GB2585448A

GB2585448A - Long pipes with reduced defects and method of production

Info

Publication number: GB2585448A
Application number: GB2005600.8A
Authority: GB
Inventors: Mullineaux Nicholas; Simmonite James
Original assignee: Victrex Manufacturing Ltd
Current assignee: Victrex Manufacturing Ltd
Priority date: 2019-04-17
Filing date: 2020-04-17
Publication date: 2021-01-13
Anticipated expiration: 2040-04-17
Also published as: GB2585448A8; EP3956133A1; BR112021019390A2; WO2020212704A1; GB2585448B; GB202005600D0; GB201905432D0

Abstract

The present invention relates to a very long pipe formed in a single extrusion process from polyaryletherketone (PAEK) family, such as polyetheretherketone (PEEK). Such pipes are manufactured by passing a pipe through a calibrating device, said device having two or more cooling zones, the first cooling zone having cooling fluid at 60° or less, the second cooling zone having cooling fluid at 127-150°C, and wherein vacuum sizing is applied to the pipe as it passes through the calibration device.

Description

LONG PIPES WITH REDUCED DEFECTS AND METHOD OF PRODUCTION

The present invention relates to very long pipes formed in a single extrusion process from certain types of thermoplastic polymer where such pipes are manufactured in a way that delivers a particularly low occurrence of certain types of defect or weakness. The invention further relates to a process for forming such long polymer pipes in a single extrusion process without such defects or weaknesses. For example, such defects could include an area of the pipe wall that has a wall thickness that is too high or too low vs a desired specification or a section of pipe where the outside diameter is too high or too low versus a desired specification.

Pipes formed from thermoplastic polymers -for example a polyaryletherketone (PAEK) polymer such as polyetheretherketone (PEEK) may be of value in a range of industries, including the oil, gas and aerospace sectors. In such sectors it can be especially useful to have an extremely long length of pipe that is formed from a single extrusion process rather than being made from many smaller pipes connected by some form of joint. Such polymer pipes would need to have a range of high-specification properties in order to be deemed acceptable for use in, for example, certain oil and gas applications. Prior to the present invention the inventors suggest it has been very difficult to extrude long lengths of pipes from PAEK or similar polymers, because unacceptable defects tend to occur increasingly over time during the long extrusion processes. In general, in the broader technical field of thermoplastic pipe extrusions, pipe defects can sometimes occur because of die drool. But with the extrusion of very long pipes made from PAEK and similar polymers, the present inventors believe that many of the troublesome pipe defects they encountered did not seem to be simply attributable to die drool issues. In this context, defects may include areas of pipe wall that are too thick or too thin vs intended specification, or areas of pipe where the outside diameter of the pipe is too large or too small vs intended specification. A further form of defect can be where a particular cross-section of a pipe is found to be deviated too much from the intended circular shape. In some technology applications it can also be important to achieve a polymer pipe that also exhibits good stability to certain types of chemicals. After extensive studies, the present inventors have now established a method of manufacture for the above-mentioned long pipes that addresses a number of the above-mentioned problems.

Therefore, the present inventors contend that the process of the present invention allows the formation of high specification extruded polymer pipes, using PAEK and similar polymers, in long continuous lengths that have hitherto not been achievable.

W02012/107753 Al describes a process and apparatus for producing a PEEK pipe having a length greater than 250 metres. The process of the present invention also uses a calibrator device similar to that described in W02012/107753 Al.

One aspect of the present invention is the provision of certain long thermoplastic polymer pipes, formed in a single extrusion process, where the pipes have especially low variability in wall thickness along the full length of the finished pipe. It is possible to measure the wall thickness of a pipe along multiple axes, and several times per second, using inline measuring apparatus during the manufacture process, or afterwards. One way of expressing the low wall thickness variability that is achieved in a given pipe is by determining the difference between the maximum and minimum wall thickness measurements after taking thousands or millions of wall thickness measurements from along the full length of the finished pipe. A further aspect of the invention is a process for manufacture of such pipes, described in more detail hereinafter.

Accordingly, in the first aspect of the invention there is provided a pipe having a length of at least 275 metres, wherein the pipe has a composition comprising one or more polymeric materials each comprising: (a) phenylene moieties; (b) ether and/or thioether moieties; and optionally (c) ketone and/or sulfone moieties; wherein the wall that defines the pipe has a minimum thickness and a maximum thickness, each defined in millimetres, wherein the minimum thickness is in the range from 0.7mm to 7mm; and wherein the maximum thickness is not greater than (1.5 x the minimum thickness) + 0.5mm.

In some embodiments the minimum thickness is in the range from 0.8mm to 7mm.

In some embodiments the minimum thickness is in the range from 0.7mm to 6.5mm.

In some embodiments the minimum thickness is in the range from 0.7mm to 4.5mm.

In some embodiments the minimum thickness is in the range from 0.8mm to 4.5mm.

In some embodiments, in relation to the wall that defines the pipe, the maximum thickness is not greater than (1.4 x the minimum thickness) + 0.5mm.

In some embodiments, in relation to the wall that defines the pipe, the maximum thickness is not greater than (1.35 x the minimum thickness) + 0.5mm.

In some embodiments, in relation to the wall that defines the pipe, the maximum thickness is not greater than (1.3 x the minimum thickness) + 0.5mm.

In some embodiments, in relation to the wall that defines the pipe, the maximum thickness is not greater than (1.25 x the minimum thickness) + 0.6mm.

In some embodiments, in relation to the wall that defines the pipe, the maximum thickness is not greater than (1.2 x the minimum thickness) + 0.6mm.

In some embodiments the minimum and maximum thicknesses of the pipe are determined from at least 100 separate thickness measurements per meter length of pipe.

In some embodiments the maximum and minimum thicknesses of the pipe are determined from at least 250 separate thickness measurements per meter length of pipe.

In some embodiments the maximum and minimum thicknesses of the pipe are determined from at least 400 separate thickness measurements per meter length of pipe.

A further aspect of the invention is the provision of certain long thermoplastic polymer pipes, formed in a single extrusion process, where the pipes have especially low variability in the outside diameter along the full length of the finished pipe. It is possible to measure the outside diameter of a pipe using inline measuring apparatus several times per second during the manufacturing process (or afterwards). For example, the outside diameter measurements can be carried out in three directions simultaneously, at 120° relative to each other within the cross-sectional plane of the pipe. One way of expressing the low variability in outside diameter is by determining the difference between the maximum and minimum outside diameters measured along the full length of finished pipe. A further aspect of the invention is a process for manufacture of such pipes.

Accordingly, in one aspect of the invention there is provided a pipe having a length of at least 275m, wherein the pipe has a composition comprising one or more polymeric materials each comprising: (a) phenylene moieties; (b) ether and/or thioether moieties; and optionally (c) ketone and/or sulfone moieties; wherein the pipe has a minimum outside diameter and a maximum outside diameter, each defined in millimetres, wherein the minimum outside diameter is in the range from 4mm to 350mm; and wherein the maximum outside diameter is not greater than the higher of (1) 1.03 x the minimum outside diameter; and (2) the minimum outside diameter + 0.35mm.

