US20050285297A1

US20050285297A1 - Extrusion or pultrusion of a polymer undergoing polymerization

Info

Publication number: US20050285297A1
Application number: US10/873,525
Authority: US
Inventors: Edward Park; Chad Bauer
Original assignee: Individual
Current assignee: Freudenberg NOK GP
Priority date: 2004-06-21
Filing date: 2004-06-21
Publication date: 2005-12-29
Also published as: MXPA05006776A; CA2509693A1

Abstract

A polymerizing fluid polymer (thermoplastic, elastomer, thermoset polymer, thermoplastic elastomer, thermoplastic vulcanizate) with an optional filler (such as magnetizable ferrite powder or carbon nanotubes) is extruded or pultruded into shaped polymer (optionally multilayer shaped polymer) so that all portions of the shaped polymer conform within a desired state of polymerization (in a multilayer coating, that the quality-related performance characteristics of shaped polymer are consistent within any coating layer). At least one (tear-drop shaped) flow diverter is described for diverting flow within an extrusion (pultrusion) die so that fluid polymer moving through a short residence time portion of the die will have a more substantial residence time (than would be the case if the diverter were not used) with commensurately greater thermal, pressure, and shear stress history so that the desired conformance respective to polymerization states for all portions in the shaped polymer is achieved.

Description

This invention relates to a die and a method for forming a polymerizing fluid polymer into a conduit.
Extrusion of plastic pipe (“pipe” including such alternative items as a fluid conduit channel pipe capable of conveying a fluid, a solid pipe having no conduit, a pole, a bar, a filament, or a wire) and pultrusion of coated pipe (or coated alternative articles such as just identified for the term “pipe”) are established processes. In extrusion, a continuous stream of fluid polymer (resin) is driven into a die. The die has an exit aperture for forming the fluid polymer into shaped polymer to make the desired pipe and for continuously discharging the shaped polymer from the die. Pultrusion is similar to extrusion except that the polymer fluid is deposited on solid pipe (or other continuous pulling device) to form coated pipe; in this regard, the polymeric fluid is forced through the die and also “pulled” (as solid pipe is independently driven through the die and exit aperture of the die) onto the solid pipe per surface tension between the fluid polymer and the exterior surface of the solid pipe.
Extrusion and pultrusion have been very useful in processing essentially stable (respective to the quality needs of the target shaped article) polymers. In this regard, a polymer undergoes stress when resident in a die as it proceeds from fluid polymer to shaped polymer. The state of polymerization in the shaped polymer accordingly is an indication of the stress history its fluid polymer experienced. This stress history frequently includes a temperature history from residence time in the die at an elevated temperature, a pressure history from residence time in the die at the extrusion pressure, and a shear history from the various shear stresses derived from fluid passage of the fluid polymer through the die. While most extruded polymers are generally robust for such stress histories, some die designs have traditionally used a deflection ramp within the die to eliminate very long periods of residence time for fluid polymer that would linger in an “eddy space” within the die if a deflection ramp were not present. Deflection ramps are frequently used when the die has a fluid polymer inlet port that is perpendicular to an axis of flow that is in-line with the discharge aperture of the die.
Injection molding processes have traditionally shaped polymers such as thermoplastic elastomer and thermoplastic vulcanizate into items such as encoders, seals, retainer rings, and gaskets. In this regard, these items frequently are made with polymerizing fluid polymers. A polymerizing fluid polymer significantly transitions from a first (fluid) polymerization state to a second (shaped polymer) polymerization state while it is in the forming mold. Many such polymers cure within the mold. Control of polymerization consistency across all portions of the shaped polymer when made with such injection molding approaches is usually fairly straightforward insofar as all polymer portions in the item have an essentially identical stress history.
In general comparison to extrusion (pultrusion) forming, injection molding, however, is an expensive batch process approach where each item is made as an independent piece of shaped polymer having an independent stress history. Use of extrusion in making such complex items as encoders, seals, retainer rings, and gaskets could be beneficial when compared to injection molding insofar as extrusion is a steady state process rather than a batch process, with comparable benefits in consistency and productivity that should be apparent to those of skill in the plastic processing art. However, a significant problem in extrusion of polymerizing fluid polymers is that control of overall polymerization consistency in all portions of the shaped polymer is not straightforward. In this regard, different portions of the extruded polymer will have different stress histories derived from different residence times in the die. This problem is especially significant when the polymer is pultruded as a coating onto a solid base (pipe), since pultrusion usually involves a die having a fluid polymer inlet port essentially perpendicular to the axis of flow that is in-line with the discharge aperture of the die.
Improved extrusion and pultrusion approaches are therefore needed for polymerizing fluid polymers and/or for polymers that are sensitive (respective to their application) to stress. This and other needs are resolved with the present invention.

SUMMARY

The invention provides a method for forming a polymerizing fluid polymer into a conduit of shaped polymer, comprising extruding the fluid polymer through a die, the die forming the fluid polymer into the shaped polymer and discharging the shaped polymer from the die through an exit aperture having a center-point, the shaped polymer having a plurality of portions with each portion positioned at a unique angular location in polar relation to the center-point, wherein, in operation, the polymerizing fluid polymer is in a first state of polymerization when fluidly communicated into the die, the shaped polymer in each portion is in an independent second state of polymerization when discharged from the exit aperture, and all the portions have second states of polymerization that are mutually conformant within a predefined threshold of deviation.
Another aspect of the invention is for a die for forming a polymerizing fluid polymer into a conduit of shaped polymer, comprising:

- (a) a die housing having an inner surface defining an internal cavity, an entrance port for fluid communication of the fluid polymer into the internal cavity, and an exit aperture for forming the fluid polymer into the shaped polymer and for discharging the shaped polymer from the die, the exit aperture in fluid communication with the internal cavity and having a center-point;
- (b) a mandrel (or other die core member) disposed within the internal cavity to define a generally annular cavity between the inner surface and the mandrel, the mandrel having an axis of elongation and an end positioned to interact with the exit aperture in the forming so that a channel is established in the conduit; and
- (c) at least one flow diverter disposed within the annular cavity;
- where the shaped polymer has a plurality of portions with each portion positioned at a unique angular location in polar relation to the center-point, and where, in operation, the polymerizing fluid polymer is in a first state of polymerization when fluidly communicated through the entrance port into the internal cavity, and the shaped polymer in each portion is in an independent second state of polymerization when discharged from the exit aperture; and
- where the flow diverter is shaped and positioned to provide that all shaped polymer portions have second states of polymerization that are mutually conformant within a predefined threshold of deviation.

In another aspect, the flow diverter has a tear-drop shape and is optionally attached to the mandrel.
In another aspect, a plurality of mandrels (or similar die core-members) are used within the die with at least one of the mandrels (die core-members) having at least one flow diverter.
In further alternative aspects, the fluid polymer is a fluid polymer selected from a thermoplastic elastomer, a thermoplastic vulcanizate, a thermoset polymer, a thermoplastic, an elastomer, or combinations of those polymers.
In further alternative aspects, a filler such as magnetizable ferrite powder, metal fiber, carbon nanotubes, or combinations of these is/are admixed into the fluid polymer prior to extrusion or pultrusion.
In yet further alternative aspects, the fluid polymer is pultruded upon a pipe (plastic pipe, plastic bar, plastic filament, ceramic pipe, ceramic bar, ceramic filament, metal pipe, metal bar, or metal filament) progressing through the mandrel and exit aperture. The pultruded shaped polymer in some aspects is a coating. The pultruded shaped polymer in other aspects is a multilayer coating.
In yet another aspect, a conduit or coated pipe (such as a plastic pipe, plastic bar, plastic filament, ceramic pipe, ceramic bar, ceramic filament, metal pipe, metal bar, or metal filament) is made through use of the above methods and/or processes.
In yet another aspect of the invention, a die is made by iteratively designing a die with at least one flow diverter, constructing the die, extruding the polymer through the die, and measuring the second polymerization state of all portions of the extruded shaped polymer until the measured deviation among the second polymerization state of all portions of the extruded shaped polymer is less than a desired predefined threshold of deviation.
In yet a further aspect, the new extrusion and pultrusion methods, products, and dies produce a continuously extruded pipe or wire which is then cut or segmented to make any of an encoder, O.D. (outside diameter) seal, I.D. (inside diameter) seal, static seal, retainer ring, and the like.
The new extrusion and pultrusion methods, products, and dies provide a more efficient and economical solution over the injection molding approach for making parts for encoders, O.D. and I.D. seals, static seals, retainer rings, and the like.
Further areas of applicability will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating embodiments of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will become more fully understood from the detailed description and the accompanying drawings of FIGS. 1 to 11.
FIG. 1 presents a pultrusion die mandrel with an attached ramped-sleeve deflector and an attached flow diverter;
FIG. 2 shows a simplified overview of an extrusion die;
FIG. 3A and FIG. 3B show portions defined in shaped extruded polymer;
FIG. 4 shows an exploded view of a die housing, inner layer insertion hold plug, and a pultrusion mandrel with a ramped-sleeve deflector;
FIG. 5 presents a perpendicular view of a representative thickness plane of a tear-drop shaped flow diverter;
FIG. 6 shows pultrusion die detail;
FIG. 7 shows an overview of a pultrusion process;
FIG. 8A and FIG. 8B show portions defined in shaped polymer pultruded coating;
FIG. 9 shows pultrusion die detail for making a multilayer coating in pultruded pipe;
FIG. 10A and FIG. 10B show portions defined in multilayer shaped polymer pultruded coating; and
FIG. 11 presents a pultrusion die mandrel with an attached ramped-sleeve deflector and a plurality of attached flow diverters.
It should be noted that the figures set forth herein are intended to exemplify the general characteristics of an apparatus, materials and methods among those of this invention, for the purpose of the description of such embodiments herein. These figures may not precisely reflect the characteristics of any given embodiment, and are not necessarily intended to define or limit specific embodiments within the scope of this invention.

