This application relates to U.S. Provisional Patent Application Ser. No. 61/569,055, filed Dec. 9, 2011, titled: “DIE AND METHOD FOR IMPREGNATING FIBER ROVINGS”, which is hereby incorporated by reference in its entirety.
Fiber rovings have been employed in a wide variety of applications. For example, such ravings have been utilized to form fiber-reinforced composite rods. The rods may be utilized as lightweight structural reinforcements. For example, power umbilicals are often used in the transmission of fluids and/or electric signals between the sea surface and equipment located on the sea bed. To help strengthen such umbilicals, attempts have been made to use pultruded carbon fiber rods as separate load carrying elements.
Another application that is particularly suited for the use of fiber rovings is in the formation of profiles. Profiles are pultruded parts with a wide variety of cross-sectional shapes, and may be employed as a structural member for window lineals, decking planks, railings, balusters, roofing tiles, siding, trim boards, pipe, fencing, posts, light posts, highway signage, roadside marker posts, etc. Hollow profiles have been formed by pulling (“pultruding”) continuous fiber rovings through a resin and then shaping the fiber-reinforced resin within a pultrusion die.
Further, fiber rovings may generally be utilized in any suitable applications to form, for example, suitable fiber reinforced plastics. As is generally known in the art, rovings utilized in these applications are typically combined with a polymer resin.
There are many significant problems, however, with currently known rovings and the resulting applications that utilize such rovings. For example, many rovings rely upon thermoset resins (e.g., vinyl esters) to help achieve desired strength properties. Thermoset resins are difficult to use during manufacturing and do not possess good bonding characteristics for forming layers with other materials. Further, attempts have been made to form rovings from thermoplastic polymers in other types of applications. U.S. Patent Publication No. 2005/0186410 to Bryant, et al., for instance, describes attempts that were made to embed carbon fibers into a thermoplastic resin to form a composite core of an electrical transmission cable. Unfortunately, Bryant, et al, notes that these cores exhibited flaws and dry spots due to inadequate wetting of the fibers, which resulted in poor durability and strength. Another problem with such cores is that the thermoplastic resins could not operate at a high temperature.
As such, a need currently exists for an improved die and method for impregnating a fiber roving. Specifically, a need currently exists for a die and method that produce fiber ravings which provide the desired strength, durability, and temperature performance demanded by a particular application.
In accordance with one embodiment of the present invention, a die for impregnating at least one fiber roving with a polymer resin is disclosed. The die includes an impregnation section. The impregnation section includes an impregnation zone configured to impregnate the roving with the resin. The impregnation zone includes a plurality of contact surfaces. At least one of the plurality of contact surfaces is configured such that a normal force of the roving is less than or equal to a lift force of the resin at an impregnation location on the contact surface during impregnation of the roving with the resin by the contact surface.
In accordance with another embodiment of the present invention, a method for impregnating at least one fiber roving with a polymer resin is disclosed. The method includes flowing a polymer resin through a manifold assembly of a die, the manifold assembly including a plurality of branched runners, and coating at least one fiber roving with the resin. The method further includes traversing the coated roving through an impregnation zone of the die to impregnate the roving with the resin, the impregnation zone including a plurality of contact surfaces. At least one of the plurality of contact surfaces is configured such that a normal force of the roving is less than or equal to a lift force of the resin at an impregnation location on the contact surface during impregnation of the roving with the resin by the contact surface.
Other features and aspects of the present invention are set forth in greater detail below.
A full and enabling disclosure of the present invention, including the best mode thereof to one skilled in the art, is set forth more particularly in the remainder of the specification, including reference to the accompanying figures, in which:
Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present invention.
It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Generally speaking, the present invention is directed to a die and method for impregnating fiber rovings with a polymer resin. The impregnated fiber rovings may be utilized in composite rods, profiles, or any other suitable fiber reinforced plastic applications. The die according to the present invention generally includes a manifold assembly, an impregnation zone at least partially defined in an impregnation section, and a gate passage therebetween. The manifold assembly distributes a polymer resin therethrough. Upon exiting the manifold assembly, the resin flows into and through the gate passage. The rovings are traversed through the die such that the resin, upon exiting the gate passage, coats the rovings. After being coated with the resin, the rovings are traversed through the impregnation zone and impregnated therein with the resin.
According to further aspects of the present invention, an extrusion device may be employed in conjunction with the die to impregnate the rovings with the polymer. Among other things, the extrusion device further facilitates the ability of the polymer to be applied to the entire surface of the fibers, as discussed below.
