us: cu») United States cz) Patent Application Publication Chen (34) HIGH-SPEE (76) Investor: Buo Chen, Hillsborough, NJ (US) (21) Appl. No. 12997,.716 (22) PCT Filed Jun, 18, 2009 (86) PCT No, PCTIUSOATT44 $371 M0), (2),(4)Date: Dee. 13,2010 Related US. Application Data (60) Provisional application No, 61/076,223. filed on Jun. 27, 2008 -/4 2011 43641 (10) Pub. No.: US 2011/0104364 Al (43) Pub, Date May 5, 2011 ication Classification GI) Incl, BosD 720 200501) BOSD VIZ (200501) BOSD 1/02 (2006.01), (2) US.CL 427188 on ABSTRACT The pullrusjon process for making the composite cere of aa aluminum conducior composite core (ACCC) cable is improved by replaciag the tritional wer-outstep of dipping the fer in a bath of liquid resm with a high-pressure spray \Wet-out step Ina preferred process, the fibers spread out into its constituent laments, and the resin is sprayed onto the speead-out filaments using a high-pressuie spay’ nozzle, The Sprayed filaments are then rebindled by passing. them through a series of pre-form plates before the rebundled fiber js passed through adie for fis shaping and cure High pressure spray nozzle _-— Polymer resin particles — Spraying area eT So Grounded fiber Spherical spreading surface iyPatent Application Publication May 5, 2011 US 2011/0104364 AI FIGURE 1 " a / ‘ ff cht Breform Plates Heated Die Igoe 2 lh a High prosstite spray poze _— Polymer resin particles Spraying area Grounded fiber ~ Spherical spreading surfaceUS 2011/0104364 AI "EED PULTRUSION PROCESS FOR ‘THE MANUFACTURE OF FIBER REINFORCED COMPOSITES, $S-REFERENCE TO RELATED "APPLICATIONS, {0001} The present application claims priority to US. patent application See No, 61/076,225, led on hun. 27, 2008, the entire content of which is incorporated by reference herein FIELD OF THE INVENTION 10002] This iavention relates to fiber reinforced compos: ites, Inoue aspect, the invention ates oa puliusion process {or fiber reinforced composites while in another aspect, the invention relates to the wet-out step of such a process. In yet ‘another aspect, the invention relates toa pultrusion process in ‘hich the wet-out step employs a highly reactive epoxy resin system applied with a high-pressure spray nozzle while in still another aspect, the invention relates to such a wet-out step in which the filaments of the fiber are spread spat from ‘one another before the resin system is applied BACKGROUND OF THE INVENTION [0003] The current bare aluminum conductor overhead ‘cable such as aluminum conductor stelreinforeed (ACSR), fr alumiaum core stcel supported (ACSS), cable are con- structed with stool core to carry their weight (eg. US. Pat. No. 3.813.481). Alternatively, the steel core can be replaced with a fiber reinforced polymeric composite to produce an aluminum conductor composite core (ACCC) reinforced ‘cable (e.g, US, Pat, Nos. 7,015,395 and 7,060,326). ACCC. ‘able can provide advantages over ACSR cable in tems of ‘weight and strength, [0004] The composite core of ACCC eable is generally made by a pultrasion proces, continuous process in whieh ‘Aber reinforcement is frst pulled through a resin impeegna- tion area to coat the reinforcement with resin, then through pre-form plates to hegin to shape the fber/esin bundle, and finally through a heated die to cure the resin. Due to the ‘continuous nature of the pultrusion process, composites of ny desired length can he produced. The pultrusion process ‘ean be usod to fabricate profiles with simple or complex. ‘geometry; however, the part will have a constant erossso2~ Tonal area over its entire length [0005] The existing pultrsion methods normally involve passing fiers through a resin bath ortankin order to achieve ‘good fiber Wetout, This Wet out stepor method as a number ‘oftisadvantages including that itis wer time intensive, adit builds hh hydrostatic pressure atthe entrance of the die (sich, in tum, results in high pulling forces over the length ‘ofthe process), These disadvantages are magnified ia appli ‘ations, eg, ACCC cable, in which the volume content of ‘her in the composite core is relatively high (e.g. >65%) due to the strength requirements ofthe composite. This high fiber volume content, in combination with other factors, greatly slows the wet out and pulling steps of the process, which ia ‘umn slows the