DESCRIPTION

The following definitions and non-limiting guidelines must be considered in reviewing the description of this invention set forth herein.
The headings (such as “Introduction” and “Summary”) used herein are intended only for general organization of topics within the disclosure of the invention, and are not intended to limit the disclosure of the invention or any aspect thereof. In particular, subject matter disclosed in the “Introduction” may include aspects of technology within the scope of the invention, and may not constitute a recitation of prior art. Subject matter disclosed in the “Summary” is not an exhaustive or complete disclosure of the entire scope of the invention or any embodiments thereof.
The citation of references herein does not constitute an admission that those references are prior art or have any relevance to the patentability of the invention disclosed herein. All references cited in the Description section of this specification are hereby incorporated by reference in their entirety.
The description and specific examples, while indicating embodiments of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. Moreover, recitation of multiple embodiments having stated features is not intended to exclude other embodiments having additional features, or other embodiments incorporating different combinations the stated of features.
As used herein, the words “preferred” and “preferably” refer to embodiments of the invention that afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
As used herein, the word “include,” and its variants, is intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that may also be useful in the materials, compositions, devices, and methods of this invention.
Turing now to FIG. 1, pultrusion mandrel 100 with attached ramped-sleeve deflector 114 and attached flow diverter 106 illustrates a component for use in an extrusion die or a pultrusion die for retarding the flow of some of the fluid polymer so that the state of polymerization of all polymer portions discharged from die will be comparable. In this regard, the portion of polymer that flows along the thickness surface 108 of diverter 106 would, without the benefit of diverter 106, pass through the die very rapidly compared to the remainder of fluid polymer which must transit through the die via a longer fluid flow path on the opposite side (from the side having diverter 106) of mandrel 100 (as will be further discussed with reference to FIG. 2). As such, the portion passing through the die quickly has a relatively brief polymerization history (per a shorter stress history from a shorter temperature history, pressure history, and shear history) when compared to the longer polymerization history of the remainder of fluid polymer transiting through the die via the longer fluid flow path.
In further detail of FIG. 1, flow diverter 106 is attached with connectors such as connector 110 to mandrel 102. End 118 of mandrel 102 is positioned to interact with an exit aperture (FIG. 2) in forming the fluid polymer into shaped polymer so that a channel is established within the shaped polymer. Mandrel 102 is attached to base 116 and has a conduit channel 104 along (in parallel with) the axis of elongation of mandrel 102. In operation, a pipe (in various alternative embodiments, any of a fluid conduit channel pipe capable of conveying a fluid, a solid pipe, a pole, a bar, a filament, a wire, plastic pipe, plastic bar, plastic filament, ceramic pipe, ceramic bar, ceramic filament, metal pipe, metal bar, or metal filament) progresses through mandrel 102 via an entrance hole (not shown) in base 116, channel 104, and the opening of channel 104 in end 118. Ramped-sleeve deflector 114 slides over mandrel 104 and is attached to or tightly retained against mandrel 104 against the inboard surface of base 116. Surface 112 on deflector 114 is shaped to smoothly divert flow of flowing polymer entering through a fluid polymer inlet port perpendicular to the general elongation axis (not shown, but which should be apparent from the figure) of mandrel 102. In this regard, the flow of fluid polymer changes in direction from a flow direction perpendicular to the mandrel elongation axis to a flow direction parallel along the mandrel elongation axis. In an alternative embodiment, mandrel 102 is machined as a single piece with comparably identified portions.
The functions of deflector 114 and flow diverter 106 are further appreciated from a consideration of FIG. 2 that shows a simplified overview of an extrusion die 200 where die 200 has fluid polymer inlet port 206 perpendicular to mandrel axis of elongation 204. Mandrel axis of elongation 204 is in-line with discharge aperture 214 of die 200. Fluid polymer 202 enters die 200 via entrance port 206 in die housing 218. Housing inner surface 220 defines an internal cavity inside housing 218 with the internal cavity being in fluid communication with entrance port 206 so that fluid polymer 202 enters die 200 via port 206. Exit aperture 214 forms fluid polymer 202 into shaped polymer 216 and discharges shaped polymer 216 from die 200. Exit aperture 214 is in fluid communication with the internal cavity and has a center-point at the place where axis 204 passes through aperture 214.
Mandrel 210 is disposed within the internal cavity to define a generally annular cavity 208 between inner surface 220 and mandrel 210. Mandrel 210 has an end 212 positioned to interact with exit aperture 214 in forming a channel (further discussed with reference to FIG. 3) within the conduit of shaped polymer 216.
Fluid polymer flowing through annular cavity 208 enters the general internal cavity of die 200 through fluid polymer inlet port 206 (via a flow path perpendicular to general elongation axis 204 of mandrel 210) and, as the fluid polymer moves through die 200, changes flow direction to a flow direction parallel to mandrel elongation axis 204.
As can be appreciated from a consideration of die 200 in FIG. 2, fluid polymer 202 flowing from port 206 to aperture 214 along the shortest (“top”) path of cavity 208 “above” mandrel 210 will have a shorter residence time within die 200 than fluid polymer 202 flowing from port 206 to aperture 214 along the longest (“bottom”) path of cavity 208 “below” mandrel 210. If fluid polymer 202 is a polymerizing polymer (a polymer in a first state of polymerization when fluidly communicated through entrance port 206 into the internal cavity of die 200, and where shaped polymer 216 is made of portions where each portion is in an independent second state of polymerization when discharged from exit aperture 214), then the portion of shaped polymer 216 that passed through die 200 “above” mandrel 210 (with the “shorter” residence time) has a relatively brief polymerization history (per a shorter stress history from a shorter temperature history, pressure history, and shear history) when compared to the “longer” polymerization history of the portion of fluid polymer transiting through the die via the longer fluid flow path “below” mandrel 210. In a polymerizing polymer (a polymer undergoing a curing process and/or a polymer whose polymerization state is modified by a stress history), the two derived portions of shaped polymer 216 will have commensurately differentiated quality properties due to those different residence times. Essential elimination of these differentiated quality properties is the focal concern resolved by the preferred embodiments (such as with pultrusion mandrel 100) where flow diverter 106 is an example of a flow diverter that would, if inserted into annular cavity 208 in the flow path “above” mandrel 210, provide for a “longer” stress history (an essentially longer residence time within die 200) for that portion of shaped polymer 216 which passed through die 200 “above” mandrel 210. By being so positioned, a flow diverter in the portion of annular cavity 208 “above” mandrel 210 thereby provides for an essentially equivalent stress history for all portions of shaped polymer 216.
Mandrel 100 and mandrel 210 are each a specific type of a die core member (die core-member) around which a fluid material (such as fluid polymer) flows so that it can be molded or otherwise shaped. In this regard, alternative embodiments have other die core-members for holding flow diverter 106 or have other die core-members defining a flow cavity.
The nature of the portions of shaped polymer 216 are further appreciated from consideration of FIG. 3A and FIG. 3B as they show portions defined in a transverse view 300 and a cross section view 350 of shaped extruded polymer (such as shaped polymer 216). In transverse view 300 of FIG. 3A, shaped polymer 302 forms a conduit having channel 306. Since shaped polymer 302 is an example of shaped polymer 216 (FIG. 2), axis 304 is essentially identical to axis 204. Accordingly, as exit aperture 214 (FIG. 2) has a center-point at the place where axis 204 passes through aperture 214, shaped polymer 302 has a commensurate center-point 310 in cross-section view 350 from axis 304. The cross-sectional perspective on axis 304 in the shaped polymer cross-section view 350 of FIG. 3B is accordingly defined as center-point 310. In cross-section view 350, center-point 310 is the reference point for polar co-ordinates with zero-π-radian axis 308. Segment 318 of shaped polymer 302 within radian arc 312 defines a first portion of shaped polymer 302. Segment 316 of shaped polymer 302 within radian arc 314 defines a second portion of shaped polymer 302. The functional goal of the embodiments is to provide that the state of polymerization of shaped polymer in first portion 318 is essentially equivalent to the state of polymerization of shaped polymer in second portion 316 so that the quality-related performance characteristics of shaped polymer 302 is consistent in all of its portions. As should be apparent, portions 316 and 318 are exemplary; in an alternative embodiment, second portion 316 is defined as all of shaped polymer 302 that is not within radian arc 312. In yet another embodiment, thirty-six portions are defined, with each portion having a radian arc of 1/18 π. What is important in defining the nature of each portion of shaped polymer for state of polymerization evaluation is that the portion definitions are useful for quality control respective to the ultimate application of the shaped polymer.
Turning now to a further consideration in pultrusion, FIG. 4 shows exploded view 400 of die housing 402, pultrusion mandrel 404 with ramped-sleeve deflector 406, and inner layer insertion hold plug 410. In one embodiment of operation, a pultusion die initiates operation as an extrusion die with hold plug 410 inserted into the conduit running along the elongation axis (such as axis 204) of mandrel 404. In this mode, the die operates as an extrusion die similar to die 200 of FIG. 2. The die is operated in a first stage of operation to extrude a conduit of shaped polymer until all portions of the shaped polymer are acceptable in shape and polymer quality (an acceptable state of polymerization is present in each identified portion). After the first stage of operation has yielded shaped polymer of acceptable quality, plug 410 is removed and a solid pipe (such as, without limitation, plastic pipe, plastic bar, plastic filament, ceramic pipe, ceramic bar, ceramic filament, metal pipe, metal bar, or metal filament) is propelled through the conduit running along the elongation axis (such as axis 204) of mandrel 404 so that the shaped polymer is now deposited as a coating or outside layer onto the pipe. In another embodiment, a die is operated as an extrusion die for an extended time with plug 410 inserted into mandrel 404 to make a first product of shaped polymer. The die is subsequently operated for an extended time without plug 410 to make a second product of coated pipe. In yet another embodiment, hold plug 410 has a conduit terminating in exit end 412, with the conduit running along the elongation axis (such as axis 204) of mandrel 404 so that a particular outside dimension of solid pipe may be propelled through the conduit of plug 410 (within the conduit of mandrel 404) running along the elongation axis (such as axis 204) of mandrel 404 so that the shaped polymer is deposited as a coating or outside layer onto the pipe. In one embodiment, multiple plug 410 designs enable different pipes to be propelled (at different times) through the same mandrel 404 and die. In yet a further embodiment, plug 410 has a surface finish or coating on the periphery surface of the exit hole in end 412, with the finish or coating being specific to the pipe being driven through the die.
