The present invention is related to a closed resin impregnation process and an apparatus for closed resin impregnation; and more specifically, to a closed resin impregnation process and apparatus for impregnating a continuous fiber in a closed resin impregnation process for forming fiber composite articles.
Filament winding is a known process in the prior art. For example, Canadian Patent No. CA2006/2535149A1 discloses an apparatus for resin-impregnation of fibers for filament winding and describes a conventional filament winding process which utilizes a resin bath containing resin for impregnating the fibers. The fibers are submerged in the bath and then pass through and from the resin bath to other apparatuses for further handling.
A majority of wet filament winding applications utilize the above conventional filament winding process and resin bath which can also be referred to as a submersion method for resin impregnation of dry fiber filaments. However, a significant drawback to the submersion method is that the reacting chemical system is exposed to the open air which may cause undesired reactions.
Heretofore, there have been some attempts in improving the submersion method for resin impregnation of dry fiber filaments. For example, U.S. Pat. No. 6,387,179B1 discloses a method and device for impregnating fiber bundles with a resin (e.g., epoxy, polyurethane, and the like) utilizing a multi-chambered impregnation head or box. The pressure within the impregnation box is adjusted so that the resin flows upstream against the movement of the fibers and creates a “wall” of resin through which the fibers can pass.
U.S. Patent Application Publication No. US 1998/5766357A1 discloses an apparatus and a method for resin impregnation into fiber bundles through the use of a manifold with individual grooves for each fiber. The manifold has channels for the resin to flow through and wet the fiber bundles. A control system measures and meters the resin flow.
U.S. Pat. No. 6,179,945B1 discloses a process and apparatus for filament winding composite work pieces. The process includes using an injection die to impregnate fibers just before the fibers are wound around a composite part. However, the above patent is silent on the design of the injection apparatus or the contents therein.
The aforementioned prior art discloses certain aspects of a resin injection box but does not disclose any details of a resin injection box, how a resin injection box is used in a closed system, or how impregnation is done in a closed system. It would be desirable to provide a process improvement to a filament winding process by eliminating the open bath and replacing the open bath with a closed in-line impregnation device and process.
A solution to the problems of the prior art is presented herein and which removes the need for an open resin bath system. For example, the present invention removes the open resin bath and replaces the open resin bath with a resin injection box or device in a closed system. The present invention also includes a process for manufacturing a fiber-reinforced composite article in the closed injection system utilizing a closed impregnation/injection device for impregnating a fiber reinforcement material, such as continuous fibers, with a thermosetting resin composition such as a polyurethane resin or an epoxy resin.
In one embodiment of the present invention, a closed impregnation/injection device for impregnating a fiber reinforcement material with a thermosetting resin composition includes:
(a) a housing;
(b) an entry means disposed in the housing adapted for feeding a dry fiber reinforcement material into the housing of (a);
(c) a means for feeding a dry fiber reinforcement material through, and into, the housing of (a) via the entry means of (b);
(d) a passageway from the entry means of (b) into the housing adapted for allowing the fiber from (b) to enter into the housing of (a);
(e) an injection means disposed in the housing adapted for injecting a thermosetting resin composition into the housing of (a); and contacting and wetting the dry fiber reinforcement material of (b);
(f) a means for feeding a thermosetting resin composition through, and into, the housing of (a) via the injection means of (e);
(g) an exit means disposed in the housing adapted for discharging a wetted fiber reinforcement material from the housing of (a); and
(h) a passageway from the inside of the housing (a) to the outside of the housing adapted for allowing the wetted fiber from (d) to exit the housing of (a).
Another embodiment of the present invention includes a process for injecting a thermosetting resin into a fiber reinforcement material using the above closed impregnation/injection device.
Still other embodiments of the present invention includes a filament winding apparatus and process for manufacturing a cured fiber reinforced composite article using the above closed impregnation/injection device.
For the purpose of illustrating the present invention, the drawings show a form of the present invention which is presently preferred. However, it should be understood that the present invention is not limited to the precise arrangements and instrumentation shown in the drawings. In the drawings, like elements are referenced with like numerals. Therefore, the following drawings illustrate non-limiting embodiments of the present invention wherein:
In its broadest scope, the present invention includes a device or apparatus for, and a process for, manufacturing a fiber-reinforced composite article. The process includes a closed fiber impregnation (also referred to as fiber infusion or fiber injection) step, using a closed fiber impregnation device. The closed fiber impregnation device can be used, for example, in-line in a filament winding process.