Referring to
A continuous fiber roving 142 or a plurality of continuous fiber ravings 142 are supplied from a reel or reels 144 to die 150. The rovings 142 are generally positioned side-by-side, with minimal to no distance between neighboring rovings, before impregnation. The feedstock 127 may further be heated inside the die by heaters 133 mounted in or around the die 150. The die is generally operated at temperatures that are sufficient to cause and/or maintain the proper melt temperature for the polymer, thus allowing for the desired level of impregnation of the rovings by the polymer. Typically, the operation temperature of the die is higher than the melt temperature of the polymer, such as at temperatures from about 200° C. to about 450° C. When processed in this manner, the continuous fiber rovings 142 become embedded in the polymer matrix, which may be a resin 214 (
As used herein, the term “roving” generally refers to a bundle of individual fibers 300. The fibers 300 contained within the roving can be twisted or can be straight. The rovings may contain a single fiber type or different types of fibers 300. Different fibers may also be contained in individual rovings or, alternatively, each roving may contain a different fiber type. The continuous fibers employed in the rovings possess a high degree of tensile strength relative to their mass. For example, the ultimate tensile strength of the fibers is typically from about 1,000 to about 15,000 Megapascals (“MPa”), in some embodiments from about 2,000 MPa to about 10,000 MPa, and in some embodiments, from about 3,000 MPa to about 6,000 MPa. Such tensile strengths may be achieved even though the fibers are of a relatively light weight, such as a mass per unit length of from about 0.05 to about 2 grams per meter, in some embodiments from about 0.4 to about 1.5 grams per meter. The ratio of tensile strength to mass per unit length may thus be about 1,000 Megapascals per gram per meter (“MPa/g/m”) or greater, in some embodiments about 4,000 MPa/g/m or greater, and in some embodiments, from about 5,500 to about 20,000 MPa/g/m. Such high strength fibers may, for instance, be metal fibers, glass fibers (e.g., E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, S2-glass, etc.), carbon fibers (e.g., amorphous carbon, graphitic carbon, or metal-coated carbon, etc.), boron fibers, ceramic fibers (e.g., alumina or silica), aramid fibers (e.g., Kevlar® marketed by E. I. duPont de Nemours, Wilmington, Del.), synthetic organic fibers (e.g., polyamide, polyethylene, paraphenylene, terephthalamide, polyethylene terephthalate and polyphenylene sulfide), and various other natural or synthetic inorganic or organic fibrous materials known for reinforcing thermoplastic and/or thermoset compositions. Carbon fibers are particularly suitable for use as the continuous fibers, which typically have a tensile strength to mass ratio in the range of from about 5,000 to about 7,000 MPa/g/m. The continuous fibers often have a nominal diameter of about 4 to about 35 micrometers, and in some embodiments, from about 9 to about 35 micrometers. The number of fibers contained in each roving can be constant or vary from roving to roving. Typically, a roving contains from about 1,000 fibers to about 50,000 individual fibers, and in some embodiments, from about 5,000 to about 30,000 fibers.
Any of a variety of thermoplastic or thermoset polymers may be employed to form the polymer matrix in which the continuous fibers are embedded. For example, suitable thermoplastic polymers for use in the present invention may include, for instance, polyolefins (e.g., polypropylene, propylene-ethylene copolymers, etc.), polyesters (e.g., polybutylene terephalate (“PBT”)), polycarbonates, polyamides (e.g., Nylon™), polyether ketones (e.g., polyetherether ketone (“PEEK”)), polyetherimides, polyarylene ketones (e.g., polyphenylene diketone (“PPDK”)), liquid crystal polymers, polyarylene sulfides (e.g., polyphenylene sulfide (“PPS”), poly(biphenylene sulfide ketone), poly(phenylene sulfide diketone), poly(biphenylene sulfide), etc.), fluoropolymers (e.g., polytetrafluoroethylene-perfluoromethylvinylether polymer, perfluoro-alkoxyalkane polymer, petrafluoroethylene polymer, ethylene-tetrafluoroethylene polymer, etc.), polyacetals, polyurethanes, polycarbonates, styrenic polymers (e.g., acrylonitrile butadiene styrene (“ABS”)), and so forth.
The properties of the polymer matrix are generally selected to achieve the desired combination of processability and performance. For example, the melt viscosity of the polymer matrix is generally low enough so that the polymer can adequately impregnate the fibers. In this regard, the melt viscosity typically ranges from about 25 to about 1,000 Pascal-seconds (“Pa-s”), in some embodiments from 50 about 500 Pa-s, and in some embodiments, from about 60 to about 200 Pa-s, determined at the operating conditions used for the polymer (e.g., about 360° C.). Likewise, when the impregnated rovings are intended for applications involving high temperatures (e.g., high voltage transmission cables), a polymer is employed that has a relatively high melting temperature. For example, the melting temperature of such high temperature polymers may range from about 200° C. to about 500° C., in some embodiments from about 225° C. to about 400° C., and in some embodiments, from about 250° C. to about 350° C.
