method, thermoset polymer composite yarn and interlaced cable

专利摘要:
COMPOUND WIRES AND THERMOFIXED POLYMER CABLES LOADED WITH FIBER REINFORCED NANOPARTICLES, AND METHODS. The present invention relates to yarns composed of thermosetting polymer including a multiplicity of substantially continuous fibers embedded in a solidified polymer composite matrix and the formation of a substantially continuous filament, the matrix of a solidified polymer composite including additionally a polymer formed by curing of a polymer precursor from a liquid state and a multiplicity of nanoparticles having a median diameter of one micrometer or smaller dispersed substantially uniformly throughout the polymeric composite matrix, and optionally, a corrosion resistant wrap around the filament substantially continuous. In some embodiments, the multiplicity of particles includes surface-modified particles that have a core and a surface-modifying agent associated with the core and reacted with the polymer cured from a liquid state. Interwoven cables including one or more of these wires composed of thermoset polymer, and methods of making and using these wires composed of thermoset polymer and interwoven cables are also described.
公开号:BR112013006116B1
申请号:R112013006116-2
申请日:2011-09-14
公开日:2021-01-05
发明作者:David M. Wilson；David R. Mekala；Colin Mcculough；Herve E. Deve；Michael F. Grether；Emily S. Goenner；Kristin L. Thunhorst；Per M. Nelson
申请人:3M Innovative Properties Company；
IPC主号:

专利说明:

