EP3956381A1

EP3956381A1 - Improved pipe and method of production

Info

Publication number: EP3956381A1
Application number: EP20721709.2A
Authority: EP
Inventors: Nicholas MULLINEAUX; James SIMMONITE; Gayle SIMPSON; Geoff Small
Original assignee: Victrex Manufacturing Ltd
Current assignee: Victrex Manufacturing Ltd
Priority date: 2019-04-17
Filing date: 2020-04-17
Publication date: 2022-02-23
Also published as: GB2585449B; BR112021019085A2; GB2585449A8; GB202005608D0; WO2020212706A1; GB201905431D0; GB2585449A

Abstract

The present invention relates to certain types of polymer pipes (e.g. polyaryletherketone pipes and similar polymers containing sulfone groups) having a particularly beneficial (i.e. low) level of residual stress within their structure and at the same time a beneficially low variability in residual stress levels along the length of the pipe. The invention further relates to a process for forming such high specification polymer pipes.

Description

IMPROVED PIPE AND METHOD OF PRODUCTION

The present invention relates to certain types of polymer pipes having a particularly beneficial (i.e. low) level of residual stress within their structure and at the same time a beneficially low variability in residual stress levels along the full length of the pipe. The invention further relates to a process for forming such high specification polymer pipes.

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 for example. One aspect of the present invention is the provision of certain thermoplastic polymer pipes having a particularly low residual stress level that the inventors believe has not been previously achieved in such pipes - and at the same time, achieving very low variability in residual stress along the length of a pipe. The inventors have also established conditions that provide a certain beneficial level of chemical stability in the pipes that are formed. Low residual stress in a polymer pipe can afford several technical advantages - for example, when a pipe is cut to size, low residual stress in the pipe reduces the problem of the pipe shattering outwards, or cracking from the line of the intended cut. Furthermore, a pipe with lower residual stress will be less prone to failure through fatigue, slow crack propagation or physical impact and be more suitable for use in situations where the pipe carries high pressure fluid or is subject to high external forces. Achieving a low variability in residual stress levels all along the length of a pipe can provide a number of technical benefits. For example, it may avoid locally increased stresses which could act as initiation sites for failure. It may also minimise or completely avoid unwanted bends in different places along the length of the pipe. Furthermore, ensuring consistent properties may assist subsequent processing - for example a process to bond composite laminates onto the outer surface of the pipe. The invention further provides pipes that also exhibit good stability against exposure to certain types of chemicals. Such chemical-resistant and consistently low stress pipes may be attractive for use in the oil and gas industries, aerospace industry and other industrial sectors where high specification pipes are of particular value.

WO2012/107753 A1 describes a process and apparatus for producing a polyetheretherketone (PEEK) pipe having a length greater than 250 metres and a residual stress of less than 5MPa. Example 1 of WO2012/107753 A1 reports an 8 inch pipe with a residual stress measurement of 1 .64MPa.

The process of the present invention also uses a calibrator device like the one described in WO2012/107753. One aspect of the present invention provides particularly beneficial conditions for using a calibrator device that delivers an extruded polymer pipe having especially low residual stress levels and where the low stress level shows little variation along the entire length of the pipe. More specifically the invention relates to the use of a calibrator where the first plate of the calibrator is in contact with a heat-transfer fluid at a temperature of 60°C or lower, and later plate(s) of the calibrator is/are in contact with a heat-transfer fluid which is at a temperature in the range of 80°C to 150°C. Use of such conditions has surprisingly led to a particularly low residual stress level in the resulting pipe product, and furthermore, where the particularly low stress level shows little variation as measured at different places along the length of the pipe. Such conditions also deliver pipes with a high degree of resistance to certain types of chemical, as described in more detail later. The residual stress present in a pipe can be expressed as an absolute value of circumferential residual stress within the pipe in question. As mentioned above, residual stress in pipes can be problematic when above certain levels as it can contribute to and exacerbate slow crack growth in the pipe. From an engineering perspective it can be important to keep residual stress as low as possible when making or sourcing pipes. When talking about residual stress levels in polymer pipes, the significance of a given residual stress level is best appreciated by reference to the tensile strength (Omax) of material from the pipe. For example, a certain numerical level of stress in a pipe of lower tensile strength will be more detrimental than that same numerical level of stress in a pipe of higher tensile strength. Therefore, it may be more meaningful to express residual stress of a pipe as a function of the tensile strength of polymer taken from the pipe. Expressing residual stress in this way / Omax) provides a normalising factor for all polymers within the same polymer‘family’ which may have somewhat different mechanical properties. In this application the terms“Absolute Residual Stress” and“Relative Residual Stress” / Omax) may be used in some places to more clearly refer to the different forms of residual stress data. Examples are provided below for some pipes made from two different polymers as an illustration of this principle:

The improved manufacturing process of the present invention can achieve particularly low levels of relative residual stress / Omax) - for example 1 .5% or lower in the pipes that are formed, in combination with a low level of stress variability (maximum - minimum), with absolute residual stress variability less than 0.4MPa and more typically 0.2MPa along the length of the pipe. Furthermore, the process of the present invention can deliver pipes with good levels of stability to certain types of chemical, for example, stability against a powerful organic solvent such as methylethylketone (MEK) as described in more detail hereinafter. Accordingly, in one aspect of the invention provides a pipe having a length of at least 1 metre, 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 residual stress of the pipe, as measured in at least three different places located along the length of the pipe, divided by the tensile strength of the composition of the pipe, is less than or equal to 1 .4%; and wherein the difference between the maximum and minimum values of residual stress in the pipe, as measured in at least three different places located along the length of the pipe, is less than 0.4 MPa.

In one embodiment there is provided a pipe having a length of at least 1 metre, 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 residual stress of the pipe divided by the tensile strength of the composition of the pipe is less than or equal to 1 .4%; and wherein the difference between the maximum and minimum values of residual stress in the pipe is less than 0.4 MPa.

In some embodiments the residual stress of the pipe is measured according to Test Method A or Test Method B (defined hereinafter). In some embodiments the tensile strength of the composition of the pipe is measured according to Test Method C (defined hereinafter). In some embodiments the pipe passes the chemical stability test described in Test Method D (defined hereinafter).

In one embodiment the thickness of the wall that defines the pipe is from 0.6mm to 6mm

In one embodiment the thickness of the wall that defines the pipe is from 0.6mm to 4.5mm.

In one embodiment the thickness of the wall that defines the pipe is from 0.8mm to 4.5mm.

In one embodiment the residual stress of the pipe divided by the tensile strength of the composition of the pipe is less than or equal to 1 .35%.

In one embodiment the residual stress of the pipe divided by the tensile strength of the composition of the pipe is less than or equal to 1 .3%.

In one embodiment the residual stress of the pipe divided by the tensile strength of the composition of the pipe is less than or equal to 1 .25%. In one embodiment the difference between the maximum and minimum values of residual stress in the pipe, as measured in at least three different places located along the length of the pipe, is less than 0.35 MPa. In a further embodiment this value is less than 0.3 MPa. In a further embodiment this value is less than 0.25 MPa. In a further embodiment this value is less than 0.2MPa. In a further embodiment this value is less than 0.175MPa. In a further embodiment this value is less than 0.15MPa.

In some embodiments the difference between the maximum and minimum values of residual stress in the pipe, as measured in at least 5 different places located along the length of the pipe, is less than 0.4 MPa (or other value as may be mentioned herein).

In some embodiments the measurements in at least 3 different places along the length of the pipe are places that are at least 30cm apart from each other.

In some embodiments the measurements in at least 3 different places along the length of the pipe are places that are spaced apart from each other by at least 30% of the length of the pipe.

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 thereafter the 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 & 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 1 metre, 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 residual stress of the portion that forms a pipe, as measured in at least three different places located along the length of the pipe, divided by the tensile strength of the composition of the portion that forms the pipe, is less than or equal to 1 .4%; and wherein the difference between the maximum and minimum values of residual stress in the portion that forms a pipe, as measured in at least three different places located along the length of the pipe, is less than 0.4 MPa.

In one embodiment there is provided a raw 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 1 metre, wherein the raw polymeric extrusion (including the portion that forms a 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;

wherein the residual stress of the portion that forms a pipe divided by the tensile strength of composition of the portion that forms the pipe is less than or equal to 1.4%; and wherein the difference between the maximum and minimum values of residual stress in the portion that forms a pipe is less than 0.4 MPa.

A further 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 a 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 heat-transfer fluid used for the subsequent temperature- controlled region(s) is/are in the range of 80°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 addition to the two or more temperature-controlled regions whose heat-transfer fluid is temperature-controlled 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. For example, the additional region(s) could be situated after the“subsequent temperature-controlled region(s)” mentioned in step (v) of the process described above, or might be positioned in between the“first temperature controlled- region” and the“subsequent temperature-controlled region(s)” as mentioned in steps (iv) and (v) in 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, 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, 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 a 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 of heat-transfer fluid used for the subsequent temperature- controlled region(s) is/are in the range of 80°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 calibrator device for use in the process of manufacture of a pipe as described herein, said calibrator device comprising 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 a 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.