Polyarylene sulfides are particularly suitable for use in the present invention as a high temperature matrix with the desired melt viscosity. Polyphenylene sulfide, for example, is a semi-crystalline resin that generally includes repeating monomeric units represented by the following general formula:
These monomeric units typically constitute at least 80 mole %, and in some embodiments, at least 90 mole %, of the recurring units, in the polymer. It should be understood, however, the polyphenylene sulfide may contain additional recurring units, such as described in U.S. Pat. No. 5,075,381 to Gotoh, et al., which is incorporated herein in its entirety by reference thereto for all purposes. When employed, such additional recurring units typically constitute no more than about 20 mole % of the polymer. Commercially available high melt viscosity polyphenylene sulfides may include those available from Ticona LLC (Florence, Ky.) under the trade designation FORTRON®. Such polymers may have a melting temperature of about 285° C. (determined according to ISO 11357-1,2,3) and a melt viscosity of from about 260 to about 320 Pascal-seconds at 310° C.
A pressure sensor 137 (
Perspective views of one embodiment of a die 150 according to the present disclosure are further shown in
Within the impregnation die, it is generally desired that the rovings 142 are traversed through an impregnation zone 250 to impregnate the rovings with the polymer resin 214. In the impregnation zone 250, the polymer resin may be forced generally transversely through the rovings by shear and pressure created in the impregnation zone 250, which significantly enhances the degree of impregnation. This is particularly useful when forming a composite from ribbons of a high fiber content, such as about 35% weight fraction (“Wf”) or more, and in some embodiments, from about 40% Wf or more. Typically, the die 150 will include a plurality of contact surfaces 252, such as for example at least 2, at least 3, from 4 to 7, from 2 to 20, from 2 to 30, from 2 to 40, from 2 to 50, or more contact surfaces 252, to create a sufficient degree of penetration and pressure on the rovings 142. Although their particular form may vary, the contact surfaces 252 typically possess a curvilinear surface, such as a curved lobe, pin, etc. The contact surfaces 252 are also typically made of a metal material.
As shown in
The plurality of channels 222 may, in exemplary embodiments as shown in
If desired, the runners 222 may include a second branched runner group 234 diverging from the first branched runner group 232, as shown in
If desired, the runners 222 may include a third branched runner group 236 diverging from the second branched runner group 234, as shown in
In some exemplary embodiments, as shown in
Further, the manifold assembly 220 may in some embodiments define an outlet region 242. The outlet region 242 is that portion of the manifold assembly 220 wherein resin 214 exits the manifold assembly 220. Thus, the outlet region 242 generally encompasses at least a downstream portion of the channels or runners 222 from which the resin 214 exits. In some embodiments, as shown in
In some embodiments, as shown in
As shown in
As further illustrated in
In some embodiments, as shown in
Further, as shown in
Upon exiting the manifold assembly 220 and the gate passage 270 of the die 150 as shown in
As shown in
For example, as discussed above, in exemplary embodiments as shown in
In some embodiments, as shown in
In exemplary embodiments, as shown in
Angle 254 at which the rovings 142 traverse the contact surfaces 252 may be generally high enough to enhance shear and pressure, but not so high to cause excessive forces that will break the fibers. Thus, for example, the angle 254 may be in the range between approximately 1° and approximately 30°, and in some embodiments, between approximately 5° and approximately 25°.
As stated above, contact surfaces 252 typically possess a curvilinear surface, such as a curved lobe, pin, etc. In exemplary embodiments as shown, a plurality of peaks, which may form contact surfaces 252, and valleys are thus defined. Further, in many exemplary embodiments, the impregnation zone 250 has a waveform cross-sectional profile. In one exemplary embodiment as shown in
In other embodiments, as shown in
In other alternative embodiments, as shown in
In further alternative embodiments, the contact surfaces 252 and impregnation zone 250 may comprise any suitable shapes and/or structures for impregnating the rovings 142 with the resin 214 as desired or required.