In some embodiments the minimum outside diameter is in the range from 5mm to 320mm.

In some embodiments the minimum outside diameter is in the range from 5mm to 310mm.

In some embodiments, the maximum outside diameter is not greater than the higher of: (1) 1.025 x the minimum outside diameter; and (2) the minimum outside diameter + 0.35mm.

In some embodiments, the maximum outside diameter is not greater than the higher of: (1) 1.02 x the minimum outside diameter; and (2) the minimum outside diameter + 0.35mm.

In some embodiments, the maximum outside diameter is not greater than the higher of (1) 1.015 x the minimum outside diameter; and (2) the minimum outside diameter + 0.35mm.

In some embodiments, the maximum outside diameter is not greater than the higher of: (1) 1.012 x the minimum outside diameter; and (2) the minimum outside diameter + 0.35mm.

In some embodiments, the maximum outside diameter is not greater than the higher of: (1) 1.012 x the minimum outside diameter; and (2) the minimum outside diameter + 0.3mm.

In some embodiments the minimum outside diameter and maximum outside diameter are determined from a set of at least 1000 outside diameter measurements from different positions along the length of the pipe.

In some embodiments the minimum outside diameter and maximum outside diameter are determined from a set of at least 10000 outside diameter measurements from different positions along the length of pipe.

In some embodiments the minimum outside diameter and maximum outside diameter are determined from a set of at least 50000 outside diameter measurements from different positions along the length of pipe.

In some embodiments the minimum and maximum outside diameter measurements of the pipe are determined using at least 100 separate outside diameter measurements per metre length of pipe.

In some embodiments the minimum and maximum outside diameter measurements of the pipe are determined using at least 250 separate outside diameter measurements per metre length of pipe.

In some embodiments the minimum and maximum outside diameter measurements of the pipe are determined using at least 400 separate outside diameter measurements per metre length of pipe.

One aspect of the current invention is a process (described hereinafter) that can provide a very long length of extruded pipe where the above-defined avoidance of wall thickness defects is achieved simultaneously with the above-defined avoidance of outside-diameter defects in the pipe that is produced.

Therefore, in one embodiment of the invention there is provided a pipe having a length of at least 275 metres, wherein the pipe has a composition comprising one or more polymeric materials each comprising: (a) phenylene moieties; (b) ether and/or thioether moieties; and optionally (c) ketone and/or sulfone moieties; wherein the wall that defines the pipe has a minimum thickness and a maximum thickness, each defined in millimetres, wherein the minimum thickness is in the range from 0.5mm to 7mm; and wherein the maximum thickness is not greater than (1.5 x minimum thickness) + 0.5mm; and wherein the pipe has a minimum outside diameter and a maximum outside diameter, each defined in millimetres, wherein the minimum outside diameter is in the range from 4mm to 350mm; and wherein the maximum outside diameter not greater than the higher of (1) 1.03 x the minimum outside diameter; and (2) the minimum outside diameter + 0.35mm.

The formation of such high specification pipes involves an extrusion process where the initial polymer material extruded during equipment set-up may not have the form of a pipe and thereafterthe extrusion may need to continue for a little time before the operator can be confident that the processing line is settled and that good quality pipe is being extruded. In this context it will be appropriate to take the raw polymeric extrusion and cut off the initial section and also cut off a later section in order to deliver a pipe having the technical specifications of the current invention.

Accordingly, in this specification, the "pipe" is to be taken as the segment (or segments) of quality pipe that is/are cut (or could be cut) from a longer 'unfinished' polymeric extrusion, and the measurement and evaluation of technical parameters discussed in this specification should be considered in that context.

Accordingly, in one aspect of the invention there is provided an unfinished polymeric extrusion having a length which includes within its length a portion that forms a pipe, wherein the portion that forms a pipe has a length of at least 275 metres, wherein the raw polymeric extrusion (including the portion that forms a pipe) has a composition comprising one or more polymeric materials each comprising: (a) phenylene moieties; (b) ether and/or thioether moieties; and optionally (c) ketone and/or sulfone moieties; wherein the wall that defines the pipe has a minimum thickness and a maximum thickness, each defined in millimetres, wherein the minimum thickness is in the range from 0.5mm to 7mm; and wherein the maximum thickness is not greater than (1.5 x the minimum thickness) + 0.5mm.

Accordingly, in one aspect of the invention there is provided an unfinished polymeric extrusion having a length which includes within its length a portion that forms a pipe, wherein the portion that forms a pipe has a length of at least 275 metres, wherein the raw polymeric extrusion (including the portion that forms a pipe) has a composition comprising one or more polymeric materials each comprising: (a) phenylene moieties; (b) ether and/or thioether moieties; and optionally (c) ketone and/or sulfone moieties; wherein the pipe has a minimum outside diameter and a maximum outside diameter, each defined in millimetres, wherein the minimum outside diameter is in the range from 4mm to 350mm; and wherein the maximum outside diameter is not greater than the higher of: (1) 1.03 x the minimum outside diameter; and (2) the minimum outside diameter + 0.35mm.

Accordingly, in one aspect of the invention there is provided an unfinished polymeric extrusion having a length which includes within its length a portion that forms a pipe, wherein the portion that forms a pipe has a length of at least 275 metres, wherein the raw polymeric extrusion (including the portion that forms a pipe) has a composition comprising one or more polymeric materials each comprising: (a) phenylene moieties; (b) ether and/or thioether moieties; and optionally (c) ketone and/or sulfone moieties; wherein the wall that defines the pipe has a minimum thickness and a maximum thickness, each defined in millimetres, wherein the minimum thickness is in the range from 0.5mm to 7mm; and wherein the maximum thickness is not greater than (1.5 x minimum thickness) + 0.5mm; and wherein the pipe has a minimum outside diameter and a maximum outside diameter, each defined in millimetres, wherein the minimum outside diameter is in the range from 4mm to 350mm; and wherein the maximum outside diameter not greater than the higher of (1) 1.03 x the minimum outside diameter; and (2) the minimum outside diameter + 0.35mm.