Returning to a consideration of flow diverter 106, FIG. 5 presents a perpendicular view 500 of a representative thickness plane of an exemplary flow diverter (such as a plane taken through thickness surface 108 of flow diverter 106). View 500 indicates a tear-drop shaped flow diverter with a tear-drop perimeter 502 shape relative to a perpendicular perspective to a general thickness plane of the diverter. Angular location 504 on perimeter 502 defines one point of symmetrical axis 506 extending through the diverter. As shown in the FIG. 1 embodiment of mandrel assembly 100, symmetrical axis 506 is essentially in parallel with the axis of elongation for the mandrel (for example mandrel 102) to which the flow diverter of the axis is attached. Furthermore, angular location 504 is positioned to be the initial contact point of the diverter (106) to flow of fluid polymer through the annular cavity (208 of FIG. 2) of the die. In another embodiment (not shown), diverter (106) is rotated by 180 degrees so that angular location 504 is positioned to be the final contact point of the diverter (106) to flow of fluid polymer through the annular cavity (208 of FIG. 2) of the die. Flow diverter designs with thickness planes substantially according to the tear-drop shape of view 500 are preferred embodiments for achieving mutually conformant in shaped polymer portions. In this regard, perimeter 502 preferably provides a generally symmetrical thickness plane profile about axis 506, with axis 506 extending through an angular location (such as location 504) where two concave (respective to orientation planar with and outside of view 500) portions of perimeter 502 either connect or, in one case of a perimeter 502 that is consistently convex (or in an alternative case of a perimeter 502 that is convex in the general area of location 504) merge to provide a significantly rounded tear-drop tip having a significant curvature such as would be subtended by an angle providing a height to chord ratio of greater than about ⅓ (a value of one-third) to the subtended curvature. Respective to the orientation of the tear drop shown in FIG. 5, the ratio of the length of the diverter along axis 506 to the width, in perpendicular orientation to axis 506, of the maximum separation of the right side of perimeter 502 respective to the left side of perimeter 502 ranges in substantially accordant tear-drops from a ratio of about 10 to about 1 (a ratio having a value of about ten) to a ratio of from about 1 to about 3 (a ratio having a value of about one-third).
In another embodiment (not shown), angular location 504 of a flow diverter is positioned to be the final contact point of the flow diverter (such as flow diverter 106 if rotated by 180 degrees respective to the axis of elongation of mandrel 102)) to flow of fluid polymer through the annular cavity (208 of FIG. 2) of the die. The exact orientation of flow diverter 106 is that which will enable the desired functionality of shaped polymer portions having states of polymerization that are mutually conformant within a predefined desired threshold of deviation.
Further in this regard, while a tear-drop-shaped flow diverter provides in one embodiment for portions that have second states of polymerization that are mutually conformant within a predefined threshold of deviation, other shapes can be used can be used in other embodiments. In yet another embodiment, a plurality of flow diverters are deployed at various places within the die to stabilize and balance the polymeric flows to achieve the desired properties in the shaped polymer. The flow diverter(s) is/are attached to the mandrel(s) in one embodiment; in an alternative embodiment, the flow diverter(s) is/are attached to the internal housing surface of the flow cavity for the fluid polymer. In yet another embodiment, at least one flow diverter is/are attached to the mandrel and at least one flow diverter is/are attached to the internal housing surface of the flow cavity for the fluid polymer. Therefore, any specific modification of the internal die geometry directed to providing a minimum residence time for all portions of the flowing fluid polymer so that the derived shaped polymer has consistency in the polymerization state of its various portions enables an alternative embodiment for achieving the function goals of the invention.
In one embodiment in this regard, a die is made by iteratively designing a die with a flow diverter, constructing the die, extruding the polymer through the die, and measuring the second polymerization state of all portions of the extruded shaped polymer until the measured deviation among the second polymerization state of all portions of the extruded shaped polymer is less than a desired predefined threshold of deviation. A flow diverter (or a set of flow diverters) of any perceived useful design is designed and positioned within the die in each iteration with a comparison of the measurements of the second polymerization state of all portions of the extruded shaped polymer respective to desired predefined threshold of deviation being used in each instance of the iterative process to design the subsequent die.
Respective to a minimum residence time for the fluid polymer in the die, the temperature and pressure of the die environment (in one embodiment) promotes the curing of the polymerizing polymer by enabling either or both of polymer chain growth and cross-linking to occur. Cross-linking (or any other aspect of curing) may also occur with a particular residence time at a particular die temperature and pressure to favor the polymerization state of the shaped polymer respective to measure of any or any combination of a particular polymeric matrix fractal (macromolecular branching pattern), crystalline state, spherulitic dimension, density, elasticity, solvent resistance, density, melting point, glass transition temperature, average molecular weight, tensile strength, elongation, impact strength, electrical resistance, solubility, swelling, molecular conformation, or other like macro-polymeric property desired for the derived shaped polymer and for local (portion-specific) aspects of the shaped polymer. In this regard, a die that does not provide sufficient residence time history for all portions of the shaped polymer will not provide consistent quality in the shaped polymer. In other embodiments, a stress sensitive polymer “degrades” from a first polymerization state toward a second polymerization state as a result of residence time in the die, but the shaped polymer will best perform in its application if the degradation is consistent for all portions of the shaped polymer. In this regard, for example, modification of any of color, transparency, and/or opacity of the polymer might occur with residence time in the die. In such a case, a flow diverter is shaped and positioned in one die embodiment to provide a predefined desired consistency for any of these critical properties across all portions of the shaped polymer.
The consistency is determined by measuring as least one of the above macro-polymeric properties in each defined portion of shaped polymer and then comparing the measurements to each other and/or to a standard. In this regard, a desired threshold of deviation is established either empirically or via a functional definition for comparing the measurements in order to determine the acceptability of the measured properties. For example, a melting point sample in one embodiment of each portion is taken and the melting point of each sample is compared to a desired deviation threshold of from about 300 to about 310 degrees Fahrenheit. In another embodiment, the desired threshold deviation for elongation for all portions is defined as a maximum variance of 10 percent among the measured elongations for the portions.
FIG. 6 shows a substantial amount of pultrusion die detail in die cutaway view 600. Extruder 604 propels fluid polymer 602 thorough inlet port 608 in die housing 616. A ramped-sleeve deflector is in tight adherence around mandrel 610 to provide surface 618 for smoothly diverting flow of flowing polymer (602) from a flow direction perpendicular to the mandrel (610) elongation axis to a flow direction parallel with that axis. Flow of fluid polymer in the “upper” portion of annular cavity 606 is diverted to provide a minimum residence time for the portion of fluid polymer flowing within that part of annular cavity 606 by flow diverter 624, preferably a tear-drop shape diverter according to the shape indicated in FIG. 1 and FIG. 5. Inner layer insertion-hold plug 614 is inserted into the conduit of mandrel 610. Inner layer insertion hold plug 614 has conduit 622 in line with the mandrel (610) elongation axis so that a particular outside dimension of solid pipe is consistently propelled through conduit 622 of plug 614. Shaped polymer discharged from exit aperture 620 is therefore deposited as a coating or outside layer onto solid pipe propelled through conduit 622 and exit aperture 620 along vector 612.
FIG. 7 shows overview 700 of a pultrusion process using a die such as shown in view 600 of FIG. 6. Extruder 604 and housing 616 are reprised from view 600 of FIG. 6. Pipe 702 (such as, without limitation, plastic pipe, plastic bar, plastic filament, ceramic pipe, ceramic bar, ceramic filament, metal pipe, metal bar, or metal filament) is propelled through die 616 and is coated with fluid polymer from extruder 604 to produce coated pipe 706 (such as, without limitation, coated plastic pipe, coated plastic bar, coated plastic filament, coated ceramic pipe, coated ceramic bar, coated ceramic filament, coated metal pipe, coated metal bar, coated metal wire, or coated metal filament) having coating (or outside layer shaped polymer) 708.
FIG. 8A and FIG. 8B show portions defined in a shaped pultruded coating such as would result from process 700 of FIG. 7. FIG. 8A and FIG. 8B show portions defined in a transverse view 800 and a cross section view 850 of shaped pultruded polymer coated onto pipe 804 (such as pipe 706 of FIG. 7). In transverse view 800 of FIG. 8A, shaped polymer 806 essentially forms a conduit inside of which pipe 804 is tightly held (note that, while pipe 804 is usually considered to be a coated or multilayer pipe, a view of coated pipe from the standpoint of coating 806 is that pipe 804 may also be considered as “inserted tightly with” or as “tightly retained by” a polymeric-polymeric or polymeric-metal bond within the “conduit” of shaped polymer 806). Pipe 804 has elongation axis 802 and (optional) channel 808.
Turning to FIG. 8B, exit aperture 620 and elongation axis 802 define a commensurate (to axis 802) center-point 810 in cross-section view 850 (see parallel detailed considerations in this regard in the discussion of FIG. 2 and FIG. 3). In cross-section view 850, center-point 810 is the reference point for polar co-ordinates with zero-x-radian axis 824. Segment 816 of shaped polymer 806 within radian arc 820 defines a first portion of shaped polymer 806. Segment 818 of shaped polymer 806 within radian arc 822 defines a second portion of shaped polymer 806. The functional goal of the embodiments is to provide that the state of polymerization of shaped polymer in first portion 816 is essentially equivalent to the state of polymerization of shaped polymer in second portion 818 so that the quality-related performance characteristics of shaped polymer 806 is consistent in all of its portions. As should be apparent, portions 816 and 818 are exemplary; in an alternative embodiment, second portion 818 could be defined as all of shaped polymer 806 that is not within radian arc 820. In yet another embodiment, thirty-six portions are defined, with each portion having a radian arc of 1/18 π. What is important in defining the nature of each portion of shaped polymer for state of polymerization evaluation is that the portion definitions are useful for quality control respective to the ultimate application of shaped polymer 806 and coated pipe 804.