Reference to the related order
[001] This application claims the benefit of US provisional patent application No. 61 / 383,906, filed on September 17, 2010, and 61 / 427,941, filed on November 29, 2010. Technical Field
[002] The present description relates to thermoset polymer composite yarns that include reinforcement fibers and nanoparticles, cables made using these thermoset polymer composite yarns, and methods of manufacturing and using these composite yarns and polymer cables. Background
[003] Cable interlacing is a process in which individual wires are combined, typically in a helical arrangement, to produce a finished cable. The resulting interlaced cable provides greater flexibility than is available from a solid rod of equivalent cross-sectional area. The interlaced arrangement is also beneficial, as the braided cable maintains a circular shape in cross section from end to end, when the cable is subjected to flexing during handling, installation and use. These interlaced cables are used in a variety of applications such as crane cables, aircraft cables, submarine cables and chains, and cables for the transmission of electricity.
[004] Interlaced electric power transmission cables are typically produced from ductile metals, such as steel, aluminum or copper. In some cases, such as exposed overhead power transmission cables, a core of twisted wire is surrounded by a conductive layer of twisted wire. The interlaced wire core can comprise ductile metal wires produced from a first material such as steel, for example, and the energy conducting outer layer can comprise ductile metal wires produced from another material such as aluminum, for example. In some cases, the twisted wire core may be a pre-twisted cable used as an input material for making a larger diameter electrical power transmission cable. Interwoven power transmission cables can generally comprise only seven individual wires to more common constructions containing 50 or more wires.
[005] During the cable interlacing process, ductile metallic wires are subject to stresses beyond the elastic limit of the metallic material, but before the maximum limit or failure limit. This stress acts to plastically deform the metallic wire as it is wound helically around a relatively small radius of the previous wire layer or central wire. Recently, useful cables produced using composite yarns made from materials that cannot be readily deformed plastically into a new shape, and that can be brittle, have been introduced.
[006] An example of such composite wire cables is provided by a metal matrix composite wire cable containing fiber reinforced metal matrix composite wires. These metal matrix compound wires are attractive due to their improved mechanical properties over ductile metal wires, but which are elastic mainly in their response to stretching stress. Some polymer composite yarn cables containing fiber-reinforced polymer matrix composite yarns are also known in the art, for example, fiber-reinforced polymer matrix composite yarns disclosed in U.S. Patent No. 4,961,990; 5,126,167; 7,060,326; 7,093,416; 7,179,522; 7,438,971; 7,683,262; and PCT International Publication No. WO 97/00976. summary
[007] In short, in one aspect, the present description describes a method which comprises impregnating a plurality of substantially continuous fibers with a polymeric composite matrix comprising a liquid polymeric precursor and a plurality of particles having a median diameter of a micrometer or smaller (ie, nanoparticles) dispersed substantially uniformly throughout the liquid polymer precursor, pulling the fibers impregnated with the polymer compound matrix through a mold, at least partially solidifying the polymer composite matrix in the mold to form a substantially continuous thermoset polymer composite yarn filament, and optionally surrounding the substantially continuous composite yarn filament with a corrosion resistant wrap. In certain exemplifying modalities, the multiplicity of particles is formed by nanoparticles that have a median diameter of no more than 1,000 nm, 900 nm, 800 nm, 750 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 250 nm , 200 nm, 100 nm, or even 50 nm.
[008] In some exemplifying modalities, the multiplicity of particles comprises nanoparticles with modified reactive surface that comprise a nucleus and a reactive surface modifying agent associated with the nanoparticle nucleus. In certain exemplifying embodiments, the multiplicity of nanoparticles has a median diameter of no more than 1,000 nm, 900 nm, 800 nm, 750 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 250 nm, 200 nm, 100 nm, or even 50 nm. In some particular embodiments, the multiplicity of particles comprises no more than 40% by weight of the polymeric composite matrix.
[009] In some aspects and embodiments, the multiplicity of substantially continuous fibers are substantially parallel in a direction substantially parallel to a longitudinal axis of the substantially continuous composite yarn filament. In some particular exemplifying embodiments, the multiplicity of substantially continuous fibers additionally comprises a multiplicity of fiber surfaces, and the multiplicity of particles does not come into substantial contact with the multiplicity of fiber surfaces. In some of the aforementioned embodiments, the corrosion resistant wrap comprises at least one radiation cured polymer, thermoset polymer, thermoplastic polymer that has a glass transition temperature of at least 145 ° C, fluoropolymer, tape, or a combination thereof.
[0010] In other exemplary embodiments mentioned above, the cured liquid polymer precursor has a glass transition temperature of at least 150 ° C. In some exemplary embodiments, the liquid polymer precursor comprises an epoxy resin, and a multiplicity of particles comprising 0.5 to 40%, by weight, of the polymeric composite matrix. In certain exemplary embodiments, the cured liquid polymer precursor comprises a vinyl ester resin, and a plurality of particles comprising 0.5 to 40%, by weight, of the polymeric composite matrix.
[0011] In other examples mentioned above, the solidification at least partially of the polymeric composite matrix in the mold comprises the crosslinking of the liquid polymer precursor. In additionally exemplifying modalities, the method also comprises pulling the continuous fibers impregnated with the matrix through a prefabrication and reduction of the volume of the fibers. In certain exemplary embodiments, the method further comprises post-curing the partially cured liquid polymer precursor after at least partially solidifying the polymeric composite matrix in the mold to form the composite yarn filament. In some specific exemplifying embodiments, a tensile force necessary to form the yarn filament composed of the specified composition at a specified line speed is reduced by at least 20% compared to a tensile force necessary to form, at the specified line speed , a composite yarn that has the specified composition, but omitting the multiplicity of particles.
[0012] In another aspect, the description describes a yarn composed of thermoset polymer produced according to any of the previous methods.
[0013] In yet another aspect, the description describes a yarn composed of thermoset polymer that comprises a multiplicity of substantially continuous fibers embedded in a polymeric composite matrix and forming a substantially continuous filament, and the solidified polymer composite matrix further comprises , a polymer formed by curing a polymeric precursor from a liquid state and a multiplicity of particles that have a median diameter of one micrometer or smaller (ie, nanoparticles) and dispersed substantially uniformly throughout the entire composite matrix polymeric, and optionally, a corrosion resistant wrap surrounding the substantially continuous filament.
[0014] In some exemplifying embodiments, the multiplicity of particles comprises particles with modified surface that further comprise a core of nanoparticles and a reactive surface modifying agent associated with the core of the nanoparticle and reacted with the polymer cured from a state liquid. In certain exemplifying embodiments, the multiplicity of nanoparticles has a median diameter of no more than 1,000 nm, 900 nm, 800 nm, 750 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 250 nm, 200 nm, 100 nm, or even 50 nm.
[0015] In some of the thermosetting polymer composite yarn modalities, the multiplicity of substantially continuous fibers is substantially parallel in a direction substantially parallel to a longitudinal axis of the substantially continuous composite yarn filament. In some specific exemplifying embodiments, the multiplicity of substantially continuous fibers further comprises a multiplicity of fiber surfaces, and the multiplicity of particles (i.e., nanoparticles) does not come into substantial contact with the multiplicity of fiber surfaces. In some of the aforementioned embodiments, the corrosion resistant wrap comprises at least one radiation cured polymer, thermoset polymer, thermoplastic polymer that has a glass transition temperature of at least 145 ° C, fluoropolymer, tape, or a combination thereof.
[0016] In other exemplary embodiments of any of the thermofixed polymer composite yarn mentioned above, the solidified polymer composite matrix has a glass transition temperature of at least 150 ° C. In additional exemplary embodiments of any of the aforementioned polymer composite yarn modalities, the polymer formed by curing a polymer precursor from a liquid state comprises at least one thermoset resin selected from an epoxy resin, a resin from vinyl ester, a polyimide resin, a polyester resin, a cyanate ester resin, a phenolic resin, a bis-maleimide resin, or a combination thereof. In some exemplary embodiments, the polymer formed by curing a polymer precursor from a liquid state comprises an unsaturated polyester resin.
[0017] In certain presently preferred embodiments, the solidified polymer composite matrix comprises the cured (i.e. crosslinked) liquid polymer precursor. In certain presently preferred embodiments, the solidified polymer composite matrix comprises an anhydride-cured epoxy resin. In some presently preferred embodiments, the solidified polymer composite matrix has a glass transition temperature of at least 150 ° C.
[0018] In some presently preferred embodiments, the cured liquid polymer precursor has a glass transition temperature of at least 150 ° C. In other specific exemplifying embodiments, the cured liquid polymer precursor comprises an epoxy resin, and the multiplicity of particles comprises from 0.5 to 40%, by weight, of polymeric composite matrix. In certain presently preferred embodiments, the cured liquid polymer precursor comprises a vinyl ester resin, and the multiplicity of particles comprises from 0.5 to 40%, by weight, of the polymeric composite matrix.
[0019] In additionally exemplifying modalities of any of the previous polymer composite yarn modalities, the multiplicity of continuous fibers comprises at least one fiber selected from the group consisting of aramid fibers, glass fibers, ceramic fibers, metallic fibers , polymeric fibers, carbon fibers, or combinations thereof. In some exemplary embodiments, the multiplicity of continuous fibers comprises at least 66 in volume of substantially continuous filaments.
[0020] In additional exemplary embodiments of any of the above polymer composite yarn embodiments, the plurality of particles comprises at least one surface modifying agent associated with a particle surface. In some exemplary embodiments, the multiplicity of particles comprises particles of silica, particles of calcite, or combinations thereof. In certain presently preferred embodiments, the plurality of particles comprises particles of silica that additionally comprise at least one surface modifying agent covalently attached to a surface of the silica particles. In other presently preferred embodiments, the multiplicity of particles comprises calcite particles which additionally comprise a surface modifying agent ionically associated with a surface of the calcite particles.
[0021] In some of the previous embodiments, the multiplicity of particles preferably has a median diameter of no more than 400 nm. In other exemplary embodiments, the multiplicity of particles preferably has a median diameter of no more than 250 nm. In certain exemplary embodiments, the multiplicity of particles preferably has a median diameter of no more than 100 nm. In some specific exemplifying modalities, the multiplicity of particles has a multimodal distribution of particle diameter on a numerical basis. In some specific exemplifying embodiments, the polymeric composite matrix comprises a multiplicity of filler particles that have a median diameter of at least 1 micrometer.
[0022] In certain exemplary embodiments, the wire composed of thermoset polymer has a cross-sectional diameter of about 1 mm to about 2.54 cm.
[0023] In yet another aspect, the description describes a thermoset polymer composite cable comprising at least one thermoset polymer composite yarn as described above. In some exemplary embodiments, the cable is an interlaced cable that comprises a core yarn defining a central longitudinal axis, a first multiplicity of wires intertwined around a core yarn, and a second multiplicity of yarn interlaced around the first multiplicity of wires.
[0024] In certain presently preferred embodiments, at least one of the core yarn, the first multiplicity of threads, or the second multiplicity of threads comprises at least one thread composed of thermoset polymer as described above. In some presently preferred embodiments, the core yarn is a yarn composed of thermoset polymer as described above. In addition to presently preferred embodiments, each core yarn, the first multiplicity of threads, and the second multiplicity of threads is selected to consist of threads composed of thermoset polymer as described above. In presently additional preferred embodiments, each of the multiplicity of threads in the cable is a thread composed of thermoset polymer.
[0025] In yet another aspect, the description describes a helical-woven thermofix polymer composite cable, which comprises at least one thermoset-polymer composite wire as described above, and the helical-woven cable having a core comprising a core yarn defining a central longitudinal axis, a first multiplicity of wires interlaced helically around the core in a first configuration direction and a first configuration angle defined in relation to the longitudinal axis and having a first configuration length, and a second multiplicity of wires interlaced in a helical shape around a first multiplicity of composite wires in a second configuration direction at a second configuration angle defined in relation to the central longitudinal axis and having a second configuration length.
[0026] In some of the previous interlaced cable modalities, the core wire is selected from the group consisting of a thermoset polymer composite wire, a thermoplastic polymer composite wire, a metallic matrix polymer composite wire, or a ductile metallic thread. In certain exemplifying embodiments, at least one of the first multiplicity of threads is selected from the group consisting of a thread composed of thermoset polymer, a thread composed of thermoplastic polymer, or a ductile metallic thread. In some exemplifying embodiments, at least one of the second multiplicity of threads is selected from the group consisting of a thread composed of thermoset polymer, a thread composed of thermoplastic polymer, or a ductile metallic thread.
[0027] In certain presently preferred embodiments, at least one of the core yarn, the first multiplicity of threads, or the second multiplicity of threads comprises at least one thread composed of thermoset polymer as described above. In certain presently preferred embodiments, the core yarn is a yarn composed of thermoset polymer as described above. In addition, in presently preferred embodiments, each core yarn, the first multiplicity of threads, the second multiplicity of threads is selected to constitute the threads composed of thermoset polymer as described above. In additional presently preferred embodiments, each of the plurality of threads in the cable is a thread composed of thermoset polymer.
[0028] In some specific exemplifying modalities, each wire has a cross section in a direction substantially normal to the central longitudinal axis, and the cross section shape of each wire is selected from the group that includes a circular, elliptical, and trapezoidal shape. In some specific examples of specific interlaced cable, the cross-sectional shape of each wire is circular, and the diameter of each wire is from about 1 mm to about 2.54 cm. In addition to exemplary interlaced cable modalities, each of the first multiplicity of composite wires and the second multiplicity of composite wires has a configuration factor of 10 to 150. In some presently preferred embodiments, the first configuration direction is equal to the second direction of settings. In certain presently preferred embodiments, a relative difference between the first configuration angle and the second configuration angle is greater than 0 ° and not greater than about 4 °.
[0029] In additionally exemplary interlaced cable modalities, the interlaced cable further comprises a third multiplicity of interlaced composite wires, most preferably helically interlaced around the second multiplicity of composite wires in a third configuration direction, in one third configuration angle defined in relation to the central longitudinal axis and having a third configuration length. In some exemplary embodiments, each of the third multiplicity of composite yarns has a configuration factor of 10 to 150. In certain presently preferred embodiments, the third configuration direction is the same as the second configuration direction. In some presently specific preferred embodiments, a relative difference between the third configuration angle and the second configuration angle is greater than 0 ° and not greater than about 4 °.
[0030] In additional exemplifying interlaced cable modes, the interlaced cable further comprises a fourth multiplicity of interlaced composite wires, more preferably helically interlaced around the third multiplicity of composite wires in a fourth configuration direction in a fourth configuration angle defined in relation to the central longitudinal axis and having a fourth configuration length. In some exemplary embodiments, each of the fourth multiplicity of composite yarns has a configuration factor of 10 to 150. In certain presently preferred embodiments, the fourth configuration direction is the same as the third configuration direction. In some presently specific preferred embodiments, a relative difference between the fourth configuration angle and the third configuration angle is greater than 0 ° and not greater than about 4 °.
[0031] In any of the aforementioned cable modalities, the multiplicity of continuous fibers comprises at least one fiber selected from metal fibers, polymer fibers, carbon fibers, ceramic fibers, glass fibers, or combinations thereof. In some exemplary embodiments, at least one continuous fiber comprises titanium, tungsten, boron, alloy with shape memory, carbon, graphite, silicon carbide, aramid, poly (p-phenylene-2,6-benzobisoxazole or combinations thereof). In some specific exemplifying embodiments, at least one fiber comprises a ceramic fiber selected from silicon carbide, aluminum, or aminosilicate In certain exemplifying embodiments, the polymer composite matrix comprises a (co) polymer selected from the group that includes in an epoxy, an ester, a vinyl ester, a polyimide, a polyester, a cyanate ester, a phenolic resin, a bis-maleimide resin, and combinations thereof.
[0032] In some specific examples of the aforementioned interlaced cable modalities, at least one of the composite wires is a fiber-reinforced metal matrix composite wire that further comprises at least one continuous fiber in a metal matrix, optionally being at least a portion of the composite yarns surround the at least one fiber-reinforced metal matrix composite yarn. In certain exemplifying embodiments, at least one continuous fiber comprises a material selected from the group including ceramics, glass, carbon, silicon carbide, boron, iron, steel, ferrous alloys, tungsten, alloy with format memory, and combinations the same. In some specific exemplifying embodiments, the metal matrix comprises aluminum, zinc, tin, magnesium, alloys thereof or combinations thereof. In certain currently preferred exemplary embodiments, the metal matrix comprises aluminum, and at least one continuous fiber comprises fiber-ceramic. In some particular preferred embodiments of the present invention, the ceramic fiber comprises polycrystalline α-Al2O3.
[0033] In any of the aforementioned interlaced cable modalities, the interlaced cable can also comprise a multiplicity of ductile metallic wires around the core wire defining the central longitudinal axis. In some exemplary embodiments, at least a portion of the multiplicity of ductile metallic threads is interwoven in a helical shape in the first layer direction. In certain exemplifying embodiments, at least a portion of the multiplicity of ductile metallic wires is interwoven in a helical shape in a second configuration direction opposite to the first configuration direction. In some specific embodiments, the multiplicity of ductile metal wires is interwoven around the core wire defining a longitudinal center axis in a multiplicity of radial layers that surround the composite wires. In certain specific exemplifying modalities, each radial layer is interlaced in a direction of configuration opposite to that of an adjacent radial layer.
[0034] In additional examples of the aforementioned interlaced cable modalities, each ductile metal wire can be selected to have a cross section in a direction substantially normal to the center longitudinal axis, and a cross section shape of each ductile wire is selected from the group that includes circular, elliptical, trapezoidal, S-shaped, and Z-shaped. In some specific exemplifying modalities, a multiplicity of metallic wires comprises at least one metal selected from the group that includes iron, steel, zirconium , copper, tin, cadmium, aluminum, manganese, zinc, cobalt, nickel, chromium, titanium, tungsten, vanadium, their alloys with each other, their alloys with other metals, their alloys with silicon, and combinations thereof.
[0035] In the additional exemplary interlaced cable modes, the relative difference between the first configuration angle and the second configuration angle is selected to be greater than 0 ° and not greater than about 4 °. In some exemplary embodiments, the relative difference between the first configuration angle and the second configuration angle is not greater than about 0.5 °. In certain exemplary embodiments, the first configuration length equals the second configuration length.
[0036] In a further aspect, the description describes a cable comprising a core and a conductive layer around the core, the core comprising any of the aforementioned interlaced cables. In some exemplary embodiments, the conductive layer comprises a plurality of interlaced conductive wires.
[0037] In another aspect, the description describes a cable as described above used for transmission of electrical energy. In some exemplifying modalities, the electric power transmission cable is selected from the group consisting of an overhead power transmission cable, an underground electric power transmission cable, and a submarine electric power transmission cable. In certain exemplifying modalities, the cable is a submarine electric power transmission cable selected from a submarine cable or a submarine umbilical cable.
[0038] In a final aspect, the description describes a method of making a thermoset polymer composite cable intertwined using at least one thermoset polymer composite yarn as described above, optionally combined with any non-polymer composite yarn thermoset described above. The method comprises the helical interlacing of a first multiplicity of wires around a core wire defining a central longitudinal axis, with the helical interlacing of the first multiplicity of wires being performed in a first configuration direction in a first configuration angle defined in relation to the central longitudinal axis; and the helical interlacing of a second multiplicity of wires around a first multiplicity of wires, and the helical interlacing of the second multiplicity of wires is carried out in the first configuration direction at a second configuration angle defined in relation to the central longitudinal axis. At least one of the core strands, the first strand multiplicity, or the second strand multiplicity comprises the at least one strand composed of thermoset polymer.
[0039] In certain exemplary embodiments, the first multiplicity of threads and / or the second multiplicity of threads includes a plurality of threads composed of thermoplastic polymer. In these exemplifying modalities, the method optionally includes heating the first and second multiplicity of helical interlaced wires, at a temperature sufficient to retain the helical interlaced wires in a helically interlaced configuration under cooling to 25 ° C. Optionally, the method includes surrounding the first and second pluralities of wires with a corrosion resistant wrap.
[0040] In some exemplary embodiments of a method of making an interlaced cable using any of the polymer compound wires described above, the multiplicity of particles comprise particles with modified surface comprising a nanoparticle core and a modifying agent surface associated with the nanoparticle core and reacted with the polymer cured from a liquid state. In other exemplary embodiments of a method of making a braided cable using any of the polymer composite wires described above, the relative difference between the first configuration angle and the second configuration angle is greater than 0 ° and not greater that about 4 °. In certain exemplary embodiments, the method of fabricating a cable intertwined using any of the polymer composite yarns described above further comprises interweaving a multiplicity of ductile metallic yarns around the core yarn defining the central longitudinal axis .
[0041] Several unexpected results and advantages are obtained in the exemplary modalities of the description. In some exemplifying modalities, the inclusion of a multiplicity of particles that have a median diameter of one micrometer or smaller, dispersed substantially uniformly throughout the polymeric composite matrix, allows the achievement of a carbon fiber volume fraction load in fiber-reinforced polymer composite yarn, thereby increasing compressive strength, shear modulus, hardness, and yarn bending resistance. The inclusion of a multiplicity of particles having a median diameter of one micrometer or less, dispersed in a substantially uniform manner throughout the polymer composite matrix was also shown with a decrease in the thermal expansion coefficient (CTE) and shrinkage after curing.
[0042] For example, a 25% reduction in CTE and a 37% reduction in linear shrinkage was obtained for a fiber-reinforced polymeric composite, including a multiplicity of particles having a median diameter of 500 nm or less dispersed in a manner substantially uniform throughout the polymer composite matrix compared to a control without the particles. These carbon fiber-reinforced polymer wires are particularly attractive for use in overhead electrical power transmission cables. In addition, carbon fiber reinforced polymer composite yarns may, in some cases, be produced at a lower cost than conventional ceramic fiber reinforced metal matrix polymer composite yarns.
[0043] Furthermore, in certain exemplifying embodiments, the inclusion of nanoparticles in the thermoset polymer composite yarn increases one or both of the flexural strength and flexural strength of the thermoset polymer composite yarn, and in some exemplary embodiments, one or both of flexural strength and flexural strength of a composite cable that incorporates this thermoset polymer composite wire. This not only improves the performance of the wire and / or cable, but provides significant advantages in the handling, transportation, and installation of the thermoset polymer composite wires and composite cables that incorporate these wires.
[0044] Additionally, in some exemplary embodiments, the polymer matrix of the composite core is mixed from an exclusive combination of an epoxy resin with a high glass transition temperature and a curative agent that makes the polymer matrix more stable at high temperatures (for example, as high as 280 ° C). Furthermore, in some exemplary embodiments, the use of high temperature glass transition epoxy resins (eg 240 ° C, 250 ° C, 260 ° C, or even greater Tg) in the polymer composite matrix can provide unequivocally improved high temperature performance compared to conventional thermoplastic polymer composite yarns known in the art. These unique high temperature performance characteristics are ideally suited for high voltage power transmission applications.
[0045] In other exemplary embodiments, the multiplicity of particles comprises particles with modified surface that further comprise a nanoparticle core and a reactive surface modifying agent associated with the nanoparticle core and reacted with the polymer cured from a liquid state . These chemically treated particles disperse particularly well in liquid polymer precursor matrix materials of epoxy resin and generally require lower pultrusion forces to pull the fibers through the mold during the process of making the composite yarn. This facilitates the production of thermoset polymer composite yarns at higher fiber loads, which is highly desirable to optimize the strength and mechanical properties of the composite yarns. This can also facilitate the production of composite yarns loaded with nanoparticles at a higher pultrusion line speed, or at a lower pultrusion pull force, compared to a resin system without nanoparticles.
[0046] Thus, in some exemplifying modalities, the tensile force required to form a wire composed of thermoset polymer is reduced by at least 30% in relation to the tensile force necessary to form the same fiber-reinforced polymer composite under the same conditions , but without the multiplicity of particles having a median diameter of one micrometer or less, it disperses substantially uniformly throughout the liquid polymeric precursor. In some embodiments, the tensile force required to form the fiber-reinforced polymer composite at a line speed of at least 20% greater than the baseline speed is less than the tensile force required to form the same reinforced polymer composite with fiber at base speed and without the multiplicity of particles that have a median diameter of one micrometer or less, dispersed substantially uniformly throughout the liquid polymer precursor.
[0047] Various aspects and advantages of exemplary modalities of the present invention have been summarized. The above summary is not intended to describe each illustrated modality or any implementation of the present certain exemplary modalities of the present description. The drawings and the detailed description below, more particularly exemplify certain preferred embodiments using the principles of the present invention presented. Brief description of the drawings
[0048] Figure 1A is a perspective view of a wire composed of thermoset polymer exemplifying the present description.
[0049] Figure 1B is a perspective view of an exemplary interlaced thermoset polymer composite cable that incorporates thermoset polymer composite yarns in accordance with certain exemplary embodiments of the present description.
[0050] Figure 1C is a perspective view of an exemplary interlaced thermoset polymer composite cable that incorporates thermoset polymer composite wires in accordance with certain other exemplary embodiments of the present description.
[0051] Figures 2A-2I are seen in cross section of end of several thermoset polymer composite cables that incorporate thermoset polymer composite wires according to certain exemplary embodiments of the present description.
[0052] Figures 3A and 3B are seen in end cross section of several exemplary thermoset polymer composite cables that incorporate thermoset polymer composite yarns and optional ductile metallic yarns in accordance with certain embodiments of the present description.
[0053] Figure 4A illustrates an exemplifying pultrusion process useful in the formation of thermoset polymer composite yarns according to certain exemplary embodiments of the present description.
[0054] Figure 4B illustrates an exemplary yarn interlacing process, useful in the formation of thermosetting polymer composite cables in helical shape that incorporate thermosetting polymer composite yarns and optional ductile metallic yarns according to certain exemplifying embodiments of the present description.
[0055] Figure 5A is a Scanning Electron Micrograph (SEM) image of a pultruded thermoset polymer composite bar containing a plurality of particles having a median diameter of one micrometer or less dispersed substantially uniformly throughout the matrix. polymeric composite.
[0056] Figure 5B is a SEM image with high magnification of the pultruded thermoset polymer composite bar exemplifying Figure 5A.
[0057] Figure 5C is a SEM image of another pultruded thermoset polymer composite bar containing a plurality of particles having a median diameter of one micrometer or less dispersed substantially uniformly throughout the polymer composite matrix.
[0058] Figure 5D is a SEM image with high magnification of the pultruded thermoset polymer composite bar exemplifying Figure 5C.
[0059] Same reference numerals in the drawings indicate identical elements. The drawings of the present invention are not represented to scale, and in the drawings, the components of the wires composed of thermoset polymer and cables are dimensioned to emphasize the selected characteristics. Detailed Description Glossary
[0060] Certain terms are used throughout the description and claims that, although most are well known, may require some explanation. It should be understood that, as used throughout this application:
[0061] The term "nanoparticle" means a particle (or plurality of particles) that has a median diameter of one micrometer (1,000 nm) or less, more preferably 900 nm or less, more preferably 800 nm or less, 750 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, 100 nm or less, 75 nm or less, or 50 nm or less.
[0062] The term "nanoparticle nucleus" means the solid interior portion of a surface treated with nanoparticle, a function being attributed to that outer surface.
[0063] The term "agglomerate" describes a weak association of primary particles commonly joined by charge or polarity. Agglomerated nanoparticles can typically be decomposed into smaller entities, for example, by shear forces encountered during the dispersion of the agglomerated nanoparticles in a liquid.
[0064] The terms "aggregate" and "aggregates" are descriptions of a strong association of primary particles commonly linked to each other, for example, by residual chemical treatment, covalent chemical bonds or ionic chemical bonds. Further decomposition of aggregates into smaller entities is very difficult to achieve. Typically, the aggregated nanoparticles are not decomposed into smaller entities through, for example, shear forces encountered during the dispersion of the aggregated particles in a liquid.
[0065] The term "(co) polymer" means a homopolymer or a copolymer.
[0066] The term "(meth) acrylate" means an acrylate- or a functional methacrylate compound.
[0067] The term "heat-hardened polymer" means a (co) polymer that is capable of undergoing a chemical reaction (for example, polymerization) for irreversible curing induced by the action of heat or appropriate actinic radiation (for example, by exposure to ultraviolet light, visible light, infrared light, and / our radiation by electronic beam (e-beam)), thus forming an infusible, insoluble (co) polymer matrix, preferably solid or reticulated semi-solid.
[0068] The terms "liquid polymer precursor," "uncured liquid polymer precursor," "heat-cured liquid polymer precursor," or "liquid-polymer material" collectively refer to chemically active heat-cured resins and any optional reactive diluents (for example monomers, oligomers, prepolymers, and the like) that are present initially in a viscous or viscoelastic liquid state and that are capable of chemically reacting (for example, curing, polymerization, crosslinking, and the like) to form a (co) polymer matrix.
[0069] The terms "liquid polymer precursor system," "liquid polymeric system," or "heat-cured liquid polymeric material" all refer to the combination of nanoparticles (which may have a modified surface), the liquid polymer precursor, and any additional components, for example solvents, dispersants, hardeners, dressings, initiators, promoters, cross-linking agents, hardeners, and fillers (for example, clay).
[0070] The term "thermoset" refers to a liquid polymer precursor system that is subjected, at least partially, to an irreversible curing process to change a meltable and soluble product to a highly intractable, preferably reticulated, form. solid or semi-solid that cannot be readily molded by flow.
[0071] The term “ceramic” means glass, crystalline ceramics, glass-ceramics and combinations thereof.
[0072] The term "polycrystalline" means a material that has predominantly a plurality of crystalline grains in which the grain size is smaller than the diameter of the fiber in which the grains are present.
[0073] The term "bending" or "flexing" when used to refer to the deformation of a wire includes two-dimensional and / or three-dimensional bending deformation, such as bending the wire in a helical shape during interlacing. When referring to a yarn as having bending deformation, this does not exclude the possibility that the yarn also has deformation resulting from tensile and / or interlacing forces.
[0074] Deformation by "significant elastic bending" means bending deformation that occurs when the wire is flexed to a radius of curvature of up to 10,000 times the radius of the wire. As applied to a wire with a circular cross section, this deformation by significant elastic bending gives an elongation to an external fiber of the wire of at least 0.01%.
[0075] The term "ductile" when used to refer to the deformation of a thread, means that the thread would be substantially subjected to plastic deformation during flexion or under tensile load without fracture or rupture.
[0076] The term "brittle" when used to refer to the deformation of a wire, means that the wire will be broken during flexion or under tensile load with minimal plastic deformation.
[0077] The term "wire" refers to matter (for example, metal in the case of a ductile metallic wire) formed in a single filament or cord.
[0078] The term "composite yarn" refers to a yarn formed from a combination of materials with different compositions or shapes that are bonded together.
[0079] The term "polymer composite yarn" refers to a composite yarn comprising one or more reinforcing materials attached to a matrix that includes one or more (co) polymeric phases, which may comprise thermoset (co) polymers or ( co) thermoplastic polymers with high glass transition temperature.
[0080] The term "thermoplastic polymer composite yarn" refers to a composite yarn that comprises one or more reinforcing fiber materials bonded in a matrix and including one or more thermoplastic (co) polymeric phases, and which exhibit ductile behavior.
[0081] The term "polymer composite yarn" refers to a composite yarn including one or more reinforcing fiber materials bonded in a cured matrix derived from a heat-hardened liquid (co) polymer precursor system comprising nanoparticles dispersed substantially uniformly in an uncured liquid polymer precursor system.
[0082] The term "polymer-ceramic composite yarn" refers to a composite yarn comprising one or more reinforcing ceramic fiber materials bonded in a matrix including one or more (co) polymeric phases.
[0083] The term "metallic matrix composite yarn" refers to a composite yarn that comprises one or more reinforcing fiber materials bonded in a matrix including one or more metallic phases, and which have a non-ductile and brittle behavior.
[0084] The terms "cabling" and "interlacing" are used interchangeably, in the same way as "wired" and "interlaced".
[0085] The term "layer" describes the way in which the wires in a twisted layer of a helically twisted cable are wound in a spiral.
[0086] The term "configuration direction" refers to the interweaving direction of the bundles of wires in a helically interlaced layer. To determine the layer direction of a helically twisted layer, an observer looks at the surface of the helically twisted wire layer as the cable points away from the observer. If the strands of wire appear to rotate clockwise as the strands advance away from the viewer, then the cable is called as having a "right side layer". If the strands of wire appear to rotate counterclockwise as the strands advance away from the viewer, then the cable is called as having a "left side layer".
[0087] The terms "central axis" and "central longitudinal axis" are used interchangeably to denote a longitudinal axis positioned radially in the center of a helically twisted multilayer cable.
[0088] The term "configuration angle" refers to the angle, formed by a twisted wire in helical shape, in relation to the central longitudinal axis of a twisted cable in helical shape.
[0089] The term "transverse angle" means the relative (absolute) difference between the layer angles of the adjacent wire layers of a helically twisted wire cable.
[0090] The term "layer length" refers to the length of a helical stranded cable in which a single strand in a helical stranded layer completes a helical revolution around the central longitudinal axis of a stranded stranded cable helical.
[0091] The term "continuous fiber" means a fiber that has a length that is relatively infinite when compared to the average fiber diameter. Typically, this means that the fiber has a ratio (i.e. ratio of fiber length to average fiber diameter) of at least 1 x 105 (in some embodiments, at least 1 x 106, or even at least 1 x 107 ). Typically, such fibers have a length of the order of at least about 15 cm to at least several meters, and can even have lengths of the order of kilometers or more.
[0092] Various exemplary embodiments of the present invention will be described below with specific reference to the drawings. The exemplary modalities of the present description can have several modifications and alterations without deviating from the spirit and scope of the description. Consequently, it should be understood that the modalities of the present description should not be limited to the exemplary modalities described below, but must be controlled by the limitations established in the claims and any equivalents thereof. Thermoset polymer composite yarns
[0093] In an exemplary embodiment of a thermosetting polymer composite yarn, the present description describes a thermosetting polymer composite yarn comprising a plurality of substantially continuous fibers embedded in a solidified polymer composite matrix and forming a substantially continuous filament, the matrix polymeric composite material further comprising a polymer formed by curing a polymeric precursor from a liquid state and a plurality of particles having a median diameter of one micrometer or smaller (i.e., nanoparticles) dispersed substantially uniformly throughout the matrix of polymeric composite, and optionally, a corrosion resistant wrap (described further below) surrounding the substantially continuous filament.
[0094] In some exemplary embodiments of such a wire composed of thermoset polymer, the plurality of particles comprise particles with modified surface that further comprise a nanoparticle core and a reactive surface modifying agent associated with the nanoparticle core and reacted with the precursor of liquid polymer during curing.
[0095] In certain embodiments of yarn composed of thermofixed polymer mentioned above, the plurality of substantially continuous fibers are substantially parallel in a direction substantially parallel to a longitudinal axis of the yarn composed of substantially continuous thermoset polymer. In some specific exemplary embodiments, the plurality of substantially continuous fibers further comprises a plurality of fiber surfaces, and the plurality of particles do not come in substantially contact with the plurality of fiber surfaces.
[0096] Although the present description can be practiced with any suitable thermoset polymer composite yarn, in certain exemplary embodiments, each of the thermoset polymer composite yarns is selected to be a fiber reinforced thermoset polymer composite yarn comprising at least one of a continuous fiber tow, or a continuous monofilament fiber, in a thermoset polymer matrix. In some embodiments, at least 85% (in some embodiments, at least 90%, or even at least 95%) the number of fibers in the yarns composed of thermoset polymer is continuous. In some currently preferred embodiments, yarns composed of thermoset polymer preferably have a tensile strength to failure of at least 0.4%, more preferably at least 0.7%.
[0097] Now with reference to the drawings, a wire composed of thermoset polymer 2 is illustrated in Figure 1A. The polymer composite yarn 2 comprises fibers 1 and cured liquid polymer precursor 5 containing nanoparticles 3 suitably dispersed (i.e. substantially non-agglomerated). In general, all fibers 1 are aligned in the direction of the wire length. In addition to the exemplary circular cross section illustrated in Figure 1A (i.e., a cylindrical handle), any known or desired cross section can be produced by the proper design of the wire forming mold, as will be further described below. Polymeric Composite Matrix
[0098] In some specific exemplifying embodiments, the polymeric composite matrix of the thermosetting polymer composite yarn comprises a high temperature thermoset (co) polymer selected from an epoxy, a vinyl ester, a polyimide, a polyester, a cyanate ester, a phenolic resin, a bis-maleimide resin, a (meth) acrylate resin, and combinations thereof. The currently preferred high temperature thermoset (co) polymers include epoxy resins with high glass transition temperature (Tg), for example, epoxy resins that have a Tg of at least about 250 ° C, 255 ° C, 260 ° C, or even higher Tg. In some specific, currently preferred embodiments, the solidified polymer composite matrix comprises an anhydride-cured epoxy resin.
[0099] Other materials that can optionally be included in the polymeric composite matrix are hydroxyl-terminated liquid epichlorohydrin polymers (for example, HTE, available from BF Goodrich Company, Avon Lake, Ohio, USA) as well as other high temperature polymers such as Polyphenylene sulfide (PPS), liquid crystalline polymers (LCP), and polyimides (PI).
[00100] In certain exemplary embodiments, the polymeric matrix of the wire composed of thermoset polymer and / or the optional corrosion resistant wrap can additionally comprise a thermoplastic (co) polymer selected from (meth) acrylate, a polyester, a cyanate ester , polyether ketone (PEEK), and combinations thereof. A high temperature (i.e., high Tg) thermoplastic polymer is preferred, for example, a thermoplastic (co) polymer that has a Tg of at least about 140 ° C, 145 ° C, 150 ° C, or even a Higher Tg. A high temperature thermoplastic (co) -polymer is PEEK, which has a Tg of about 145 ° C.
[00101] In some exemplary embodiments, the polymeric composite matrix may additionally comprise one or more thermoplastic fluoropolymers. Suitable thermoplastic fluoropolymers include perfluoroalkoxy (PFA) copolymers, fluorinated ethylenepropylene copolymer (FEP), polytetrafluoroethylene (PTFE), ethylene tetrafluoroethylene (ETFE), ethylene chlorofluoroethylene (ECTFE), polyvinyl fluoride (copolymer) and copolymer ), tetrafluoroethylene polymer (TFV).
[00102] Suitable thermoplastic fluoropolymers may be those sold under the trade names DYNEON THV FLUOROPLASTICS, DYNEON ETFE FLUOROPLASTICS, DYNEON FEP FLUOROPLASTICS, DYNEON PFA FLUOROPLASTICS, and DYNEON PVDF FLUOROPLASTICS (USA), all, available to us. . Liquid Polymeric Precursors
[00103] In additionally exemplifying embodiments, the polymeric composite matrix is derived by curing a liquid polymer precursor system comprising a plurality of nanoparticles dispersed in a liquid polymer precursor. The cured liquid polymer precursor system forms a polymeric composite matrix at least partially solidified. In certain currently preferred embodiments, the solidified polymer composite matrix comprises a crosslinked liquid polymer precursor.
[00104] In general, any known liquid polymer precursor can be used in the practice of various embodiments of the present description. In certain presently preferred embodiments, a curable liquid polymer precursor is preferred. In general, any known curable liquid polymer precursor compatible with a pultrusion process can be used, including, for example, epoxy liquid polymer precursors, unsaturated polyester liquid polymer precursors, and vinyl ester liquid polymer precursors. In some exemplary embodiments, the liquid polymer precursor has a glass transition temperature of at least about 150 ° C, more preferably about 160 ° C, 170 ° C, 180 ° C, 190 ° C, 200 ° C, 210 ° C, 220 ° C, 230 ° C, or even 240 ° C.
[00105] Thus, in some exemplary embodiments, the polymer formed by curing a liquid polymer precursor of a liquid state comprises at least one epoxy resin, a vinyl ester resin, a polyimide resin, a resin polyester, a cyanate ester resin, a phenolic resin, a bis-maleimide resin, a (meth) acrylate resin, or a combination thereof. In certain exemplary embodiments, the polymer formed by curing a liquid-state polymer precursor comprises an unsaturated polyester resin. In other exemplary embodiments, the cured liquid polymer precursor comprises a vinyl ester resin, and the plurality of particles comprise 5 to 40%, by weight, of the polymeric composite matrix.
[00106] In certain currently preferred embodiments, the cured liquid polymer precursor comprises an epoxy resin. In some particularly preferred embodiments today, the cured liquid polymer precursor comprises an epoxy resin, and the plurality of particles comprises from 0.5 to 40%, by weight, of the polymeric composite matrix. Epoxy resin liquid polymer precursors are well known in the art and comprise compounds or mixtures of compounds that contain one or more epoxy groups. The compounds can be saturated or unsaturated, aliphatic, alicyclic, aromatic or heterocyclic, or can comprise combinations thereof. In some embodiments, compounds that contain more than one epoxy group (i.e., polyepoxides) are preferred.
[00107] Polyepoxides that can be used include, for example, both aliphatic and aromatic polyepoxides. Aromatic polyepoxides may be preferred for some high temperature applications, and aliphatic polyepoxides may be preferred for some electrical power transmission applications due to their low chloride content. Aromatic polyepoxides are compounds that contain at least one aromatic ring structure, for example, benzene ring, and more than one epoxy group. Exemplary aromatic polyepoxides include polyglycidyl ethers of polyhydric phenols (eg bisphenol A-derived liquid polymer precursors, cresol-novolac epoxy liquid polymer precursors, phenol F-derived liquid polymer precursors, phenol epoxy liquid polymer precursors -novolac), glycidyl esters of aromatic carboxylic acids, and glycidyl amines of aromatic amines. Exemplary epoxy liquid polymer precursors include those based on bisphenol A and bisphenol F, for example, some of those available under the trade name EPON ™ from Hexion Specialty Chemicals, Inc., Houston, Texas, USA.
[00108] Particularly preferred epoxy resin precursors today include low viscosity epoxy resins with a high glass transition temperature (Tg), such as Lindoxy 190 (3,4-Epoxycyclohexylmethyl 3,4-Epoxycyclohexane carboxylate) with Lindride LS-252V (a methyl naic anhydride) can be used. Mixtures of Lindride 252V and Lindride 25K (methyl naic anhydride) can also be used. Lindoxy 190, Lindride 25K and Lindride LS-252V are all available from Lindau Chemicals (Columbia, SC, USA).
[00109] In some exemplary embodiments, the curable liquid polymer precursor may be a curable liquid polymer precursor unsaturated with ethylene. For example, in some embodiments, liquid polymer precursor of unsaturated polyester may be used. In some embodiments, the liquid polymer precursor of unsaturated polyester is the product of the condensation of one or more carboxylic acids or derivatives of these substances (for example, anhydrides and esters) with one or more alcohols (for example, polyhydric alcohols).
[00110] In other embodiments, precursors of liquid vinyl ester polymer can be used. For use in the present invention, the term "vinyl ester resin" refers to the product of the reaction of epoxy liquid polymer precursors with ethylenically unsaturated monocarboxylic acids. Epoxy liquid polymer precursors include bisphenol A diglyclic ether (eg, EPON 828, available from Hexion Specialty Chemicals, Columbus, Ohio, USA). Exemplary monocarboxylic acids include acrylic acid and methacrylic acid. Although such reaction products are acrylic or methacrylic esters, the term "vinyl ester" is used consistently in the gel coating industry. (See, for example, Handbook of Thermoset Plastics (“Manual of Thermoset Plastics”) (Second Edition), William Andrew Publishing, page 122 (1998)).
[00111] In other embodiments, precursors of liquid polymer, (meth) acrylate, including, for example, urethane (meth) acrylates, polyethylene glycol (multi) (meth) acrylates, and epoxy (multi) (meth) acrylates. For use in the present invention, the term (meth) acrylate refers to an acrylate and / or methacrylate, i.e., ethyl (meth) acrylate refers to ethyl acrylate and / or ethyl methacrylate.
[00112] In some embodiments, the liquid polymer precursor systems of the present description also include any number of well-known additives. Exemplary additives include hardeners, dressings, initiators, promoters, cross-linking agents, stiffeners, and fillers (for example, clay). In general, large fillers that have an average particle size of at least 1 micrometer, for example, at least 2 micrometers, and even at least 5 micrometers, can be used. Nanoparticles and Nanoparticles with Modified Surface
[00113] In all exemplary embodiments of the present description, the liquid polymer precursor system (liquid polymer system or heat-hardened liquid polymer material) comprises a plurality of nanoparticles, which may additionally include nanoparticles with modified surface as further described below . Particle Size and Size Distribution
[00114] In certain exemplary embodiments, the plurality of nanoparticles has a median diameter not greater than 1000 nm, 900 nm, 800 nm, 750 nm, 700 nm, 600 nm 500 nm, 400 nm, 300 nm, 250 nm, 200 nm , 150 nm, 100 nm, or even 50 nm. In some currently preferred exemplifying modalities, the plurality of nanoparticles has a median diameter not greater than 250 nm. In other exemplary embodiments, the plurality of nanoparticles has a median diameter of no more than 100 nm. In some specific exemplifying embodiments, the polymeric composite matrix comprises a plurality of filler particles that have a median diameter of at least 1 micrometer.