As discussed, a roving 142 traversed through an impregnation zone 250 according to the present disclosure may become impregnated by resin 214, thus resulting in an impregnated roving 142 exiting the impregnation zone 250, such as downstream of the contact surfaces 252 in the run direction 282. Further, in exemplary embodiments of the present disclosure, such impregnated roving 142 may desirably be generally uniform. A uniform impregnated roving 142 may have fibers 300 generally or approximately uniformly distributed therein, and/or may have a generally uniform coating of resin 214 surrounding those fibers. Thus, a generally uniform impregnated roving 142 may have a cross-section, as shown in
To facilitate the production of uniform impregnated rovings 142 according to the present disclosure, one or more contact surfaces 252 may have various characteristics that adjust the various forces applied to and by the rovings 142 and resin 214 during impregnation. For example,
As shown in
The normal force of a roving 142 at an impregnation location 302 during impregnation may be calculated as a vector component of the tension of the roving 142. Such calculation may be made at an impregnation location 302 for a contact surface 252, 253, and may be based on the angle 254 and tension of a roving 142 at such location.
a=sin(A)*h.
It should be understood that calculation of the normal force is not limited to the above-disclosed equation, and rather that any suitable calculation of the normal force of a roving 142 traversing a contact surface 252, 253 is within the scope and spirit of the present disclosure.
Further, various other variables may be determined for a roving 142 and associated resin 214 according to the present disclosure. For example, the speed of a roving 142 as well as the width of the roving 142 at or within the impregnation location 302 may be determined. Further, the viscosity of the resin 214 as well as the length of the impregnation location 302 and the height of resin 214 within the impregnation location 302 may be determined. A porosity factor may additionally be determined for the resin. These various factors for a particular roving 142 and contact surface 252, 253 may be determined at or throughout an impregnation location 302 or portion thereof on the contact surface 252, 253.
The lift force, such as the hydraulic lift force, of resin 214 at an impregnation location 302 during impregnation may be calculated utilizing the above-determined factors.
F=(((6ηUL)/h2)*(((ho−h)*(h−hL))/(ho2−hL2)))*C*(w*L)
It should be understood that calculation of the lift force is not limited to the above-disclosed equation, and rather that any suitable calculation of the lift force of resin 214 for a roving 142 traversing a contact surface 252, 253 is within the scope and spirit of the present disclosure.
It should further be understood that the various determinations of variables utilized in the above-disclosed equations may be measured or estimated before or during operation of a die 150 and traversal therethrough of various rovings 142 and resin 214 to produce impregnated rovings 142. Further, such measurements or estimates may be made based on the rovings 142 and resin 214 utilized in the die 150, or may be made based on general knowledge or information for rovings 142 and/or resin 214 having similar characteristics. Still further, the various variables may be adjusted as desired or required, and the lift force and/or normal force thus adjusted, to obtain the desired performance wherein the normal force is less than or equal to the lift force at an impregnation location 302 on a contact surface 253 during impregnation of a roving 142 with resin 214 by that contact surface 253.
In exemplary embodiments, as further shown in
In other embodiments, the angle 254 of a contact surface 253 may be reduced through any other suitable technique, such as by altering the shape of the contact surface 253. Still further, in other embodiments, the contact surface 253 may be adjusted through any other suitable technique to reduce the normal force for a roving 142 traversing that contact surface 253.
It should be understood that an impregnated roving 142 according to the present disclosure may have any suitable cross-sectional shape and/or size. For example, such roving may have a generally oval or circular cross-sectional shape, or may have a generally rectangular shape or other suitable polygonal or otherwise shape. Further, it should be understood that in some embodiments a plurality of impregnated rovings 142 having been traversed through the impregnation zone 250 may together form a sheet or ribbon, with the resin 214 of the various rovings 142 connected to form such ribbon. The various above variables may thus in exemplary embodiments be determined for a single roving 142 or a plurality of impregnated rovings 142, whether connected or separate, as desired or required.
To further facilitate impregnation of the ravings 142, they may also be kept under tension while present within the die 150, and specifically within the impregnation zone 250. The tension may, for example, range from about 5 to about 300 Newtons, in some embodiments from about 50 to about 250 Newtons, and in some embodiments, from about 100 to about 200 Newtons per roving 142 or tow of fibers.
As shown in
As further shown in
Additionally, other components may be optionally employed to assist in the impregnation of the fibers. For example, a “gas jet” assembly may be employed in certain embodiments to help uniformly spread a roving of individual fibers, which may each contain up to as many as 24,000 fibers, across the entire width of the merged tow. This helps achieve uniform distribution of strength properties. Such an assembly may include a supply of compressed air or another gas that impinges in a generally perpendicular fashion on the moving ravings that pass across exit ports. The spread ravings may then be introduced into a die for impregnation, such as described above.