Multilayer coatings are enabled in one embodiment by using a die such as provided in FIG. 9 along with a balance of viscosity and thickness in each polymer (coating) layer so that the plurality of coatings in the shaped polymer all “cure” or “solidify” to a desired consistency and quality of physical shape. In this regard, viscosities in the polymer are balanced so that a fluid polymer being deposited upon a previously deposited (still fluid) polymer deposits without disrupting the geometry of the previously deposited polymer. Thickness control of individual coatings in preferred embodiments is also controlled to be less than or equal to 1 mm in order to achieve the desired geometry within the shaped polymer after hardening. In one embodiment, 20 separate layers are deposited through a die similar to the die of FIG. 9 but with 20 layers instead of the 2 illustrated in FIG. 9.
Turing now to consideration of flow diversion in multilayer pultrusion, FIG. 9 shows detail in die cutaway view 900 for a multilayer-coating pultrusion die. Extruder 604, fluid polymer 602, annular cavity 606, inlet port 608, die housing 616, mandrel 610, flow diverter 624, inner layer insertion-hold plug 614, conduit 622, and vector 612 are all reprised from single-layer coating die view 600 of FIG. 6. These components operate essentially as discussed with respect to FIG. 6 to provide a first layer of coating at about location 908 on pipe input through conduit 622 along vector 612. The coated pipe with one layer of coating of polymer 620 then proceeds through conduit 910 and is coated with a second layer of coating (polymer 904) from cavity 912. Extruder 902 propels fluid polymer 904 into cavity 912 within second die housing 918 (the exterior surface of housing 616 serving as a die core-member for cavity 912). The annular portion 920 of cavity 912 has polymer (904) flow diverted by flow diverter 906, preferably a tear-drop shape diverter according to the shape indicated in FIG. 1 and FIG. 5. The shaped polymer discharged along vector 916 (preferably in-line with vector 612) from exit aperture 914 is therefore deposited as a multilayer coating onto solid pipe propelled along vectors 612 and 914 through conduit 622, conduit 910, and exit aperture 914.
FIG. 10A and FIG. 10B show portions defined in a shaped multilayer pultruded coating such as would result from a die of view 900 of FIG. 9. FIG. 10A and FIG. 10B show portions defined in a transverse view 1000 and a cross section view 1050 of shaped multilayer pultruded polymer coated onto pipe 1008. In transverse view 1000 of FIG. 10A, shaped polymer 1018 is made of first coating 1010 and second coating 1012. As in FIG. 8A and FIG. 8B, shaped polymer 1018 of FIG. 10A and FIG. 10B essentially forms a conduit inside of which pipe 1008 is tightly held. Pipe 1008 has elongation axis 1002 and (optional) channel 1006.
Turning to FIG. 10B, center-point 1054 in cross-section view 1050 is the reference point for polar co-ordinates with zero-π-radian axis 1052. Segment 1064 of shaped polymer 1018 within radian arc 1062 defines a first portion of (first) coating layer 1010 of shaped polymer 1018. Segment 1066 of shaped polymer 1018 within radian arc 1060 defines a second portion of (first) coating layer 1010 of shaped polymer 1018. Segment 1070 of shaped polymer 1018 within radian arc 1058 defines a first portion of (second) coating layer 1012 of shaped polymer 1018. Segment 1068 of shaped polymer 1018 within radian arc 1056 defines a second portion of (second) coating layer 1012 of shaped polymer 1018. The functional goal of the embodiments is to provide that the state of polymerization of shaped polymer in first portion 1064 of coating 1010 is essentially equivalent to the state of polymerization of shaped polymer in second portion 1066 of coating 1010 so that the quality-related performance characteristics of shaped polymer in coating 1010 is consistent in all of its portions. The functional goal of the embodiments is to further provide that the state of polymerization of shaped polymer in first portion 1070 of coating 1012 is essentially equivalent to the state of polymerization of shaped polymer in second portion 1068 of coating 1012 so that the quality-related performance characteristics of shaped polymer in coating 1012 is consistent in all of its portions. Overall within the multilayer coating of shaped polymer 1018, the functional goal is that the state of polymerization of shaped polymer in any first portion of a coating layer is essentially equivalent to the state of polymerization of shaped polymer in any second portion of that coating layer so that the quality-related performance characteristics of shaped polymer are consistent within any coating layer (1010 or 1012) derived from any one of the fluid polymers (602 or 904).
As should be apparent, portions 1064, 1066, 1068, and 1070 are exemplary; in this regard, parallel considerations in alternative embodiments are essentially similar to alternative embodiment considerations put forward in the discussion of FIG. 9.
FIG. 11 shows view 1100 of a further embodiment of a pultrusion mandrel 1108 with an attached ramped-sleeve deflector 1110 (with ramped surface 1112) and a plurality of attached flow diverters. Flow diverter 1102, flow diverter 1104, and flow diverter 1106 all retard flow of fluid polymer progressing along the general elongation axis of mandrel 1108 so that the state of polymerization of all polymer discharged from the die using mandrel 1108 will be comparable. In this regard, the portion of polymer that flows along the thickness surface 108 of diverters 1002, 1104, and 1106 would, without the benefit of diverters 1002, 1104, and 1106, pass through the die very rapidly compared to the remainder of fluid polymer which must transit through the die via a longer fluid flow path on the opposite side (from the side having diverters 1002, 1104, and 1106) of mandrel 1108.
In one embodiment of mandrel 1108 development, a first extrusion die using mandrel 1108 is constructed according to first die design where only flow diverter 1102 is attached to mandrel 1108. Fluid polymer is then extruded through this first extrusion die to form shaped polymer. The state of polymerization in each portion of the shaped polymer is measured and a deviation among all the measured states of polymerization provides a comparison of the measured deviation to a desired predefined threshold of deviation.
In this exemplary embodiment of development, the comparison indicates that the desired threshold is not achieved, and, accordingly, flow diverter 1104 is then added in a second extrusion die using mandrel 1108 with flow diverters 1102 and 1104 attached. Fluid polymer is then extruded through this second extrusion die to again form shaped polymer. The state of polymerization in each portion of the shaped polymer is measured and a deviation among all the measured states of polymerization provides a comparison of the measured deviation to a desired predefined threshold of deviation.
In this exemplary embodiment of development, the comparison indicates that the desired threshold still is not achieved, and, accordingly, flow diverter 1106 is then added in a third extrusion die using mandrel 1108 with flow diverters 1102, 1104, and 1106 attached. Fluid polymer is then extruded through this third extrusion die to again form shaped polymer. The state of polymerization in each portion of the shaped polymer is measured and a deviation among all the measured states of polymerization provides a comparison of the measured deviation to a desired predefined threshold of deviation.
In this exemplary embodiment of iterative die development, the comparison indicates that the desired threshold has been finally achieved. Accordingly, the die forms a polymerizing fluid polymer into a conduit of shaped polymer having a plurality of portions with each portion in an independent state of polymerization such that all portions have states of polymerization that are mutually conformant within the predefined desired threshold of deviation.
Examples of materials for fluid polymer within the extrusion or pultrusion die embodiments include thermoplastics, thermoset polymers, elastomer, thermoplastic elastomer, and thermoplastic vulcanizate; combinations of these may also be extruded or pultruded. Fillers such as magnetizable ferrite powder, metal fiber, carbon nanotubes, or combinations of these are, in some embodiments, admixed into the fluid polymer prior to extrusion or pultrusion.
In various embodiments, the fluid polymer is and the shaped polymer is derived from any of silicone-thermoplastic vulcanizate (such as a Dow Corning experimental VMQ-TPV also commonly known as TPSiV), nitrile butyl rubber thermoplastic vulcanizate, ethylene acrylic rubber thermoplastic vulcanizate (such as a Dupont experimental AEM-TPV also commonly known as ETPV), thermoplastic polyurethane, acrylic acid ester rubber/polyacrylate rubber thermoplastic vulcanizate (such as Zeon Chemical's Zeotherm™ acrylic acid ester rubber/polyacrylate rubber thermoplastic vulcanizate), thermoplastic polyester elastomer (such as Dupont's Hytrel™ polyester elastomer), polyether-block co-polyamide resins (such as Modified Polymer Components' Pebax™ polyether-block co-polyamide resin), fluoroelastomer, acrylic acid ester rubber/polyacrylate rubber curable elastomer, ethylene acrylic rubber curable elastomer, nitrile butyl rubber curable elastomer, hydrogenated nitrile butyl rubber curable elastomer, silicone curable elastomer, combinations thereof, and the like.
In alternative embodiments, the coated pipe is further converted into an article such as an encoder, an O.D. (outside diameter) and I.D. (inside diameter) seal, a static seal, a retainer ring, or a gasket. In one embodiment, coated pipe (with a coating made by pultruding fluid polymer into a coating of shaped polymer with all portions of the shaped polymer coating in a comparable state of polymerization as described herein) is cut across (in a perpendicular plane to) the elongation axis of the coated pipe so that the pipe is “sliced” (after cooling and solidification of the shaped polymer) into a plurality of thin rings. One embodiment application for these rings is for an encoder such as a TPE encoder (where magnetic powdered filler is admixed within the shaped polymer of the coating).
In another embodiment, coated wire or coated filament (with a coating made by pultruding fluid polymer into a coating of shaped polymer with all portions of the shaped polymer coating in a comparable state of polymerization as described herein) is cut into segments (in a perpendicular plane to) the elongation axis of the coated pipe so that the continuously pultruded wire (filament) is cut into a plurality of segments with each segment being of sufficient length to provide a perimeter length for a gasket. Each segment is then shaped into a gasket, and the ends of the filament are then bonded together using any of an adhesive, polymeric fusion, a mechanical clamp, or a combination of these. In one embodiment, the segment is cut into a sufficient length so that overlapping end portions of the segment are provided in the gasket where bonding is effected between these end portions along the (curved) elongation axis of the coated wire or coated filament in the gasket.
The examples and other embodiments described herein are exemplary and not intended to be limiting in describing the full scope of compositions and methods of this invention. Equivalent changes, modifications and variations of specific embodiments, materials, compositions and methods may be made within the scope of the present invention, with substantially similar results.