As mentioned hereinabove, the process of the present invention uses a calibrator device similar to that described in W02012/107753 A1. One aspect of the present invention provides particularly beneficial conditions for using a calibrator device that can deliver a very long length of extruded pipe (where the pipe contains a PAEK or similar type of polymer) where the above-mentioned avoidance of wall thickness defects is achieved simultaneously with the above-defined avoidance of outside-diameter defects in the long length of pipe that is produced. More specifically, this aspect of the invention relates to the use of a calibrator device to receive hot newly-extruded polymer pipe, where the first plate of the calibrator that comes into contact with the hot extruded pipe is cooled by heat-transfer fluid at a temperature of 60°C or lower, and later plate(s) of the calibrator are maintained at a temperature in the range from 127°C to 150°C. In this context, the 127°C-150°C temperature range refers to the temperature at (or very close to) the surface of the calibrator in the regions that closely surround the hot pipe as it passes through the calibrator, rather than it being, for example, the set temperature of any heat transfer fluid used to achieve the above-mentioned target temperature range. For example, in some cases it may be possible that heat-transfer fluid at a temperature of 95°C may nevertheless achieve a temperature in the range of 127-150°C at the surface of the calibrator in the region closely surrounding the hot pipe as it passes through the calibrator. The temperature of the calibrator -in the regions of the calibrator that are very close to the hot pipe -can be measured using one or more small thermocouple device(s) built in to the calibrator. The temperature of heat-transfer fluid required to achieve the intended 127°C-150°C temperature range may vary according to the temperature of the pipe being extruded, and how much or little it has been cooled during its transit through the first temperature-controlled region of the calibrator device. A pipe with a thicker wall will likely retain more heat than a pipe with a thinner wall, so that a cooler heat transfer fluid (and/or higher flow rate) may be more appropriate to achieve the target temperature range when making thicker-walled pipes. The use of the above-mentioned thermocouple device(s) is/are recommended so that the skilled person can easily determine an appropriate set temperature for their heat transfer fluid in order to achieve the target temperatures at the calibrator surface (127-150°C) for any particular pipe extrusion that they intend to achieve. This can be done during the early part of the extrusion process while adjustments are still being made to the production line as part of normal production line set-up. The use of such temperature-controlled conditions with a calibrator device for pipe manufacture has surprisingly led to the various beneficial effects described above in the resulting pipes, which are particularly of value when trying to manufacture very long lengths of extruded pipe without any of the troublesome dimensional defects arising.

In one aspect of the invention the pipe (as described herein) passes the chemical stability test as described hereinafter as Test A. Accordingly, this aspect of the invention provides a process for making a pipe (for example a pipe as described herein), the process comprising: (i) using a calibrator device which includes an elongate opening for receiving a hot extruded pipe, wherein the elongate opening includes a vacuum applying region arranged to apply a vacuum to the outer surface of the pipe within the elongate opening, said device further comprises two or more temperature-controlled regions spaced apart along the length of the calibrator, said temperature controlled regions being arranged to apply a cooling effect to the pipe as it passes through the elongate opening, said calibrator device being in contact with one or more heat transfer fluids so as to assist said cooling effect on the pipe in each of the two or more temperature-controlled regions; (ii) introducing at least 275m of hot extruded pipe into the elongate opening of the calibrator and conveying the pipe through the elongate opening; while (iii) applying a vacuum to the outer surface of the pipe as it passes through the calibrator; wherein (iv) the temperature of the heat-transfer fluid used for the first temperature-controlled region to come into contact with the hot extruded pipe is 60°C or lower; (v) the temperature of the surface of the calibrator surrounding the pipe in the subsequent temperature-controlled region(s) is/are in the range of 127°C to 150°C; and wherein (vi) the pipe has a composition comprising one or more polymeric materials each comprising: (a) phenylene moieties; (b) ether and/or thioether moieties; and optionally (c) ketone and/or sulfone moieties.

In one embodiment the temperature of the surface of the calibrator surrounding the pipe in the subsequent temperature-controlled region(s) of the calibrator is/are in the range of 128°C to 145°C.

In one embodiment the process involves introducing at least 1000m of hot extruded pipe into the elongate opening. In one embodiment the aforementioned length is at least 2000m. In one embodiment the aforementioned length is at least 3000m.

In addition to the two or more temperature-controlled regions as described herein, the calibrator may also comprise further region(s) which may be temperature-controlled or might be left to equilibrate at whatever temperature naturally results from the hot pipe passing by. In particular, the additional region(s) could be situated after the "subsequent temperature-controlled region(s)" mentioned in step (v) of the process described above. If such additional region(s) are themselves temperature-controlled to some degree, they will typically be at temperatures lower than used in the "subsequent temperature-controlled region(s)" mentioned in step (v) of the above-mentioned process.

A suitable heat transfer fluid is conveniently a thermally-stable non-viscous liquid around the temperatures it experiences during use in the process. For example, the heat transfer agent may be water provided that the operating temperatures are less than 100°C. Alternatively an oil may be used as a heat transfer agent. Preferably a suitable heat transfer agent flows against one or more hot surfaces of the calibrator and then away from the calibrator in order to efficiently and continuously transfer heat away from a hot pipe as it is being conveyed through the elongate opening of the calibrator.

In this specification, it is to be understood that "subsequent" in the term "subsequent temperature-controlled region(s)" makes reference to the fact that a pipe being extruded and passing through the calibrator will first make contact with the first temperature-controlled region, and then the "subsequent temperature-controlled region(s)" are positioned suitably close and in suitable alignment so that any portion of the pipe being conveyed through the first temperature controlled region will very soon experience and be present within the "subsequent temperature-controlled region(s)".

In one embodiment as the hot extruded pipe travels through the calibrator, any given segment of the pipe is present within the first temperature-controlled region of the calibrator for a time period in the range from 0.25 to 6 seconds. In one embodiment this range is 0.3 to 5 seconds. In one embodiment this range is 0.3 to 4 seconds.

In one embodiment as the hot extruded pipe travels through the calibrator, any given segment of the pipe is present within the subsequent temperature-controlled region(s) for at least 2 seconds. In another embodiment this period is at least 3 seconds. In another embodiment this period is at least 4 seconds. In one embodiment this period is at least 5 seconds. In one embodiment this period is at least 6 seconds.

Further details and embodiments of the invention are described below. It is intended that any two or more aspects, embodiments or claims listed hereinabove or hereinbelow may be combined in any possible way (unless the context does not permit) to provide further aspects, embodiments and/or potential claims.

In the process described herein, a vacuum refers to the use of a reduced pressure that may be achieved using a normal vacuum pump. The vacuum for use in the process of the present invention may be in the range of 70 mbar to 300 mbar, for example 100 mbar to 200 mbar.

The pipe of the present invention may be extruded using a composition comprising a single polymeric material, or from a mixture of two or more polymeric materials. As explained hereinafter, the composition may include one or more fillers and/or colouring materials etc. A suitable solvent material for the process is a polar aprotic solvent that is a liquid at the elevated temperature used for the extrusion process, for example, a diarylsulfone, for example diphenylsulfone. The elongate opening of the calibrator device preferably includes a tapered mouth at the end of the elongate opening where the hot extruded pipe is received. The use of a mould-release agent [mold-release agent (in USA-English)] on the calibrator device in the area where a hot extruded pipe is received may be beneficial.