[00115] In some embodiments, nanoparticles are selected to achieve a multimodal particle size distribution. In general, a multimodal distribution is a distribution that has two or more modes, that is, a bimodal distribution has two modes, while a trimodal distribution has three modes.
[00116] In some modalities, the multimodal distribution of nanoparticles with modified surface has a first mode (as determined by TEM) that have several average particle sizes between 50 and 250 nanometers (nm), inclusive. In some embodiments, the average particle size of the first mode is at least 50 nm, at least 60 nm, or even at least 70 nm. In some embodiments, the average particle size of the first mode (“D1”) is not greater than 150 nm, for example, not greater than 100 nm, or even not greater than 80 nm.
[00117] In some modalities, the multimodal distributions of nanoparticles with modified surface have a second mode. The number of average diameter of the nanoparticles in the second mode is less than the average diameter of the nanoparticles in the first mode. In some embodiments, the average particle size of the second mode, D2, is not greater than 50 nm, for example, not greater than 30 nm, not greater than 20 nm, not greater than 15 nm, or even not greater than 10 nm . In some embodiments, D2 is at least 3 nm, for example, at least 5 nm, for example, at least 10 nm, or even at least 20 nm. In some modalities, D2 is between 3 and 10 nm, inclusive. In some modalities, D2 is between 20 and 50 nm, inclusive. Nanoparticles
[00118] In some embodiments, the plurality of nanoparticles comprises silica nanoparticles. For use in the present invention, the term "silica nanoparticle" refers to a nanoparticle that has a nanoparticle core with a silica surface. This includes nanoparticle cores that are substantially and entirely silica, as well as nanoparticle cores that comprise other inorganic (for example, metal oxide) or organic cores that have a silica surface. In some embodiments, the nanoparticle core comprises a metallic oxide. Any known metal oxide can be used. Exemplary metal oxides include silica, titanium oxide, alumina, zirconia, vanadium, chromium, antimony oxide, tin oxide, zinc oxide, ceria, and mixtures thereof. In some embodiments, the nanoparticle core comprises a non-metallic oxide.
[00119] Commercially available silicas include those available from Nalco Chemical Company, Naperville, Illinois, USA (for example, NALCO 1040, 1042, 1050, 1060, 2326, 2327 and 2329); Nissan Chemical America Company, Houston, Texas, USA (e.g. SNOWTEX-ZL, SNOWTEX-OL, SNOWTEX-YL, SNOWTEX-O, SNOWTEX-N, SNOWTEX-C, SNOWTEX-20L, SNOWTEX-40, and SNOWTEX-50 ); and Admatechs Co., Ltd., Japan (for example, SX009-MIE, SX009-MIF, SC1050-MJM, and SC1050-MLV). Nanoparticles with modified surface
[00120] In general, "nanoparticles with modified surface" comprise surface treatment agents attached to the surface of a nanoparticle core. In some embodiments, the nanoparticle core is substantially spherical. In some embodiments, the nanoparticle cores are relatively uniform in size of the primary particle. In some embodiments, the nanoparticle cores have a narrow particle size distribution. In some embodiments, the nanoparticle core is substantial and completely condensed. In some embodiments, the nanoparticle core is amorphous. In some embodiments, the nanoparticle core is isotropic. In some embodiments, the nanoparticle core is at least partially crystalline. In some embodiments, the nanoparticle core is substantially crystalline. In some embodiments, the particles are substantially non-agglomerated. In some embodiments, the particles are substantially non-aggregated in contrast to, for example, smoked or fumed silica. Surface Treatment Agents
[00121] In general, surface treatment agents for silica nanoparticles are organic species that have a first functional group capable of attaching covalently to the surface of a nanoparticle, the surface treatment agent altering one or more properties of the nanoparticle. In some embodiments, surface treatment agents have no more than three functional groups for attachment to the nanoparticle core. In some embodiments, surface treatment agents have a low molecular weight, for example, a weight average molecular weight less than 1000 gm / mole.
[00122] In some modalities, nanoparticles with modified surface are reactive; In some embodiments, surface-modified nanoparticles used to modify the surface of the nanoparticles of the present description may include a second functional group capable of reacting with one or more curable liquid polymer precursor (s) and / or one or more diluent (s) reactive (s) of the liquid polymer precursor system. For the sake of clarity, even when the nanoparticles are reactive modified surface nanoparticles, they are considered as constituents of the liquid polymer precursor system. A class of reactive surface treatment agents suitable for use with nanosilicate particles include functional silanes, for example, aminopropylsilane.
[00123] Surface treatment agents often include more than one functional group capable of fixing to the surface of a nanoparticle. For example, alkoxy groups are the first common functional groups that are able to react with free silanol groups on the surface of a silica nanoparticle forming a covalent bond between the surface treatment agent and the silica surface. Examples of surface treatment agents that have multiple alkoxy groups include trialoxy alkylsilanes (for example, 3- (trimethoxysilyl) propyl methacrylate) and trialoxy arylsilanes (for example, trimethoxy phenyl silane).
[00124] In some embodiments, the nanoparticles comprise calcite nanoparticles. Calcite is the crystalline form of calcium carbonate and typically forms rhombohedral crystals. In some embodiments, 70%, for example, at least 75% of the calcite nanoparticle cores have an average size of less than 400 nm. In some modalities, at least 90%, in some modalities, at least 95%, or even at least 98% of the calcite nanoparticle cores have an average size less than 400 nm.
[00125] In general, the surface treatment agent for calcite nanoparticles is a surface modifying agent including at least one bonding group and a compatibilizing segment: Comp. Mon - Liaison group; being that “Comp. Mon." refers to the compatibility segment of the surface modifying agent.
[00126] The compatibilizing segment is selected to optimize the compatibility of the calcite nanoparticles with the curable liquid polymer precursor. In general, the selection of the compatibilization group depends on a variety of factors, including the nature of the curable liquid polymer precursor, the concentration of the nanoparticles and the desired degree of compatibility. For epoxy liquid polymer precursor systems, useful compatibilizing agents include polyalkylene oxides, for example, polypropylene oxide, polyethylene oxide and combinations thereof.
[00127] The bonding group attaches to the calcite, connecting the surface modifying agent to the core of the calcite nanoparticle. Unlike many silica-based nanoparticle systems in which the surface modifying agents are covalently linked to silica, the surface modifying agents of the present description are ionically linked to (e.g., associated with) calcite.
[00128] In order to retain the surface modifying agents with the calcite nanoparticle cores during the processing of the compositions, it may be desirable to select linking groups with high calcite binding energy. Binding energies can be predicted using density functional theory calculations. In some embodiments, the calculated connection energies can be at least 0.6, for example, at least 0.7 electron volt. In general, the greater the binding energy, the greater the likelihood that the linking group will remain ionically associated with the particle surface. In some embodiments, binding energies of at least 0.8, for example, at least 0.9, or even at least 0.95 electron volt, can be useful.
[00129] In some embodiments, the linking group comprises a phosphonic acid and / or sulfonic acid. In some embodiments, the surface modifying agent also comprises a reactive group, that is, a group capable of reacting with the curable liquid polymer precursor, for example, during the curing process. This can result in the nanocalcite particle being strongly bound to the cured liquid polymer precursor matrix and can lead to an improvement in the physical properties of the resulting cured nanocomposite. In general, the reactive group is selected based on the nature of the curable liquid polymer precursor. In some embodiments, the reactive group may be located at the end of the matching segment. A class of reactive surface treatment agents suitable for use with nanocalcite particulates includes aminofunctional compounds that have a bonding group comprising phosphonic acid and / or sulfonic acid.
[00130] In some modalities, a liaison group is present connecting the compatibility segment with the liaison group: Comp. Sec. - Connection Group - Connection Group.
[00131] For example, in some embodiments, the surface modifying agent comprises a polyetheramine. Exemplary polyetheramines include those available under the trade name JEFFAMINE® available from Huntsman Corporation, The Woodlands, Texas, USA. The polyether serves as a compatibilizing segment, while the amine is the bonding group that joins the compatibilizing segment to the bonding group.
[00132] In some embodiments, the surface modifying agent comprises a zwitterion, that is, a compound that carries a net charge equal to zero, but which is capable of carrying a positive and negative formal charge on different atoms. In some embodiments, the negative formal charge is carried by the liaison group. In some embodiments, the positive formal charge is charged to the nitrogen atom of an amine, for example, an amine-binding group. In such embodiments, the amine can serve as both the linking group and the reactive group. Optional additives
[00133] The liquid polymer precursor may optionally include one or more additives. Optional additives, including, for example, solvents, dispersants, hardeners, dressings, initiators, promoters, cross-linking agents, hardeners, and fillers (for example, clay), can, in some exemplary embodiments, be advantageously used as components of the precursor system of liquid polymer. Currently preferred additives include reactive thinners as shown below. Reactive thinners
[00134] Depending on the selection of the liquid polymer precursor, in some embodiments, the liquid polymer precursor system may also include a reactive diluent. Exemplary reactive diluents include styrene, alpha-methyl styrene, vinyl toluene, divinyl benzene, trialyl cyanurate, methyl methacrylate, diallyl phthalate, ethylene glycol dimethacrylate, ethyl hydroxy methacrylate, hydroxy ethyl acrylate, and others (mono-acrylates and mono acrylates and mono-acrylates and mono-acrylates) .
[00135] Reactive diluents for epoxy liquid polymer precursors include mono- and multifunctional, aliphatic and aromatic glycidyl ethers, including, for example, those available under the trade name HELOXY from Hexion Specialty Chemicals, Columbus, Ohio, USA. Exemplary reactive diluents include, for example, trimethylol propane triglycidyl ether, 1,4-butane diglycidyl ether, diglycidyl neopentyl glycol ether, n-butyl glycidyl ether, 2-ethyl hexyl glycidyl ether, p-tertiary butyl phenyl glycidyl ether, phenyl ether glycidyl, and diglycidyl cyclohexane dimethanol ether. Reinforcing fibers
[00136] In all the exemplary embodiments of the present description, the yarns composed of thermoset polymer comprise at least one continuous fiber in a thermoset polymer matrix formed by curing a liquid polymer precursor system, as described above. In general, any fibers suitable for use in fiber-reinforced polymer composite yarns can be used. In some exemplary embodiments, the at least one continuous fiber comprises a metal, a polymer, ceramics, glass, carbon, and combinations thereof. Exemplary fibers include carbon fibers (e.g., graphite), glass fibers, ceramic fibers, silicon carbide fibers, polyimide fibers, polyamide fibers or polyethylene fibers. In other embodiments, the fibers may comprise titanium, tungsten, boron, format memory alloy, graphite, silicon carbide, boron, aramid, poly (p-phenylene-2,6-benzobisoxazole), and combinations thereof. Combinations of materials or fibers can also be used. In general, the shape of the fibers is not particularly limited. Exemplary fiber shapes include unidirectional layouts of individual continuous fibers, yarn, preliminary spinning, and braided constructions. Fabric and non-woven mats can also be included.
[00137] In some exemplary embodiments, the plurality of continuous fibers comprises at least 60, more preferably at least 62, most preferably at least 64, with the most preference at least 66 percent by volume of the yarn filament composed of substantially continuous thermoset polymer. Thermoset polymer composite cables
[00138] In exemplary embodiments, the description describes a thermoset polymer composite cable that comprises at least one thermoset polymer composite wire as described above. In some embodiments, the cable is an interlaced cable that comprises a core of yarn defining a central longitudinal axis, a first plurality of interlaced yarns around the core, and a second plurality of interlaced yarns around the first plurality of yarns. In certain exemplary embodiments, the cable comprises a core comprising at least one wire composed of thermoset polymer as described above.
[00139] In certain presently preferred embodiments, at least one core yarn, the first multiplicity of yarns, or the second multiplicity of yarns comprises at least one thermoset polymer composite yarn, as described above. In some presently preferred embodiments, the core yarn is a thermoset polymer composite yarn as described above. In addition to presently preferred embodiments, each core yarn, the first multiplicity of threads, and the second multiplicity of threads is selected to be thermoset polymer composite threads, as described above. In presently additional preferred embodiments, each of the multiplicity of threads in the cable is a thread composed of thermoset polymer.
[00140] Additionally in exemplary embodiments, the description describes a thermoset polymer composite cable comprising at least one thermoset polymer composite yarn as described above, the interlaced cable comprising a core yarn defining a central longitudinal axis, a first plurality of yarns helically intertwined around the core wire in a first configuration direction, and which has a first configuration length at a first angle defined in relation to the central longitudinal axis, and which has a first configuration length, and a second plurality of wires interlaced in helical shape around the first plurality of wires in a second configuration direction at a second configuration angle defined in relation to the central longitudinal axis, and which has a second configuration length.
[00141] In some of the previous interlaced cable modalities, the core wire is selected from the group consisting of a thermoset polymer composite wire, a thermoplastic polymer composite wire, a metallic matrix polymer composite wire, or a ductile metallic thread. In certain exemplary embodiments, at least one of the first multiplicity of threads is selected from the group consisting of a thread composed of thermoset polymer, a compound of thermoplastic polymer, or a ductile metallic thread. In some exemplary embodiments, at least one of the second multiplicity of threads is selected from the group consisting of a thread composed of thermoset polymer, a compound of thermoplastic polymer, or a ductile metallic thread.
[00142] In certain currently preferred embodiments, at least one of the core yarn, the first, multiplicity of threads, or the second multiplicity of threads comprises at least one thread composed of thermoset polymer as described above. In certain presently preferred embodiments, the core yarn is a yarn composed of thermoset polymer as described above. Additionally, in presently preferred embodiments, each core yarn, the first multiplicity of threads, the second multiplicity of threads is selected to consist of threads composed of thermoset polymer, as described above. In presently additional preferred embodiments, each of the multiplicity of threads in the cable is a thread composed of thermoset polymer. Interlaced thermoset polymer composite cables
[00143] Again with reference to the drawings, Figure 1B illustrates a perspective view of an interlaced thermoset polymer composite cable 10 (which can be helically interlaced as shown) comprising at least one thermoset polymer composite wire as described above according to an exemplary embodiment of this description.
[00144] As illustrated, the woven thermoset polymer composite cable 10 includes a core comprising a single filament core yarn 2 (which may, for example, comprise one or more wires composed of thermoset polymer as shown, and / or a or more yarns composed of thermoplastic polymer, yarns composed of metallic matrix, and / or ductile metallic yarns) defining a central longitudinal axis, a first layer 20 comprising a first plurality of yarns 2 '(which may, for example, comprise one or more wires composed of thermoset polymer as shown, and one or more wires composed of thermoplastic polymer, wires composed of metallic matrix, and / or ductile metallic wires) intertwined around the core wire 2 in a first configuration direction (shown in direction) corresponding to a right-hand configuration), and a second layer 22 comprising a second plurality of 2 '' threads (which may, for example, comprise one or more f the thermoset polymer compounds as shown, and / or one or more threads composed of thermoplastic polymer, threads composed of metallic matrix, and / or ductile metallic threads) intertwined around the first plurality of threads 2 'in a first configuration direction.
[00145] As further illustrated by Figure 1B, optionally, a third layer 24 comprising a third plurality of 2 '' 'threads (which may for example comprise one or more threads composed of thermoset polymer as shown, and / or one or more wires composed of thermoplastic polymer, wires composed of metallic matrix, and / or ductile metallic wires) can be woven around the second plurality of wires 2 '' in the first layer direction to form the polymer composite cable 10. In other embodiments example, an optional fourth layer (not shown) or even more additional layers of threads (not shown in the drawings, but which may, for example, comprise one or more threads composed of thermoset polymer, threads composed of thermoplastic polymer, threads composed of matrix metallic, and / or ductile metallic wires) can be woven around the third plurality of 2 '' wires in the first configuration direction.
[00146] In some exemplifying embodiments, the core 2 wire is a thermoset polymer composite yarn as shown in Figure 1B, although in other embodiments, the core 2 yarn may be a single thermoplastic polymer yarn, a yarn composed of metallic matrix, or a single ductile metallic wire. In certain exemplary embodiments, all wires (2, 2 ', 2' ', 2' ''; which may, for example, comprise one or more wires composed of thermoset polymer, wires composed of thermoplastic polymer, wires composed of metallic matrix , and / or ductile metallic wires) in the first (20), second (22), and third (24), and fourth or higher layers can be selected to be the same or different within each layer and / or between adjacent layers.
[00147] In additional illustrative exemplary embodiments of the description, two or more interlaced layers (e.g., 20, 22, 24, and the like) of two thermoset polymer compounds (e.g., 2 ', 2' ', 2' '' , and the like) can be interlaced (in some embodiments helically interlaced) around the single central thermoset polymer composite yarn 2 defining a central longitudinal axis, so that each successive layer of thermoset polymer composite yarn wound in the same direction as configuration that each previous layer of the wires composed of thermoset polymer. In addition, it will be understood that while a right side configuration is illustrated in Figure 1B for each layer (20, 22, and 24), a left side configuration can be used alternatively for each layer (20, 22, 24, and the like ), as shown for the exemplified interlaced thermoset polymer cable, shown in Figure 1C.
[00148] Figure 1C illustrates a perspective view of a 10 'interlaced thermoset polymer composite cable (which can be helically woven) comprising at least one thermoset polymer composite yarn according to an alternative embodiment of the present description. As illustrated, the braided thermoset polymer composite cable 10 'includes a core comprising a core 2 wire (which may be, for example, a thermoset polymer composite wire as shown, and one or more thermoplastic polymer composite wires, a wire composed of a metallic matrix, or a ductile metallic wire) defining a central longitudinal axis, a first layer 20 comprising a first plurality of wires 2 'intertwined around the core wire 2 in a first configuration direction (counterclockwise) shown, corresponding to a left-side configuration), a second configuration 23 comprising a second plurality of 2 '' threads (which may, for example, comprise one or more threads composed of thermoset polymer as shown, and / or one or more wires composed of thermoplastic polymer, wires composed of metallic matrix, or ductile metallic wires) intertwined around a first plurality of wires 2 'in the second direction of conf opposite the first configuration direction, and a third layer 24 comprising a third plurality of 2 '' wires (which may, for example, comprise one or more wires composed of thermoset polymer, wires composed of metal matrix, or metal wires ductile) intertwined around the second plurality of 2 '' wires in a first configuration direction to form the polymer composite cable 10 '.
[00149] In other exemplary embodiments, an optional fourth layer (not shown in the drawings, but which may, for example, comprise threads composed of thermoset polymer, threads composed of thermoplastic polymer, threads composed of metallic matrix, or ductile metallic threads) be interwoven around a third plurality of 2 '' wires in the second configuration direction. In preferred embodiments presently exemplifying the description, two or more alternating interlaced layers of yarns composed of thermoset polymer (eg 2 'and 2' ') and other yarns (eg 2' '', which may, for example, comprise yarns composed of thermoplastic polymer, yarns composed of metallic matrix, and / or ductile metallic yarns) can be wound in a helical shape around core yarn 2, defining a central longitudinal axis, so that each successive layer of yarns is wound in same configuration direction as each previous wire layer, as shown in Figure 1B. In addition, it will be understood that although the left side configuration is illustrated in Figure 1C for layer 23, and a right side configuration is illustrated for layers 20 and 24, a right side configuration can be used alternatively for layer 23 and a left-side configuration can be used alternatively for layers 20 and 24, and the like.
[00150] Preferably, in any of the aforementioned embodiments, the core 2 wire is selected to be a thermoset polymer composite yarn, while in other embodiments, the core 2 yarn can be a non-thermoset polymer composite yarn, such as, for example, a wire composed of thermoplastic polymer, a wire composed of a metallic matrix, and / or a ductile metallic wire.
[00151] In the types of cable composed of thermoset polymer interlaced in helical exemplary shapes, mentioned above, the first configuration direction is preferably equal to the second configuration direction, the third configuration direction is preferably equal to the second configuration direction, the fourth configuration direction can be the same as the third configuration direction, and in general, any external layer configuration direction is preferably equal to the configuration direction of the adjacent inner layer. However, in other exemplary embodiments, the first configuration direction can be opposite the second configuration direction, and the third configuration direction can be opposite the second configuration direction, and the fourth configuration direction can be opposite the third configuration direction, and in general, any outer layer configuration direction can be opposite the adjacent inner layer configuration direction.
[00152] In certain presently preferred modalities of any of the exemplary modalities mentioned above, the relative difference between the first configuration angle and the second configuration angle is preferably greater than 0 ° and not greater than about 4 °, the difference relative between the third configuration angle and the second configuration angle is preferably greater than 0 ° and not greater than about 4 °, and the relative difference between the fourth configuration angle and the third configuration angle is preferably greater than 0 ° and no greater than about 4 °, and in general, any inner layer configuration angle and adjacent outer layer configuration angle, is preferably no greater than 0 ° and no greater than about 4 °, more preferably not greater than 3 °, and with the maximum preference not greater than 0.5 °.
[00153] In presently preferred exemplary embodiments, one or more of the first layer length is less than or equal to the second layer length, the second layer length is preferably less than or equal to the third layer length, the fourth length layer length is preferably less than or equal to an immediately subsequent layer length, and / or each successive layer length is less than or equal to the immediately preceding layer length. In other embodiments, the first layer length is equal to the second layer length and / or the second layer length is equal to the third layer length and / or the third layer length is equal to the fourth layer length. In some exemplary embodiments, it may be preferable to use a parallel layer, as is known in the art.
[00154] In additionally exemplifying embodiments (see Figures 3A and 3B described further below), the cable composed of interlaced thermoset polymer may comprise additional layers (for example, subsequent), (for example, fourth, fifth or subsequent subsequent layers) of yarns (which may, for example, comprise one or more yarns composed of thermoset polymer, yarns composed of thermoplastic polymer, yarns composed of metallic matrix, and / or ductile metallic yarns) interlaced (preferably interlaced in helical shape) around a third plurality of 2 '' threads (which may, for example, comprise one or more threads composed of thermoset polymer, threads composed of thermoplastic polymer, threads composed of metallic matrix, and / or ductile metallic threads).
[00155] Helical interlacing is preferably performed in the first configuration direction at a configuration angle (not shown in the Figures) defined in relation to the common longitudinal axis, with the wires in each layer having a characteristic configuration length (not shown) in the Figures), and in addition the relative difference between the third and fourth configuration angles or a subsequent configuration angle is greater than 0 ° and not greater than about 4 °. The modalities in which four or more layers of interlaced yarns are employed can make use of one or more (or even all) yarns composed of thermoset polymer in each layer. Such interlaced threads generally have a cross-sectional dimension (for example, a diameter of threads having a circular cross-section) from about 0.5 mm to about 40 mm.
[00156] Various configurations of composite woven cables (preferably helical woven) including at least one thermoset polymer composite wire as described above are further illustrated by cross-sectional views in Figures 2A to 2I. These exemplifying modalities are intended to be illustrative only; Additional configurations are within the scope of this description. In each of the illustrated modalities of Figures 2A and 2I, it is understood that the wires (for example, 2, 2 ', 2' ', 2' '') selected to comprise at least one wire composed of thermoset polymer, can include any number (or none) of threads composed of thermoplastic polymer, threads composed of metallic matrix, and / or ductile metallic threads) intertwined in a configuration direction (not shown) around core thread 2 (which can, for example , comprise at least one thread composed of thermoset polymer, threads composed of thermoplastic polymer, and / or ductile metallic threads) defining a central longitudinal axis (not shown).
[00157] Such configuration direction can be clockwise (configuration to the right) or counterclockwise (configuration to the left). In addition, this configuration direction can be the same for each back layer of interlaced wires, as shown in Figures 1B-1C, or can switch to the opposite configuration layer on each back layer of interlaced wires (not shown in Figures). It is also understood that each layer of interlaced threads has a configuration length (not shown in Figures 2A-2I), and that the configuration length of each layer of threads can be different, or preferably, equal to the length of settings.
[00158] Figure 2A illustrates a cross-sectional view of an exemplary 10 '' interlaced composite cable (preferably interlaced in helical shape), which comprises a core 2 wire (shown as a thermoset polymer composite wire, but which it may alternatively be a thermoplastic composite wire, a metallic matrix composite wire, or a metallic wire) defining a central longitudinal axis, a plurality of 2 'wires (shown as a thermoset polymer composite wire, but which may alternatively be a composite wire thermoplastic, a metallic matrix composite yarn, or a metallic yarn) interlaced (preferably helicoidal interlaced) around core 2 yarn, and a second plurality of 2 '' yarns (shown with a thermoset polymeric composite yarn, but which may alternatively be a thermoplastic composite wire, a metallic matrix composite wire, or a metallic wire) interlaced (preferably helically interlaced) around a first plurality of wires 2 '. An optional corrosion resistant wrap 9 (further described below) surrounds the plurality of wires.
[00159] Figure 2B illustrates a cross-sectional view of another 10 '' 'interlaced composite cable (preferably helicoidal interlaced) as shown in Figure 1A, the cable comprising a core 2 wire (shown as a wire composed of thermosetting polymer, but which may alternatively be a non-thermosetting polymeric thread, for example, a thermoplastic composite thread, a metallic matrix composite thread, or a metallic thread) defining a central longitudinal axis, a plurality of 2 'threads (shown as a thermoset polymer composite yarn, but which may alternatively be a non-thermoset polymer composite yarn, for example, a thermoplastic composite yarn, a metallic matrix composite yarn, or a metallic yarn) interlaced (preferably interlaced in shape) helical) around the core yarn 2, a second plurality of yarns 2 '' (shown as a yarn composed of thermoset polymer, but which may alternatively be a yarn composed of of non-thermosetting polymer, for example, a thermoplastic composite yarn, a metallic matrix composite yarn, or a metallic yarn) interlaced (preferably helically interlaced) around the first plurality of 2 'wires, and a third plurality of 2 '' yarn (shown as a thermoset polymer composite yarn, but which may alternatively be a non-thermoset polymer composite yarn, for example, a thermoplastic composite yarn, a metallic matrix composite yarn, or a metallic yarn) intertwined ( preferably interlaced in a helical shape) around the second plurality of 2 '' threads. an optional corrosion resistant wrap 9 (further described below) surrounds the plurality of wires.
[00160] Figure 2C illustrates a cross-sectional view of an exemplary interlaced composite cable 11 (preferably helicoidal interlaced), including a core 2 wire (shown as a thermoset polymer composite wire, but which can alternatively be a non-thermoset polymer composite yarn, for example, a thermoplastic composite yarn, a metallic matrix composite yarn, or a metallic yarn) defining a central longitudinal axis, a plurality of 2 'yarns (shown as a thermoset polymer composite yarn, but which may alternatively be a wire composed of thermoplastic polymer, a wire composed of a metallic matrix, or a metallic wire) interlaced (preferably helically interlaced) around the core wire 2, a second plurality of wires 2 '' ( shown as a wire composed of thermoset polymer, but which may alternatively be a wire composed of thermoplastic polymer, a wire composed of a metallic matrix, or a metallic wire) wrapped (preferably helically interlaced) around the first plurality of yarns 2 ', the third plurality of yarns 2' '' (shown as a yarn composed of thermoset polymer, but which may alternatively be a yarn composed of thermoplastic polymer, a wire composed of metallic matrix, or a metallic wire) interlaced (preferably interlaced in helical shape) around the second plurality of wires composed of 2 '' thermoplastic polymer, and a fourth plurality of wire 16 (shown as a wire composed of thermofixed polymer, but which may alternatively be a wire composed of thermoplastic polymer, a wire composed of a metallic matrix, or a metallic wire) interlaced (preferably helically interlaced) around the third plurality of 2 '' wires. An optional corrosion resistant wrap 9, 9 ’, 9’ ’(further described below) surrounds the plurality of wires surrounding each individual wire.
[00161] Figure A 2D illustrates a cross-sectional view of an exemplary 11 'interlaced composite cable (preferably helicoidal interlaced), including a core 2 wire (shown as a thermoset polymer composite wire, but which can alternatively be a non-thermoset polymer composite yarn, for example, a thermoplastic composite yarn, a metallic matrix composite yarn, or a metallic yarn) defining a central longitudinal axis, a plurality of 2 'yarns (shown as a polymer composite yarn thermoset, but which may alternatively be non-thermoset polymer composite yarns, for example, a thermoplastic composite yarn, a metallic matrix composite yarn, or a metallic yarn) interlaced (preferably helically interlaced) around the core yarn 2 , a second plurality of 2 '' yarns (shown as a yarn composed of thermoset polymer, but which may alternatively be a yarn composed of non-thermoset polymer, for example, a thermoplastic composite yarn, metallic matrix composite yarn, or metallic yarn) intertwined (preferably helically interlaced) around the first plurality of 2 'strands, and a third plurality of 2' strands (shown as a strand composed of thermosetting polymer, but which may alternatively be a non-thermosetting polymer composite yarn, for example, a thermoplastic composite yarn, a metallic matrix composite yarn, or a metallic yarn) interlaced (preferably helically interlaced) around the second plurality of wires 2 ''.
[00162] An optional corrosion resistant wrap 9, 9 ’, 9’ ’(described further below) surrounds the plurality of wires surrounding each individual wire. In addition, an optional protective element 15 (which can also be insulating and / or resistant to corrosion) surrounds the entire plurality of wires. An optional corrosion resistant and / or insulating load material 13 can also be included to fill any empty spaces between the wires.
[00163] Figure 2E illustrates a cross-sectional view of another exemplary alternative configuration of an 11 '' helicoidal polymer composite wire interlaced including a core 2 wire (shown as a thermoset polymer composite wire, but which can be alternatively a non-thermoset polymer composite yarn, for example, a thermoplastic polymer composite yarn, metallic matrix composite yarn, or a metallic yarn) defining a central longitudinal axis, a plurality of 2 'yarns (shown as a polymer composite yarn thermofixed, but may alternatively be a non-thermosetting polymer composite yarn, for example, a thermoplastic polymer composite yarn, metallic matrix composite yarn, or a metallic yarn) interlaced (preferably interlaced in helical shape) around the core yarn 2, a second plurality of 2 '' threads (shown as a thermoset polymer composite yarn, but may alternatively be a polymer composite yarn thermoplastic ether, wire composed of metallic matrix, or a metallic wire) interlaced (preferably interlaced in helical shape) around the first plurality of 2 'wires. An optional corrosion resistant and / or insulating load material 13 can also be included to fill any empty spaces between the wires.
[00164] In all the modalities presently described, in at least one of the core yarn, the first multiplicity of threads, or the second multiplicity of threads comprises at least one thread composed of thermoset polymer as described above. In certain of the exemplary embodiments mentioned above, at least the central yarn 2 can be selected to be a yarn composed of thermoset polymer. However, although Figures 2A to 2E show a core yarn 2 defining a central longitudinal axis (not shown) that is a yarn composed of thermoset polymer, it should be further understood that core yarn 2 may alternatively be a yarn composed of thermoplastic polymer, a wire composed of metallic matrix, or a metallic wire.
[00165] In presently preferred embodiments illustrated by Figure 2A to 2I, each of the core yarns, the first multiplicity of threads, and the second multiplicity of threads is selected to consist of threads composed of thermoset polymer as described above. In presently additional preferred embodiments, each of the multiplicity of threads in the cable is a thread composed of thermoset polymer.
[00166] Furthermore, it is understood that in some exemplifying modalities, each of the composite wires can have a cross-sectional shape, in a direction substantially perpendicular to the central longitudinal axis, generally circular, elliptical or trapezoidal. In certain exemplary embodiments, each yarn has a cross-sectional shape that is generally circular, and the diameter of each polymer composite yarn is at least about 0.1 mm, more preferably at least 0.5 mm; Even more preferably, at least 1 mm, even more preferably at least 2 mm, most preferably, at least 3 mm; and at most about 15 mm, more preferably at most 10 mm, even more preferably at most 5 mm, most preferably at most 4 mm, most preferably at most 3 mm. In other exemplary embodiments, the diameter of each wire made of thermoplastic polymer may be less than 1 mm, or greater than 5 mm.
[00167] Typically the average diameter of the core wire, which has a generally circular cross-sectional shape, is in a range of about 0.1 mm to about 2.54 cm. In some embodiments, the average cross-sectional diameter of the core wire is desirably at least about 0.1 mm, at least 0.5 mm, at least 1 mm, at least 2 mm, at least 3 mm, at least 4 mm, or even at least about 5 mm. In other modalities, the average diameter of the single central wire is less than about 0.5 mm, less than 1 mm, less than 3 mm, less than 5 mm, less than 10 mm, less than 15 mm, less than 25 mm , or less than about 20 mm.
[00168] In additional exemplary embodiments not illustrated by Figures 2A to 2F, the woven thermoset polymer composite cable may include more than three interwoven layers of wires around the core wire defining a central longitudinal geometric axis. In certain exemplary embodiments, each of the wires in each layer of the cable composed of interlaced thermoset polymer can be of the same construction (preferably wires composed of thermoset polymer) and shape; however, this is not necessary to achieve the benefits described in the present invention.
[00169] Exemplary embodiments of the present description preferably provide very long thermoset polymer composite cables. It is also preferred that any composite wires within the woven thermoset polymer composite cable are continuous over the entire length of the woven cable. In a preferred embodiment, the wires composed of thermoset polymer are substantially continuous and are at least 150 meters long. More preferably, the composite wires are continuous and are at least 250 meters long, more preferably at least 500 meters, even more preferably at least 750 meters and, most preferably, at least 1000 meters long on the cable. thermofixed polymer composite. Optional corrosion resistant wrap
[00170] As noted above, a corrosion-resistant wrap or tape (9, 9 ', 9' 'in Figures 2C and 2D) can optionally be applied around each individual wire in the thermoset polymer composite cable, or to the around each individual thermoset polymer compound wire in the cable. Thus, in some exemplifying modalities, a corrosion-resistant wrap surrounds at least one wire composed of thermoset polymer. A corrosion resistant wrap around a thermoset polymer composite yarn is preferred for thermoset polymer composite yarns that comprise carbon fibers, particularly in thermoset polymer composite cable constructions, which incorporate metallic matrix composite yarns and / or ductile metallic yarns . Although it is not intended to stick to any particular theory, it is believed that undesirable electrochemical reactions that can lead to corrosion of wires in the thermoset polymer composite cable can be avoided or reduced by incorporating a corrosion resistant wrap around the wires thermoset polymer compounds.
[00171] In certain exemplary embodiments further described below, the corrosion resistant wrap comprises at least one radiation cured polymer, thermoset polymer, thermoplastic polymer that has a glass transition temperature of at least 145 ° C or a fluoropolymer, a tape, a fibrous material (for example, fiberglass mat or wick), or a combination thereof (see for example 9, 20, 22, and 24 in Figure 2G; 9 and 20 in Figure 2H). In certain presently preferred embodiments, the corrosion resistant wrap can also be insulating (i.e., electrically and / or thermally and / or acoustically insulating). In some specific exemplifying embodiments, the thermoset polymer composite cable may additionally include an optional protective element (see for example 15 in Figure 2D) to improve the pressure or puncture resistance of the thermoset polymer composite cable. The additional protective element 15 can also be insulating and / or resistant to corrosion.
[00172] In various illustrative embodiments, the corrosion resistant wrap can surround each individual thermoset polymer compound yarn (see, for example, 9, 9 'and 9' 'in Figures 2C to 2D), it can surround a plurality of composite yarns of thermosetting polymer forming a layer (see, for example, 9 in Figure 2B), you can surround the entire plurality of thermosetting polymer wires forming a core (see, for example, 9 in Figures 2A-2B), or all of the above (see, for example, 9 ', 9' 'and corrosion resistant wrap and shield layer 15 combined in Figure 2D).
[00173] In other exemplary embodiments, a corrosion resistant wrap or tape can optionally be applied around a cable core containing only wires composed of thermoset polymer, or between any suitable layer containing only wires composed of thermoset polymer, and any layer adjacent wires as desired. Thus, in some presently preferred embodiments, the corrosion resistant wrap (9, 9 ', 9' ', and 9' '' ') provides a protective layer surrounding an underlying wire core cable (see, for example, 10 '' and 10 '' in Figures 2A-2B, 11 'and 11' 'in Figures 2D-2E, 10' ', 10' '' and 10 '' '' in Figures 2F-2I, and 10 '' ' in 3A). The protective outer layer can, for example, optimize puncture resistance, optimize corrosion resistance, optimize resistance to extremes of high or low temperature, optimize resistance to friction, and the like.
[00174] Returning now to the drawings, Figure 2F is a side view of an exemplary 10 '' interlaced thermoset polymer composite cable, with a corrosion resistant wrap 9 applied around an outer layer 22 of the outer layer of the wires composed of 2 '' interlaced thermoset polymer. As shown most clearly in the cross-sectional view of Figure 2G, the corrosion resistant wrap 9 can be a tape with an adhesive layer 22 on a support 20 covering one or more layers of wires composed of thermoset polymer 2, 2 'and 2' '.
[00175] Adhesives suitable for adhesive layer 22 include, for example, (meth) acrylate (co) polymer based adhesives, poly (α-olefin) adhesives, block copolymer based adhesives, adhesives based on natural rubber, silicone based adhesives, and hot melt adhesives. Pressure sensitive adhesives may be preferred in certain embodiments.
[00176] Suitable materials for support 20 (whether used with or without an adhesive layer 22) include polymeric films, including polyester; polyimide; fluoropolymer films (including those comprising fully or partially fluorinated (co) polymers), glass-reinforced supports; and combinations thereof; provided that the tape is strong enough to maintain elastic flexion deformation and capable of retaining its self-rolled configuration, or is sufficiently restricted if necessary.
Alternatively, as shown in Figure 2H, the tape may comprise only a reinforcement layer 20 without an adhesive covering one or more layers of threads composed of thermoset polymer 2, 2 'and 2' '. The tape acts as a corrosion resistant wrap 9, and can also act as an electrically insulating layer surrounding the interwoven composite wires 2, 2 ’and 2’ ’making up the 10’ ’’ ’thermoset polymer composite cable.
[00178] Figure 2I illustrates another alternative modality exemplifying a 10 '' '' woven thermofix polymer composite cable with a corrosion resistant wrap in the form of a binder 24 applied to the wires (for example 2, 2 ', and 2' ') in its interlaced arrangement. In certain embodiments, ligand 24 can also act as an electrically insulating envelope surrounding the interlaced strands. Binder 24 may additionally be applied around each individual yarn, or between any suitable layer of thermoset composite yarns and other yarns (for example, thermoplastic polymer composite yarns, metallic matrix compound yarns, and / or ductile metallic yarns) as wanted.
[00179] Suitable binders 24 (which, in some exemplary embodiments, can be used as insulating fillers as shown in Figure 2I) include pressure sensitive adhesive compositions comprising one or more homopolymers, copolymers, terpolymers and poly (alpha-tetrapolymers) olefin) derived from monomers containing 6 to 20 carbon atoms and photoactive crosslinking agents as described in US Patent No. 5,112,882 (Babu et al.). The radiation curing of these materials provides adhesive films that have an advantageous balance of adhesive properties of peeling and shearing.
[00180] Alternatively, binder 24 may comprise thermoset materials, including, but not limited to, epoxies. For some binders, it is preferable to extrude or otherwise coat the binder 24 over the 10 ’’ ’’ non-insulated woven composite cable while the wires are exiting the cabling machine as discussed below. Alternatively, binder 24 can be applied in the form of an adhesive provided as a transfer tape. In this case, binder 24 is applied to a transfer sheet or removable protection (not shown). The release sheet is wound around the composite wires of the 10 ’’ ’’ ’woven composite cable. The substrate is then removed, leaving the adhesive layer behind as the binder 24.
[00181] In addition, the intended application for the thermoset polymer composite cable may suggest that certain corrosion resistant wrap materials are more suitable for the application. For example, as shown in Figures 2G-2I, when the thermoset polymer composite cable is used as a submersible or underground electrical power transmission cable, binder 24 or tape 20 without an adhesive 22 could be selected advantageously to do not adversely affect the electrical energy transmission properties of the cable at temperatures, depths, and other conditions experienced in this application. In addition, when an adhesive tape 20 is used as the corrosion resistant wrap 9, both the adhesive 22 and the reinforcement must be selected to suit the intended application.
[00182] Returning to the drawings, in certain presently preferred embodiments, the corrosion resistant wrap 9 is a tape (which can be an adhesive tape comprising an adhesive 22 coated over a reinforcement layer 20, or just a reinforcement layer 20) which is preferably wound so that each successive winding overlaps, or at least remains in contiguity with, the previous winding without forming a gap, as shown in Figure 2F. In a presently preferred embodiment (not shown), the ribbon is wound so that each winding overlaps the previous winding by approximately 1/3 to 1/2 the width of the ribbon. Alternatively, in some embodiments (for example, those in which a corrosion-resistant element and / or insulating protective element 15 surrounds all of the wires included in the thermoset polymer composite cable), successive windings can be spaced so as to leave a gap between each winding.
[00183] the corrosion resistant wrap 9 (for example, an adhesive coated tape or an adhesive-free reinforcement) can be applied to the interlaced cable with a conventional tape winding apparatus as is known in the art. Suitable tape machines include those available from Watson Machine, International, Patterson, NJ, USA, such as model number CT-300 Concentric Taping Head. The ribbon overwrapping station is generally located at the outlet of the cable interleaver and is applied to the helically twisted composite wires before the cable 10 is wound onto a take-up reel. Corrosion-resistant wrap 9 can also be selected so as to maintain the interlaced arrangement of elastically deformed composite yarns, whether these wires are included in the 10 '', 10 '' '' or 10 '' '' 'interlaced cable.
[00184] Returning again to the drawings, in some exemplary modalities, a thermoset polymer composite cable can be used advantageously as a core cable in the construction of a cable with a larger diameter, for example, a 90 power transmission cable. Thus, as illustrated in Figure 3A, an interlaced thermoset polymer composite cable 90 may comprise a first plurality of ductile metal wires 28 interlaced around a ribbon-wound wrap (9) surrounding a plurality of thermoset polymer composite wires (2 , 2 ', 2' ') forming a wire core composed of 10' '' thermoset polymer. A second plurality of ductile metal wires 28 'is shown interlaced around the first plurality of ductile metal wires 28.
[00185] The tape is shown as a backsheet 20 (but alternatively it can be an adhesive 22 on a backsheet 20) wrapped around the core of the 10 '' 'thermoset polymer polymer yarn, which includes a single thermoset polymer compound yarn 2 defining a central longitudinal axis, a first layer comprising a first plurality of yarns composed of thermosetting polymer 2 ', which can be interlaced (preferably in helical shape) around the yarn composed of thermosetting polymer 2 in a first configuration direction , and a second layer comprising a second plurality of yarns composed of thermosetting polymer 2 '' that can be interlaced (preferably in helical shape) around the first plurality of yarns composed of thermosetting polymer 2 'in the first configuration direction.
[00186] The tape 20 forms a corrosion resistant wrap 9, which is optionally also electrically insulated, surrounding the plurality of wires composed of thermoset polymer (e.g. 2, 2 ', 2' ') comprising the core (10' ''). Optionally, a protective element 15, which can also be resistant to corrosion and / or electrically isolated, surrounds both the plurality of composite wires (for example, 2, 2 'and 2' ') and the plurality of ductile metallic wires (for example, example 28 and 28 '').
[00187] In certain exemplary embodiments, the corrosion resistant wrap is not significantly added to the total diameter of the thermoset polymer composite cable. Preferably, the thickness of the corrosion-resistant wrap is not more than 10% of the outer diameter of the thermoset polymer composite cable or core that it surrounds, more preferably not more than 5%, and most preferably not more than 2 % or even 1%; and at least 0.1%, more preferably at least 0.2%, most preferably at least 0.3% or even 0.5% of the outer diameter of the thermoset polymer composite cable or core that it surrounds.
[00188] In yet another alternative exemplary embodiment illustrated in Figure 3B, the thermoset polymer composite cable 100 may include one or more layers comprising a plurality of individually insulated thermoset polymer wires (2 '' and 2 '' ') intertwined around a core comprising a plurality of individually insulated wires (1 and 5), and an optional and additional (or alternative) corrosion resistant protected wrap surrounding the entire plurality of wires composed of thermoset polymer (2 '' and 2 '' ').
[00189] Thus, as shown in Figure 3B, the insulated thermoset polymer composite cable 100 includes a single core wire 1 (shown as a ductile metallic wire, but which may alternatively be a thermoset polymer composite wire, a wire composed of thermoplastic polymer, wire composed of metal matrix, or fiber optic wire as further described below) defining a central longitudinal axis. At least one first layer of yarn surrounds the single core yarn 1, shown comprising a first plurality of ductile metal yarns 5 as described below (which can be optionally interlaced, but preferably helically interlaced around a single core yarn 1 in a first configuration direction). A second layer, shown comprising a first plurality of yarns composed of 2 '' thermoset polymer (which can be optionally interlaced, more preferably helically interlaced around a single core yarn 1 in a first configuration direction) is shown surrounding the first plurality of ductile metal wires 5.
[00190] An optional third layer comprising a second plurality of yarns composed of 2 '' 'thermoset polymer (which can be optionally interlaced, more preferably helically interlaced around a first mode of yarn composed of 2' thermoset polymer) 'in the first configuration direction) is shown surrounding the first plurality of wires composed of thermoset polymer 2' '. An additional protective element 15 (which can be resistant to corrosion and / or insulation) is shown surrounding the entire plurality of wires composed of thermoset polymer (2 '' and 2 '' '), and an additional and optional insulating wrap ( 9, 9 ', 9' ', 9' '') is shown around each individual wire (1, 5, 2 '', 2 '' ').
[00191] Additionally, Figure 3B illustrates the use of an optional insulating charge 11 (which can be a binder as described above, or which can be an insulating material such as a non-electrically conductive liquid or solid) to substantially fill any empty spaces between the individual wires (1, 5, 2 '' and 2 '' ') and the additional protection element 15 surrounding the entire plurality of wires.
[00192] In some exemplary embodiments, the corrosion resistant wrap comprises a thermoplastic polymer material, which preferably comprises a thermoplastic polymer with a glass transition temperature of at least about 100 ° C, more preferably about 120 ° C , 130 ° C, 145 ° C, or even 150 ° C or higher. Preferably, the thermoplastic polymeric material is selected from high density polyolefins (for example, high density polyethylene), medium density polyolefins (for example, medium density polyethylene), and / or thermoplastic fluoropolymers, which are presently preferred .
[00193] Suitable thermoplastic fluoropolymers include fluorinated ethylenepropylene copolymer (FEP), polytetrafluoroethylene (PTFE), ethylene tetrafluoro ethylene (ETFE), ethylene chloro trifluoro ethylene (ECTFE), polyvinylidene fluoride (PVDF), polyethylene (PVDF) fluoride, polyethylene fluoride TFV). Thermoplastic suitable fluoropolymers are those sold under the trade names DYNEON THV FLUOROPLASTICS, DYNEON ETFE FLUOROPLASTICS, DYNEON FEP FLUOROPLASTICS, DYNEON PFA FLUOROPLASTICS, and DYNEON PVDF FLUOROPLASTICS (all available from MN, Company.