Claims

1. A die for forming a polymerizing fluid polymer into a conduit of shaped polymer, comprising:

(a) a die housing having an inner surface defining an internal cavity, an entrance port for fluid communication of said fluid polymer into said internal cavity, and an exit aperture for forming said fluid polymer into said shaped polymer and for discharging said shaped polymer from said die, said exit aperture in fluid communication with said internal cavity and having a center-point;

(b) a mandrel disposed within said internal cavity to define a generally annular cavity between said inner surface and said mandrel, said mandrel having an axis of elongation and an end positioned to interact with said exit aperture in said forming so that a channel is established in said conduit; and

(c) at least one flow diverter disposed within said annular cavity;

wherein said shaped polymer has a plurality of portions with each portion of said plurality of portions positioned at a unique angular location in polar relation to said center-point, wherein, in operation, said polymerizing fluid polymer is in a first state of polymerization when fluidly communicated through said entrance port into said internal cavity, and said shaped polymer in each said portion is in an independent second state of polymerization when discharged from said exit aperture; and

wherein each said flow diverter is shaped and positioned to provide that all said portions have second states of polymerization that are mutually conformant within a predefined threshold of deviation.

2. A die according to claim 1 wherein at least one said flow diverter has a tear-drop perimeter shape relative to a perpendicular perspective to a general thickness plane of said diverter, said diverter having one angular location on said perimeter and a symmetrical axis extending through said diverter from said angular location, said symmetrical axis in parallel with said axis of elongation for said mandrel, and said angular location positioned as the initial contact point of said diverter to flow of said fluid polymer within said annular cavity.