overall speed of the process. As a result, a May 5, 2011 typical maxi the composite core of AC ‘minute Vin). speed ofa pultusion process for making ‘able is less than 8 feet per BRIEP SUMMARY OF THE INVENTION [0006] In one embodiment, the invention is an improved \wet-ot step or method in a conventional pultasion process In this embodiment, the curable, thermoset resin is not applied to the fiber by pulling the fiber through a bath or ank cof resin. Rather, the resin is applied to the fiber as high resize spray. The spray is delivered from high-pressire Spray nozzles which may armay nat be heated, These nozzles allow forthe application ofa controlled amount of resi tothe fiber, and they deliver the resin in a manner that promotes resin penetration into the fber. 0007} In another embodiment of the invention, the fila- that comprise the fiber for if tow, the fibers that ‘comprise the tow) are spread apart prior othe application of the resin (othe fer (either as a high-pressure spray or by ‘conventional dipping in resin bath). This spreading of the ther filaments or tow fibers can maximize the area of filament ‘or fiber surface that receives resin from thenozzes Ga tow is spread out into its constituent fibers, then the high-peessore also maximizes the penetration of the resi into the entangled filaments of the consttvent fibers). The combination of fk sent spread and high-pressure spray can greatly reduce the timeto complote the we-out step. Moreover, ducto the ap cation ofa controled amount of resin to te ier, 2. avoid ing the excess resin on the fiber that results from pulling the {Ther hrougha bath or tank, the hydrostatic pressure atthe die head is duced, This, too, contributes toa faster and more energy efficient overall pultusion proces. [0008] In another embodiment of the invention, fiber is ‘brought to its near net-hape by passing it though a series of the ber pre-forms (also known as pre-form plaes o car). After th ilaments of the fiber ar impregnated with the esi, the filaments are rebundled by passing the fiber through one ‘or moro pre-forms which fist rebundl them into the fiber, ‘nd then begin to shape the fer into its desired final net shape. Each preform brings the fiber closer is deste final ‘et shape andby the time the fiber reaches the etry tothe fil die (Which abo serves as acu station), itis very’ closet its Tinal desired shape. This sequence of pre-orms greatly redces the hycrostate pressure atthe final die entry. and this in tm allows fora smaller, ic, shorter, final die and a faster ‘overall proces. 0009} In another embodiment of the invention, the shape ofthe die entrance and overall engl ofthe de (cure station) Js designed to minimize the hydrostatic pressure atthe die hhead and the time necessary to the eure the resin that is ‘impregnated into and onto the fiber. The inal die imparts the ‘nal net shape othe fer, andthe eure ofthe resin in. and on the fiber is at last initiated, if not comploted, asthe resin- impregnated fiber passes through and exits the die (some postedie cure may or may not occur depending @ number of Tictors including the nature ofthe resin and eure package, the eure conditions inthe inal die, the eure conditions during collection and storage of the cable, ete). Using standard {design tools, finite element analysis (PA), the entrance tothe dies designed to minimize hydrostatic pressure, More- ‘over, the length ofthe die i designed to minimize the time necessary for the fiber to passthrough it and stil affect suf- ficient cureo the resin sc tha the fiber can he eollected and stored, or subjected to futher processing,US 2011/0104364 AI [0010] | Thecombination ofthese improvements tothe over all pulirasion process allows for the ime to fabricate a com- posite cor foruse in ACCC cable to increase 15-20 fin Moreover, itallows fora more eflicient use of resin, lowers the energy necessary for the pulling the fiber through the process (and ths lowers the energy costs ofthe process) and allows for the use of smaller equipment (and thus lowers the capital cost of the overall process). BRIEF DESCRIPTION OF THE DRAWING! 