[00194] As noted above, in some exemplary embodiments, the corrosion resistant wrap 15 comprises a protective element which, preferably, also functions as a resistance element. In other exemplary embodiments, the shielding and / or resistance element comprises a plurality of wires that surround the core cable and arranged in a generally cylindrical layer. Preferably, the yarns are selected to be yarns composed of thermoset polymer, but may additionally include yarns composed of non-thermoset polymer, for example yarns composed of thermoplastic polymer, yarns composed of metallic matrix, ductile metallic yarn, and combinations thereof. Optional additional wires used to make composite polymer cables
[00195] As noted above, in all thermosetting polymer composite cable modes in accordance with the present description, the cable comprises at least one thermosetting polymer composite wire in accordance with the aforementioned description. In certain presently preferred embodiments, each yarn (for example 2, 2 ', 2' ', 2' '', and the like) is selected to be a yarn composed of thermoset polymer as described above. However, in some embodiments, it may be advantageous to optionally include one or more additional yarns selected from yarns that are not yarns made of thermoset polymer, for example, yarns made of thermoplastic polymer, yarns composed of metallic matrix, and ductile metal yarns, as will be discussed in more detail below. Optional thermoplastic polymer composite yarns
[00196] In some exemplary embodiments, the thermoset polymer composite cable may optionally include a plurality of threads composed of thermoplastic polymer. Preferably, the yarns composed of thermoplastic polymer are included within one or more layers of yarns in the core of the thermoset polymer composite cable, more preferably within at least the most distant yarn layer, more preferably within the two layers of yarn. more distant strands, or even the three most distant strands of strands.
[00197] In general, wires composed of thermoplastic polymer can be plastically deformed when heated during (or subsequent to) the cabling operation, unlike conventional metallic matrix wires or composite matrix wires. Thus, for example, a conventional cabling process could be performed in order to plastically and permanently deform the polymer composite wires in their interlaced arrangement, eliminating the need for retention means to maintain the interlaced configuration of the thermoplastic polymer composite wires.
[00198] Yarns composed of thermoplastic polymer are disclosed, for example, US Patent Nos. 4,680,2246,180,232; 6,245,425; 6,329,056; 6,336,495; 6,344,270; 6,447,927; 6,460,597; 6,544,645; 6,559,385, 6,723,451; and 7,093,416, and PCT Patent Publication No. WO 2005/123999, the entire descriptions of which are incorporated herein by reference.
[00199] Optionally including at least some wires composed of thermoplastic polymer to form an interlaced cable or cable core (preferably helicoidal interlaced) can thus provide the desired characteristics compared to conventional metallic matrix composite wires. The use of thermoplastic polymer composite yarns may also allow a helical-woven thermofix polymer composite cable to be handled more conveniently as a final cable article, or to be handled more conveniently as an intermediate cable core before be incorporated into a final cable article.
[00200] Examples of suitable fibers that could be used in a yarn composed of thermoplastic polymer within the present description include ceramic fibers, glass fibers, silicon carbide fibers, carbon fibers, and combinations of these fibers.
[00201] Examples of suitable ceramic fibers include metal oxide fibers (eg, alumina), boron nitride fibers, silicon carbide fibers and a combination of any of these fibers. Typically, the oxide ceramic fibers are crystalline ceramics and / or a mixture of crystalline ceramics and glass (i.e., a fiber can contain both the crystalline and vitreous ceramic phases). Typically, such fibers have a length of the order of at least 50 meters, and can have lengths of the order of up to kilometers or more. Typically, continuous ceramic fibers have an average fiber diameter in a range of about 5 micrometers to about 50 micrometers, about 5 micrometers to about 25 micrometers about 8 micrometers to about 25 micrometers or even about 8 micrometers to about 20 micrometers. In some embodiments, crystalline ceramic fibers have an average tensile strength of at least 1.4 GPa, at least 1.7 GPa, at least 2.1 GPa and or even at least 2.8 GPa. crystalline ceramic fibers have a modulus greater than 70 GPa to approximately no greater than 1000 GPa, or even no greater than 420 GPa.
[00202] An example of a particularly suitable ceramic fiber is a silicon carbide fiber. Typically, silicon carbide monofilament fibers are crystalline and / or a mixture of crystalline ceramic and glass (i.e., a fiber can contain both crystalline and glassy ceramic phases). Typically, such fibers have a length of the order of at least 50 meters, and can have lengths of the order of up to kilometers or more. Typically, silicon carbide monofilament fibers have an average fiber diameter in the range of about 100 micrometers to about 250 micrometers. In some embodiments, crystalline ceramic fibers have an average tensile strength of at least 2.8 GPa, at least 3.5 GPa, at least 4.2 GPa or even at least 6 GPa. In some embodiments, crystalline ceramic fibers they have a module greater than 250 GPa to approximately no greater than 500 GPa, or even no greater than 430 GPa.
[00203] A presently preferred ceramic fiber comprises polycrystalline α-Al2O3. Suitable aluminum fibers are described, for example, in US Patent No. 4,954,462 (Wood et al.) And 5,185,299 (Wood et al.). Exemplary alpha alumina fibers are marketed under the trade name “NEXTEL 610” (3M Company, St. Paul, MN, USA). In some embodiments, alumina fibers are polycrystalline alpha alumina fibers and comprise, on a theoretical oxide basis, more than 99 percent by weight of Al2O3 and 0.2 to 0.5 percent by weight of SiO2, based on the total weight of the alumina fibers. In another aspect, some desirable polycrystalline alpha alumina fibers comprise alpha alumina which has an average grain size of less than one micrometer (or even, in some embodiments, less than 0.5 micrometer). In another aspect, in some embodiments, alpha alumina polycrystalline fibers have an average tensile strength of at least 1.6 GPa (in some embodiments, at least 2.1 GPa, or even at least 2.8 GPa) .
Suitable aluminosilicate fibers are described, for example, in U.S. Patent No. 4,047,965 (Karst et al). Exemplifying aluminosilicate fibers are marketed under the trade name "NEXTEL 440", "NEXTEL 550" and "NEXTEL 720" with the 3M Company of St. Paul, MN, USA. Aluminoborosilicate fibers are described, for example, in U.S. Patent No. 3,795,524 (Sowman). Exemplary borosilicate aluminum fibers are marketed under the trade name "NEXTEL 312" with 3M Company. Boron nitride fibers can be produced, for example, as described in U.S. Patent Nos. 3,429,722 (Economy) and 5,780,154 (Okano et al.). Exemplary silicon carbide fibers are marketed, for example, by COI Ceramics of San Diego, CA, USA, under the trade name “NICALON” in bundles of 500 fibers, with UbeIndustries in Japan, under the trade name “TYRANNO” , and with Dow Corning of Midland, MI, USA, under the trade name “SYLRAMIC”.
[00205] Examples of suitable glass fibers include Glass A, Glass B, Glass C, Glass D, Glass S, AR Glass, Glass R, glass fibers and paraglass, as known in the art. Other glass fibers can also be used; the list is not limiting, and there are many different types of glass fibers commercially available, for example, from Corning Glass Company (Corning, NY, USA).
[00206] In some exemplary embodiments, continuous glass fibers may be preferred. Typically, continuous glass fibers have an average fiber diameter in the range of about 3 micrometers to about 19 micrometers. In some embodiments, the glass fibers have an average tensile strength of at least 3 GPa, 4 GPa and / or even at least 5 GPa. In some embodiments, the glass fibers have a modulus in the range of about 60 GPa at 95 GPa, or about 60 GPa to about 90 GPa.
[00207] Suitable carbon fibers include commercially available carbon fibers such as those designated as PANEX® and PYRON® (available from ZOLTEK, Bridgeton, MO, USA), THORNEL (available from CYTEC Industries, Inc., West Paterson, NJ USA), HEXTOW (available from HEXCEL, Inc., Southbury, CT, USA) and TORAYCA (available from TORAY Industries, Ltd. Tokyo, Japan). Such carbon fibers can be derived from a polyacrylonitrile (PAN) precursor. Other suitable carbon fibers include PAN-IM, PAN-HM, PAN UHM, PITCH or by-products of rayon, as known in the art.
[00208] Suitable additional commercially available fibers include ALTEX (available from Sumitomo Chemical Company, Osaka, Japan) and ALCEN (available from Nitivy Company, Ltd., Tokyo, Japan). Suitable fibers also include alloy with shape memory (that is, a metallic alloy that undergoes a martensitic transformation so that the metallic alloy is deformable by a twin mechanism below the transformation temperature, and such deformation is reversible when the twin structure reverts to the original phase by heating above the transformation temperature). Commercially available format memory alloy fibers are available, for example, from the Johnson Matthey Company (West Whiteland, PA, USA).
[00209] In some modalities, the ceramic fibers are in untwisted bundles of continuous filaments (tows). Unwoven bundles of continuous filaments are known in the fiber art and refer to a plurality of (individual) fibers (typically at least 100 fibers, more typically at least 400 fibers) collected in a form similar to fibers for weaving. In some embodiments, the bundles comprise at least 780 individual fibers per bundle, in some cases at least 2600 individual fibers per bundle and in other cases at least 5200 individual fibers per bundle. Bundles of ceramic fibers are generally available in a variety of lengths, including 300 meters, 500 meters, 750 meters, 1000 meters, 1500 meters, 2500 meters, 5000 meters, 7500 meters and longer. The fibers may have a cross-sectional shape that is circular or elliptical.
[00210] Commercially available fibers can typically include an organic ironing material added to the fiber during manufacture to provide lubricity and to protect fiber twists during handling. The ironing can be removed, for example, by dissolving or burning the ironing of the fibers. Typically, it is desirable to remove the sizing before the formation of the metallic matrix composite yarn. The fibers may also have coatings used, for example, to improve the wettability of the fibers, to reduce or prevent the reaction between the fibers and molten metal matrix material. Such coatings and techniques for providing these coatings are known in the fiber and polymeric composite art.
Preferred thermoplastic polymer composite yarns according to the present description can have a fiber density of between about 3.90 to 3.95 grams per cubic centimeter. Preferred fibers include those described in US Patent No. 4,954,462 (Wood et al., Assigned to Minnesota Mining and Manufacturing Company, St. Paul, MN, USA), the instructions of which are hereby incorporated by reference. Preferred fibers are commercially available under the trade name “NEXTEL 610” which consists of fibers based on alpha alumina (available from 3M Company, St. Paul, MN, USA). The thermoplastic polymer matrix is selected so that it does not react significantly chemically with the fiber material (i.e. it is relatively chemically inert with respect to the fiber material), thus eliminating the need to provide a protective coating on the outer fiber . Optional metallic matrix composite wires
[00212] In additional exemplary embodiments, the thermoset polymer composite cable can optionally include one or more wires composed of fiber-reinforced metal matrix. A presently preferred fiber-reinforced metal matrix composite wire is a fiber-reinforced aluminum matrix composite wire. Yarns composed of aluminum matrix reinforced with ceramic fiber preferably comprise continuous fibers of polycrystalline α-Al2O3 encapsulated in a substantially pure elemental aluminum matrix or a pure aluminum alloy with up to about 2% by weight of copper based on the total weight of the matrix. Preferred fibers comprise equidimensional grains smaller than about 100 nm in size of a fiber diameter in the range of about 1 to 50 micrometers. A fiber diameter in the range of about 5 to 25 micrometers is preferred and most preferably in the range of about 5 to 15 micrometers.
[00213] In certain presently preferred embodiments of a wire composed of fiber-reinforced metal matrix, the use of a matrix comprising substantially pure elemental aluminum or an elemental aluminum alloy with up to about 2% by weight of copper, based on the total weight of the matrix, it has been shown to produce yarns successfully. For use in the present invention, the terms "substantially pure elemental aluminum", "pure aluminum" and "elemental aluminum" are interchangeable and are intended to mean aluminum containing less than about 0.05% by weight of impurities.
[00214] In a presently preferred embodiment, the yarns composed of fiber-reinforced metal matrix comprise between about 30 to 70% by volume of polycrystalline fibers α-Al2O3, based on the total volume of the yarn composed of fiber-reinforced metal matrix, within a substantially elementary aluminum matrix. It is presently preferred that the matrix contains less than about 0.03% by weight of iron and more preferably less than about 0.01% by weight of iron based on the total weight of the matrix. A fiber content of about 40 to 60% polycrystalline α-Al2O3 fibers is preferred. Wires composed of fiber-reinforced metallic matrix, formed with a metallic matrix that has an elastic limit of less than about 20 MPa, and fibers that have a longitudinal tensile strength of at least about 2.8 GPa have been found to have excellent resistance characteristics.
[00215] The matrix can also be formed from an elemental aluminum alloy with up to about 2% by weight of copper, based on the total weight of the matrix As in the embodiment in which a substantially pure elemental aluminum matrix is used, fiber-reinforced metal matrix composite yarns having an aluminum / copper alloy matrix comprise between about 30 to 70% by volume of polycrystalline α-Al2O3 fibers, and more preferably therefore about 40 to 60 % by volume of α-Al2O3 polycrystalline fibers based on the total volume of the polymeric composite. In addition, the matrix preferably contains less than about 0.03% by weight of iron and more preferably less than about 0.01% by weight of iron based on the total weight of the matrix. The aluminum / copper matrix preferably has an elastic limit of less than about 90 MPa, and, as above, α-Al2O3 polycrystalline fibers have a longitudinal tensile strength of at least about 2.8 GPa.
[00216] The yarns composed of fiber-reinforced metal matrix are preferably formed of polycrystalline α-Al2O3 fibers contained within the substantially pure elementary aluminum matrix or in the matrix formed from the elemental aluminum alloy and up to about 2%, by weight of copper described above. Such yarns are produced, in general, through a process in which a coil of substantially continuous fibers of polycrystalline α-Al2O3, arranged in a fiber tow, and is traversed by a bath of molten matrix material. The resulting segment is then solidified, thereby providing encapsulated fibers within the matrix.
Exemplary metal matrix materials include aluminum (for example, high purity, (for example, greater than 99.95%) elemental aluminum, zinc, tin, magnesium and alloys thereof (for example, an aluminum alloy and copper). Typically, the matrix material is selected so that it does not react significantly chemically with the fiber (i.e., it is relatively chemically inert with respect to the fiber material), for example, to eliminate the need for supply of a protective coating on the outer fiber. In some embodiments, the matrix material desirably includes aluminum and alloys of that substance.
[00218] In some embodiments, the metallic matrix comprises at least 98% by weight of aluminum, at least 99% by weight of aluminum, more than 99.9% by weight of aluminum, or even more than 99.95% by weight of aluminum. Exemplary aluminum alloys of aluminum and copper comprise at least 98 percent by weight of Al and up to 2 percent by weight of Cu. In some embodiments, the useful alloys are aluminum alloys series 1000, 2000, 3000, 4000, 5000, 6000, 7000 and / or 8000 (designations of the Aluminum Association). Despite the fact that metals with higher purities tend to be desirable for the manufacture of yarns with higher tensile strengths, less pure forms of metals are also useful.
[00219] Suitable metals are commercially available. For example, aluminum is available under the trade name “SUPER PURE ALUMINUM; 99.99% Al ”with Alcoa in Pittsburgh, PA, USA. Aluminum alloys (for example, Al-2% by weight of Cu (0.03% by weight of impurities)) can be obtained, for example, from Belmont Metals, New York, NY, USA. Zinc and tin are available, for example, from Metal Services, St. Paul, MN ("pure zinc"; 99.999% purity and "pure tin"; 99.95% purity). For example, magnesium is available under the trade name "PURE" from Magnesium Elektron, Manchester, England. Magnesium alloys (eg WE43A, EZ33A, AZ81A and ZE41A) can be obtained, for example, from TIMET, Denver, CO, USA.
[00220] The fiber-reinforced metal matrix composite yarns typically comprise at least 15%, by volume (In some embodiments, at least 20, 25, 30, 35, 40, 45 or even 50%, by volume) of based on the total combined volume of the fibers and matrix material. More typically, composite cores and yarns comprise in the range of 40 to 75 (in some embodiments, 45 to 70) percent, by volume, of fibers, based on the total combined volume of fibers and matrix material.
[00221] Wires composed of metal matrix reinforced with fiber can be produced using techniques known in the technical field. The metallic matrix composite wire can be produced, for example, by continuous metallic matrix infiltration processes. A suitable process is described, for example, in US Patent No. 6,485,796 (Carpenter et al.), The entire description of which is incorporated herein by reference. Optional ductile metal wires
[00222] In additional exemplary embodiments, the thermoset polymer composite cable may optionally include one or more ductile metallic wires. Ductile metal wires can be particularly preferred for weaving around a thermoset polymer composite core to provide a woven thermoset polymer composite cable that has high electrical conductivity, for example, an electrical power transmission cable in accordance with certain modalities of this description.
[00223] Preferred ductile metal wires include wires produced from iron, steel, zirconium, copper, tin, cadmium, aluminum, manganese, and zinc; its alloys with other metals and / or silicon; and the like. Copper wires are commercially available, for example from the Southwire Company, Carrolton, GA, USA. Aluminum wires are commercially available, for example from Nexans, Weyburn, Canada or Southwire Company, Carrolton, GA, USA, under the trade names “1350-H19 ALUMINUM” and “1350-H0 ALUMINUM”.
[00224] Typically, copper wires have a coefficient of thermal expansion in a range of about 12 ppm / ° C to about 18 ppm / ° C above at least a temperature range of about 20 ° C to about 800 ° C. Copper alloy (for example copper bronzes such as Cu-Si-X, Cu-Al-X, Cu-Sn-X, Cu-Cd; where X = Fe, Mn, Zn, Sn and or Si; commercially available, for example, from Southwire Company, Carrolton, GA, USA; oxide dispersion reinforced copper, commercially available, eg from OMG Americas Corporation, Research Triangle Park, NC, USA, under the designation “GLIDCOP”). In some embodiments, the copper alloy wires have a coefficient of thermal expansion in the range of about 10 ppm / ° C to about 25 ppm / ° C in at least a temperature range of about 20 ° C to about 800 ° C. The wires can be in any of a variety of shapes (for example, circular, elliptical, and trapezoidal).
[00225] Typically, aluminum wire has a coefficient of thermal expansion in a range of about 20 ppm / ° C to about 25 ppm / ° C in at least a temperature range of about 20 ° C to about 500 ° C. In some embodiments, aluminum wires (for example, “1350-H19 ALUMINUM”) have a tensile strength of at least 138 MPa (20 ksi), at least 158 MPa (23 ksi), at least 172 MPa ( 25 ksi) or at least 186 MPa (27 ksi) or at least 200 MPa (29 ksi). In some embodiments, aluminum wires (for example, “1350-H0 ALUMINUM”) have a tensile strength of more than 41 MPa (6 ksi) to no more than 97 MPa (14 ksi), or even no more than 83 MPa (12 ksi).
[00226] Aluminum alloy wires are commercially available, for example, aluminum-zirconium alloy wires available under the trade name “ZTAL”, “XTAL” and “KTAL” (available from Sumitomo Electric Industries, Osaka, Japan ) or “6201” (available from Southwire Company, Carrolton, GA, USA). In some embodiments, aluminum alloy wires have a coefficient of thermal expansion in the range of about 20 ppm / ° C to about 25 ppm / ° C in at least a temperature range of about 20 ° C at about 500 ° C.
[00227] In additionally exemplifying modalities, some or all of the ductile metallic wires may have a cross-sectional shape, in a direction substantially normal to the central longitudinal axis, which is in the form of "Z" or "S" (not shown). Yarns of such shapes are known in the art and may be desirable, for example, to form an interlaced outer layer of the cable. Methods of preparing yarn composed of thermoset polymer
[00228] In general, yarns composed of thermosetting polymer according to the present description can be advantageously produced using a pultrusion process instead of an extrusion process. In general, "extrusion" involves pushing the material through a cylinder equipped with one or more heated spindles that provide a significant amount of shear and mixing force before the material leaves the cylinder through, for example, a mold. In contrast, in a "pultrusion" process, materials are pulled through the mold. Pultrusion is often used to form fiber-reinforced polymer composite yarns that have a uniform cross section. In a typical pultrusion process, the continuous fibers and the liquid polymer precursor are pushed through a heated mold where the composite part is formed and the liquid polymer precursor is hardened. The fiber-reinforced polymer composite can then be cooled and cut to desired lengths to produce pultruded yarns. Exemplary pultruded yarns include rods, posts, cables, rods, tubes, beams, for example, I-beams, floors, arrow rods, poles, and the like.
[00229] An exemplary pultrusion process is illustrated by apparatus 200 in Figure 4A. Coils 104 of fiber 105 are supported on, for example, supports 102. Each fiber 105 is often a bundle of fibers, for example a tow or wick. Although not shown, the fibers can also be supplied as a mat containing continuous and batch fibers. In some embodiments, the fibers are combined with additional fibrous layers, for example, continuous cord mat 106.
[00230] As the fibers are pulled through the guide 110, they are aligned and distributed as desired for the specific pultruded thread. The fibers 105 then enter the liquid polymer precursor bath 120 where they are saturated or "impregnated" with the liquid polymer precursor system 130. At the exit of the liquid polymer precursor bath, the fibers enter the preform 140 where the foil saturated flat fiber is preformed and, in a process of decreasing volume, the excess liquid polymer precursor is removed.
[00231] In some embodiments, a continuous cord mat and / or surface mat can be applied after bathing the liquid polymer precursor to, for example, optimize the strength and / or surface properties of the pultruded part. In general, the added surface blankets are saturated with a portion of the excess liquid polymer precursor as they are squeezed from the saturated fibers in preform 140. In some embodiments, a preheater, for example, a preheater radio frequency heater, can be positioned between the preform 140 and the mold 150 to raise the temperature and lower the viscosity of the liquid polymer precursor.
[00232] After alignment and volume reduction, the fibers impregnated with liquid polymer precursor are ready to pass through the yarn forming mold 150. In general, the mold is machined precisely so that the fibers and the polymer precursor liquid are compacted to conform to the desired finished cross section. The mold 150 is typically heated in one or more zones to provide the desired temperature profile for curing or otherwise hardening the liquid polymer precursor system. In this way, the liquid polymer precursor cures and undergoes a reduction in volume as the liquid polymer precursor and fibers pass through the heated mold.
[00233] In some embodiments, a preform may not be present and the reduction in volume and saturation of any surface mat occurs at the entrance of the mold. In addition, as the materials are not preformed, the conversion of the materials to their final shape takes place within the mold.
[00234] After being cured and pultruded, the yarn composed of fiber-reinforced polymer (“FRP”) 2 melts out of the mold, can be cooled or otherwise treated before entering the “grip” section 170 A wide variety of grabbing approaches have been used to continuously pull materials through the pultrusion mold including, for example, 175 track tracks, hydraulic clamps, reciprocating pull blocks, and the like. Following the gripping section, the FRP 2 composite yarn can be cut (for example, with a cutting saw, not shown) to the desired lengths as finished thermoset polymer composite yarns, or wound on a 180 spool.
[00235] Several modifications to this general description of pultrusion are adequately understood. For example, as an alternative to fiber saturation in a liquid polymer precursor bath, the liquid polymer precursor can be injected into the mold in a process typically called injected pultrusion. In general, the fibers are unrolled from a basket, aligned and distributed as needed, and passed through the mold. Near the entrance of the mold, the liquid polymer precursor is injected, and as the fibers are pulled through the liquid polymer precursor injection area, the fibers are saturated, the liquid polymer precursor is cured in the mold, and a FRP composite yarn is produced and ready to be cut into threads or wound on a 180 bobbin.
[00236] As in many manufacturing processes, there is a desire to increase the mechanical properties of pultruded yarns. Typically, manufacturers try to achieve this by increasing the fiber volume fraction in the yarns. However, as is well known, even small increases in the fiber volume fraction can lead to significant increases in tensile strength, that is, the force required to pull the liquid polymer precursor and the fiber through the mold. As processing speed and throughput are also critical, there are significant practical limitations to the maximum fiber load that can be achieved.
[00237] In general, the lower the volume fraction of fiber in the composite, the greater the reduction in the volume of the composite part resulting from the shrinkage of the liquid polymer precursor during curing in the mold. As the resulting composite part has reduced contact with the mold surface, friction is reduced and a lower tensile force is required. As the fiber volume increases, there is less liquid polymer precursor, resulting in less shrinkage, more friction, and greater tensile forces.
[00238] The viscosity of the liquid polymer precursor also affects the tensile strength. In general, as the viscosity increases, greater tensile forces are required. In some applications, the liquid polymer precursor can be preheated before entering the mold, in part to reduce its viscosity.
[00239] The present inventors have found that, in some embodiments, the inclusion of even small amounts of nanoparticles in the liquid polymer precursor system can produce a dramatic and unexpected decrease in tensile strength in a fixed fiber load. This effect can be used to increase the fiber volume load and / or processing speed without exceeding the maximum desirable tensile strength. These results are all the more surprising as the addition of nanoparticles to a liquid polymer precursor system is known to both increase viscosity and reduce shrinkage, both of which typically increase the required tensile strength.
[00240] In addition to maintaining the pulling force below a desired maximum value, it is also desirable to maintain a constant pulling force. Often, sudden, or even gradual increases in tensile strength indicate processing problems, usually at the entrance to, or inside the mold. This can lead to a break in production as the mold is cleaned or other variables are adjusted. These pauses or temporary stops in the process can also cause blockages in the pulling force as the line movement is restarted. Thus, higher and more stable tensile forces may be desirable than lower and unstable tensile forces.
[00241] In some embodiments, the present inventors have found that the addition of even small amounts of nanoparticles can lead to a stable tensile force. Although reductions in tensile strength are more often desired, even for those circumstances where the average tensile strength is higher with a nanoparticle-loaded liquid polymer precursor system than a similar system without nanoparticles (for example, due to the fraction high fiber volume), greater (albeit stable) tensile forces can be tolerated, providing greater flexibility in the selection of other parameters such as fiber volume load, line speed, and liquid polymer precursor viscosity. Methods of making interlaced cables comprising at least one wire composed of thermoset polymer
[00242] In additional exemplifying embodiments, the description provides a method of making composite woven cables as described in any of the aforementioned embodiments, wherein the method comprises interweaving a first plurality of wires around a core (for example , a wire) defining a central longitudinal axis, with the helical interlacing of the first plurality of threads composed of thermoplastic polymer carried out in a first configuration direction in a first configuration angle defined in relation to the central longitudinal axis, the first plurality of wires has a first configuration length; the helical interlacing of a second plurality of thermoplastic composite yarns around a first plurality of thermoplastic polymer composite yarns, the interleaving of the second plurality of thermoplastic polymer yarns being performed in the first configuration direction at a second angle of configuration defined in relation to the central longitudinal axis, and the second plurality of wires having a second configuration length; and heating a first and second plurality of wires composed of thermoplastic polymer interlaced in helical shape and for a sufficient time to hold the wires composed of polymer interlaced in helical shape in a twisted configuration in helical shape in cooling to 25 ° C.
[00243] A presently preferred temperature is at least about 100 ° C, more preferably about 150 ° C, more preferably at least 200 ° C, and even more preferably at least about 250 ° C or even 300 ° Ç. In some exemplary embodiments, the temperature should not exceed 600 ° C, 550 ° C, 500 ° C, 450 ° C, or even 350 ° C.
[00244] The time is preferably about one second to no more than about one hour. Preferably, the time is no more than 30 minutes, more preferably no more than about 15 minutes, no more than about 10 minutes, no more than about five minutes; no more than about four minutes, no more than about three minutes, no more than about two minutes, or even no more than about a minute.
[00245] In an exemplary embodiment, the thermofixed polymer composite cable in helical shape includes a plurality of wires composed of thermoplastic polymer that are helically shaped in a configuration direction to have a configuration factor of 6 to 150. O The "configuration factor" of an interlaced cable is determined by dividing the length of the interlaced cable in which a wire 12 completes a helical revolution by the maximum nominal limit of the diameter of the layer that includes that cord.
[00246] Although any appropriately sized thermoplastic polymer composite yarns can be used, it is preferred for many modalities and many applications that the thermoplastic polymer composite yarns have a diameter of 1 mm to 4 mm, however, larger or thermoplastic polymer composite yarns smaller ones can be used. Methods of preparing an interlaced cable comprising a plurality of wires composed of thermoset polymer
[00247] In a final aspect, the description describes methods of preparing an interlaced cable including at least one of the thermoset polymer composite yarns described above. In certain exemplary embodiments, the description describes a method for making a helical twisted cable including at least one of the wires composed of thermoset polymer.
[00248] Thus, in an exemplifying modality, the method comprises the interlacing in helical shape of a first plurality of wires around a core wire defining a central longitudinal axis, with the interlacing in helical shape of the first plurality of wires it is executed in a first configuration direction at a first configuration angle defined in relation to the central longitudinal axis; helical interlacing of a second plurality of wires around the first plurality of wires, the helical interlacing of the second plurality of wires being performed in the first configuration direction at a second configuration angle defined in relation to the central longitudinal axis. In at least one of the core yarn, the first plurality of yarns, or the second plurality of yarns is selected to be a yarn composed of thermoset polymer as described above.
[00249] Optionally, the first and second plurality of twisted wires in helical shape can be heated to a temperature sufficient to retain the twisted wires in helical shape in a twisted configuration in helical shape by cooling to 25 ° C. Optionally, the first and second pluralities of wires can be surrounded with a corrosion resistant wrap and / or shielding element.
[00250] In other exemplary modalities of a method of preparing a thermofixed polymer composite cable in helical shape, the relative difference between the first configuration angle and the second configuration angle is greater than 0 ° and not greater than about 4th. In certain exemplary embodiments, the method additionally comprises the interweaving of a plurality of ductile metallic threads around the core thread defining the central longitudinal axis.
[00251] An exemplary apparatus 80 for preparing thermofixed polymer composite cables in accordance with the modalities of the present description is shown in Figure 4B. Composite wires can be helically woven or wound as is known in the art on any suitable cable weaving equipment, such as planetary cable weavers available from Cortinovis, Spa, Bergamo, Italy, and from Watson Machinery International, from Patterson, NJ, USA. In some embodiments, it may be advantageous to employ a rigid supporter, one or rotary shaft to achieve a core tension greater than 100 kg, as is known in the art.
[00252] An exemplary interlacing process is described, for example, in US patent No. 5,126,167. During the cable interlacing process, the central wire or the unfinished intermediate thermofixed polymer composite cable, which will have one or more additional layers wrapped around it, is pulled through the center of several cars, with each car adding a layer to the interlaced cable. The individual wires to be added as a layer are simultaneously pulled from their respective coils as they are rotated around the central axis of the cable by the motor driven car. This is done in sequence for each desired layer. The result is a composite core of thermoset polymer interlaced in a helical shape.
[00253] A coil of wire 81 used to supply the core wire 2 of the helicoidal polymeric composite wire in helical shape is provided on the head of a conventional planetary interlacing machine 80, with coil 81 being free to rotate, with tension capable of being applied through a brake system where tension can be applied to the core during the outcome (in some modalities, in the range 0 to 91 kg (0 to 200 lbs.)). The core wire 90 is threaded through the bobbin carriages 82 and 83, through closing molds 84 and 85, around the rotary axis wheels 86 and attached to the take-up bobbin 87. The bobbin of thread 81 may comprise a thread composite, for example, a thermoset polymer composite yarn, a thermoplastic polymer composite yarn, or a metallic matrix composite yarn. Alternatively, the bobbin of thread 81 may comprise a metallic thread, for example, a ductile metallic thread.
[00254] In some exemplary embodiments, the interlaced cable passes (that is, is threaded) through optional heat sources 96 and 97. Closing molds 84 and 85 can also incorporate heating elements. The heat sources supply enough heat for a sufficient time to allow any polymeric composite yarn to be at least partially cured. The heat sources can be long enough to provide sufficient heating time to heat the thermoset polymer composite cable to a temperature so that any strands composed of thermoplastic polymer (if present) are plastically deformed.
[00255] Various heating methods can be used, including for example, convective heating with air, and radiative heating, such as with a tube furnace. Alternatively, the cable can be passed through a heated liquid bath. Alternatively, the twisted cable can be wound on a bobbin and then heated in an oven for a sufficient temperature and time so that the wires are plastically deformed.
[00256] Prior to the application of the outer weaving layers, individual composite yarns (for example, thermoset polymer composite yarns, as well as any optional thermoplastic polymer composite yarns and / or metallic matrix composite yarns) are supplied in separate coils 88 which they are placed in several motor-powered cars 82 and 83 of the interlacing equipment. In some embodiments, the voltage range required to pull the wires 89A and 89B from the coils 88 is typically 4.5 to 22.7 kg (10 to 50 lbs.). Typically, there is a carriage for each layer of the thermoset polymer composite cable woven into a finished helical shape. The wires 89A and 89B of each layer are gathered at the exit of each car in a closing mold 84 and 85 and arranged on the core wire or on the previous layer.
[00257] Layers of composite yarns (for example, thermoset polymer composite yarns, as well as any optional thermoplastic polymer composite yarns and / or metallic matrix yarns) can be interlaced in helical shape as described previously. During the cable interlacing process, the core wire or thermoset polymer composite cable interlaced in an unfinished helical shape, which will have one or more additional layers wrapped around it, is pulled through the center of several cars with each car by adding a layer to the interlaced cable. The individual wires to be added as a layer are simultaneously pulled from their respective coils as they are rotated around the central axis of the cable by the motor driven car. This is done in sequence for each desired layer. The result is a thermofixed polymer composite cable in helical shape 91 that can be cut and handled conveniently without loss of shape or disassembly of the entanglement.
[00258] In some exemplary embodiments, the woven composite cables of thermoset polymer interlaced in helical shape comprise composite wires that are at least 100 meters long, at least 200 meters, at least 300 meters, at least 400 meters, at least 500 meters, at least 1000 meters, at least 2000 meters, at least 3000 meters, or even at least 4500 meters or more.
[00259] The core wire and any wires for a given layer are placed in intimate contact through closing molds. With reference to Figure 3, the closing molds 84 and 85 are typically sized to minimize deformation stresses on the strands of the layer being wound. The inner diameter of the closing mold is made to the size of the outer layer diameter. To minimize stresses on the layer wires, the closure mold is dimensioned so that it is in the range of 0 to 2.0% larger, in relation to the outer diameter of the cable, (that is, the inner diameters of the mold are in the range from 1.00 to 1.02 times the diameter of the external cable). Exemplary closing molds are cylinders and are held in position, for example, with the use of dowels or other suitable fixings. The molds can be made, for example, of hardened tool steel.
[00260] The resulting thermofixed polymer composite cable in the resulting finished helical shape can pass through other interlacing stations, if desired, and finally wound onto the take-up coil 87 of sufficient diameter to prevent damage to the cable. In some presently preferred embodiments, the corrosion-resistant wrap 9, such as a ribbon provided from a cylinder 289, can be applied to the outer surface of the thermofixed polymer composite cable using a 298 ribbon applicator, thus forming a 10 '' interlaced thermoset polymer composite cable that has a corrosion resistant outer wrap.
[00261] In some embodiments, techniques known in the cable alignment technique may be useful. For example, the finished cable can pass through an alignment device comprising rollers (each roll being, for example, 10 to 15 cm (4 to 6 inches), linearly arranged on two banks, with, for example, 5 to 9 rolls The distance between the two roller banks can be varied so that the rollers basically impact the cable or cause severe flexing of the cable The two roller banks are positioned on opposite sides of the cable, with the rollers on a bench of rollers in one bank matching the spaces created by the opposing rollers in another bank, so the two banks can compensate for each other. As the helix-woven thermofix polymer composite cable passes through the alignment device, the cable it is flexed back and forth on the rollers, allowing the wires interlaced in the conductor to extend the same length, thereby reducing or eliminating loosening.
[00262] In some embodiments, it may be desirable to supply the core wire at an elevated temperature (for example, at least 25 ° C, 50 ° C, 75 ° C, 100 ° C, 125 ° C, 150 ° C, 200 ° C, 250 ° C, 300 ° C, 400 ° C, or even, in some embodiments, at least 500 ° C) above room temperature (for example, 22 ° C). The core yarn can be brought to the desired temperature, for example, by heating the coiled yarn (for example, in an oven for a few hours). The heated coiled wire is placed on the feed coil (see, for example, feed coil 81 in Figure 3) of an interlacing machine. Desirably, the high temperature coil is in the process of interlacing while the wire is at or near the desired temperature (typically about 2 hours).
[00263] In additional exemplary embodiments, it may be desirable to supply all yarns at an elevated temperature (for example, at least 25 ° C, 50 ° C, 75 ° C, 100 ° C, 125 ° C, 150 ° C, 200 ° C, 250 ° C, 300 ° C, 400 ° C, or even, in some embodiments, at least 500 ° C) above room temperature (for example, 22 ° C). The threads can be brought to the desired temperature, for example, by heating the coiled thread (for example, in an oven, for a few hours). The heated coiled wire is placed in the supply coil (see, for example, supply coil 81 in Figure 4B) and coils (88A and 88B) of interlacing machine 300. Desirably, the coil at high temperature is in the process of interlacing while the wire is at or near the desired temperature (typically about 2 hours).
[00264] In certain exemplary embodiments, it may be desirable to have a temperature differential between the core yarn and the other yarns that form the outer composite layers during the interlacing process. In additional embodiments, it may be desirable to conduct interlacing with a core wire tension of at least 100 kg, 200 kg, 500 kg, 1000 kg, or even at least 5000 kg.
[00265] The ability to handle helical-woven polymer composite wire in helical shape is a desirable feature. Although not intended to stick to theory, helix-woven thermofix polymer composite cables may be more readily able to maintain their helix-weaving arrangement during manufacture when optional thermoplastic polymer compound wires are included in one or more layers the cable. When these threads composed of thermoplastic polymer are heated to a sufficient temperature, they are plastically deformed, and the stresses within the threads are relaxed. The bending stresses and other stresses imparted to the yarns composed of thermoplastic polymer during interlacing can then be greatly reduced or even eliminated (ie reduced to zero) if the yarns composed of thermoplastic polymer interlaced are heated to a temperature sufficient to soften the polymeric matrix inside the interlaced wires, causing the wires composed of thermoplastic polymer to be adhered to each other and thus maintain their interlaced configuration in helical shape by cooling to 25 ° C.
[00266] In certain presently preferred exemplary embodiments, the yarns composed of thermoplastic polymer are heated to a temperature at least above the glass transition temperature of the (co) polymer matrix material forming the yarn composed of thermoplastic polymer for sufficient time for the thermoplastic polymer undergo stress relaxation. In some exemplary embodiments, the optional thermoplastic polymer composite yarns on the helix-woven polymer composite cable are heated to a temperature of at least 50 ° C, more preferably at least 100 ° C, 150 ° C, 200 ° C, 250 ° C, 300 ° C, 350 ° C, 400 ° C, 450 ° C or even at least 500 ° C.
[00267] Preferably, the wires composed of thermoplastic polymer in the helix-woven polymeric thermofix composite cable are not heated to the temperature above the melting temperature of the thermoplastic (co) polymer matrix. In some embodiments, the resident warm-up time may be less than one minute. In other exemplary embodiments, the wires composed of thermoplastic polymer in the helix-shaped thermofix polymer composite cable are heated for a period of time of at least 1 minute, 2 minutes, 5 minutes, 10 minutes, 20 minutes, half an hour, with more preferably 1 hour, 1.5 hours, or even two hours.
[00268] Applications for woven thermoset polymer composite cables
[00269] The thermofixed polymer composite cables of the present description are useful in numerous applications. Such cables are believed to be particularly desirable for use in power transmission cables, which may include overhead, underground and submarine power transmission cables, due to the combination of low weight, high strength, good electrical conductivity, low coefficient thermal expansion, high usage temperatures, and corrosion resistance. Thermosetting polymer composite cables in helical shape can also be used as intermediate articles that are later incorporated into final articles, for example, tow cables, winch cables, power transmission cables, and the like.
[00270] Electricity transmission cables can include two or more optional layers of ductile metallic conductors. More layers of ductile metallic conductors can be used as desired. When used as an electrical power transmission cable, the optional ductile metal wires can act as electrical conductors, that is, conductors of ductile metal wire. Preferably, each conductive layer comprises a plurality of ductile metallic conductors as is known in the art. Suitable materials for ductile metallic conductors include aluminum and aluminum alloys. Ductile metallic conductive wires can be woven around a composite core of thermoplastic polymer woven into a helical shape by equipment and woven wire as is known in the art.
[00271] The weight percentage of wires composed of thermoset polymer within the power transmission cable will depend on the design of the transmission line. In the electrical power transmission cable, the conducting wires of aluminum or aluminum alloy can be of any material of the various known in the air power transmission technique, including, but not limited to, 1350 Al (ASTM B609- 91), 1350-H19 Al (ASTM B230-89) or 6201 T-81 Al (ASTM B399-92).
[00272] A presently preferred application of the power transmission cable is an overhead power transmission cable, an underground power transmission cable, an underwater electric power transmission cable, such as an underwater cable or an umbilical cable submarine. For a description of suitable overhead power transmission cables, underground power transmission cables, submarine power transmission cables, submarine cables and submarine umbilical cables, see, for example, copending US provisional patent application No. 61 / 226,151 (“INSULATED COMPOSITE POWER CABLE AND METHOD OF MAKING AND USING SAME”, filed on July 16, 2009) Copending US Provisional Patent Application No. 61 / 226,056 (“SUBMERSIBLE COMPOSITE CABLE AND METHODS”, filed on July 16 2009).
[00273] For a description of suitable electrical power transmission cables and processes in which the interlaced cable of this description can be used, see, for example, Standard Specification for Concentric Lay Stranded Aluminum Conductors, Coated, Steel Reinforced (ACSR) ASTM B232-92; or US Patent Nos. 5,171,942 and 5,554,826 or US Patent Nos. 5,171,942 and 5,554,826. In these electrical power transmission orders, the wires used in the manufacture of the cable must be selected in general for use at temperatures of at least 240 ° C, 250 ° C, 260 ° C, 270 ° C, or even 280 ° C, depending on application.
[00274] As discussed above, the electric power transmission cable (or any of the individual wires used in the formation of the interlaced composite cable) can be optionally surrounded by an insulating layer or wrap. A shielding layer or wrap can also be used to encircle and protect the power transmission cable (or any of the individual wires used to form the interlaced composite cable).
[00275] In some other applications, in which the interlaced composite cable must be used as a final article (for example, as a winch cable), it may be preferable that the interlaced composite cable be free of conductive layers of electrical energy. Unexpected results and benefits
[00276] Several unexpected results and advantages can be obtained in exemplary modalities of the description. In some exemplifying modalities, the inclusion of a plurality of particles that have a median diameter of one micrometer or smaller, dispersed substantially uniformly throughout the polymeric composite matrix, allows the achievement of a more carbon fiber volume fraction load high in the fiber-reinforced polymer composite yarn, thus increasing the compressive strength, shear modulus, hardness, and yarn bending resistance. The inclusion of a plurality of particles having a median diameter of one micrometer or less dispersed substantially uniformly throughout the polymer composite matrix has also been shown with a decrease in the thermal expansion coefficient (CTE) and shrinkage after curing.
[00277] For example, a 25% reduction in CTE and a 37% reduction in linear shrinkage was obtained for a thermoset polymer composite reinforced with cured carbon fiber (including a plurality of particles having a median diameter of one micrometer or smaller dispersed substantially uniformly throughout the polymer composite matrix compared to a particle-free control.These carbon fiber-reinforced polymer composite wires are particularly attractive for use in overhead power transmission cables. carbon fiber-reinforced polymer composite yarns can, in some cases, be produced at a lower cost than conventional metal-matrix polymer composite yarns reinforced with conventional ceramic fiber.
[00278] Furthermore, in certain exemplifying embodiments, the inclusion of nanoparticles in the thermoset polymer composite wire increases one or both of the flexural strength and flexural strength of the thermoset polymer composite wire, and in some exemplary embodiments, one or both of flexural strength and flexural strength of a composite cable incorporate this thermoset polymeric composite wire. This not only improves the performance of the wire and / or cable, but provides significant advantages in the handling, transportation, and installation of the thermoset polymer composite wires and composite cables that incorporate these wires.
[00279] Additionally, in some exemplary embodiments, the polymer matrix of the composite core is mixed from an exclusive combination of an epoxy resin with a high glass transition temperature and a curative agent that makes the polymer matrix more stable at high temperatures ( for example, as high as 280 ° C). Furthermore, in some exemplary embodiments, the use of high temperature glass transition epoxy resins (eg 240 ° C Tg or greater) in the polymeric composite matrix can unequivocally provide enhanced high temperature performance in comparison with conventional polymeric composite yarns known in the art. These unique high temperature performance characteristics are ideally suited for high voltage power transmission applications.
[00280] In other exemplary embodiments, the plurality of particles comprise particles with modified surface which further comprise a nanoparticle core and a reactive surface modifying agent associated with the nanoparticle core and reacted with the cured polymer from a state liquid (the precursor matrix material of liquid polymer). These chemically treated particles disperse particularly well in liquid polymer precursor matrix materials of epoxy resin and generally require lower pultrusion forces to pull the fibers through the mold during the process of making the composite yarn. This facilitates the production of thermoset polymer composite yarns at higher fiber loads, which is highly desirable to optimize the strength and mechanical properties of the composite yarns. This can also facilitate the production of composite yarns loaded with nanoparticles at a higher pultrusion line speed or at a lower pultrusion pull force.
[00281] Thus, in some exemplifying modalities, the tensile strength required to form a thermoset polymer composite wire is reduced by at least 30% compared to the tensile strength required to form the same fiber-reinforced polymer composite under the same conditions , but without the multiplicity of particles having a median diameter of one micrometer or smaller, dispersed substantially uniformly throughout the liquid polymeric precursor. In some embodiments, the tensile force required to form the fiber-reinforced polymer composite at a line speed of at least 20% greater than the baseline speed is less than the tensile force required to form the same reinforced polymer composite with fiber at base speed and without the plurality of particles having a median diameter of one micrometer or less dispersed substantially uniformly throughout the liquid polymer precursor.
[00282] The operation of the present description will be further described with respect to the examples detailed below. These examples are offered to better illustrate the various specific and preferred modalities and techniques. It should be understood, however, that many variations and modifications can be made that are within the scope of this description. Examples Summary of Materials Table 1