In one embodiment there is provided a process for making a pipe (for example a pipe as described herein), the process comprising: (i) using a calibrator device which includes an elongate opening for receiving a hot extruded pipe, wherein the elongate opening includes a vacuum applying region arranged to apply a vacuum to the outer surface of the pipe within the elongate opening, said device further comprises two or more temperature-controlled regions spaced apart along the length of the calibrator, said temperature controlled regions being arranged to apply a cooling effect to the pipe as it passes through the elongate opening, said calibrator device being in contact with one or more heat transfer fluids so as to assist said cooling effect on the pipe in each of the one or more temperature controlled regions; (ii) applying a mould release agent to the mouth of the elongate opening where a hot extruded pipe is to be received; then (iii) introducing at least 275m of hot extruded pipe into the elongate opening of the calibrator and conveying the pipe through the elongate opening; while (iv) applying a vacuum to the outer surface of the pipe as it passes through the calibrator; wherein (v) the temperature of heat-transfer fluid used for the first temperature-controlled region to come into contact with the hot extruded pipe is 60°C or lower; (vi) the temperature the surface of the calibrator surrounding the pipe in the subsequent temperature-controlled region(s) is/are in the range of 127°C to 150°C; and wherein (vii) the pipe has a composition comprising one or more polymeric materials each comprising: (d) phenylene moieties; (e) ether and/or thioether moieties; and optionally (f) ketone and/or sulfone moieties.

A thin insulating plate may be beneficially installed in between portions of the calibrator device held at different temperatures, to reduce heat exchange between the two zones and thereby achieve greater control over the temperature profile experienced by the newly extruded hot pipe during its transition through the calibrator.

Accordingly, one aspect of the invention provides a process for making a pipe (for example a pipe as described herein), as described above, wherein the calibrator device further comprises a heat insulating means arranged to reduce heat exchange between the two or more temperature-controlled regions of the calibrator device during use.

Therefore, one embodiment of the invention provides a process for making a pipe (for example a pipe as described herein), the process comprising: (i) using a calibrator device which includes an elongate opening for receiving a hot extruded pipe, wherein the elongate opening includes a vacuum applying region arranged to apply a vacuum to the outer surface of the pipe within the elongate opening, said device further comprises two or more temperature-controlled regions spaced apart along the length of the calibrator, said temperature controlled regions being arranged to apply a cooling effect to the pipe as it passes through the elongate opening, wherein the calibrator device further comprises a heat insulating means arranged to reduce heat exchange between the two or more temperature-controlled regions of the calibrator device during use, said calibrator device being in contact with one or more heat transfer fluids so as to assist said cooling effect on the pipe in each of the two or more temperature-controlled regions; (ii) introducing at least 275m of hot extruded pipe into the elongate opening of the calibrator and conveying the pipe through the elongate opening; while (iii) applying a vacuum to the outer surface of the pipe as it passes through the calibrator; wherein (iv) the temperature of the heat-transfer fluid used for the first temperature-controlled region to come into contact with the hot extruded pipe is 60°C or lower; (v) the temperature of the surface of the calibrator surrounding the pipe in the subsequent temperature-controlled region(s) is/are in the range of 127°C to 150°C; and wherein (vi) the pipe has a composition comprising one or more polymeric materials each comprising: (g) phenylene moieties; (h) ether and/or thioether moieties; and optionally (i) ketone and/or sulfone moieties.

In one embodiment the elongate opening of the calibrator has a circular profile.

In one embodiment the elongate opening of the calibrator has a width between 0.5cm to 35cm. In one embodiment the elongate opening of the calibrator has a circular profile wherein the diameter of the circle is between 0.5cm and 35cm.

In one embodiment the elongate opening of the calibrator has a width between 0.6cm and 31cm.

In one embodiment the elongate opening of the calibrator has a circular profile wherein the diameter of the circle is between 0.6cm and 31cm.

One aspect of the invention provides a pipe (as defined according to any definitions, embodiments or claims herein) formed by the process (as defined according to any definitions, embodiments, or claims herein).

Therefore, in one aspect there is provided a pipe having a length of at least 275 metres, formed by a process comprising: (i) using a calibrator device which includes an elongate opening for receiving a hot extruded pipe, wherein the elongate opening includes a vacuum applying region arranged to apply a vacuum to the outer surface of the pipe within the elongate opening, said device further comprises two or more temperature-controlled regions spaced apart along the length of the calibrator, said temperature controlled regions being arranged to apply a cooling effect to the pipe as it passes through the elongate opening, said calibrator device being in contact with one or more heat transfer fluids so as to assist said cooling effect on the pipe in each of the two or more temperature-controlled regions; (ii) introducing at least 275m of hot extruded pipe into the elongate opening of the calibrator and conveying the pipe through the elongate opening; while (iii) applying a vacuum to the outer surface of the pipe as it passes through the calibrator; wherein (iv) the temperature of the heat-transfer fluid used for the first temperature-controlled region to come into contact with the hot extruded pipe is 60°C or lower; (v) the temperature of the surface of the calibrator surrounding the pipe in subsequent temperature-controlled region(s) is/are in the range of 127°C to 150°C; and wherein (vi) the pipe has a composition comprising one or more polymeric materials each comprising: (j) phenylene moieties; (k) ether and/or thioether moieties; and optionally (I) ketone and/or sulfone moieties.

One aspect of the invention provides an unfinished polymeric extrusion (as defined according to any definitions, embodiments or claims herein) formed by the process (as defined according to any definitions, embodiments or claims herein).

Conveniently the calibrator device is made of a metal, for example stainless steel or brass. An example of a suitable calibrator design is shown in the figures and description of W02012/107753 which is incorporated herein by reference. The temperature of the hot extruded polymer used in the process described herein may vary according to the specific polymer being used and the skilled person will appreciate that a suitable temperature is, for example, a little above (e.g. 20°C to 50°C above) the melting temperature of the polymer. For example, when extruding polyetheretherketone polymer (PEEK) a temperature in the range from 370°C to 410°C may be suitable.

In one embodiment the temperature of the first temperature-controlled region to come into contact with the hot extruded pipe is in the range from 0°C to 60°C. In another embodiment this range is from 5°C to 60°C. In another embodiment this range is from 8°C to 58°C. In another embodiment this range is from 5°C to 58°C. In another embodiment this range is from 20°C to 58°C. In one embodiment this range is from 30°C to 58°C. In one embodiment this range is from 35°C to 58°C.

In one embodiment, air flow is directed onto a first surface of the calibrator device. Optionally, deionized air is directed onto the first face of the calibrator device. The first surface of the calibrator may be a front plate.

In one embodiment the pipe comprises one or more polymeric materials each comprising (a) phenylene moieties; (b) ether moieties and optionally (c) ketone moieties.

In one embodiment the pipe comprises one or more polymeric materials each comprising (a) phenylene moieties; (b) ether moieties and (c) ketone moieties.

In one embodiment any polymeric material has a repeat unit of formula (I):

E-EA

and/or a repeat unit of formula (10: and/or a repeat unit of formula (Ill): 0 SO G 0 soZ 0 1/ /t wherein: m, r, s, t, v, w and z each independently represent zero or a positive integer; E and E' each independently represent -0-, -S-or a direct bond; G represents -0-, -3-, a direct bond or -0-phenylene-0-; and Ar is -phenylene-C(0)-phenylene-, -phenylene-C(CH3)2-phenylene-, -phenylene-O-(1,4phenylene)-0-phenylene-, -phenylene-or-phenylene-C(0)-phenylene-C(0)-phenylene-.