10011] FIG. 1 is a schematic drawing of a conventional Pulirsion process. [0012] | FIG.2isa schematic drawing ofone embodiment of the improved we-out step ofthis invention which employs both a high-pressure spray nozzle and filament spreader. DBIAILED DESCRIPTION OF THE PREFERRED EMBODIMENT [0013] ‘The numerical ranges in this disclosure are approxi- ‘mate, and thus may inclode values outside of the range unless ‘otherwise indicated. Numerical ringes include all values from and including the ower and the upper values, in inene- ‘ments ofone unit, povided that there saseparation of at least ‘0 units berween any lower value and any higher value. As ‘an example, if compositional, physical or other peopeny, such as, for example, equipment dimensions, process param” ‘eters, et. 8 rom 100 to 1,000, its intended that all ind vidual valves, such as 100, 101, 102, et., and sub ranges, suchas 1000 144, 155 t0 170,197 10 200, ete, areexpressiy ‘enumerated. Por ranges containing values which ae less than ‘one of containing feetional numbers greater than one (@:. 11,1S.ete-).one units considered to be 0.0001,0.001, 0.01 ‘or0.1, as appropriate. For ranges containing single digit num. bers ss thanten (eg. 1105), one unit istypically considered to be 0.1. These are only examples of what is specifically ‘intended, and all possible combinations of numerical values between the lowest value and the highest value enumerated, are ta be considered to he expressly’ stated in this disclosure Numerical ranges are provided within this disclosure for, among other things process parameters, equipment dimen- ‘sions and component concentrations in resin Formulations. 10014) “Comprising”, “including”, having” and like terms fre not intended to exclude the presence of any additional ‘component, step or procedure, whether or not the sume is ically dselosed, In order 10 avoid aay’ dubs, all pro- ‘cesses claimed through use of the tem “comprising” may ‘include one or more aitiona steps, pieces of equipment or ‘component parts, and/or materials unless stated to the cons teary. In contrast, the term, “consisting essentially of” ‘excludes from the scope of sny succeeding recitation any ‘ther component, step or procedure, excepting those tht are notessentsI to operability. The tem “consisting” of excludes ‘any component, step or procedure not specifically delineated or listed. The temo", unless stated otherwise refers tothe Fisted members individually as well as in any combination [0015] “Tow “fihertow", “roving”, “sliver and lke terms ‘can an elongated column of entangled fihers having a gen- ‘erally rounded eross-section, [0016] “Fiber” and ike terms mean an elongated column of ‘entangled filament having a generally round erose-scction ‘and length to diameter ratio greater han 10. May 5, 2011 [0017] “Filament andlike terms meana single, coatinnous strind of elongated material having a engl to diameter tio of greater than 10. [0018] “Netshape", “final net-shape” and similar teems ‘cat thesizeand shape of the cable tert leaves inal die ‘nd cure station. The net-shape of cable is measured in terms ofits diameter and cross-sectional configuration, 0019} In the figures, various items of equipment such as electrical or pneumatie connections iings aad the ike have been selectively omitted so as to simplify thedrawings. Addi- tionally, Tike reference numerals are used to indicate Tike ‘components toughout the drawings. [0020] FIG. 1 is a schematic drawing of a conventional, continous pultrusion process. Although the process is deseribed in temas of impregnating her with resin, the ‘description also applies toa process for impregnating a tvs ‘with resin [0024] Fibers 10 stored on a plurality of spools 11 are pulled by puller 12 through resin bath 13 of liquid resin in ‘whieh the fibers are impregnated with resin. The impregnated fibers are pulled from the bath and through a series of pre- ‘orm plates 14, are combined with one another into a shape that resembles the desired final net shape of the final proc. As the fiber passes through each pre-form plate, excess resin js removed and the fiber contintes to approach its desired ‘inal net shape, Eventually, the fiber enter final die 15, yp cally a heated die, in which it receives its final net shape and the resin is subjectod to eure conditions, these conditions dependent upon, aniong other things, the nature and aasonat ‘of resin, the distribution of the resin over and thronghout the ihe, the residence time ofthe fiber