Test procedures Particle size procedure
[00283] The particle size of the nanoparticles was measured by laser diffraction using a HORIBA LA-950. The nanoparticle dispersion was diluted to approximately 1% solids with acetone. The sample was then added to the measurement cell, which was filled with acetone, until the transmittance was within the recommended levels of 85% to 95%. The optical model for the calculation used a refractive index of 1.6000 for calcite and 1.3591 for acetone, and assumed spherical particles. The second differential method was used for smoothing and was based on 150 iterations. The reported values of particle size were based on the averages of volume fraction and static light scattering. Electron microscopy procedure
[00284] Images of cross section samples of bar and polished wires prepared in accordance with the present description were obtained with the use of scanning electron microscopy. A HITACHI S-4700 field emission scanning electron microscope (FESEM) S-4700 was used to obtain electron micrograph images. The imaging conditions used were: 2.0 KV 5.5 m WD, UHR-A, slope = 0 °, ExB mode and 10 beam current microamperes. The images were typically collected at 5000x and 15,000x magnification.
[00285] The polished cross sections of each sample were bombarded with ions coated with Au / Pd for 10 seconds with a plasma stream of 10 milliamps, and attached to an adapter to support FESEM samples with conductive carbon tape. All images were collected using electronic imaging by retrograde diffusion (BSEI) using an ExB filter. The ExB filter allowed BSEI imaging at low beam electrical voltages and areas of high average atomic number will appear illuminated in BSEI images. Gas chromatography (GC) procedure Gas chromatography was used to analyze residual solvents. The gas chromatography was run using an AGILENT 6890N gas chromatograph equipped with an HP-5MS (5% phenyl) -methylpolysiloxane column that has a length of 30 meters and an internal diameter of 320 micrometers (both the chromatograph and the column are available from Agilent Technologies, Incorporated, Santa Clara, California, USA)). The following parameters were employed: a 1 microliter aliquot of a 10% sample solution (in GC in grade tetrahydrofuran) was injected; burst inlet mode set to 250 ° C, 65.6 kPa (9.52 psi) and a total inlet flow of 111 mL / min; column constant pressure mode set to 65.6 kPa (9.52 psi); speed set at 34 centimeters / second; total gas flow was 2.1 mL / min; detector and injector temperatures were 250 ° C; and an equilibrium temperature sequence at 40 ° C for 5 minutes followed by a ramp rate of 20 ° C / minute at 260 ° C. A thermal conductivity detector was used. Thermogravimetric analysis procedure
[00286] The silica or calcite content of liquid polymer precursor systems was measured using thermogravimetric analysis. The samples were analyzed using a TA Instruments TGA Model Q500 and its associated software (available from TA Instruments, New Castle, Delaware, USA) employing a temperature ramp rate of 20 degrees Celsius (° C) / minute from 35 ° C to 900 ° C, in the air. For samples containing silica, the sample weight (as a percentage of the initial weight) that remained at 850 ° C was taken as the weight percentage of non-combustible material and is reported as the weight percentage of the product consisting of solids of silica. For samples containing calcite, the residual weight was considered to be the remaining CaO in the sample after the volatilization of all organics and carbon dioxide from the calcite. The weight fraction of calcite in the original sample was calculated by dividing the weight percentage of the CaO residue by 0.56. Viscosity procedure
[00287] The viscosity of liquid polymer precursor was measured using a Brookfield DVII (Brookfield, Middleboro, MA, USA) with a No. 4 RV spindle at 20 rpm. Viscosity is reported in Pascal seconds. Pure resin fracture resistance procedure
[00288] Fracture strength was measured according to ASTM D 5045-99 using standard stress geometry, with specimens having nominal dimensions of 3.18 cm by 3.05 cm by 0.64 cm with W = 2.54 cm, a = 1.27 cm, and B = 0.64 cm. A modified loading rate of 1.3 mm / minute (0.050 inch / minute) was used. Pure resin tensile test procedure
[00289] The traction modules of the resins at room temperature were measured according to ASTM D638 using a “Type I” specimen. The loading rate was 1.3 mm / min (0.05 inch / min). Five specimens were tested for each type of resin. Flexure test procedure
[00290] The flexure test was conducted following the ASTM D790 using a nominal elongation rate of (0.10 mm / mm / min). Five to ten specimens measuring 152 x 12.7 x 3.2 mm. An extension ratio: 32: 1 depth was used. The mean value of the flexure, elongation and resistance modulus are reported. Mechanical analysis test procedure
[00291] The glass transition temperature (Tg) of the composite parts was obtained by Dynamic Mechanical Analysis (AMD) using an RSA2 Solid Analyzer (Rheometrics Scientific, Inc, Piscataway, NJ, USA) in cantilever beam mode . Experiments were carried out using a temperature ramp from -30 ° C to 220 ° C at 5 ° C / minute, a frequency of 1 Hz, and an elongation of 0.03 to 0.10%. The peak of the delta tangent curve was reported as Tg. Short beam shear test procedure
[00292] The short beam shear test was conducted according to ASTM 2344. Ten specimens were prepared by cutting them from the center of the pultruded part, so that both side edges were removed to create narrow specimens. The dimensions of the specimen were nominally 2 times the dimension of the thickness in width, 6 times the dimension of the thickness in length, and the amplitude of the support cylinders was 4 times the dimension of the thickness. The entire test was conducted under laboratory conditions at approximately 20 ° C. The average value of short beam shear strength is reported. Preparatory methods Nanoparticle procedure with modified surface
[00293] Silica nanoparticles with modified surface were prepared by placing 1157 grams of NALCO 2326 silica nanoparticles sol (16.1%, by weight, 5 nm silica in aqueous dispersion) in a glass container. In a separate container, 2265 grams of 1-methoxy-2-propanol and 64.5 grams of trimethoxy phenyl silane were added during stirring. The 1-methoxy-2-propanol mixture was added over a period of approximately 5 minutes to NALCO 2326 sol with continuous stirring. The resulting uniform solution was heated in an oven at 80 ° C for 16 hours. This process was repeated several times and combined in one batch. The resulting sol (SOL-1) contained 5.3 percent by weight of surface-modified silica in a blend of water and methoxy propanol.
[00294] Additional silica nanoparticles with modified surface were prepared by placing 1,689 part by weight of NALCO 2329K silica nanoparticle (40.8%, by weight 70-95 nm silica in an aqueous dispersion) in a vessel of an open-head stainless steel mixture and a part by weight of 1-methoxy-2-propanol was added slowly during stirring. Then, 0.0197 part by weight of trimethoxy phenyl silane was added slowly to the mixture. The mixture was left to stir with a pneumatically operated propeller for 30 minutes. Hydrothermal reactor procedure
[00295] A 27 liter continuous flow hydrothermal reactor, as described in the international publication PCT No. WO2009 / 120846 A2 was used to functionalize the surface of the silica particles. The 27-liter hydrothermal reactor was 18.3 meters in 1.27 cm (DE) outside diameter; 1.09 cm internal diameter (DI) stainless steel pipe, followed by 0.95 cm 12.2 meters and DE; 0.77 cm DI stainless steel tubing, followed by 198.1 meters PTFE flat-hole inner tube with 1.27 DI with a high-strength 304 stainless steel outer shell. The oil temperature in the hydrothermal reactor was maintained at 155 ° C, and the TESCOM back pressure regulator (TESCOM, Elk River, MN, USA) was maintained at 2.14 MPa (310 psig). A diaphragm pump (LDC1 ECOFLOW, American Lewa, Holliston, MA, USA) was used to control the flow rate, and therefore the residence time, so that a flow rate of 770 ml / min was obtained through the hydrothermal reactor, providing a residence time of 35 minutes. The effluent from the continuous flow hydrothermal reactor was collected in an HDPE drum. The resulting sol (SOL-2) contained 25.4 by weight per center of surface-modified silica in a blend of water and methoxy propanol.
[00296] A first liquid polymer precursor system (“RS-1”) was prepared by combining 14.6 kg of EPON 828 liquid epoxy polymer precursor with 3.6 kg of HELOXY 107 liquid epoxy polymer precursor.
[00297] A second liquid polymer precursor system (“RS-2”) was prepared by adding 12.4 kg of SOL-1, 90.9 kg of SOL-2, 19.1 kg of liquid epoxy polymer precursor EPON 826, 4.8 kg of liquid epoxy precursor HELOXY 107, and 16.9 kg of methoxy propanol for a 380 Liter Boiler with agitation forming a feed mixture. The boiler was maintained at 25 ° C and the components were stirred for a minimum of 14 hours. Greased film evaporator (EFU) procedure
[00298] The mixture was measured at the top entrance of a Greased Film Evaporator (EFU) as described above in US provisional application No. 61/181052 (filed on May 26, 2009; Attorney Summary No. 65150US002), with the use of a 1 meter square BUSS FILTRUDER polymer processing machine with a BLB series external rotating sprocket and a chemical function gear pump (Zenith Pumps, Sanford, NC, USA). The EFU rotor, of the BUSS FILMTRUDER type, was set at a speed of 340 rpm with a 25 horsepower drive. Vacuum was applied at a level of 2.6 to 2.8 kPa. The feed stream mixture was fed at a rate of 69 kg / hour and had water vapor zone temperatures as follows: zone 1 108 ° C, zone 2 108 ° C, zone 3 150 ° C, and zone 4 134 ° C. The resulting product, RS-2, had a temperature of 121 ° C at the EFU outlet. A liquid polymer precursor system RS-2 had a silica content of 49.4% by weight, as determined by TGA, of which 97%, by weight, of the nanoparticles with modified surface were derived from SOL-2 (70 to 95 nm) and 3% by weight, were derived from SOL-1 (5 nm)).
[00299] A third liquid polymer precursor system (“RS-3”) was prepared by combining 20.68 kg of SOL-1, 3.81 kg of RS-1 liquid polymer precursor, and approximately 1 kg of 1 -methoxy-2-propanol. The mixture was subjected to rectification by injection of water vapor and 1-methoxy-2-propanol in a concentration of 9.8%, by weight, of 1-methoxy-2-propanol (and no remaining water) with the use rotary evaporation (vacuum and gentle heating). The mixture was then rotated in a Rolled Film Evaporator (RFE) (Chem Tech Inc, Rockdale, IL, USA) that had a surface area of 0.06 m2, an internal condenser, and a stainless steel jacket. The sample partially subjected to water vapor injection rectification from the rotary evaporator was placed in a glass container from which it was pumped into the RFE with a peristaltic pump (Masterflex L / S, Cole-Parmer Instrument Company, Vernon Hills, Illinois, USA) at a rate of 18 grams / minute. The RFE jacket was kept at a temperature of 150 ° C and the system was subjected to vacuum for approximately 2500 Pascals. The product discharge line was maintained at a temperature of 120 ° C. The condenser temperature was maintained at -10 ° C. The rotor was operated at a rate of 354 rpm. The output of the RFE (RS-3) consisted of properly dispersed epoxy and functionalized nanoparticles, and methanol propanol (measured by GC). The final concentration of nanoparticles with modified surface in RS-3 (as measured by TGA) was 23.1% by weight. Liquid polymer precursor systems
[00300] A series of liquid epoxy polymer precursor systems were prepared by combining various amounts of functional epoxy polymer precursors (RS-1, RS-2, and RS-3) as summarized in Table 2. Table 2