In some embodiments the phenylene groups mentioned in this specification are 1,4-linked to adjacent groups.

In one embodiment where Ar is -phenylene-C(0)-phenylene-C(0)-phenylene-the central phenylene may be 1,3-or 1,4-substituted to the adjacent carbonyl groups.

In one embodiment where Ar is -phenylene-C(0)-phenylene-C(0)-phenylene-the central phenylene is 1,4-substituted to the adjacent carbonyl groups.

In one embodiment, the polymeric material may comprise a repeat unit of formula (I) and no other repeat units. In one embodiment the polymeric material may be polyphenylenesulphide. In one embodiment, the polymeric material may include more than one different type of repeat unit of formula (0; and more than one different type of repeat unit of formula (10; and more than one different type of repeat unit of formula (111).

In one embodiment the polymeric material only includes repeat units of formula (I).

In one embodiment the polymeric material only includes repeat units of formula (II). In one embodiment the polymeric material only includes repeat units of formula (Ill).

In one embodiment the polymeric material has repeat units consisting essentially of repeat units of formula (I), (II) and/or (III).

In some embodiments the phenylene groups in units of formula (I), (II) and (III) are not additionally substituted. In some embodiments the phenylene groups in units of formula (I), (II) and (III) are not cross-linked.

Where w and/or z is/are greater than zero, each phenylene may independently be 1,4-or 1,3-linked to adjacent atoms in the repeat units of formula (II) and/or (III).

In some embodiments where w and/or z is/are greater than zero, each phenylene is 1,4-linked.

In one embodiment G represents -0-, a direct bond or a -O-phenylene-0-group.

In one embodiment G is a direct bond.

"a", "b" and "c" can be defined to represent the mole% of units of formula (I), (II) and (III) respectively within the polymeric material.

In one embodiment each unit of formula (I) in said polymeric material is the same.

In one embodiment each unit of formula (II) in said polymeric material is the same.

In one embodiment each unit of formula (III) in said polymeric material is the same.

In one embodiment a is 20 or less. In one embodiment a is 10 or less. In one embodiment a is 5 or less. In one embodiment a is in the range from 45 to 100. In one embodiment a is in the range from 45 to 55. In one embodiment a is in the range from 48 to 52. In one embodiment b+c is in the range from 0 to 55. In one embodiment b+c is in the range from 45 to 55. In one embodiment b+c is in the range from 48 to 52. In one embodiment a/(b+c) is in the range from 0.9 to 1.1. In one embodiment a/(b+c) is about 1. In one embodiment a+b+c is at least 90. In one embodiment a+b+c is at least 95. In one embodiment a+b+c is at least 99. In one embodiment a+b+c is about 100. In one embodiment b is at least 20. In one embodiment b is at least 40. In one embodiment b is at least 45.

In one embodiment the polymeric material comprises repeat units where at least 98% of said repeat units consist essentially of moieties (I), (II) and/or (III).

In one embodiment the polymeric material comprises a homopolymer having a repeat unit of general formula (IV): E4Ar, 0 1m E 0 CO 0 -HG //\.. 0 IV m A \ /w OH-co

I /B

or a homopolymer having a repeat unit of general formula (V): so2 0 )D v or a random or block copolymer formed from at least two different units of (IV) and/or (V), wherein: A and B each represent 0 or 1, wherein at least one of A and B is 1; C and D each represent 0 or 1, wherein at least one of C and D is 1; and E, E', G, Ar, m, r, s, t, v, w and z are each as defined according to any statement herein.

In one embodiment m is an integer in the range from 0 to 3. In one embodiment m is 0, 1 or 2. In one embodiment m is 0 or 1. In one embodiment r is an integer in the range from 0 to 3. In one embodiment r is 0, 1 or 2. In one embodiment r is 0 or 1. In one embodiment t is an integer in the range from 0 to 3. In one embodiment t is 0, 1 or2. In one embodiment t is 0 or 1. In one embodiment s is 0 or 1. In one embodiment v is 0 or 1. In one embodiment w is 0 or 1. In one embodiment z is 0 or 1. In one embodiment the polymeric material is a homopolymer having a repeat unit of general formula (IV).

In one embodiment Ar is -(1,4-phenylene)-C(0)-(1,4-phenylene)-, -(1,4-phenylene)-O-(1,4- phenylene)-O-(1,4-phenylene)-, -(1,4-phenylene)-C(CH3)2-(1,4-phenylene)- -(1,4-phenylene)-C(0)-phenylene-C(0)-(1,4-phenylene)-or -(1,4-phenylene)-.

In one embodiment the middle phenylene group of -(1,4-phenylene)-C(0)-phenylene-C(0)-(1,4-phenylene)-may be 1,3-or 1,4-linked. In one embodiment it is 1,4-linked.

In one embodiment Ar is -phenylene-C(0)-phenylene-, -phenylene-, -phenylene-0-(1,4-phenylene)-0-phenylene-or -phenylene-C(0)-phenylene-C(0)-phenylene-.

In one embodiment Ar is -phenylene-C(0)-phenylene-C(0)-phenylene-, -phenyleneor -phenylene-C(0)-phenylene-.

In one embodiment Ar is -(1,4-phenylene)-C(0)-phenylene-C(0)-(1,4-phenylene)-, -(1,4- phenylene)-C(0)-(1,4-phenylene)-, -(1,4-phenylene)-O-(1,4-phenylene)-O-(1,4-phenylene)-or -(1,4-phenylene)-.

In one embodiment Ar is -(1,4-phenylene)-C(0)-phenylene-C(0)-(1,4-phenylene)-, -(1,4-phenylene)-C(0)-(1,4-phenylene)-or -(1,4-phenylene)-.

In one embodiment the polymeric material includes at least 60mole% of repeat units which do not include -S-or-SO2-moieties. In one embodiment the polymeric material includes at least 70mole% of repeat units which do not include -S-or-502-moieties. In one embodiment the polymeric material includes at least 80mole% of repeat units which do not include -S-or -802-moieties. In one embodiment the polymeric material includes at least 90mole% of repeat units which do not include -5-or -502-moieties.

In one embodiment the polymeric material comprises at least 60mole% of repeat units which consist essentially of phenylene moieties, ether moieties and ketone moieties. In one embodiment the polymeric material comprises at least 70mole% of repeat units which consist essentially of phenylene moieties, ether moieties and ketone moieties. In one embodiment the polymeric material comprises at least 80mole% of repeat units which consist essentially of phenylene moieties, ether moieties and ketone moieties. In one embodiment the polymeric material comprises at least 90mole% of repeat units which consist essentially of phenylene moieties, ether moieties and ketone moieties.

In one embodiment the polymeric material(s) (potentially including co-polymers) comprises repeat units that consist essentially of phenylene moieties in conjunction with ketone and/or ether moieties.