within the final de, and the like. The esin-imprepnated, cured or partially cured fiber is then eut by saw 16 or any other cutting device into its esired length. [0022] In the conventional pultasion process and as illus- {rated in FIG. 1, the resin i apie to the fiber by passing the fiber through a bath or tank holding the resi, The degree to ‘which the fiber i impregnated with he resin is function of ‘number of diferent variables including such things as the residence time ofthe fiber in the bath, the surface ares of fiber exposed to the resin, the temperature ofthe resin bath, the ‘composition the fiber and resin an theie compatibility with ‘one another, and the lke. Typically, these conditions require thatthe fiber eannot pass through the resin bath quickly. ‘Morsover, this technigue almost always results in excess resin clinging to the fiber after the fiber exits the resin bath, and this excess resia must eventually be stripped or otherwise removed from te fibers jt passes through the pre-forms and ‘inal die. Not only does this esult in wasted resin, but itbuilds pressureatthe head of he pre-form plates andor finale, and this too detracts from the overall eneny eleency and speed of the proces, [0023] FIG. 2 illustrates one embodiment ofthe improved \wet-out process ofthis invention. As fiber 10 eomes off letolf service rack or creel (not shown). they pass over a centering guide pulley (not shown), under grounding pulley 17 and over spreader roll 18. The centering guide pulley is typically grooved s0 a6 to constrain the Iteral movement of the fiber as it passes under the grounding pulley and onto the spreader roll, The grounding pulley flattens and stably pos tions the fiber above the center of te spreader rol. [0024] Spreader roll 18, or eodesie fer spreader, is typi- cally a sphere with a hard, smooth surlace to minimize fiber abrasion and resist wear, As the fiber passes over the surfaceUS 2011/0104364 AI ‘of the spreader, the individual filaments ofthe fiber will tend to follow the pathof shortest length from the centering pulley 10 the first pre-fom plate. This tendeney spreads the ind Vidal filaments out dad apart from one another snd this, ia turn, maximizes the fiber surface ate that is available to be sprayed with resin 10025] | Other equipment (not shown) can be employed t© Facilitate the operation of the wet-out step. For example, 2 braking system canbe installed on the let-if service rack 0 that tension en be applied othe fibers. Additonal grounding pulleys canalso be installed to improve the spreading process. desired, a metal comb (preferably with 2 ceramic coating) ‘canbe installed after the spreader rll so that asthe filaments Jeave the surface of the spreader rol, thei spread relative to ‘one another cat be maintained or increased sos faiitte their impregnation with resin, 10026] Once spread, the flaments are impregnated with resin rom one of more high-pressure spray nozzles 19. Such nozes are commercially available in many sizes and ‘designs, and the V+ JAU vatiable spray ar atomizing nozzles with heat jacket manufactured by Spray Systems are repre- sentative. The nozzles ean be fixed or mobile relative othe ‘ber, and they can be positioned or moved in any direction relative to the fiber. Typically, the nozzles are mobile and travel in the traverse direction oF the ber movement through the equipment tein, and they spray resin diretly onto the ‘Ther surtice, The high pressure, g,200 03,000 pounds per square inch (psi, inthe spray helps resin flow in-between the ‘laments and achieve @ good wet out rapidly. The spraying heads can be installed in series and/or on both sides of andor ‘above and under the fibers, The traveling speed ofthe spray ing heads and their spraying velocity and Row sre controlled Jn such a manner sos to minimize resin waste, The spraying mechanics ofthe method, eg. the size ofthe spray area, the shape ofthe spray’ patter, the siz ofthe resin particles, the distance between the spray nozzle and the filaments, and the Tike can vary to convenience and eptimization ofthe process. “The resin and ite curing agent can be mixed prior to the ‘coating process, or they can be mixed right at the mixing head, ‘depeoding on the pot life of dhe resin system, If desirable, the spray nozzles can have a heating capability to reduce the viscosity of the resin and improve the spraying process. 