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 a hot extruded pipe into the elongate opening of the calibrator and conveying the pipe through the elongate opening; while

(a) phenylene moieties;

(b) ether and/or thioether moieties; and optionally

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

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 1 metre, formed by a process comprising:

(ii) introducing a 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

(a) phenylene moieties;

(b) ether and/or thioether moieties; and optionally

(c) 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 WO2012/107753 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 57°C. In another embodiment this range is from 5°C to 57°C.

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): and/or a repeat unit of formula (II):

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 -O-phenylene-O-; and

Ar is -phenylene-C(0)-phenyiene-, -phenylene-C(CH3)₂-phenylene-, -phenylene-0-(1 ,4- phenylene)-0-phenyiene-, -phenylene- or -phenylene-C(0)-phenyiene-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)-phenyiene-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)-phenyiene-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 (I); and more than one different type of repeat unit of formula (II); and more than one different type of repeat unit of formula (III). 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 (III). 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-O- 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):

or a homopolymer having a repeat unit of general formula (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 or 2. 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)-0-(1 ,4- phenylene)-0-(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-phenyiene- or -phenylene-C(0)-phenylene-C(0)-phenylene-.

In one embodiment Ar is -phenylene-C(0)-phenylene-C(0)-phenylene·, -phenylene- or -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)-0-(1 ,4-phenylene)-0-(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 -SC>2- moieties. In one embodiment the polymeric material includes at least 70mole% of repeat units which do not include -S- or -SC>2- moieties. In one embodiment the polymeric material includes at least 80mole% of repeat units which do not include -S- or -SO2- moieties. In one embodiment the polymeric material includes at least 90mole% of repeat units which do not include -S- or -SO2- 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 materials) (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 -SC>2- 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. 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):

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 v1 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 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 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 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% 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.

Preferably, said filler comprises one or more fillers selected from glass fibre, carbon fibre, carbon black and a fluorocarbon resin. More preferably, 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% of said polymeric material.

In one embodiment the composition includes 50-100wt% of said polymeric material.

In one embodiment the composition includes 65-100wt% 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 50wt% 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 10wt% 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 1 wt% 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 embodiment the 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 herein, the pipe comprises a single extrusion.

In a further embodiment the pipe comprises a single extrusion, has substantially constant cross- section along its entire length and has a length of at least 100m.

In one embodiment the pipe has a length of at least 5m.

In one embodiment the pipe has a length of at least 10m.

In one embodiment the pipe has a length of at least 50m.

In one embodiment the pipe has a length of at least 100m.

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

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

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 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) for technology applications that require such shorter lengths.

In some embodiments the pipe has an outside diameter of at least 0.6cm.

In some embodiments the pipe has an outside diameter of at least 2.5cm.

In some embodiments the pipe has an outside diameter of at least 7cm.

In some embodiments the pipe has an outside diameter of at least 10cm.

In some embodiments the pipe has an outside diameter of at least 15cm.

In some embodiments the pipe has an outside diameter of less than 50cm.

In some embodiments the pipe has an outside diameter of less than 40cm.

In some embodiments the pipe has an outside diameter of less than 30cm.

In some embodiments the pipe has an outside diameter in the range from 0.5cm to 35cm. In some embodiment the pipe has an outside diameter in the range from 0.6cm to 31 cm.

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. In one aspect of the invention, the pipe (as described herein) is pulled through a heated or cooled die, post extrusion. The diameter of the die may be no less than 95% of the pipe outside diameter, for example, the diameter of the die may be from 95% the diameter of the pipe to 99.9% the diameter of the pipe. In one example, the die may be from 96% the diameter of the die to 98% the diameter of the die. It has been surprisingly found that a pipe being passed or pulled through a die post extrusion exhibits a significant reduction in residual stress.

Experimental Details

Measurement of Residual Stress in a Pipe - Split Ring Methods

Two methods are described hereinbelow for the measurement of Absolute Residual Stress (in MPa) in a pipe. Test Method A is more suitable for smaller diameter pipes (e.g. up to 20 mm diameter) while Test Method B is more suitable for larger diameter pipes (e.g. above 20 mm diameter). These methods assume that the residual stress is tensile on the pipe bore and compressive on the outer surface, which is why the split rings close up to some degree.