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In one preferred embodiment, the resin fluid injection means 30 may include any means of combining reactants forming the liquid resin and flowing the resin into the injection device 20. For example, as shown in
With reference to
Generally, the closed impregnation device 200 for processing a continuous filament reinforced composite includes four regions: (1) an entry region 210 of constant cross-section, said entry adapted for allowing dry fiber reinforcing material to enter into the device and a separate entry region for feeding a mixed polymer system into the device; (2) a contact region 220 of constant cross-section where the mixed polymer system and dry fiber tows contact one another; (3) a metering region 230 with a converging cross section; and (4) an exit region 240 with a constant cross-section to allow the resin impregnated fibers to exit the device.
As shown in
When the device 200 is in use, fibers enter the unit or device 200 through an opening generally indicated by numeral 217a of the unit; pass through the device 200 via a channel 217c; and then the fibers exits the device 200 through an exit opening generally indicated by numeral 217b of the unit. The opening 217a and the channel 217c with a predetermined gap shown as dotted line 217d is formed when the top 211 and bottom 212 sections of the device 200 are in contact with each other as shown in
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After the impregnated fibers 21 are wound on the mandrel 41, and the wound article is heated to completely cure, the cured wound composite article can be removed from the mandrel 41 and cut to any desired or predetermined length. With reference to
The process for impregnating a continuous filament reinforced composite generally includes: (a) introducing dry fiber tows into the injection device, wherein the fiber tows have a constant cross-section; (b) introducing a polymer resin system into the injection device; (c) contacting the polymer resin system with the dry fiber tows inside the injection device; (d) metering the resin system into the injection device to coat and impregnate the dry fiber tows for a sufficient time to wet the fibers inside the device to form wetted fibers; (e) withdrawing wetted fiber tows impregnated with the polymer resin system from the device. The continuous fibers are pulled through the impregnation device using a pulling means of the filament winding process; and the fibers are contacted with the reaction mixture in the impregnation device for a time period and at a temperature sufficient to cause begin polymerization of the reaction mixture within the impregnation device and continuing the polymerization of the reaction mixture to produce a composite of fibers coated by the reaction mixture. The polymerization is carried to form a partially cured composition or gel or a substantially cured composition depending on a particular processing need. The composite of coated fibers may be passed through a heated curing apparatus to at least partially further advance the cure of the reaction mixture to produce a gelled material/fiber composite or to produce a solid fiber reinforced polymer matrix. The gelling can take place at from about 10 seconds to about 500 seconds; and the solid composite can be drawn from the curing means, wherein the reaction mixture cures between about 100 seconds and about 1,000 seconds at 60° C.
Another broad aspect of the present invention is directed to a process for closed impregnation of continuous fibers and processing the continuous fibers to prepare a fiber composite including the steps of: (I) providing a dry fiber tow; (II) providing a polymer resin system; (III) providing the closed impregnation device 200; (IV) passing the polymer resin system and the dry fiber tow in contact with each other through the closed impregnation device 200; (V) passing the impregnated fiber from the closed device 200 to a roller member or a mandrel of a filament winding unit; and (VI) heating the impregnated fiber to form a fiber-reinforced composite article.
One preferred embodiment of the present invention process includes the closed fiber impregnation device or apparatus 200 described above incorporated into a filament winding process for manufacturing a fiber-reinforced composite article. With reference to
In one broad preferred embodiment of processing the continuous fibers to manufacture a fiber-reinforced composite article includes the contacting the fibers with a resin composition inside an injection box or device. More specifically, the process includes admixing components to make the reactive resin system such as (i) a polymer resin, and (ii) a curing agent for curing the polymer resin; and providing (iii) a fiber reinforcement material to be impregnated with the reactive system. The admixing of the compounds or components to make the polymer resin system can be carried at a mixing rate of generally from about 0.001 grams per second to about 10,000 grams per second in one embodiment, from about 0.01 grams per second to about 1,000 grams per second in another embodiment, and from about 0.1 grams per second to about 100 grams per second in still another embodiment. The goal in the admixing step is to meter the mixed resin system at the exact speed at which the fiber is being pulled through the injection chamber (200).