10027] "After the filaments have been impregnated with the resin, they are passed throwgh a series (typically three oF ‘more of pre-form plates or cards in whieh they are ebundled and shaped near to their final net shape. The preforms also help achieve further wet out of the fibers thratgh close con- tact and macro movement of fibers. Eventually, the impreg- nated fiber arrives atthe entrance of the final die and eure ation. The entrance tothe die is designed to receive a fiber that is near its tinal net shape and as such, the hydrostatic pressureat the die bead is minimized, The length ofthe de is ‘designed for optimal cure ofthe resin based on the nature of the resin, curing system and eonltions of eure. Typically the resin is cured by exposure to heat, but other forms of eure ‘energy. e.g, UV or e-beam radiation, canalso beemployed. If necessary, an in-line pos-cure oven (aot shown) can beaded to perform post curing ofthe composite before the final sate ‘of the prodet is achieved, 10028] |The composition and structure ofthe fber, and the ‘composition of the resin and its cute system, if any, can vary May 5, 2011 ‘widely, and all are typically consistent with that use in the conventional manufacture of ACCC cable. Representative tihetsinchude Toho Teneax 30-700 24K HTA-TD F402 and ‘TIDOSC-24K-S0C carbon fiber. Representative curable, ther soso resins inclide DER 383 epoxy resin available from The Dow Chemical Company. Representative cure agents include Ancamine DL 50, Other representative hers, resins and cure ‘agents are described in US. Pat, Nos. 7,015,395 and 7,060, 326, Representative compositions of final impreynated fiber include an impregnated hber comprising 78-85 weight per- eat (Wt %) carbon flberand 15-23 we % resin. The resin ean comprise 77 wt % DER 383, 21 wt % Ancamine DL-S0, and 2wt 9h ofa release agent {029} Although the invention has been described in con siderable detail by the preceding specification and with rf- fereaces 10 the drawings, this detail is forthe purpose of illustration and i not to be construed asa liitation upon the spirit and scope of the invention a itis described in the ‘appended claims. All patents and publications cited above, specifically including for USS. practice all USS. patents, allowed patent applications and US. Patent Application Pal Tiations, are incorporated herein by reference. ‘What is elaimed is 1. Inthe process of making a composite core foran ACOC cable, the process comprising a wet-ut step in which a cur able, thermoset resin is applied to a reinforcing tow o fiber, the improvement comprising applying the resin wo the tow or Liber asa high-pressure spr’ 2. The process of claim 1 in which the tow or iberis spread ‘ut int its constituent fibers or filaments before sprayed with the resin, 3. The process of claim 2in which the resin is applied at a pressure between 200 and 3,000 pounds per square inch (ps). ‘4a the process of making a composite core foran ACCC. cable, the process comprising a wet-ut sep in which a cure able, thermoset resin is upplied toa reinforcing tow or fiber, the improvement comprising spreading out the to or fiber into its constituent fibers or laments, respectively, prior to ‘eontaeting the tow oF fiber with the resin. ', The process of claim in whieh the resin i applied as 3 high pressure spray. 6, The process of clam Sin which theresa is applied at pressure between 200 and 3,000 psi 7T.A process lor making &resit-impregnated tow or fiber, the tow comprising constituent fibers andthe fiber comprising ‘constituent laments, the process comprising the steps of: "A. Spreading the tow of fiber into its constituent fibers or ‘laments and 1B. Applying the resin sa high-pressure spray tothe spread ‘ut fibers or filaments 8. The process of claim Tin which the tow or fibers spread ino its constituent fibers or filaments, respectively, by pass- jing the tow or fiber under tension over a geodesic fiber spreader '9. The process of claim 8 in which the spread out fibers or filaments are passed through a comb pri to contact with the resin fom the high presure prey. 10, The process of elatn 9 in whic the resin is applied to the spread out fibers or filaments at a pressure between 200 and 3,000 psi