26 of the gas displacer/replacer column apparatus, the entrained air, gas and vapor substances in the solids have been significantly reduced by vacuum.
  • the lower discharge seal valve 45 of the receiving hopper 43 allows the maintenance of differentia] vacuum levels between the hopper 43 and the column 46 for more effective control of the displacement/replacement function in the gas replacer column apparatus.
  • the processed primary solid phase is air and water vapor free and flooded with condensable gas, essentially ready to begin the continuous mixing process with a primary solidifiable liquid phase (which has been previously degassed externally), to form a two primary phase unsolidified polymer concrete compound exempt of gas occlusions, and voids, as per the present invention.
  • the mixing apparatus 40 of the present invention is also provided with a motor control 68 for controlling the operation of the rotating seal valves 42,45.
  • Sensors 69,70 located in the hopper 43 sense the level of the solids therein and provide a signal to the controller 68.
  • a control signal is then provided from the controller 68 to the DC motor 72 controlling the operation of the upper rotating valve 42.
  • sensors 64 and 65 located in column 16 sense the level of the solids therein and provide a signal to the controller 68.
  • a control signal is then provided to DC motor 67 for controlling the operation of the lower rotating seal valve 45.
  • Meters 66, 71 are provided in column 46 and the hopper 43, respectively, in order to sense the vacuum level within these enclosed containers.
  • the continuous mixing apparatus 40 comprises preferably a continuous mixing device 27 of the shrouded rotating screw type, appropriately modified to comply with the following requirements:
  • Condensable gas inlet ports 48 into the screw shroud 49 must be provided with a mechanism 30 for adjusting the pressure and flow of the condensable gas. Inlet ports 48 should be suitably located adjacent to the column discharge zone 27 where the air-free primary solid phase, soaked with condensable gas, enters the screw shroud 49, so as to provide a continuous counter-current stream of condensable gas through the connection between the shroud and the discharge zone moving upwards into the gas replacer column 46.
  • the internal zone within the screw shroud 49 must be maintained continuously flooded with condensable gas at all times when the mixer 28 is running.
  • zone must be provided with a shielding, such as a double seal device 55 to maintain the drive extension 31 of the mixing screw 28 flooded with condensable gas in liquid state to prevent contamination from leaks of external atmospheric air.
  • the drive extension 31 connects a reducer 59 mounted on the drive output of DC motor 58 which rotates the mixing screw 28.
  • the level of liquid state condensable gas in the double seal chamber 55 can be determined by the gas level device 57.
  • the entry port 50 for feeding degassed, air-free primary solidifiable liquid phase into the continuous mixing device 40 must be suitably located downstream, and sufficiently away from the processed primary solid phase entry zone 32 of the shroud 49.
  • the downstream configuration of the mixing screw 28 and shroud 49 in the continuous mixing device between the solidifiable liquid phase enter zone 33 and the final discharge port 53 of the continuous mixing device is subject to the following design requirements: i) The rotating screw 28 must impart sufficient absolute pressure within any point of the two primary phase mixed state compound being formed as it advances towards the discharge port 53 and to completely condense the condensable gas within the primary liquid phase of the mix and to force liquid resin into any voids. Such pressure must be maintained over the range of screw operational speeds, including its minimum speed. This may be accomplished by means of an enlarged diameter section 54 of the multisection mixing screw 28. This section 54 serves to increase the pressure of the mixture within this condensation zone 34 by reducing the annular space between the screw 28 and the shroud 49.
  • Machine void-free compound discharge must provide means for discharge of a non-condensable gas occlusion free and void-free compound so that its characterization is assured when the machine stops, such as an air tight, sealable, flexible spout 73 to seal off the external air entrance. Also provided is a means for discharging the compound so that its void-free characterization is assured, such as air tight, sealable, flexible spout stops 35 as having spring or other biasing means to maintain tight closure.
  • the apparatus is further capable of accumulating discrete and sufficient amounts of void- free polymer concrete compound in it to enable intermittent discharge of the void-free material into discrete receiving containers of discrete unit volume, under air free conditions.
  • FIGURE 7a and FIGURE 7b illustrate an apparatus for continuously de-airing fiber rovings with a condensable gas prior to mixing with the degassed primary liquid phase.
  • the apparatus is especially useful for treating the primary solid phase in sheet molding compounds and in compounds formed by pultrusions or filament winding.
  • the apparatus operates in a manner similar to treatment of the primary solid phase in the RTM application described above.
  • the apparatus comprises a vacuum chamber 10 and a number of parallel, freely rotating rubber conveying rollers 12 that are mounted within the vacuum chamber.
  • fiber rovings are introduced into the vacuum chamber through an entrance port 14 located in the top end of the vacuum chamber, pass over the conveying rollers, and leave the vacuum chamber through the exit port 16 located in the bottom end of the vacuum chamber.
  • Condensable gas (monomer in a polyester resin system, say) is introduced into the vacuum chamber through a feed port 22 located near the exit port, flows upward in a direction counter to the direction of the fiber rovings, and exits the vacuum chamber, along with entrained air and other non-condensable gases, through a vacuum port located near the entrance port.
  • internal seals 24 force the condensable gas to pass through the fiber rovings in the gap 26 between each conveying roller.
  • the vacuum chamber can be split along its length into a front shell 28 and a back shell 30 shell.
  • a perimeter seal 32 is provided to maintain vacuum when the chamber is reassembled.
  • Electric insulators intended for high voltage applications previously have been preferably made of porcelain materials. However, more recently it bas been found that polymer concrete could be used as the material for such insulator applications. Additionally, these insulators provide advantages in both cost and performance.
  • U.S, Patent No. 4,210,774 discloses a polymer concrete insulator having dielectric and mechanical properties far superior to those of conventional porcelain insulators.
  • a void-free material would be desirable for use in high voltage electrical insulators.
  • the insulators prepared from special formulations for void-free dielectric polymer concrete, as detailed in Example 1 , produced by the generic void-free method of the present invention, are designed to be formed or shaped by machining the insulator shape directly from cast void-free polymer concrete cylindrical stock, or by conventional shape molding methods.
  • the resulting insulators formed by machining have controllable surface finish and very tight dimensional tolerances, as well as excellent and improved dielectric characteristics and mechanical strength.
  • the finish of the machined surfaces can be controlled for enhanced adhesion of specialized material coatings in thin films on to the machined surfaces, rendering the insulator non-hygroscopic and hydrophobic for outdoor service.
  • insulators fabricated from void-free dielectric polymer concrete made in accordance with the present invention exhibit dramatically increased voltage threshold for initiation of partial discharges within the body of the insulator, thus extending their useful life.
  • FIGURE 8A-8C illustrate an insulator produced from methods and materials of the present invention.
  • FIGURE 8 A and 8C are top and bottom views, respectively, and
  • FIGURE 8B is a longitudinal cross-sectional view.
  • the insulator 80 in FIGURE 8 is a resistive voltage grading device whose body 81, shields 84, all bores 83 and holes 85 to install threaded metallic contacts 82, have been machined from a cylindrical stock of void-free polymer concrete composite material complying with both the visual count void-free criteria of no visible voids of 0.5 micron diameter at 1250x magnification and dielectric criteria of no visible partial discharges seen in an oscilloscope screen when subjected to voltages of 90-100KV.
  • the good machinability of the void-free dielectric polymer concrete material of the present invention enables production of all classes and types of electric transmission and distribution insulators, as well as other devices such as bushings and insulator plates or rings.
  • Insulators include suspension pin type, strain, line post, etc., preferably in higher voltages ranges up to 100KV or even beyond.
  • material formulations appropriate for void-free, dielectric polymer concretes have also excellent machinability.
  • finished electric insulators of high quality can be efficiently shaped by conventional machining with special cutting tools from cast polymer concrete stock material produced using the inventive void-free method.
  • machining is a high efficiency and high productivity forming method far superior to the conventional method of forming insulators by shape molding materials in conventional shape molds, in that better quality insulators can be produced faster, with shorter lead times and at much reduced mold and labor costs.
  • very accurately dimensioned dielectric polymer concrete flat plates parts can be produced, cut from cast polymer concrete stock into slabs and then surface finished by milling, drilling, boring, etc. as required.
  • the present invention can be implemented in many apparatus, methods and processes to produce a variety of void-free compounds and composites. Accordingly, the scope of the invention should be determined by the claims and not limited to the preferred embodiments described above.