[00301] A pultrusion liquid polymer precursor system (“R-REF1”) was prepared by combining 1.18 kg of EPON 828 liquid epoxy polymer precursor, 1.12 kg of LS81K anhydride dressing, and 0.12 kg of ASP400 clay.
[00302] A control liquid polymer precursor without nanoparticles (“R-CTL1”) was prepared by combining 0.97 kg of RS-1 liquid polymer precursor, 0.95 kg of LS-81K dressing, and 0.10 kg of ASP400 clay. The resulting liquid polymer precursor system contained 5.0% by weight of clay and had a viscosity of 0.58 Pa ^ sec. Pultrusion process
[00303] Pultrusion experiments were conducted on a commercial pultrusion machine. Sixty-eight 12K graphite fiber tow (GRAFIL 34-700 Grafil Inc. fiber) was mounted in a warp without bearings and without an external tensioning device. As summarized in Table 3, the graphite fiber from trailers 58 to 68 was pulled from the warper and guided to an open liquid polymer precursor bath containing a liquid polymer precursor system. The wet fibers were pulled through a mold, with the removal of excess volume at the entrance of the mold. The gripping section consisted of reciprocating traction blocks used to pull the fiber-reinforced polymer composite and completely cured at a line speed of 38.1 cm per minute. The finished wires were cut to length with a cutting saw.
[00304] The mold was 91 cm long and had a rectangular cross section measuring 1.32 cm wide by 0.33 height. The mold had a first heating zone set at 160 ° C followed by a second zone set at 182 ° C. The exotherm that occurred during curing of the liquid polymer precursor contributed to the temperature in the process when, for example, the temperature of the composite part was 168 ° C, as measured between the heating zones.
[00305] The mold was supported on a portion of the pultrusion line structure, but was not rigidly attached to the structure. As the materials were pulled through the mold, the mold moved in the direction of tension and was forced against a load cell recording the tensile force. The results of the tractive force are summarized in Table 3. With this equipment and mold geometry, a constant tractive force not greater than about 1569.1 N (160 kg of force) was required, since greater tractive forces tended resulting in erratic performance including sudden increases in tractive force and line stop. In general, narrow variations in the tractive force were indicative of a controlled process, while larger variations indicated an unstable process. Thus, although the material can be processed for a short time with higher tensile forces, these high tensile forces may not be sustainable and may be impractical for production. In general, for any specific liquid polymer precursor system, experiments were performed on increasing fiber loads until a maximum fiber load level was achieved as indicated by a stable process at an acceptable maximum tensile strength.
[00306] Precursor systems of liquid epoxy polymer with the aid of silica nanoparticle processing with modified surface. Table 3