3. A die according to claim 2 wherein said tear-drop perimeter shape is substantially according to FIG. 5.

4. A die according to claim 2 wherein said flow diverter is attached to said mandrel.

5. A die according to claim 3 wherein said flow diverter is attached to said mandrel.

6. A die according to claim 1 wherein said fluid polymer is a fluid polymer selected from the group of fluid polymers consisting of a thermoplastic elastomer, a thermoplastic vulcanizate, a thermoplastic, a thermoset polymer, an elastomer, and combinations thereof.

7. A die according to claim 1 wherein said mandrel has a conduit channel in parallel with said axis of elongation, and said fluid polymer is disposed upon a pipe progressing through said mandrel, through said end of said mandrel, and through said exit aperture.

8. A die according to claim 7 wherein said pipe is any of a plastic pipe, plastic bar, plastic filament, metal pipe, metal bar, metal filament, ceramic pipe, ceramic bar, and ceramic filament.

9. A die according to claim 6 wherein said fluid polymer further comprises admixed filler of the group of fillers consisting of magnetizable ferrite powder, metal fiber, carbon nanotubes, and combinations thereof.

10. A die according to claim 6 wherein said fluid polymer is selected from the group of fluid polymers consisting of silicone-thermoplastic vulcanizate, nitrile butyl rubber thermoplastic vulcanizate, curable ethylene acrylic rubber thermoplastic vulcanizate, acrylic acid ester rubber/polyacrylate rubber thermoplastic vulcanizate, thermoplastic polyester elastomer polyether-block co-polyamide resins, fluoroelastomer, thermoplastic polyurethane, acrylic acid ester rubber/polyacrylate rubber curable elastomer, ethylene acrylic rubber curable elastomer, nitrile butyl rubber curable elastomer, hydrogenated nitrile butyl rubber curable elastomer, silicone curable elastomer, and combinations thereof.

11. A die according to claim 7 wherein said shaped polymer is a coating on said pipe.

12. A die according to claim 7 wherein at least one said flow diverter has a tear-drop perimeter shape relative to a perpendicular perspective to a general thickness plane of said diverter, said diverter having one angular location on said perimeter and a symmetrical axis extending through said diverter from said angular location, said symmetrical axis in parallel with said axis of elongation for said mandrel, and said angular location positioned as the initial contact point of said diverter to flow of said fluid polymer within said annular cavity.

13. A die according to claim 12 wherein said tear-drop perimeter shape is substantially according to FIG. 5

14. A die according to claim 12 wherein said flow diverter is attached to said mandrel.

15. A die according to claim 13 wherein said flow diverter is attached to said mandrel.

16. A die according to claim 7 wherein said fluid polymer is a fluid polymer selected from the group of fluid polymers consisting of a thermoplastic elastomer, a thermoplastic vulcanizate, a thermoplastic, a thermoset polymer, an elastomer, and combinations thereof.

17. A die according to claim 7 wherein said fluid polymer is selected from the group of fluid polymers consisting of silicone-thermoplastic vulcanizate, nitrile butyl rubber thermoplastic vulcanizate, curable ethylene acrylic rubber thermoplastic vulcanizate, acrylic acid ester rubber/polyacrylate rubber thermoplastic vulcanizate, thermoplastic polyester elastomer polyether-block co-polyamide resins, fluoroelastomer, thermoplastic polyurethane, acrylic acid ester rubber/polyacrylate rubber curable elastomer, ethylene acrylic rubber curable elastomer, nitrile butyl rubber curable elastomer, hydrogenated nitrile butyl rubber curable elastomer, silicone curable elastomer, and combinations thereof.

18. A die according to claim 8 wherein at least one said flow diverter has a tear-drop perimeter shape relative to a perpendicular perspective to a general thickness plane of said diverter, said diverter having one angular location on said perimeter and a symmetrical axis extending through said diverter from said angular location, said symmetrical axis in parallel with said axis of elongation for said mandrel, and said angular location positioned as the initial contact point of said diverter to flow of said fluid polymer within said annular cavity.

19. A die according to claim 18 wherein said tear-drop perimeter shape is substantially according to FIG. 5.

20. A die according to claim 18 wherein said flow diverter is attached to said mandrel.

21. A die according to claim 19 wherein said flow diverter is attached to said mandrel.

22. A die according to claim 8 wherein said fluid polymer is a fluid polymer selected from the group of fluid polymers consisting of a thermoplastic elastomer, a thermoplastic vulcanizate, a thermoplastic, a thermoset polymer, an elastomer, and combinations thereof.

23. A die according to claim 8 wherein said shaped polymer is a coating on said pipe.

24. A die according to claim 9 wherein at least one said flow diverter has a tear-drop perimeter shape relative to a perpendicular perspective to a general thickness plane of said diverter, said diverter having one angular location on said perimeter and a symmetrical axis extending through said diverter from said angular location, said symmetrical axis in parallel with said axis of elongation for said mandrel, and said angular location positioned as the initial contact point of said diverter to flow of said fluid polymer within said annular cavity.

25. A die according to claim 24 wherein said tear-drop perimeter shape is substantially according to FIG. 5.

26. A die according to claim 24 wherein said flow diverter is attached to said mandrel.

27. A die according to claim 25 wherein said flow diverter is attached to said mandrel.

28. A die according to claim 9 wherein said fluid polymer is a fluid polymer selected from the group of fluid polymers consisting of a thermoplastic elastomer, a thermoplastic vulcanizate, a thermoplastic, a thermoset polymer, an elastomer, and combinations thereof.

29. A die according to claim 9 wherein said shaped polymer is a coating on said pipe.

30. A method for forming a polymerizing fluid polymer into a conduit of shaped polymer, comprising extruding said fluid polymer through a die forming said fluid polymer into said shaped polymer and discharging said shaped polymer from said die through an exit aperture having a center-point, said shaped polymer having a plurality of portions with each portion of said plurality of portions positioned at a unique angular location in polar relation to said center-point, wherein, in operation, said polymerizing fluid polymer is in a first state of polymerization when fluidly communicated into said die, and said shaped polymer in each said portion is in an independent second state of polymerization when discharged from said exit aperture, and all said portions have second states of polymerization that are mutually conformant within a predefined threshold of deviation.

31. The method of claim 30 wherein said extruding further comprises diverting flow of said fluid polymer within said die so that, in operation, all said portions are shaped from fluid polymer having an essentially similar residence time within said die.

32. The method of claim 31 wherein said diverting uses at least one flow diverter in said die, at least one said flow diverter having a tear-drop perimeter shape relative to a perpendicular perspective to a general thickness plane of said diverter, said diverter having one angular location on said perimeter and a symmetrical axis extending through said diverter from said angular location, said symmetrical axis in parallel with an axis of elongation for a mandrel of said die, said mandrel disposed within an internal cavity of said die to define a generally annular cavity between an inner surface of said die and said mandrel, said mandrel having an axis of elongation and an end positioned to interact with an exit aperture used in said forming of said extruding so that a channel is established in said conduit, said angular location positioned as the initial contact point of said diverter to flow of said fluid polymer within said annular cavity.

33. The method of claim 30 wherein said tear-drop perimeter shape is substantially according to FIG. 5

34. The method of claim 30 wherein said fluid polymer is a fluid polymer selected from the group of fluid polymers consisting of a thermoplastic elastomer, a thermoplastic vulcanizate, a thermoplastic, a thermoset polymer, an elastomer, and combinations thereof.

35. The method of claim 30 wherein said fluid polymer is selected from the group of fluid polymers consisting of silicone-thermoplastic vulcanizate, nitrile butyl rubber thermoplastic vulcanizate, curable ethylene acrylic rubber thermoplastic vulcanizate, acrylic acid ester rubber/polyacrylate rubber thermoplastic vulcanizate, thermoplastic polyester elastomer polyether-block co-polyamide resins, fluoroelastomer, thermoplastic polyurethane, acrylic acid ester rubber/polyacrylate rubber curable elastomer, ethylene acrylic rubber curable elastomer, nitrile butyl rubber curable elastomer, hydrogenated nitrile butyl rubber curable elastomer, silicone curable elastomer, and combinations thereof.

36. The method of claim 30 wherein extruding disposes said fluid polymer upon a pipe.

37. The method of claim 36 wherein said pipe is any of a plastic pipe, plastic bar, plastic filament, metal pipe, metal bar, metal filament, ceramic pipe, ceramic bar, and ceramic filament.