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Abstract

L'invention concerne un procédé générique pour fabriquer des matériaux sans occlusion de gaz ni vide ainsi que des appareils servant à la fabrication en masse et en continu de ces matériaux. Ce procédé générique peut être utilisé dans la fabrication d'une vaste gamme de composés et de composites polymères. Il englobe notamment les deux extrêmes de la gamme des composites polymères, à savoir d'une part les ciments polymères et d'autre part les composites polymères renforcés par fibre de verre. Les matériaux composites de la présente invention se caractérisent visuellement par l'absence d'occlusion de gaz et de vide à l'échelle d'un micromètre, avec un grossissement x 1250. Parallèlement, l'invention permet de fabriquer des matériaux utiles à base de ciment polymère. Comparés aux matériaux composites fabriqués selon des procédés traditionnels, ces matériaux font preuve d'une meilleure intégrité, ce qui permet de les usiner à des vitesses élevées, ainsi que d'une résistance diélectrique et mécanique plus élevée. Pour ces raisons, on utilise les matériaux faisant l'objet de cette invention, notamment les matériaux isolants pour tensions élevées et les isolateurs pour lesquels la présence de poches de vide ou de fissures provoquées par l'occlusion de gaz peut avoir des effets dégradants et provoquer une panne prématurée.
EP98958677A 1998-11-23 1998-11-23 Procede et appareil d'elaboration de composites Withdrawn EP1177082A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1998/024862 WO2000030821A1 (fr) 1997-09-05 1998-11-23 Procede et appareil d'elaboration de composites

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EP1177082A1 true EP1177082A1 (fr) 2002-02-06

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EP (1) EP1177082A1 (fr)
CA (1) CA2355601A1 (fr)
MX (1) MXPA01005003A (fr)

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* Cited by examiner, † Cited by third party
Title
See references of WO0030821A1 *

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MXPA01005003A (es) 2002-04-24

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