In one embodiment the polymeric material does not include repeat units which include -S-or-SO2-moieties nor aromatic groups other than phenylene.

In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (IV) wherein Ar is -phenylene-, E and E' are each -0-, m = 0, w = 1, G is a direct bond, s = 0, and A and B are each 1. (i.e. polyetheretherketone).

In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (IV) wherein E is -0-, E' is a direct bond, Ar is -phenylene-C(0)-phenylene-C(0)-phenylene-, m = 0, A = 1 and B = 0. (i.e. polyetherketone). In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (IV) wherein E is -0-, Ar is -phenylene-C(0)-phenylene-C(0)-phenylene-, m = 0, E' is a direct bond, A = 1 and B = 0. (i.e. polyetherketoneketone).

In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (IV) wherein Ar is -phenylene-C(0)-phenylene-C(0)-phenylene-, E and E' are both -0-, G is a direct bond, m = 0, w = 1, r = 0, s = 1, and A and B are both 1. (i.e. 15 polyetherketoneetherketoneketone).

In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (IV), wherein Ar is -phenylene-, E and E' are both -0-, G is a direct bond, m = 0, w = 0 and s, r, A and B are all 1. (i.e. polyetheretherketoneketone).

In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (IV), wherein Ar is -phenylene-, E and E' are both -0-, m = 1, w = 1, A = 1, B = 0, and G is a direct bond (i.e. polyetherdiphenyletherketone).

In one embodiment the main peak of the melting endotherm (Tm) for said polymeric material may be at least 300°C.

In one embodiment the polymeric material comprises a repeat unit of formula (XX): (XX) wherein t1 = 0 or 1, w1 = 0 or 1 and v1 represents 0, 1 or 2.

In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (XX).

In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (XX) wherein t1 = 0 or 1, w1 = 0 or 1 and wl represents 0, 1 or 2. In one embodiment the polymeric material comprises a repeat unit of formula (XX) wherein t1=1, v1=0 and w1=0.

In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (XX) wherein t1=1, v1=0 and w1=0.

In one embodiment the polymeric material comprises a repeat unit of formula (XX) wherein t1=0, v1=0 and w1=0.

In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (XX) wherein t1=0, v1=0 and w1=0.

In one embodiment the polymeric material comprises a repeat unit of formula (XX) wherein t1=0, w1=1 and v1=2.

In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (XX) wherein t1=0, w1=1 and v1=2.

In one embodiment the polymeric material comprises a repeat unit of formula (XX) wherein t1=0, v1=1 and w1=0.

In one embodiment the polymeric material has at least 98% of its repeat units consisting essentially of formula (XX) wherein t1=0, v1=1 and w1=0.

In one embodiment the polymeric material comprises a repeat unit of formula (XX) wherein t1=1, v1=0 and w1=0.

In one embodiment the polymeric material comprises polyetheretherketone polyetherketone, polyetherketoneetherketoneketone, polyetherketoneketone or polyetherdiphenyletherketone In one embodiment the polymeric material is selected from polyetheretherketone polyetherketone, polyetherketoneetherketoneketone, polyetherketoneketone and polyetherdiphenyletherketone.

In one embodiment the polymeric material comprises polyetherketone or polyetheretherketone.

In one embodiment the polymeric material is polyetherketone or polyetheretherketone.

In one embodiment the polymeric material comprises polyetheretherketone.

In one embodiment the polymeric material is polyetheretherketone.

In one embodiment the pipe comprises a composition which includes said polymeric material and one or more fillers.

In one embodiment the pipe may consist essentially of a composition which consists essentially of said polymeric material and one or more fillers.

In one embodiment the polymeric material makes up at least 60wt°/0 of the total thermoplastic polymeric material in the composition from which the pipe is made. In another embodiment the above-mentioned figure is at least 70wt%. In another embodiment the above-mentioned figure is at least 80wt%. In another embodiment the above-mentioned figure is at least 90wt%. In another embodiment the above-mentioned figure is at least 95wt%.

A single polymeric material (as described herein) is preferably substantially the only thermoplastic polymer in said composition. Suitably, a reference to a thermoplastic polymer refers to a polymer which is melted in the formation of said pipe.

A filler is suitably a material which is not melted during the manufacture of said pipe. Said filler suitably has a melting temperature greater than 350°C and preferably greater than 400°C.

Said filler may include a fibrous filler or a non-fibrous filler. Said filler may include both a fibrous filler and a non-fibrous filler. A said fibrous filler may be continuous or discontinuous. A said fibrous filler may be selected from inorganic fibrous materials, non-melting and high-melting organic fibrous materials, such as aramid fibres, and carbon fibre. A said fibrous filler may be selected from glass fibre, carbon fibre, asbestos fibre, silica fibre, alumina fibre, zirconia fibre, boron nitride fibre, silicon nitride fibre, boron fibre, fluorocarbon resin fibre and potassium titanate fibre. Preferred fibrous fillers are glass fibre and carbon fibre. A fibrous filler may comprise nanofibres.

However, such a filler (particularly a fibrous filler) could detrimentally increase the roughness on the inside of the pipe and therefore reduce fluid flow through the pipe in use.

A said non-fibrous filler may be selected from mica, silica, talc, alumina, kaolin, calcium sulfate, calcium carbonate, titanium oxide, ferrite, clay, glass powder, zinc oxide, nickel carbonate, iron oxide, quartz powder, magnesium carbonate, fluorocarbon resin, graphite, polybenzimidazole (PBI), carbon powder, nanotubes and barium sulfate. The non-fibrous fillers may be introduced in the form of powder or flaky particles.

Said filler may comprise one or more fillers selected from glass fibre, carbon fibre, carbon black and a fluorocarbon resin. In one embodiment said filler comprises glass fibre or carbon, especially discontinuous, for example chopped, glass fibre or carbon fibre.

In one embodiment the composition includes 35-100wt°/0 of said polymeric material. In one embodiment the composition includes 50-100wt% of said polymeric material. In one embodiment the composition includes 65-100w1°./0 of said polymeric material. In one embodiment the composition includes at least 90wt% of said polymeric material.

In one embodiment the composition includes at least 95wt% of said polymeric material.

In one embodiment the composition includes at least 98wt% of said polymeric material.

In one embodiment the composition does not include a reinforcing filler (e.g. carbon fibre) but may include a non-reinforcing filler (e.g. talc or carbon black). Such a non-reinforcing filler may be included to reduce costs and/or to colour the pipe.

In one embodiment the total amount of filler in the composition is 65wt% or less. In one embodiment the total amount of filler in the composition is 50vvt% or less.

In one embodiment the total amount of filler in the composition is 35wt% or less.

In one embodiment the total amount of filler in the composition is lOvvt°/0 or less.

In one embodiment the total amount of filler in the composition is 7.5wt% or less.

In one embodiment the total amount of filler in the composition is 5wt% or less.

In one embodiment the total amount of filler in the composition is 5wt% or less and includes carbon black.

In one embodiment the composition includes carbon black as a filler.