38. The method of claim 34 wherein said fluid polymer further comprises admixed filler of the group of fillers consisting of magnetizable ferrite powder, metal fiber, carbon nanotubes, and combinations thereof.

39. The method of claim 36 wherein said shaped polymer is a coating on said pipe.

40. A method for forming coated pipe, comprising pultruding a polymerizing fluid polymer onto said pipe through a die forming said fluid polymer into shaped polymer coating for said pipe and discharging said shaped polymer coating from said die onto said pipe through an exit aperture having a center-point, said shaped polymer coating having a plurality of portions with each portion of said portions positioned at a unique angular location in polar relation to said center-point, wherein, in operation, said polymerizing fluid polymer is in a first state of polymerization when fluidly communicated into said die, and said shaped polymer coating in each said portion is in an independent second state of polymerization when discharged from said exit aperture, and all said portions have second states of polymerization that are mutually conformant within a predefined threshold of deviation.

41. The method of claim 40 wherein said pultruding further comprises diverting flow of said fluid polymer within said die so that, in operation, all said portions are shaped from fluid polymer having an essentially similar residence time within said die.

42. The method of claim 41 wherein said diverting uses at least one flow diverter in said die, at least one said flow diverter having a tear-drop perimeter shape relative to a perpendicular perspective to a general thickness plane of said diverter, said diverter having one angular location on said perimeter and a symmetrical axis extending through said diverter from said angular location, said symmetrical axis in parallel with an axis of elongation for a mandrel of said die, said mandrel disposed within an internal cavity of said die to define a generally annular cavity between an inner surface of said die and said mandrel, said mandrel having an end positioned to interact with said exit aperture in discharging shaped coating onto said pipe, said angular location positioned as the initial contact point of said diverter to flow of said fluid polymer within said annular cavity.

43. The method of claim 42 wherein said tear-drop perimeter shape is substantially according to FIG. 5.

44. The method of claim 40 wherein said fluid polymer is a fluid polymer selected from the group of fluid polymers consisting of a thermoplastic elastomer, a thermoplastic vulcanizate, a thermoplastic, a thermoset polymer, an elastomer, and combinations thereof.

45. The method of claim 40 wherein said fluid polymer is selected from the group of fluid polymers consisting of silicone-thermoplastic vulcanizate, nitrile butyl rubber thermoplastic vulcanizate, curable ethylene acrylic rubber thermoplastic vulcanizate, acrylic acid ester rubber/polyacrylate rubber thermoplastic vulcanizate, thermoplastic polyester elastomer polyether-block co-polyamide resins, fluoroelastomer, thermoplastic polyurethane, acrylic acid ester rubber/polyacrylate rubber curable elastomer, ethylene acrylic rubber curable elastomer, nitrile butyl rubber curable elastomer, hydrogenated nitrile butyl rubber curable elastomer, silicone curable elastomer, and combinations thereof.

46. The method of claim 40 wherein said pipe is any of a plastic pipe, plastic bar, plastic filament, metal pipe, metal bar, metal filament, ceramic pipe, ceramic bar, and ceramic filament.

47. The method of claim 44 wherein said fluid polymer further comprises admixed filler of the group of fillers consisting of magnetizable ferrite powder, metal fiber, carbon nanotubes, and combinations thereof.

48. A conduit formed from polymerizing fluid polymer into shaped polymer by a process, comprising extruding said fluid polymer through a die forming said fluid polymer into said shaped polymer and discharging said shaped polymer from said die through an exit aperture having a center-point, said shaped polymer having a plurality of portions with each portion of said portions positioned at a unique angular location in polar relation to said center-point, wherein, in operation, said polymerizing fluid polymer is in a first state of polymerization when fluidly communicated into said die, and said shaped polymer in each said portion is in an independent second state of polymerization when discharged from said exit aperture, and all said portions have second states of polymerization that are mutually conformant within a predefined threshold of deviation.

49. A conduit according to claim 48 wherein said extruding further comprises diverting flow of said fluid polymer within said die so that, in operation, all said portions are shaped from fluid polymer having an essentially similar residence time within said die.

50. A conduit according to claim 49 wherein said diverting uses at least one flow diverter in said die, at least one said flow diverter having a tear-drop perimeter shape relative to a perpendicular perspective to a general thickness plane of said diverter, said diverter having one angular location on said perimeter and a symmetrical axis extending through said diverter from said angular location, said symmetrical axis in parallel with an axis of elongation for a mandrel of said die, said mandrel disposed within an internal cavity of said die to define a generally annular cavity between an inner surface of said die and said mandrel, said mandrel having an axis of elongation and an end positioned to interact with an exit aperture used in said forming of said extruding so that a channel is established in said conduit, said angular location positioned as the initial contact point of said diverter to flow of said fluid polymer within said annular cavity.

51. A conduit according to claim 50 wherein said tear-drop perimeter shape is substantially according to FIG. 5.

52. A conduit according to claim 48 wherein said fluid polymer is a fluid polymer selected from the group of fluid polymers consisting of a thermoplastic elastomer, a thermoplastic vulcanizate, a thermoplastic, a thermoset polymer, an elastomer, and combinations thereof.

53. A conduit according to claim 48 wherein said fluid polymer is selected from the group of fluid polymers consisting of silicone-thermoplastic vulcanizate, nitrile butyl rubber thermoplastic vulcanizate, curable ethylene acrylic rubber thermoplastic vulcanizate, acrylic acid ester rubber/polyacrylate rubber thermoplastic vulcanizate, thermoplastic polyester elastomer polyether-block co-polyamide resins, fluoroelastomer, thermoplastic polyurethane, acrylic acid ester rubber/polyacrylate rubber curable elastomer, ethylene acrylic rubber curable elastomer, nitrile butyl rubber curable elastomer, hydrogenated nitrile butyl rubber curable elastomer, silicone curable elastomer, and combinations thereof.

54. A conduit according to claim 48 wherein extruding disposes said fluid polymer upon a pipe.

55. A conduit according to claim 54 wherein said pipe is any of a plastic pipe, plastic bar, plastic filament, metal pipe, metal bar, metal filament, ceramic pipe, ceramic bar, and ceramic filament.

56. A conduit according to claim 52 wherein said fluid polymer further comprises admixed filler of the group of fillers consisting of magnetizable ferrite powder, metal fiber, carbon nanotubes, and combinations thereof.

57. A conduit according to claim 54 wherein said shaped polymer is a coating on said pipe.

58. A coated pipe formed by a process, comprising pultruding a polymerizing fluid polymer onto said pipe through a die forming said fluid polymer into a shaped polymer coating for said pipe and discharging said shaped polymer coating from said die onto said pipe through an exit aperture having a center-point, said shaped polymer coating having a plurality of portions with each portion of said plurality of portions positioned at a unique angular location in polar relation to said center-point, wherein, in operation, said polymerizing fluid polymer is in a first state of polymerization when fluidly communicated into said die, said shaped coating in each said portion is in an independent second state of polymerization when discharged from said exit aperture, and all said portions have second states of polymerization that are mutually conformant within a predefined threshold of deviation.

59. A coated pipe according to claim 58 wherein said pultruding further comprises diverting flow of said fluid polymer within said die so that, in operation, all said portions are shaped from fluid polymer having an essentially similar residence time within said die.

60. A coated pipe according to claim 59 wherein said diverting uses at least one flow diverter in said die, at least one said flow diverter having a tear-drop perimeter shape relative to a perpendicular perspective to a general thickness plane of said diverter, said diverter having one angular location on said perimeter and a symmetrical axis extending through said diverter from said angular location, said symmetrical axis in parallel with an axis of elongation for a mandrel of said die, said mandrel disposed within an internal cavity of said die to define a generally annular cavity between an inner surface of said die and said mandrel, said mandrel having an end positioned to interact with said exit aperture in discharging shaped coating onto said pipe, said angular location positioned as the initial contact point of said diverter to flow of said fluid polymer within said annular cavity.

61. A coated pipe according to claim 60 wherein said tear-drop perimeter shape is substantially according to FIG. 5.

62. A coated pipe according to claim 58 wherein said fluid polymer is a fluid polymer selected from the group of fluid polymers consisting of a thermoplastic elastomer, a thermoplastic vulcanizate, a thermoplastic, a thermoset polymer, an elastomer, and combinations thereof.