Test Method A

Rings can be cut from the pipe. The wall thickness, outside diameter and average radius are then measured using appropriate instruments. The length of pipe is then slit in the axial direction along a radius of the pipe. Once the pipe is slit open, it will typically close in on itself to an extent. The diameter at this point is then measured (taking the average of at least two mutually perpendicular diameter measurements). The residual hoop stress (OR) can then be calculated using the equation:

OR E/?(DO)/4pG² where E is the modulus of the pipe material, AD is the change in outside diameter of the pipe, r is the average radius and h is the wall thickness.

Test Method B

Rings can be machined from a pipe and the widths, diameters and average wall thickness measured. The rings are then slit axially as described above in Method A, and then pulled apart on a mechanical testing machine using a thin wire to apply a load. The load versus deformation trace shows an initial rise followed by a clear change in gradient as the ring passes its unslit position and begins to open out. The maximum level of residual stress OR in the pipes can then be determined from the formula:

OR = 1 .5Pi(D-/7)(1 +1/Tt)/L/7² where Pi is the load at which the trace changes gradient and the split ring parts, D is the external diameter, h is the wall thickness and L is the length of the pipe sample.

Further information can be found in“Residual Stresses in Plastics Pipes”, J. M. Hodgkinson and J. G. Williams, Deformation, Yield and Fracture of Polymers, Cambridge, 1982.

Measurement of Tensile Strength - Test Method C

The tensile strength (Omax) of a polymer can be measured using a simple‘dog-bone’ test sample (described in Test Standards such as ISO 527) and loading the test piece in tension in a mechanical testing machine. The sample is simply gripped at both ends and loaded in tension at a known deformation rate. The extension is recorded using a clip-on extensometer and this allows the strain to be calculated. The tensile strength (calculated as the load divided by the cross-sectional area of the specimen) of the polymer is the peak stress reached before the yield occurs and the load then falls. Extension beyond yield is non-reversible.

Assessment of Chemical Stability - Test Method D

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

Table 1 and 2 show examples of pipes made according to the parameters of the present invention.

Table 1

Absolute Residual Stress measurements and Tensile Strength measurements were determined using the methods described hereinabove to calculate the Relative Residual Stress values and stress variability data included in the table below:

* These awaited values of tensile strength are expected to be in the region of -100 and therefore should also represent Examples of the invention.

Table 2

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 Method D”) described above. Use of a lower temperature than specified herein for the “subsequent temperature-controlled region(s)” has the potential to reduce the chemical resistance of the pipe, the extent of reduction being determined by a combination of factors, including the temperatures selected for cooling, cooling time and pipe dimensions. Furthermore, use of too high a temperature in the first temperature-controlled region of the calibrator can tend to deliver pipes with an undesirable physical form.

Residual stress in a pipe may be further reduced after extruding the pipe such as the pipe according to the present invention. This may be achieved by carrying out a further method for reducing residual stress in a pipe after it has been extruded by pulling it through a die which may be heated or may be cold. The method may be carried out either immediately after extrusion of the pipe or many days or months afterwards.

The method includes the step of pulling the extruded pipe through a die having a slightly smaller diameter than the outer diameter of the pipe. This process may be desirable in a number of different situations, for example, to re-round a pipe after long term storage on a spool where creep may have distorted the cross section or to reduce the diameter with the specific intention of introducing the pipe to another component and obtaining a tight fit.

In the method, the diameter of the die should be no less than 95% of the pipe outside diameter, for example, the diameter of the die should be from 95% the diameter of the pippe to 99.9% the diameter of the pipe. In one example, the die should be from 96% the diameter of the die to 98% the diameter of the die.

In the example below, the method was carried out using cut extruded sections of PEEK pipe. Two metre lengths of pipe were pulled through a die to impart some compressive forces while under tension. The internal die diamter at 23°C was 77.3mm, but when heated the thermal expansion of the die increased the internal diameter of the die to 77.45mm at 220°C. The pipe had an original diameter of approximately 78.4mm.

Table 3 shows the results for residual stress measurements carried out as described herein. The mean residual stress for the was 0.755 MPa. The diameter of the pipe was measured using a calibrated digital calliper.

Table 3 - control pipe. Table 4 shows the residual stress and diameter of the pipe after it had been passed through the die. The diameter of the pipe was measured using a calibrated digital calliper. The method provides a reduction in the pipe diameter as would be expected. However, a significant reduction in the residual stress of the pipe was also identified. The mean level of residual stress was reduced by ~60% to 0.25 MPa.

Table 4 - Pipe having been pulled through a die post extrusion.