(*) R-REF1 and R-CTL1 contain 5.0% by weight of clay.
[00307] As shown in Table 3, at a line speed of 38.1 cm / minute, the maximum fiber load using the reference liquid polymer precursor was 62 12K graphite fiber tow, which is typical of many commercial pultrusion operations. With the control liquid polymer precursor, which included a typical clay filler as well as a reactive diluent to reduce the viscosity of the liquid polymer precursor to 0.58 Pa ^ sec, no more than 60 tow could be included. However, even with only 60 tow, the process was unstable and the pulling force was erratic, stopping at 5187.7 N (529 kg-force). In 58 tow, the pulling force was still somewhat erratic with a maximum pulling force of 1637.7 N (167 kg-force).
[00308] In contrast, with the liquid polymer precursor system R-EX4, which had a viscosity approximately identical to that of the liquid polymer precursor R-CTL1, the tensile strength in 66 tow was only 1049.3 N (107 kg strength) and was stable. Thus, including only 0.5% by weight of silica, the tow count could be increased by almost 14% (66 tow versus 58 tow) while there was a simultaneous reduction in maximum pull force by more than 35% (107 kg versus 167 kg) in relation to the R-CTL1 sample. In fact, by including silica nanoparticles with modified surface in the liquid polymer precursor system, a fraction of fiber volume greater than 70% volume could be loaded in the pultruded part with stable tensile forces falling to 2069.2 N (211 kg-force). Even at tensile forces that exceed the desired maximum of 160 kg, the tensile forces were stable, indicating a satisfactorily controlled process.
[00309] Using the same procedure, an additional pultrusion test was performed using the liquid polymer precursor R-EX4 (0.5% and weight of silica nanoparticles) and 64 fiber tow. The line speed was increased to 45.7 cm / min. The resulting tensile strength was only 970.9 to 1167.0 N (99 to 119 kg-force), demonstrating that nanoparticles can be used as an aid to processing both fiber loading and line speed, simultaneously . Preparation of surface modification binders for calcite nanoparticles
[00310] A first polyetheramine sulfonate binder (JAS A binder) was prepared as follows. To 100 parts of polyetheramine (JEFFAMINE M-600 obtained from Huntsman, Mn = 600) were added 17.88 parts of molten propane-sultone (purchased from TCI America). The mixture was heated to 80 ° C and stirred for 16 hours. The 1H NMR spectrum shows the complete consumption of propanesultone. The sulfonic acid binder was isolated as a reddish brown liquid and used without further purification.
[00311] A second polyetheramine sulfonate binder (JAS B binder) was prepared as follows. To 3.78 kg (6.3 mol) of polyetheramine (JEFFAMINE M-600 obtained from Huntsman, Mn = 600) at 40 ° C was added 0.769 kg (6.3 mol) of fused sultone 1,3-propane ( purchased from HBC Chem, USA) in two portions. In the introduction of sultone propane, the reaction exotherms go to 115 ° C. The mixture was left to cool to 90 ° C, and maintained at 90 ° C with stirring for 4 hours. After 4 hours, 0.031 kg of cyclohexylamine (0.31 mol, purchased from Alfa Aesar) was added. The mixture was stirred for an additional hour. The 1H NMR spectrum shows no sultone propane residue. The sulfonic acid binder was isolated as a reddish brown liquid and used without further purification. Calcite nanoparticles in a liquid epoxy precursor system
[00312] A precursor of liquid epoxy polymer (106.7 kg of EPON 828), was placed in a stainless steel container. The JAS B binder (15 kg) was preheated to 90 ° C for ease of handling, and added to the container. A D-Blade (Hockmeyer Equipment Corporation, Elizabeth City, NC, USA) was inserted into the container and mixing started. The nanocalcite (200 kg of SOCAL 31) was then added to the vessel gradually and mixing continued until a uniform mixture was produced. The mixture was transferred to a jacketed boiler.
[00313] A basket mill (also known as an immersion mill) was lowered into the boiler. The basket mill was an HCNS-5 Immersion Mill (Hockmeyer, Harrison, New Jersey, USA) containing 4.4 L of 0.3 mm comitium stabilized zirconia capsules. The mill was run at speeds up to 969 rpm and a 0.1 mm separation screen was used. The mill was run for 6 hours and 30 minutes.
[00314] The resulting modified surface nanoparticles were dispersed in the liquid polymer precursor system and had an average particle size of 265 nm, and a peak particle size of 296 nm, as measured by the Calcite Particle Size Procedure. Particle analysis showed a narrow particle size distribution with almost all (at least 98% by volume) particles within this peak. TGA measured 62.8% by weight of calcite in the liquid polymer precursor.
[00315] A liquid polymer precursor system (“RS-4”) has been prepared by combining the above-ground nanocalcite liquid polymer precursor (16 kg) with the EPON 828 liquid epoxy polymer precursor (2.02 kg) and precursor of liquid epoxy polymer HELOXY 107 (1.79 kg) and mixed with a Cowles mixer (DISPERMAT CN-10, BYK-Gardner, Columbia, MD, USA) until the mixture is homogeneous. The TGA measured 50.7% by weight of calcite in the liquid polymer precursor.
[00316] Another liquid polymer precursor system (“RS-5”) was prepared by combining 80 parts by weight of EPON 828 cured liquid epoxy polymer precursor and 20 parts by weight of HELOXY 107 cured liquid epoxy polymer precursor. Anhydride-cured liquid epoxy polymer precursor systems
[00317] A series of liquid polymer precursor systems have been prepared by combining various amounts of liquid epoxy polymer precursors (RS-4 and RS-5) with the LS81K anhydride dressing, as summarized in Table 4. Table 4