In one embodiment the total amount of filler in the composition is 2.5wt% or less. In one embodiment the total amount of filler in the composition is 1wt% or less. In one embodiment the composition includes substantially no filler.

In one embodiment the composition includes at least 95%wt of said polymeric material and at least 0.1wt% of a non-fibrous filler that is carbon black.

In one embodiment the composition includes at least 98%wt of said polymeric material and at least 0.1wt% of a non-fibrous filler that is carbon black.

In one embodiment the pipe consists essentially of a polymeric material where at least 98% of its repeat units are of the formula (XX).

In one embodiment the pipe has a composition that consists essentially of a polymeric material where at least 98% of its repeat units are of the formula (XX) together with one or more fillers where the total amount of filler in the composition is 5wt% or less.

The incorporation of carbon black into the composition provides a pipe that works particularly well in any subsequent process where other materials are laser-welded onto the outside surface of the pipe. Accordingly, in one embodimentthe pipe has a composition where between 0.05wt% and 5wt% of the composition is a filler that is carbon black. In one embodiment this range is 0.05wt% to 2.5wt%. In another embodiment this range is 0.05wt% to 1.5wt%. In one embodiment this range is 0.05wt% to 1wt%.

In one embodiment the pipe consists essentially of a polymeric material which is polyetheretherketone together with one or more fillers where the total amount of filler in the composition is 5wt% or less.

In one embodiment the pipe has a composition consisting essentially of a polymeric material which is polyetheretherketone together with carbon black where the carbon black is between 0.05wt% and 5wt% of the composition. In one embodiment this range is 0.05wt% to 2.5wt%. In another embodiment this range is 0.05wt% to 1.5wt%. In one embodiment this range is 0.05wt% to 1wt%.

In this specification, when referring to a pipe or length of a pipe, this refers to a pipe that is extruded/extrudable in a single extrusion process, rather than the length being formed from two or more individual pipe sections that are joined together.

Accordingly, in any embodiment the pipe comprises a single extrusion.

In some embodiments the pipe comprises a single extrusion and has a substantially constant cross-section along its entire length.

In one embodiment the pipe has a length of at least 500m.

In one embodiment the pipe has a length of at least 1km. In one embodiment the pipe has a length of at least 1.5km. In one embodiment the pipe has a length of at least 2km. In one embodiment the pipe has a length of at least 2.5km.

In one embodiment the pipe has a length of at least 3km.

In one embodiment the pipe has a length of at least 3.5km.

In one embodiment the pipe has a length of at least 4km.

In one embodiment the pipe has a substantially constant cross-section along its entire length.

In one embodiment the pipe has an annular cross-section, for example a circular cross-section.

In some embodiments the elongate opening of the calibrator device has an annual cross-section, for example a circular cross-section.

The pipe produced according to this invention may be used as one continuous length or may be cut into shorter lengths (for example 0.5m, 1 m, 5m) fortechnology applications that require such shorter lengths.

The outside diameter of a pipe may be defined as "d" cm and the thickness of the pipe wall may be defined as "t" cm. Accordingly the diameter to thickness ratio (d/t) can be defined for a pipe. In some embodiments the diameter to thickness ratio of the pipe is at least 6.

In some embodiments the diameter to thickness ratio of the pipe is in the range from 6 to 40. In some embodiments the diameter to thickness ratio of the pipe is in the range from 15 to 40.

In one aspect of the invention, the pipe (as described herein) is part of an assembly which comprises said pipe as an inner part and is surrounded by an outer part, said outer part being arranged around substantially all of the outer wall of the pipe and being arranged to reinforce the pipe. In a further embodiment of this assembly, the outer part of the assembly comprises a first material and a second material, the first material comprising a thermoplastic or thermosetting polymer and said second material comprising a fibrous material. In one embodiment the first material comprises a thermoplastic polymer. In one embodiment this thermoplastic polymer comprises a PAEK polymer. In one embodiment it comprises polyetheretherketone polymer. In some embodiments the second material comprises a fibrous material wherein the fibrous material is carbon fibre. In some embodiments of this aspect of the invention the outer part comprises greater than ten layers which are overlaying each other.

Experimental Details Measurement of Pipe Wall Thickness The thickness of the pipe wall may be measured using inline measuring equipment as a pipe is fed through the equipment at a suitably slow speed relative to the measuring frequency of the equipment. Such inline measuring equipment can take accurate measurements several times per second and such data is preferably then stored on a computer to permit further scrutiny and analysis. Such inline thickness measuring equipment is commercially available. The wall thickness measuring equipment used for the Examples of this application (see below) simultaneously measured the wall thickness along 8 different axes spaced evenly around the circumference of the pipe, several times per second as the pipe moved through the device.

Measurement of Outside Diameter of the Pipe The outside diameter of the pipe may be measured using inline measuring equipment as a pipe is fed through the equipment at a suitably slow speed relative to the measuring frequency of the equipment. Such inline measuring equipment can take accurate measurements several times per second and in several different orientations. For example, the equipment used for the Examples described hereinbelow measures the outside diameter along three different axes simultaneously -each axis at 120° relative to the others in the plane of the cross section of the pipe. such data is preferably then stored on a computer to permit further scrutiny and analysis.

Such inline thickness measuring equipment is commercially available.

Chemical Stability -Test A Chemical stability may be measured according to the following method: A ring of a pipe is cut from a pipe selected for testing. The ring is then cut in half to provide a half ring. The half ring is then immersed in methylethylketone whilst being loaded so as to slightly bend the specimen.

The half ring is left in a loaded state immersed in the methylethylketone (MEK) for 24 hours and is then removed. It is then assessed under the microscope, looking for presence or absence of microscopic cracks or other structural defects on the surface of the half ring that have arisen during the test.

Examples

The following tables show Examples of pipes each made from a polymer as defined herein, in each case as one continuous extrusion according to the parameters of the present invention.

The table also includes some Comparative Examples, showing that pipes formed using parameters outside the claimed invention suffer with multiple dimensional defects that in many cases can be obvious through simple visual inspection.

Example Number Pipe Length (m) Temperature of heat Was calibrator internal surface transfer fluid used in 1st region of calibrator (°C) temperature in the range 127-150°C in subsequent region(s)? 1 2200 45 Yes 2 2600 45 Yes 3 300 55 Yes 4 2250 35 Yes Comparative 1 >300* 20 No Comparative 2 >300* 20 No Comparative 3 >300* 15 No * The pipe lengths marked ">300m" in the table above are Comparative Examples where the overall length was not recorded because the main objective of the manufacturing run was not to end up with one very long pipe, but instead to chop the long, extruded pipe into many discrete lengths of pipe as it was produced from the extrusion line. In this situation all the dimensionally defective sections of pipe (identified by visual inspection) were chopped out and disposed of and the good sections of pipe were retained.

Wall thickness and outside diameter measurements were taken for the above Examples using the inline measuring techniques described above to provide the data in the table below. The "Variation" values were calculated by simply subtracting the minimum data point from the maximum data point for a given pipe.