It can be seen from Table 4 that the additional method reduces the residual stress in the pipe to less than half the residual stress of a comparable pipe which has not undergone the additional method. Figure 1 shows the reduction in residual stress of the pipe.

Claims

1 . A pipe having a length of at least 1 metre, 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 residual stress of the pipe, as measured in at least three different places located along the length of the pipe, divided by the tensile strength of the composition of the pipe, is less than or equal to 1 .4%; and

wherein the difference between the maximum and minimum values of residual stress in the pipe, as measured in at least three different places located along the length of the pipe, is less than 0.4MPa.

2. A pipe according to claim 1 wherein the difference between the maximum and minimum values of residual stress in the pipe, as measured in at least three different places located along the length of the pipe, is less than 0.2MPa.

3. A pipe according to claim 1 or claim 2 wherein the pipe comprises a composition comprising one or more polymeric materials each having a repeat unit of formula of formula (I): and/or a repeat unit of formula (II):

II

and/or a repeat unit of formula (III):

III

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 -O-phenylene-O-; and Ar is -phenylene-C(0)-phenylene-, -phenylene-C(CH3)₂-phenylene-, -phenylene-O- (1 ,4-phenylene)-0-phenylene-, -phenylene- or -phenylene-C(0)-phenylene-C(0)- phenylene-.

4. A pipe according to claim 3 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 -SC>2- moieties.

5. A pipe according to any of claims 1 to 4 wherein the pipe has a composition comprising one or more polymeric materials each comprising a repeat unit of formula (XX):

wherein t1 = 0 or 1 , w1 = 0 or 1 and v1 represents 0, 1 or 2.

6. A pipe according to claim 5 wherein the pipe has a composition comprising one or more polymeric materials where at least 98% of the repeat units of the one or more polymeric materials consist essentially of formula (XX).

7. A pipe according to any of claims 1 to 4 wherein the pipe has a composition comprising one or more polymeric materials selected from polyetheretherketone, polyetherketone, polyetherketoneetherketoneketone, polyetherketoneketone and polyetherdiphenyletherketone.

8. A pipe according to any of claims 1 to 7 wherein the pipe has a composition comprising one polymeric material which is polyetheretherketone.

9. A pipe according to any of claims 1 to 8 wherein the pipe has a composition which includes said polymeric material(s) and one or more fillers.

10. A pipe according to claim 9 wherein the total amount of filler in the composition is 5wt% or less.

1 1 . A pipe according to claim 9 or claim 10 wherein the composition comprises 0.05wt% to 5wt% of a filler that is carbon black.

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 of claims 1 to 1 1 .

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 one or more temperature-controlled regions;

(a) phenylene moieties;

(b) ether and/or thioether moieties; and optionally

(c) ketone and/or sulfone moieties.

14. The process according to claim 13 wherein the pipe has a composition comprising one or more polymeric materials each having a repeat unit of formula of formula (I): and/or a repeat unit of formula (II):

and/or a repeat unit of formula (III): wherein:

m, r, s, t, v, w and z each independently represent zero or a positive integer;

E and E' each independently represent -O-, -S- or a direct bond;

G represents -O-, -S-, a direct bond or -O-phenylene-O-; and

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

15. The process according to claim 13 or claim 14 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

16. The process according to any of claims 13 to 15 wherein the pipe has a composition comprising one or more polymeric materials each comprising a repeat unit of formula

(XX):

wherein t1 = 0 or 1 , w1 = 0 or 1 and v1 represents 0, 1 or 2.

17. The process according to claim 16 wherein the pipe has a composition comprising one or more polymeric materials where at least 98% of the repeat units of the one or more polymeric materials consist essentially of formula (XX).

18. The process according to any of claims 13 to 15 wherein the pipe has a composition comprising one or more polymeric materials selected from polyetheretherketone polyetherketone, polyetherketoneetherketoneketone, polyetherketoneketone and polyetherdiphenyletherketone.

19. The process according to any of claims 13 to 18 wherein the pipe has a composition comprising one polymeric material which is polyetheretherketone.

20. The process according to any of claims 13 to 19 wherein the pipe has a composition which includes said polymeric material(s) and one or more fillers.

21 . The process according to claim 20 wherein the total amount of filler in the composition is 5wt% or less.

22. The process according to claim 20 or claim 21 wherein the composition comprises 0.05wt% to 5wt% of a filler that is carbon black.

23. The process according to any of claims 13 to 22 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.

24. A pipe, having a length of at least 1 metre, formed by a process as described in any of claims 13 to 23.