63. A coated pipe according to claim 58 wherein said fluid polymer is selected from the group of fluid polymers consisting of silicone-thermoplastic vulcanizate, nitrile butyl rubber thermoplastic vulcanizate, curable ethylene acrylic rubber thermoplastic vulcanizate, acrylic acid ester rubber/polyacrylate rubber thermoplastic vulcanizate, thermoplastic polyester elastomer polyether-block co-polyamide resins, fluoroelastomer, thermoplastic polyurethane, acrylic acid ester rubber/polyacrylate rubber curable elastomer, ethylene acrylic rubber curable elastomer, nitrile butyl rubber curable elastomer, hydrogenated nitrile butyl rubber curable elastomer, silicone curable elastomer, and combinations thereof.

64. A coated pipe according to claim 58 wherein said pipe is any of a plastic pipe, plastic bar, plastic filament, metal pipe, metal bar, metal filament, ceramic pipe, ceramic bar, and ceramic filament.

65. A coated pipe according to claim 62 wherein said fluid polymer further comprises admixed filler of the group of fillers consisting of magnetizable ferrite powder, metal fiber, carbon nanotubes, and combinations thereof.

66. A die for forming polymerizing fluid polymers into a conduit of multilayer shaped polymer, comprising:

(a) a die housing having a plurality of inner surfaces defining a plurality of internal cavities, an entrance port for fluid communication of a fluid polymer into each internal cavity in said plurality of internal cavities, and an exit aperture for forming said fluid polymers into said shaped polymer and for discharging said shaped polymer from said die, said exit aperture in fluid communication with each said internal cavity and having a center-point, said shaped polymer having a plurality of portions with each portion of said plurality of portions positioned at a unique angular location in polar relation to said center-point, wherein, in operation, each polymerizing fluid polymer of said polymerizing fluid polymers is in a first state of polymerization when fluidly communicated through said entrance port into said internal cavity, and said shaped polymer in each said portion is in an independent second state of polymerization when discharged from said exit aperture;

(b) a plurality of die core-members disposed within said die, each die core-member of said plurality of die core-members defining a generally annular cavity between one of said inner surfaces and one of said die core-members, each die core-member having an axis of elongation; and

(c) at least one flow diverter disposed within at least one of said annular cavities, each disposed flow diverter shaped and positioned to provide that all said portions derived from any one of said fluid polymers have second states of polymerization that are mutually conformant within a predefined threshold of deviation.

67. A die according to claim 66 wherein at least one said disposed flow diverter has a tear-drop perimeter shape relative to a perpendicular perspective to a general thickness plane of said diverter, said diverter having one angular location on said perimeter and a symmetrical axis extending through said diverter from said angular location, said symmetrical axis in parallel with said axis of elongation for said core-member, and said angular location positioned as the initial contact point of said diverter to flow of said fluid polymer within said annular cavity.

68. A die according to claim 67 wherein said tear-drop perimeter shape is substantially according to FIG. 5.

69. A die according to claim 67 wherein said flow diverter is attached to said core-member.

70. A die according to claim 68 wherein said flow diverter is attached to said core-member.

71. A die according to claim 66 wherein each of said fluid polymers is a fluid polymer selected from the group of fluid polymers consisting of a thermoplastic elastomer, a thermoplastic vulcanizate, a thermoplastic, a thermoset polymer, an elastomer, and combinations thereof.

72. A die according to claim 66 wherein each of said fluid polymers is selected from the group of fluid polymers consisting of silicone-thermoplastic vulcanizate, nitrile butyl rubber thermoplastic vulcanizate, curable ethylene acrylic rubber thermoplastic vulcanizate, acrylic acid ester rubber/polyacrylate rubber thermoplastic vulcanizate, thermoplastic polyester elastomer polyether-block co-polyamide resins, fluoroelastomer, thermoplastic polyurethane, acrylic acid ester rubber/polyacrylate rubber curable elastomer, ethylene acrylic rubber curable elastomer, nitrile butyl rubber curable elastomer, hydrogenated nitrile butyl rubber curable elastomer, silicone curable elastomer, and combinations thereof.

73. A die according to claim 66 wherein one said die core-member is a mandrel having a conduit channel in parallel with the axis of elongation for said mandrel, and each of said fluid polymers is disposed as a coating in a multilayer coating upon a pipe progressing through said mandrel, through said end of said mandrel, and through said exit aperture.

74. A die according to claim 73 wherein said pipe is any of a plastic pipe, plastic bar, plastic filament, metal pipe, metal bar, metal filament, ceramic pipe, ceramic bar, and ceramic filament.

75. A die according to claim 71 wherein said fluid polymer further comprises admixed filler of the group of fillers consisting of magnetizable ferrite powder, metal fiber, carbon nanotubes, and combinations thereof.

76. A die according to claim 73 wherein said shaped polymer is a coating on said pipe.

77. A die according to claim 73 wherein at least one said flow diverter has a tear-drop perimeter shape relative to a perpendicular perspective to a general thickness plane of said diverter, said diverter having one angular location on said perimeter and a symmetrical axis extending through said diverter from said angular location, said symmetrical axis in parallel with the axis of elongation for said core-member, and said angular location positioned as the initial contact point of said diverter to flow of said fluid polymer within said annular cavity.

78. An encoder made by a process, comprising:

(a) pultruding a polymerizing fluid polymer with admixed magnetizable ferrite powder onto a pipe through a die forming said fluid polymer with admixed magnetizable ferrite powder into a shaped polymer coating for said pipe and discharging said shaped polymer coating from said die onto said pipe through an exit aperture having a center-point, said shaped polymer coating having a plurality of portions with each portion of said plurality of portions positioned at a unique angular location in polar relation to said center-point, wherein, in operation, said polymerizing fluid polymer with admixed magnetizable ferrite powder is in a first state of polymerization when fluidly communicated into said die, said shaped coating in each said portion is in an independent second state of polymerization when discharged from said exit aperture, and all said portions have second states of polymerization that are mutually conformant within a predefined threshold of deviation;

(b) cooling said shaped polymer coating to solidify said shaped polymer coating and provide coated pipe of said shaped polymer on said pipe, said coated pipe having an elongation axis; and

(c) cutting said coated pipe in a plane perpendicular to said elongation axis to provide said encoder.

79. A gasket made by a process, comprising:

(a) pultruding a polymerizing fluid polymer onto a wire through a die forming said fluid polymer into a shaped polymer coating for said wire and discharging said shaped polymer coating from said die onto said wire through an exit aperture having a center-point, said shaped polymer coating having a plurality of portions with each portion of said plurality of portions positioned at a unique angular location in polar relation to said center-point, wherein, in operation, said polymerizing fluid polymer is in a first state of polymerization when fluidly communicated into said die, said shaped coating in each said portion is in an independent second state of polymerization when discharged from said exit aperture, and all said portions have second states of polymerization that are mutually conformant within a predefined threshold of deviation;

(b) cooling said shaped polymer coating to solidify said shaped polymer coating and provide coated wire of said shaped polymer on said wire, said coated wire having an elongation axis;

(c) cutting said coated wire in a plane perpendicular to said elongation axis to provide at least one coated wire segment, each said segment having a first end portion and a second end portion; and

(d) fusing said first end portion to said second end portion to provide said gasket.

80. A method for forming a polymerizing fluid polymer into a conduit of shaped polymer, comprising:

(a) designing a first die design for an extrusion die to extrude said fluid polymer into said shaped polymer for said conduit, said die forming said fluid polymer into said shaped polymer and discharging said shaped polymer from said die through an exit aperture having a center-point, said shaped polymer having a plurality of portions with each portion of said plurality of portions positioned at a unique angular location in polar relation to said center-point, wherein, in operation, said polymerizing fluid polymer is in a first state of polymerization when fluidly communicated into said die, and said shaped polymer in each said portion is in an independent second state of polymerization when discharged from said exit aperture, said first die design providing a flow diverter in said die wherein said flow diverter is shaped and positioned to provide that all said portions have second states of polymerization that are mutually conformant within a desired predefined threshold of deviation;

(b) constructing a first extrusion die according to said first die design;

(c) extruding said fluid polymer through said first extrusion die to form said polymer into shaped polymer;

(d) measuring said second state of polymerization in each said portion of said shaped polymer, a deviation among all said second states of polymerization, and a comparison of said measured deviation to said desired predefined threshold of deviation; and

(e) iteratively repeating said designing, constructing, extruding, and measuring for a subsequent die design to replace said first die design until said measured deviation is less than said desired predefined threshold of deviation, wherein each instance of said designing in said iteratively repeating uses said comparison in said designing of said subsequent die design.