The reactive mixture can be processed under process conditions for forming a resin system suitable for impregnating the fibers. For example, the components of the resin system can be heated at a predetermined temperature before, during or after injecting into the injection box. The temperature of heating can generally be in the range of from about room temperature to about 150° C. in one embodiment, from about room temperature to about 125° C. in another embodiment, and from about room temperature to about 100° C. in still another embodiment. In general, once the reactants are mixed, for example, in a static mixer, the reactive mixture immediately begins curing at the curing temperature upon leaving the impregnation device. There is no need for a residence time other than the time from initial mixing of the two or more component system to the time the system leaves the impregnation chamber. In another alternative embodiment, an intermediate “pot” or mixing vessel may be used for mixing the reactants such that the reactants are mixed for a predetermined residence time before entering the impregnation device.
The process of the present invention for preparing the resin system may be a batch process, an intermittent process, or a continuous process using equipment well known to those skilled in the art.
The resin system may be comprised of any thermosetting reactive polymer mixture including, but not limited to, epoxy-based, polyurethane-based, vinyl ester-based, polyester-based and phenolic-based resin systems or any advantageous combination thereof. For example, thermosetting liquid resins that may be useful in the present invention may be selected from one or more of resins described in U.S. Pat. Nos. 4,604,435 A and 4,663,397 A, both patents which are incorporated herein by reference.
The fibrous material useful in the present invention may be comprised of any known reinforcing material including but not limited, to carbon, glass, aramid or natural fibers or any combination that is advantageous. For example, fiber materials that may be useful in the present invention may be selected from one or more of fiber materials described in U.S. Pat. Nos. 4,460,639A, 4,818,448A, 3,571,901A and 3,971,669A; DE102004054228A1; and EP0671259A1, all of which are incorporated herein by reference.
With reference to
The size of the composite article of the present invention is not limited; and may depend on the final application of the part and what the specific requirements are for such part used in a particular application. The thickness of the wound composite article 100 can be generally from about 1 millimeter (mm) to about 1,000 mm in one embodiment, from about 5 mm to about 750 mm in another embodiment, and from about 10 mm to about 500 mm in still another embodiment.
The number of layers that the composite article of the present invention can include is not limited; and may depend on the final application of the part and what the specific requirements are for such part used in a particular application. The structure 100 of
The following examples and comparative examples further illustrate the present invention in more detail but are not to be construed to limit the scope thereof.
In the following Examples, various materials, terms and designations are used and are explained as follows:
VORAFORCE™ TW 103 is a formulated epoxy resin having an EEW of 179 and commercially available from The Dow Chemical Company.
VORAFORCE™ TW 152 is a formulated anhydride curing agent with a hydrogen equivalent weight (HEW) of 170 and commercially available from The Dow Chemical Company.
VORANOL 220-060 is a polyether polyol with an average functionality of 2.0 and an OH number of 260 and commercially available from The Dow Chemical Company.
VORAFORCE™ TW 1200 is a polymeric methylene diphenyl diisocyanate (pMDI) with a 131.5 equivalent weight and 32.0% NCO content and commercially available from The Dow Chemical Company.
General Procedure of Filament Winding Process
A composite pipe was manufactured using a filament winding process. Filament winding is one of the more important composite production methods in terms of number of users and total number of fabricated parts. The filament winding process begins with fiber tows coming from spools of glass or carbon fibers mounted on a creel. The fibers are gathered together and collected through a type of fiber guide (i.e., a “comb”) to form a band. The number of the fibers brought together determines the band width. The band is pulled through a resin bath (containing a resin and a hardener mixed together such that the system is active). The resin from the resin bath impregnates the pulled fiber tow. The fibers are then drawn through a roller or wiper system to achieve the desired resin content on the fibers; and then the fibers are drawn through a payoff. The “payoff” is the point at which the fiber contacts a moving carriage and directs the fibers on to a rotating mandrel. This method of production is efficient for producing any type of cylindrical part. Furthermore, as the complexity and capability of filament winding machines increases, other non-cylindrical parts can also be wound using a filament winding method.
Part A: General Procedure for Preparing the Resin Composition
An epoxy-based resin system was used to form a composite article through filament winding. The epoxy resin (“A side”) used was a bisphenol-A-based epoxy resin (VORAFORCE™103) with an epoxide equivalent weight (EEW) of ˜171. The hardener chosen (“B-side”) was a methyl tetrahydrophthalic anhydride-based hardener (VORAFORCE™ 152) with a hydrogen equivalent (HEW) weight of ˜170. The system was metered into the mixing unit at a ratio of 100 parts of resin to 102 parts of hardener at a mass flow rate of ˜0.32 grams of mixed resin system per second.