Example Number Wall thickness data (mm) Outside Diameter data (mm) Min Max Variation Min Max Variation 1 1.12 1.52 0.4 15.69 15.83 0.14 2 1.03 1.6 0.57 15.37 15.66 0.29 3 1.82 2.13 0.31 77.84 78.67 0.83 4 1.94 2.09 0.15 50.99 51.48 0.49 Comparative 1 Numerous defects obvious by visual inspection -no in-line data Comparative 2 Numerous defects obvious by visual inspection -no in-line data Comparative 3 Numerous defects obvious by visual inspection -no in-line data The inventors have found that pipes formed according to the invention parameters described herein are generally expected to pass the MEK chemical stability test ("Test A") described above.

Claims

Claims 1. A pipe having a length of at least 275 metres, wherein the pipe has a composition comprising one or more polymeric materials each comprising: (a) phenylene moieties; (b) ether and/or thioether moieties; and optionally (c) ketone and/or sulfone moieties; wherein the wall that defines the pipe has a minimum thickness and a maximum thickness, each defined in millimetres, wherein the minimum thickness is in the range from 0.7mm to 7mm; and wherein the maximum thickness is not greater than (1.5 x the minimum thickness) + 0.5mm.
2. A pipe having a length of at least 275m, wherein the pipe has a composition comprising one or more polymeric materials each comprising: (a) phenylene moieties; (b) ether and/or thioether moieties; and optionally (c) ketone and/or sulfone moieties; wherein the pipe has a minimum outside diameter and a maximum outside diameter, each defined in millimetres, wherein the minimum outside diameter is in the range from 4mm to 350mm; and wherein the maximum outside diameter is not greater than the higher of: (1) 1.03 x the minimum outside diameter; and (2) the minimum outside diameter + 0.35mm.
3. The pipe as claimed in claim 1, wherein the pipe also has a minimum outside diameter and a maximum outside diameter, each defined in millimetres, wherein the minimum outside diameter is in the range from 4mm to 350mm; and wherein the maximum outside diameter not greater than the higher of: (1) 1.03 x the minimum outside diameter; and (2) the minimum outside diameter + 0.35mm. 30
4. The pipe according to claim 1 or claim 3 wherein the maximum thickness of the wall that defines the pipe is not greater than (1.35 x the minimum thickness) + 0.5mm.
5. The pipe according to claim 2 or claim 3 wherein the maximum outside diameter of the pipe is not greater than the higher of: (1) 1.02 x the minimum outside diameter; and (2) the minimum outside diameter + 0.35mm.
6. The pipe according to any of claims 1 to 5 wherein the pipe has a length of at least 1km.
7. The pipe according to any of claims 1 to 6 wherein the pipe has a length of at least 2km.
8. The pipe according to any preceding claim wherein the pipe comprises a composition comprising a repeat unit of formula (9: and/or a repeat unit of formula (10: CO 0 and/or a repeat unit of formula (110: 02 0 wherein: m, r, s, t, v, w and z each independently represent zero or a positive integer; E and E each independently represent -0-, -S-or a direct bond; G represents -0-, -S-, a direct bond or -0-phenylene-0-; and Ar is -phenylene-C(0)-phenylene-, -phenylene-C(CH3)2-phenylene-, -phenylene-0-(1,4-phenylene)-0-phenylene-, -phenylene-or -phenylene-C(0)-phenylene-C(0)-phenylene-.
9. A pipe according to any preceding claim wherein the pipe has a composition comprising one or more polymeric materials where at least 90mole% of the repeat units of the one or more polymeric materials do not include -S-or -SO2-moieties.
10. A pipe according to any preceding claim wherein the pipe has a composition comprising one or more polymeric materials each comprising a repeat unit of formula (XX): (XX) wherein t1 = 0 or 1, w1 = 0 or 1 and vl represents 0, 1 or 2.
11. A pipe according to any preceding claim wherein the pipe has a composition comprising one polymeric material which is polyetheretherketone.
12. An unfinished polymeric extrusion having a length, which includes within its length a portion that forms a pipe, wherein the pipe is defined according to any preceding claim.
13. A process for making a pipe, the process comprising: (i) using a calibrator device which includes an elongate opening for receiving a hot extruded pipe, wherein the elongate opening includes a vacuum applying region arranged to apply a vacuum to the outer surface of the pipe within the elongate opening, said device further comprises two or more temperature-controlled regions spaced apart along the length of the calibrator, said temperature controlled regions being arranged to apply a cooling effect to the pipe as it passes through the elongate opening, said calibrator device being in contact with one or more heat transfer fluids so as to assist said cooling effect on the pipe in each of the two or more temperature-controlled regions; (ii) introducing at least 275m of hot extruded pipe into the elongate opening of the calibrator and conveying the pipe through the elongate opening; while (iii) applying a vacuum to the outer surface of the pipe as it passes through the calibrator; wherein (iv) the temperature of the heat-transfer fluid used for the first temperature-controlled region to come into contact with the hot extruded pipe is 60°C or lower; (v) the temperature of the surface of the calibrator surrounding the pipe in the subsequent temperature-controlled region(s) is/are in the range of 127°C to 150°C; and wherein (vi) the pipe has a composition comprising one or more polymeric materials each comprising: (a) phenylene moieties; (b) ether and/or thioether moieties; and optionally (c) ketone and/or sulfone moieties.
14. The process as claimed in claim 13 wherein at least 1000m of hot extruded pipe is introduced into the elongate opening of the calibrator or wherein at least 2000m of hot extruded pipe is introduced into the elongate opening of the calibrator.
15. The process according to claim 13 or 15, wherein the process further includes directing air onto a front plate of the calibrator device, preferably, the air is deionized air.
16. The process according to any of claims 13 to 15 wherein the pipe has a composition comprising a repeat unit of formula (I):E-EAand/or a repeat unit of formula (19: and/or a repeat unit of formula (119: wherein: 17. 18. 19. 20.m, r, s, t, v, w and z each independently represent zero or a positive integer; E and E' each independently represent -0-, -S-or a direct bond; G represents -0-, -S-, a direct bond or -0-phenylene-0-; and Ar is -phenylene-C(0)-phenylene-, -phenylene-C(CH3)2-phenylene-, -phenylene-0-(1,4-phenylene)-0-phenylene-, -phenylene-or -phenylene-C(0)-phenylene-C(0)-phenylene-.The process according to any of claims 13 to 16 wherein the pipe has a composition comprising one or more polymeric materials where at least 90mole% of the repeat units of the one or more polymeric materials do not include -S-or -802-moieties.The process according to any of claims 13 to 17 wherein the pipe has a composition comprising one polymeric material which is polyetheretherketone.The process according to any of claims 13 to 18 wherein the calibrator device further comprises a heat insulating means arranged to reduce heat exchange between the two or more temperature-controlled regions of the calibrator during use.A pipe as defined according to any one of claims 1 to 11, formed by a process as described in any of claims 13 to 19.