Precursor systems of liquid epoxy polymer cured with anhydride and epoxy with a modified surface calcite processing aid
[00318] Pultrusion experiments were conducted according to the Pultrusion Process with a line speed of 38.1 cm / min. The results obtained with the use of R-REF1 and R-CTL1 liquid polymer precursor systems as well as experimental liquid polymer precursor systems R-EX6 through R-EX9 are summarized in Table 5. Table 5


[00319] Using the same procedure, additional pultrusion tests were run using a liquid polymer R-EX9 system (0.5% by weight of calcite nanoparticles) and 60 tow (62.2% by volume) of the 12K graphite fiber. As summarized in Table 6, calcite nanoparticles can be used as a processing aid to increase both fiber loading and line speed, simultaneously. Table 6


[00320] Additional samples containing surface-treated calcite were conducted using larger calcite particles were prepared as follows. Curable liquid epoxy polymer precursors (96 kg of EPON 828 and 24 kg of Heloxy 107) were placed in a stainless steel container. The ligand A JAS (13.5 kg) was preheated to 90 ° C for ease of handling, and added to the container. A Cowles' slide (Dispermat CN-10, BYK-Gardner, Columbia, MD, USA) was inserted into the container and mixing started. The nanocalcite (180 kg of SOCAL 31) was then added to the vessel gradually and mixing continued until a uniform mixture was produced. The mixture was transferred to a jacketed boiler.
[00321] A basket mill (also known as an immersion mill) was lowered into the boiler. The basket mill was an HCNS-5 Immersion Mill (Hockmeyer, Harrison, New Jersey, USA) containing 4.4 L of 0.5- 0.7 mm of yttrium-stabilized zirconia microspheres. The mill speed was adjusted to 955-1273 rpm and a 0.27 mm separation screen was used. The mill was run for 13 hours and 23 minutes.
[00322] The resulting modified surface nanoparticles were dispersed in the liquid polymer precursor system and had an average particle size of 385 nm, and a peak particle size of 296 nm. Particle analysis showed a narrow particle size distribution with almost 82% of the particles within this peak. The TGA measured 57.6% by weight of calcite in the liquid polymer precursor.
[00323] The liquid polymer precursor system "RS-6" was prepared by combining the liquid polymer precursor ground nanocalcite (16 kg) with EPON 828 epoxy (1.744 kg) and HELOXY 107 epoxy (0.436 kg) and mixed with a Cowles mixer (Dispermat CN-10, BYK-Gardner, Columbia, MD, USA) until the mixture is homogeneous. The TGA measured 50.7% by weight of calcite in the liquid polymer precursor.
[00324] Curable liquid epoxy polymer precursors (1600 g of EPON 828 and 400 g of HELOXY 107) were placed in a stainless steel container. DISPERBYK-111 dispersant (225 g) was added to the container. A Cowles mixer (Dispermat CN-10, BYK-Gardner, Columbia, MD, USA) was inserted into the container and mixing started. Nanocalcite (3000 g SOCAL 31) was then added to the vessel gradually and mixing continued until a uniform mixture was produced. The mixture was transferred to a jacketed boiler.
[00325] A basket mill (also known as an immersion mill) was lowered into the boiler. The basket mill was an HCP-1/4 immersion mill (Hockmeyer, Harrison, New Jersey, USA) containing 150 milliliters of 0.5 mm of yttrium stabilized zirconia microspheres. The mill speed was set to the maximum setting of “10,” and a 0.2 mm separation screen was used.
[00326] The resulting modified surface nanoparticles were dispersed in the liquid polymer precursor system and had an average particle size of 285 nm, and a peak particle size of 296 nm as measured by the Particle Size Procedure. Particle analysis showed a narrow particle size distribution with almost all (at least 98% by volume) particles within this peak. The TGA measured 57.2% by weight of calcite in the liquid polymer precursor.
[00327] The liquid polymer precursor system “RS-7” was prepared by combining the liquid polymer precursor ground nanocalcite (3593) with EPON 828 epoxy (408 g) and HELOXY 107 epoxy (102 g) and mixed with a Cowles mixer (Dispermat CN-10, BYK-Gardner, Columbia, MD, USA) until the mixture is homogeneous. The TGA measured 50.1% by weight of calcite in the liquid polymer precursor system.
[00328] HUBERCARB Q6 calcite with a reported particle size of 6 microns (Huber Engineered Materials, Quincy, IL, USA) (1538.3 g) was combined with EPON 828 liquid epoxy polymer precursor (1006.9 g) and HELOXY 107 liquid epoxy polymer precursor (251.7 g) in a jar. The sample was mixed with a Cowles blade for approximately 30 minutes.
[00329] The “RS-8” liquid polymer precursor system was prepared by combining the above calcite dispersion (2239 g) with EPON 828 liquid epoxy polymer precursor (131.2 g) and HELOXY liquid epoxy polymer precursor 107 (32.8 g) until smooth. TGA measured 51.7% by weight of calcite in the liquid polymer precursor system. Additional anhydride-cured liquid epoxy polymer precursor systems
[00330] A series of experimental liquid polymer precursor systems have been prepared by combining various amounts of particulate liquid polymer precursor systems, RS-5, and the LS81K anhydride dressing, as summarized in Table 7. Table 7


[00331] Pultrusion experiments were conducted according to the Pultrusion Process with a line speed of 38.1 cm / min. The results obtained using the liquid polymer precursor systems R-EX10, R-EX11, and R-CE1 are summarized in Table 8, together with the results for R-EX8. Table 8
Precursor systems of liquid vinyl ether polymer containing silica nanoparticles
[00332] Nalco TX10693 silica nanoparticles (1500 g) were added to a quarter gallon jar. 1-methoxy-2-propanol (1500 g), 3- (trimethoxy silyl) propyl methacrylate (A174, 8.30 g), and polyalkylene alkoxy silane oxide (SILQUEST A1230, 16.73 g) were combined in a separate jar. The mixture of 1-methoxy-2-propanol was then added to the aqueous silica sol during stirring. A total of 13 one-quarter jars were made. The jars were heated at 80 ° C for 16 hours. The jars were then emptied into aluminum pans and dried at 100 ° C.
[00333] The precursor of liquid vinyl ester polymer VE-1398-5 (7643 g) was placed in a four-liter stainless steel boiler. To the boiler containing vinyl ester was added styrene (1320 g) and hindered amine nitroxide (1.53 g). A Cowles mixer (DISPERMAT CN-10, BYK-Gardner, Columbia, MD, USA) was attached to the boiler and the contents mixed. Under mixing, the modified dry surface silica above (5535 g) was gradually added to the boiler. Once fully mixed, the contents were transferred to another four-liter boiler attached to the horizontal mill (Netzsch LABSTAR) with 0.5 mm of YTZ medium used at 90% loading. The nanocomposite mixture was placed to circulate through the mill for 165 minutes using a 250 ml / min peristaltic pump.
[00334] The “RS-9” liquid polymer precursor system was prepared by adding silica nanoparticles with modified surface resulting in vinyl ester liquid polymer precursor to a 1 L round bottom flask and using rotary evaporation , the styrene was removed until the final styrene concentration was 19.1% by weight, as measured by a gas chromatograph. TGA was used to determine that the resulting liquid polymer precursor system contained 39.1 wt% silica.
[00335] The vinyl ester VE-1398-5 (6500 g) was placed in a four-liter stainless steel boiler. To the boiler containing vinyl ester, styrene (1721 g) was added. The ligand A JAS (532 g) was preheated to 90 ° C and then added to the boiler. A Cowles mixer (Dispermat CN-10, BYK-Gardner, Columbia, MD, USA) was attached to the boiler and the contents mixed. Under mixing, the SOCALl 31 nanocalcite (5318 g) was gradually added to the boiler. Once fully mixed, the contents were transferred to another four-liter boiler attached to the horizontal mill (Netzsch LABSTAR) with 0.5 mm of YTZ medium used at 90% loading. The nanocomposite mixture was placed to circulate through the mill for five hours using a 250 ml / min peristaltic pump.
[00336] The resulting surface modified nanoparticles were dispersed in the liquid polymer precursor system and had an average particle size of 278 nm, and a peak particle size of 259 nm as measured by the Particle Size Procedure. Particle analysis showed a narrow particle size distribution with almost all (at least 98% by volume) particles within this peak.
[00337] The liquid polymer precursor system “RS-10” was prepared by adding the resulting nanoparticles to the vinyl ester liquid polymer precursor to a 1 L round bottom flask and with the use of rotary evaporation, the styrene was removed until the final styrene concentration was 18.9% by weight, as measured by the gas chromatograph. TGA measured 42.7% by weight of calcite in the liquid polymer precursor system.
[00338] A reference liquid polymer precursor system (“RS-REF2”) was prepared by combining 3.30 kg of VE-1398-5 vinyl ester liquid polymer precursor with 0.165 kg of ASP400 clay.
[00339] Another reference liquid polymer precursor system (“RS-REF3”) was prepared by combining 1.97 kg of liquid vinyl ester polymer precursor VE-1398-5 with 0.59 kg ASP400 clay . Precursor systems of liquid vinyl ester (“VE”) polymer
[00340] An experimental series of liquid polymer precursor systems was prepared as summarized in Table 9. The primers (P-16, T-121, and TC) were combined with styrene and added together to the liquid polymer precursor system. Table 9
Pultrusion of Cylindrical Wires
[00341] To exemplify a core wire composed of single thermoset polymer in the manufacture of a high voltage conductor interlaced with ductile metal wires (eg aluminum) interlaced around the core wire, a wire composed of thermoset polymer that has a diameter of about 6.35 mm (0.25 inches) was fabricated. This core of wire made of thermoset polymer was wound around a 40.6 cm (about 16 inch) mandrel (about 64 times the diameter of the wire made of thermoset polymer) without breaking. This demonstrates the high bending performance of the thermoset composite yarns produced according to the methods of the present description.
[00342] The manufacture of yarns composed of thermoset polymer was carried out according to the Pultrusion Process described above, except that both 12K and 24K graphite tow fibers (GRAFIL 34-700 fiber from Grafil Inc.) were incorporated. Up to 28 tow from the 24K fibers were used to reach approximately 58.5% by volume of fiber (wet basis) in the composite yarns. For fiber volumes greater than 58.5% by volume, additional 12K tow of GRAFIL 34-700 graphite fiber was added individually until the fiber volume reached a maximum of 65.8% by volume (wet basis) . Additional fibers were added as 12K tow to minimize process disruptions in guide and splice operations. The results obtained with the use of R-CTL2, and R-CTL3 liquid polymer precursor systems as well as experimental R-EX12 liquid polymer precursor systems through R-EX15 are summarized in Table 10. Table 10



[00343] Pultrusion experiments were conducted according to the Pultrusion Process, except that HYBON 2026 glass fibers were used instead of graphite fibers. Twenty-eight glass fiber tow was used to reach approximately 51.2% by volume of fiber (wet basis) in the composite yarns. The tests were run using R-CTL3, R-EX14, and R-EX15 at 40.6 cm / minute. The tensile strength for R-CTL3 (no nanoparticles) was 80.4 to 115.7 N (force of 8.2 to 11.8 kg). When silica nanoparticles (R-EX14) or calcite nanoparticles (R-EX-15) were present in the liquid vinyl ester polymer precursor, the tensile strength was so low that no reading can be obtained.
[00344] Images of polished bar samples prepared using the liquid polymer precursor R-EX12 and 58 12K graphite fiber tow were obtained with the use of scanning electron microscopy. Figure 5A illustrates a cross section of this sample at 5000x magnification showing the particles properly dispersed in the liquid polymer precursor surrounding the fibers. At a 15,000x magnification, Figure 5B further illustrates the uniform distribution of nanoparticles throughout the cured liquid polymer precursor between the fibers.
[00345] Figure 5C is a SEM image of another exemplary pultruded thermoset polymer composite bar containing a plurality of particles having a median diameter of one micrometer or less dispersed substantially uniformly throughout the polymer composite matrix. Figure 5D is an enlarged SEM image of the pultruded thermofix polymer composite bar exemplifying Figure 5C. Nanoparticles with modified surface
[00346] Silica nanoparticles with modified surface were prepared by placing 1,692 parts by weight of NALCO 2329K silica nanoparticle in sol method (40.9%, by weight 70-95 nm silica in an aqueous dispersion) in a vessel of an open-head stainless steel mixture and 1 part by weight of 1-methoxy-2-propanol was added slowly during stirring. Then, 0.0198 part, by weight, of trimethoxy phenyl silane was added slowly to the mixture. The mixture was subjected to stirring with a pneumatically driven propeller for 30 minutes, and then the Hydrothermal Reactor Procedure was used. The resulting sol (SOL-3) contained 25.4 weight percent silica with surface modified in a mixture of water and methoxy propanol.
[00347] Silica nanoparticles with modified surface were prepared by placing 0.724 part, by weight, of NALCO 2327 silica nanoparticle (41.9%, by weight, 10-40 nm silica in an aqueous dispersion) in an open-top stainless steel mixing vessel and 1 part by weight of 1-methoxy-2-propanol was added slowly during stirring. Then, 0.0236 part, by weight, of trimethoxy phenyl silane was added slowly to the mixture. The mixture was subjected to stirring with a pneumatically driven propeller for 30 minutes, and then the Hydrothermal Reactor Procedure was used. The resulting sol (SOL-4) contained 17.2 weight percent of surface-modified silica in a mixture of water and methoxy propanol.
[00348] Another precursor system of liquid polymer (“RS-11”) was prepared by the addition of 5.362 parts, by weight, of SOL-3, 0.879 parts, by weight, of SOL-4, 1.0 parts, in weight, of 1-methoxy-2-propanol, and 1,546 parts, by weight, of Lindoxy 190 in a 380-liter boiler with agitation forming a feed mixture. The boiler was maintained at 25 ° C and the components were stirred for a minimum of 14 hours.
[00349] The mixture was rotated through the Greased Film Evaporator Procedure with the exception that the feed rate was 66 kg / hour, the water vapor temperature in Zone 4 was 125 ° C, and the temperature of the resulting product (RS-11) at the EFU outlet was 108 ° C. The RS-11 liquid polymer precursor system had a silica content of 49.1% by weight, as determined by TGA.
[00350] The RS-11 was combined with Lindride 25K and Lindride 252V in a DAC mixing mug (Flacktek, Landrum, SC, USA) and mixed in a DAC 600 SpeedMixer Mixer (Flacktek, Landrum, SC, USA) at 2350 rpm for 45 to produce properly dispersed blends. These blends were vacuum degassed for 3 to 5 minutes before being poured into molds suitable for liquid resin tensile testing, dynamic mechanical analysis (AMD), and fracture resistance. The samples were cured in a forced air oven for 2 hours at 90 ° C, followed by 3 hours at 150 ° C and 6 hours at 190 ° C. The resulting module values are summarized in Table 11. Table 11
Pultrusion Process
[00351] Pultrusion experiments were conducted on a commercial pultrusion machine. Sixty 12K degrafited fiber tow (GRAFIL 34-700 fiber from Grafil Inc.) were mounted in a warp without bearings and no external tensioning device. As summarized in Table 13, 58 to 66 graphite fiber tow was pulled from the warper and guided to an open liquid polymer precursor bath containing a liquid polymer precursor system. The wet fibers were pulled through a mold, with the removal of excess volume at the entrance of the mold. The gripping section consisted of reciprocating traction blocks used to pull fiber-reinforced polymeric composite and completely cured at a line speed of 20.3 cm per minute. The finished parts were cut to length with a cutting saw.
[00352] The mold was 91 cm long and had a rectangular cross section measuring 1.32 cm wide by 0.33 height. The mold had a heating zone set at 138 ° C followed by a second zone set at 149 ° C. After the mold, there was a 122 cm long heater with air at a temperature of 127 ° C to 188 ° C. The resulting tensile forces are listed in Table 12.
[00353] The R-EX17 was made by mixing RS-11 (2.12 kg) with Lindride 25K (0.51 kg) and Lindride 252V (1.05 kg). Table 12

[00354] The parts were cut to the appropriate length to obtain a short beam shear and bending test. The parts were then subsequently cured for 1 hour at 200 ° C before testing. Some of the parts remained in the oven at 200 ° C for 100 hours. The resulting flexural modulus values, flexural strength and short beam shear strengths are summarized in Table 13. Table 13

[00355] Pultrusion experiments were conducted on a commercial pultrusion machine. Sixty-eight 12K graphite fiber tow (GRAFIL 34-700 Grafil Inc. fiber) was mounted in a warp without bearings and without an external tensioning device. As summarized in Table 15, 44 to 47 graphite fiber tow was pulled from the warper and guided to an open liquid polymer precursor bath containing a liquid polymer precursor system. The wet fibers were pulled through a mold, with the removal of excess volume occurring at the entrance of the mold. The gripping section consisted of reciprocating traction blocks used to pull the polymeric composite with fiber reinforced and completely cured resulting in line speed of 15.2 to 20.3 cm per minute. The finished parts were cut to length with a cutting saw.
[00356] The mold was 121.9 cm long and had a circular cross section measuring 0.64 cm (0.25 inches) in diameter. The mold had a first heating zone at 138 ° C followed by a second zone ranging from 149 ° C to 204.4 ° C. The resulting tensile forces are listed in Table 14. Table 14

[00357] R-EX18 was made by mixing RS-11 (2.12 kg) with Lindride 25K (0.51 kg) and Lindride 252V (1.06 kg).
[00358] R-EX19 was made by mixing RS-11 (0.45 kg) with Lindride 25K (0.46 kg), Lindride 252V (0.94 kg) and Lindoxy 190 (0.75 kg). Prophetic Example 1
[00359] A polymer-coated composite wire can be produced by thermoplastic extrusion, through which a fluoroplastic (such as DYNEON THV 500 GZ or DYNEON THV 815 GZ, available from 3M, St. Paul, MN, USA) can be extruded through an annular mold (or another specifically shaped) in conjunction with a pultrusion or in a separate process on a pultruded composite yarn. In case the matrix resin is a curable matrix resin, the process can be done more advantageously in conjunction with the pultrusion step while the matrix is being cured, but not completely cured. An alternative process may include the application of a bonding promoter that would be applied to the matrix wire surface prior to thermoplastic extrusion coating. Prophetic Example 2
[00360] A polymer-coated composite wire can be produced by thermoplastic welding through which a fluoroplastic (such as DYNEON THV 500 GZ or DYNEON THV 815 GZ, available from 3M, St. Paul, MN) can be applied by wrapping a film , tape, fitting profile, slit tube or other form of thermoplastic in conjunction with a pultrusion or in a separate process on a pultruded composite wire. The welding process can then be employed to form a continuous thermoplastic layer surrounding the matrix wire. In case the matrix resin is a curable matrix resin, the process can be done more advantageously in conjunction with the pultrusion step while the matrix is being cured, but not completely cured. An alternative process may include the application of a bonding promoter that would be applied to the surface of the matrix wire prior to the thermoplastic coating.
[00361] The reference, in the course of this specification to "a modality," "certain modalities," "one or more modalities" or "a modality", including or not the term "exemplifier" preceding the term "modality," means that a particular feature, structure, material, or feature described in conjunction with the embodiment is included in at least one embodiment of certain exemplary embodiments of the present description. Thus, the appearances of expressions such as "in one or more modalities," "in certain modalities," "in a modality" or "in a modality" in various places throughout this specification are not necessarily referring to the same modality of certain exemplifying modalities of the present disclosure. In addition, specific features, structures, materials, or features can be combined in any suitable manner in one or more embodiments.
[00362] While the specification described in detail certain exemplifying modalities, it will be appreciated that those skilled in the art, with scope and understanding of the aforementioned, can readily conceive changes, variations and equivalents of these modalities. Consequently, it should be understood that this invention is not necessarily limited to the illustrative modalities presented earlier in this document. In particular, for use in the present invention, the recitation of numerical ranges by their extreme points is intended to include all numbers contained in that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4 and 5). In addition, it is assumed that all numbers used in the present invention can be modified by the term "about".
[00363] In addition, all publications and patents mentioned herein are hereby incorporated by reference in full, to the same extent as if each individual publication or patent were specifically and individually indicated to be incorporated by reference. Several exemplifying modalities have been described. These and other modalities are within the scope of the following claims.

权利要求:
Claims (14)
[0001]
1. Method CHARACTERIZED by the fact that it comprises: impregnating a plurality of continuous fibers with a polymeric composite matrix comprising a liquid polymeric precursor and a plurality of particles uniformly dispersed throughout the liquid polymeric precursor, where the plurality of particles have a diameter median of a micrometer or less as measured by laser diffraction, and wherein the plurality of particles comprise silica particles having a core comprising a metal oxide and / or silica and a surface of silica, calcite particles, or a combination thereof; pulling the fibers impregnated with the polymeric composite matrix through a mold; curing the liquid polymeric precursor to form a cured polymer and solidifying at least partially the polymeric composite matrix in the mold, thereby forming a continuous thermoset polymer composite yarn filament; and surrounding the continuous thermoset polymer composite yarn filament with a corrosion resistant wrap.
[0002]
2. Method according to claim 1, CHARACTERIZED by the fact that the plurality of particles comprise reactive surface modified particles that additionally comprise a nanoparticle core and a reactive surface modifying agent associated with the nanoparticle core, and in which the step of curing the liquid polymer precursor is achieved by reacting the liquid polymer precursor with the reactive surface modifying agent.
[0003]
3. Method, according to claim 1 or 2, CHARACTERIZED by the fact that at least partially solidify the polymeric composite matrix in the mold comprises cross-linking the liquid polymer precursor.
[0004]
4. Method, according to any one of claims 1 to 3, CHARACTERIZED by the fact that it additionally comprises post-curing of the liquid polymer precursor after solidifying at least partially the polymeric composite matrix in the mold to form the composite yarn filament.
[0005]
5. Thermoset polymer composite yarn CHARACTERIZED by the fact that it comprises: a plurality of continuous fibers embedded in a solidified polymer composite matrix and forming a continuous filament, in which the solidified polymer composite matrix further comprises a thermoset polymer formed by curing a liquid polymer precursor from a liquid state, and a plurality of particles uniformly dispersed throughout the liquid polymer precursor, wherein, in addition, the plurality of particles have a median diameter of one micrometer or less as measured by diffraction laser, and wherein the plurality of particles comprise silica particles having a core comprising a metal oxide and / or silica and a surface of silica, calcite particles, or a combination thereof; and a corrosion resistant wrap around the continuous filament.
[0006]
6. Thermosetting polymer composite yarn according to claim 5, CHARACTERIZED by the fact that the plurality of particles comprise particles with modified surface which additionally comprise a nanoparticle core and a surface modifying agent associated with the nanoparticle core and reacted with the liquid polymer precursor.
[0007]
7. Thermosetting polymer composite yarn according to claim 5 or 6, CHARACTERIZED by the fact that the plurality of particles has a median diameter not exceeding 250 nm.
[0008]
8. Thermosetting polymer composite yarn according to claim 5 or 6, CHARACTERIZED by the fact that the plurality of continuous fibers further comprises a plurality of fiber surfaces, and in which the plurality of particles does not contact the plurality of surface of fibers.
[0009]
9. Thermoset polymer composite yarn according to claim 5 or 6, CHARACTERIZED by the fact that the solidified polymer composite matrix comprises a crosslinked polymer.
[0010]
10. Thermosetting polymer composite yarn according to claim 5 or 6, CHARACTERIZED by the fact that the thermosetting polymer formed by curing a polymer precursor from a liquid state exhibits a glass transition temperature of at least 150 ° C, as determined from the peak of the delta tangent curve measured by Dynamic Mechanical Analysis in a double cantilever mode at a frequency of 1 Hertz and a heating rate of 5 ° C / minute.
[0011]
11. Thermosetting polymer composite yarn according to claim 5 or 6, CHARACTERIZED by the fact that the thermosetting polymer formed by curing a polymer precursor from a liquid state comprises at least one epoxy resin, an ester resin vinyl, a polyimide resin, a polyester resin, a cyanate ester resin, a phenolic resin, a bis-maleimide resin, or a combination thereof.
[0012]
12. Thermosetting polymer composite yarn according to claim 5 or 6, CHARACTERIZED by the fact that the plurality of particles comprises at least one surface modifying agent associated with a particle surface.
[0013]
13. Thermosetting polymer composite yarn according to claim 5 or 6, CHARACTERIZED by the fact that the plurality of particles comprise silica particles, calcite particles, or combinations thereof.
[0014]
14. Interlaced cable CHARACTERIZED by the fact that it comprises at least one composite wire of thermoset polymer, as defined in claim 5 or 6, wherein the interlaced cable is comprised of: a core wire defining a central longitudinal axis; a first plurality of threads intertwined around the core thread; and a second plurality of threads intertwined around a first plurality of threads.

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法律状态:
2018-12-26| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-03-31| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-09-24| B09A| Decision: intention to grant|

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2021-01-05| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/09/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US38390610P| true| 2010-09-17|2010-09-17|

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US61/383,906|2010-09-17|

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US201061427941P| true| 2010-12-29|2010-12-29|

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US61/427,941|2010-12-29|

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PCT/US2011/051614|WO2012037265A2|2010-09-17|2011-09-14|Fiber-reinforced nanoparticle-loaded thermoset polymer composite wires and cables, and methods|

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