The impregnated ravings that result from use of the die and method according to the present disclosure may have a very low void fraction, which helps enhance their strength. For instance, the void fraction may be about 3% or less, in some embodiments about 2% or less, in some embodiments about 1% or less, and in some embodiments, about 0.5% or less. The void fraction may be measured using techniques well known to those skilled in the art. For example, the void fraction may be measured using a “resin burn off” test in which samples are placed in an oven (e.g., at 600° C. for 3 hours) to burn out the resin. The mass of the remaining fibers may then be measured to calculate the weight and volume fractions. Such “burn off” testing may be performed in accordance with ASTM D 2584-08 to determine the weights of the fibers and the polymer matrix, which may then be used to calculate the “void fraction” based on the following equations:
Vf=100*(ρt−ρc)/ρt
where,
Vf is the void fraction as a percentage;
ρc is the density of the composite as measured using known techniques, such as with a liquid or gas pycnometer (e.g., helium pycnometer);
ρt is the theoretical density of the composite as is determined by the following equation:
ρt=1/[Wf/ρf+Wm/ρm]
ρm is the density of the polymer matrix (e.g., at the appropriate crystallinity);
ρf is the density of the fibers;
Wf is the weight fraction of the fibers; and
Wm is the weight fraction of the polymer matrix.
Alternatively, the void fraction may be determined by chemically dissolving the resin in accordance with ASTM D 3171-09. The “burn off” and “dissolution” methods are particularly suitable for glass fibers, which are generally resistant to melting and chemical dissolution. In other cases, however, the void fraction may be indirectly calculated based on the densities of the polymer, fibers, and ribbon in accordance with ASTM D 2734-09 (Method A), where the densities may be determined ASTM D792-08 Method A. Of course, the void fraction can also be estimated using conventional microscopy equipment.
The present disclosure is further directed to a method for impregnating at least one fiber roving 142 or a plurality of fiber ravings 142 with a polymer resin 214. The method generally includes flowing a polymer resin 214 through a manifold assembly 220. The manifold assembly 220 may include a plurality of channels or branched runners 222, as discussed above. The method further includes coating the fiber rovings 142 with the resin 214, as discussed above. Further, the method includes traversing the coated roving 142 through an impregnation zone 250 to impregnate the rovings 142 with the resin 214, as discussed above. Such traversing step may include contacting one or more contact surfaces 252 and one or more contact surfaces 253, as discussed above. In exemplary embodiments, as discussed above, at least one contact surface 253 may be configured such that a normal force of a roving 142 traversing the contact surface 253 may be less than or equal to a lift force of the resin 214 on the roving 142 at an impregnation location 302 on the contact surface 253 during impregnation of the roving 142 with the resin 214 by the contact surface 253.
As discussed above, in some embodiments, the step of flowing the resin 214 through the manifold assembly 220 may include flowing the resin 214 through an outlet region 242 of the manifold assembly 220. As further discussed above, the step of coating the roving 142 with the resin 214 may include flowing the resin 214 from the manifold assembly 220 through a gate passage 270. The method may further include traversing the rovings 142 from the impregnation zone 250 through a land zone 280, as discussed above. In exemplary embodiments, as discussed above, impregnated rovings 142 exiting the die 150 may be generally uniform.
As discussed above, after exiting the impregnation die 150, the impregnated rovings 142, or extrudate 152, may be consolidated into the form of a ribbon. The number of rovings employed in each ribbon may vary. Typically, however, a ribbon will contain from 2 to 20 rovings, and in some embodiments from 2 to 10 rovings, and in some embodiments, from 3 to 5 rovings. In some embodiments, it may be desired that the rovings are spaced apart approximately the same distance from each other within the ribbon. Referring to
A pultrusion process may further be utilized according to the present disclosure for certain particular applications. For example, in some embodiments, such process may be utilized to form a rod. In these embodiments, continuous fibers of rovings 142 may be oriented in the longitudinal direction (the machine direction “A” of the system of
In general, ribbons may be supplied to the pultrusion system directly from impregnation die 150, or may be supplied from spindles or other suitable storage apparatus. A tension-regulating device may be employed to help control the degree of tension in the ribbons as they are drawn through the pultrusion system. An oven may be supplied in the device for heating the ribbons. The ribbons may then be provided to a consolidation die, which may operate to compress the ribbons together into a preform, and to align and form the initial shape of the desired product, such as a rod. If desired, a second die (e.g., calibration die) may also be employed that compresses the preform into a final shape. Cooling systems may additionally be incorporated between the dies and/or after either die. A downstream pulling device may be positioned to pull products through the system.
These and other modifications and variations of the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.
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