Part B: The Fibers Used
Continuous glass fiber reinforcement were stored in creels and used in the present example. The continuous fibers were pulled from their stored state into a guiding frame. The frame may either consolidate or keep separate the continuous reinforcement. The reinforcement was then drawn through a heated injection device to impregnate the fibers with the liquid polymer resin composition described above in Part A. The speed of the continuous reinforcement throughput was an average of 15.25 meters per minute (MPM) which was sufficient to provide a residence time within the injection device of ˜2.5 seconds; which in turn, was sufficient to thoroughly impregnate the fibers.
Part C: General Procedure for Preparing Pipe Composite Structure
A pipe member was wound by winding the impregnated fibers described in Part B above onto a mandrel of a filament winding apparatus. The impregnated fibers completely cure as they are wound on the mandrel. The reinforcement/composition system was filament wound around the mandrel to build up a composite thickness of 15 millimeters (mm). The pipe member was allowed to cure at 80° C. for 2 hours and then cured post-winding at 150° C. for 6 hours to form a pipe product.
Part A: General Procedure for Preparing the Resin Composition
An epoxy-based resin system was used to form a composite article through filament winding. The epoxy resin (“A side”) used was a bisphenol-A-based epoxy resin (VORAFORCE™ TW 103) with an epoxide equivalent weight (EEW) of ˜171. The hardener chosen (“B-side”) was isophorone diamene (IPDA) with a hydrogen equivalent (HEW) weight of ˜42.5. The system was metered into the mixing unit at a ratio of 100 parts of resin to 25 parts of hardener at a mass flow rate of ˜0.32 grams of mixed resin system per second.
Part B: The Fibers Used
Continuous glass fiber reinforcement were stored in creels and used in the present example. The continuous fibers were pulled from their stored state into a guiding frame. The frame may either consolidate or keep separate the continuous reinforcement. The reinforcement was then drawn through a heated injection device to impregnate the fibers with the liquid polymer resin composition described above in Part A. The speed of the continuous reinforcement throughput was an average of 15.25 meters per minute (MPM) which was sufficient to provide a residence time within the injection device of ˜2.5 seconds which in turn, was sufficient to thoroughly impregnate the fibers.
Part C: General Procedure for Preparing Pipe Composite Structure
A pipe member was wound by winding the impregnated fibers described in Part B above onto a mandrel of a filament winding apparatus. The impregnated fibers completely cure as they are wound on the mandrel. The reinforcement/composition system was filament wound around the mandrel to build up a composite thickness of 15 mm. The pipe member was allowed to cure at 80° C. for 2 hours and then cured post-winding at 150° C. for 6 hours to form a pipe product.
Part A: General Procedure for Preparing the Resin Composition
A polyurethane-based resin system was used to form a composite article through filament winding. The polyol side (“A side”) used was a castor oil and VORANOL 220-060 based polyol. The hardener chosen (“B-side”) was a polymeric methylene diphenyl diisocyanate (pMDI) (VORAFORCE™ TW 1200). The isocyanate index for the system was 110 and had a mix ratio of 100 parts of polyol to 116 parts isocyanate. The system was metered into the mixing unit at the specified ratio at a mass flow rate of ˜0.32 grams of mixed resin system per second.
Part B: The Fibers Used
Continuous glass fiber reinforcement were stored in rolls creels and used in the present example. The continuous fibers were pulled from their stored state into a guiding frame. The frame may either consolidate or keep separate the continuous reinforcement. The reinforcement was then drawn through a heated injection device to impregnate the fibers with the liquid polymer resin composition described above in Part A. The speed of the continuous reinforcement throughput was an average of 15.25 meters per minute (MPM) which was sufficient to provide a residence time within the injection device of ˜2.5 seconds, which in turn, was sufficient to thoroughly impregnate the fibers.
Part C: General Procedure for Preparing Pipe Composite Structure
A pipe member was wound by winding the impregnated fibers described in Part B above onto a mandrel of a filament winding apparatus. The impregnated fibers completely cure as they are wound on the mandrel. The reinforcement/composition system was filament wound around the mandrel to build up a composite thickness of 15 mm The pipe member was allowed to cure at 100° C. for 4 hours.
Filing Document | Filing Date | Country | Kind |
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PCT/US2016/052570 | 9/20/2016 | WO | 00 |
Number | Date | Country | |
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62221654 | Sep 2015 | US |