GB2151238A

GB2151238A - Polymer irradiation

Info

Publication number: GB2151238A
Application number: GB08431130A
Authority: GB
Inventors: Ian Macmillan Ward; Denis William Woods; Walter Kenneth Busfield
Original assignee: National Research Development Corp UK
Current assignee: National Research Development Corp UK
Priority date: 1983-12-09
Filing date: 1984-12-10
Publication date: 1985-07-17
Also published as: GB8332952D0; GB2151238B; EP0145475A2; GB8431130D0; JPH0649732B2; US5160464A; EP0145475A3; DE3481197D1; EP0145475B1; JPS60141703A

Description

1

SPECIFICATION

Polymer irradiation This invention relates to irradiated polymers; more particularly, this invention relates to irradiated polyalkenes of high tensile strength and to processes for their production.

In US Patent No. 4228118 there has been described a process for preparing a polyethylene f ibre having a tenacity of at least 12 grams per denier, comprising:

(a) extruding a high-density polyethylene having a 9n of at least 20,000 and a 19w of less than 125,000 through a heated spinneret having at least one orifice to provide at least one molten stream, wherein 10 said heated spinneret is maintained at a temperature between 2200C and about 335,C; (b) solidifying each said molten stream in a quenching zone to form a fibre; (c) withdrawing said fibre from said quenching zone at a velocity of at least 30 metres per minute; and then (d) hot-drawing said fibre at a draw ratio of at least 20:1 while said fibre is in contact with a heated 15 environment, wherein said heated environment is maintained at a temperature between 11 50C and 132oC, said temperatures, said velocity, and said draw ratio being correlated to provide fibre having a tenacity of at least 12 grams per denier, when measured at 72% relative humidity and 25'C on a bundle of at least 8 filaments using a gauge length of at least 25 centimetres.

It has, however, been found that the tensile strength of the polyethylene fibres so produced is very sensitive to strain rate: thus, a fibre may exhibit a tensile strength of 1.2 GPa at 20'C and at a strain rate of 10-1 see' while, at 20oC and at a strain rate of 10 sec-', this may reduce to less than 0.4 GPa (Cansfield et aL Polymer Comm. 24, p. 130, (1983)), a 60% reduction in tensile strength. Polypropylene fibres may give a 20% reduction in tensile strength under comparable conditions. Associated with this very high strain rate 25 sensitivity is an unacceptably high creep rate and inverse temperature dependence of tensile strength.

This invention seeks to provide homo- and copolymers of alkenes with reduced strain rate sensitivity, creep rate and temperature dependence.

According, therefore, to the present invention, there is provided a process for the preparation of an oriented homo- or co-polyalkene material of improved strain rate sensitivity, which process comprises subjecting the oriented homo- or co-polyalkene material having a weight average molecular weight 9J 350,000, desirably:s 200,000 and preferably (particularly in the case of fibres) -- 150,000, a number average molecularweight RU 5,000, desirably 10,000, and a 2% secant modulus of at least 10 GPa at a strain rate of 2 X 10-2 sec-' to a high energy irradiation of a dosage of at least 1 Mrad, preferably of at least 5 Mrads, and not more than 60 Mrads at an elevated temperature in vacuo or in an inert or sensitising 35 atmosphere.

It is preferred to utilise the present invention in relation to homo- or copolyethene material, especially homopolyethene material.

It had hitherto been found (de Boar et aL Polymer Bull. 5, p. 317, (1981) that irradiation at room temperature of oriented polyethene materials of high tensile strength causes a decrease in strength. 40 Furthermore, it has also been found that irradiation at room temperatue of oriented polyethene materials of very high modulus resulted, in the case of tube production, in product which failed at lower loads, while requiring higher energy input for a given plastic deformation, than that not irradiated (Hope etal. J.

Mechanical Working Technology 5, p. 223 (198M and, in the case of fibres, in product with a substantial increase in creep rate (Wilding etal. Plastics and Rubber Processing and Applications 1, p. 167 (1981).

Surprisingly, it has now been found that, provided thatthe 9w of the oriented polyalkene material is below 350,000 (for example 200,000), preferably (particularly in the case of fibre) below 100,000, especially below 75,000, there is not only little reduction in high speed (above 10-4 sec- ') tensile strength but also a marked increase in low speed (below 10-4 sec-') tensile strength together with an improvement in creep properties.

Use of polyalkene materials of the aforesaid molecular weights also facilitates their fabrication and 50 orientation.

Orientation of the polyalkene material may be effected by any of the processes disclosed in our UK Patents No. 1469526; 1480479; 1498628; 1506565; 1568964 or in our GB 2060469B. The polyalkene material is oriented by deforming to a deformation ratio of at least 8x, preferably at least 1 Ox, especially at least 15x and should have a 2% secant modulus of at least 10 GPa, preferably at least 20 GPa, at a strain rate of 2 x 10-2 55 sec-'. In the case of homopolyethene material it is particularly preferred that it should have a 2% secant modulus of at least 10 GPa, preferably at least 25 GPa, at a strain rate of 2 x 10-2 sec-'.

The high energy irradiation, which may be electron or -y-irradation, in accordance with the present invention may be effected in vacuo or in an inert atmosphere, such as argon. However, in accordance with a particularly preferred feature of this invention the high energy irradiation may be effected in a sensitising 60 atmosphere. This may comprise a gaseous substance which is of sufficiently small molecular size to diffuse into the polyalkene and which, on irradiation, acts as a polyfunctional grafting moiety. Examples include substituted or unsubstituted polyunsaturated hydrocarbons; for example, acetylenic hydrocarbons such as acetylene; conjugated or unconjugated olefinic hydrocarbons such as butadiene and (meth)acrylate monomers; sulphur monochloride, with acetylene being particularly preferred. (By "gaseous" is meant 65 GB 2 151 238 A 1 2 GB 2 151 238 A 2 herein thatthe sensitising atmosphere is in the gas phase, either above or below its critical temperature, at the irradiation temperature.) Use of a sensitising atmosphere is found to increase the effectiveness for a given dose of irradiation so that a lower dose can be used to obtain a given increase in low speed tensile strength. Thus, in vacuo or inert atmosphere a dosage from 5 to 60, preferably from 15 to 40, Mrad is used whereas in a sensitising atmosphere a dosage from 1 to 40, preferably from 5 to 30 (for example from 10 to 20), Mrad may be used.

It is found essential to irradiate at elevated temperature. By "elevated temperature" is meant in temperature above ambient; for example, above WC. Provided that the polyalkene material is restrained from contracting, the favourable properties imparted by orientation may be preserved while the polyalkene material being irradiated is taken to progressively high temperatures, even up to a temperature where the 10 material incipiently ceases to be self-supporting. This may be above the temperature at which the material ceases to comprise crystallites. For example, the material may be irradiated and heated to a temperature from 300C to 1400C, preferably 400C to 1300C, especially from 6M to 12M. Such oriented polyalkene materials have, on irradiation, an improved low speed tensile strength. There may, however). be occasions where it is advantageous to have a low irradiation temperature; this is feasible, although a subsequent 15 annealing may be required.

It is also found that improved properties are obtained when the irradiated material is annealed, especially in a sensitising atmosphere; for example at a temperature from 3M to 14M, preferably from WC to 13M, especially from 6M to 120'C.

This invention also provides an oriented homo-or co-polyalkene material, especially a homopolyethene 20 fibre, of improved strain rate sensitivity whenever prepared by the aforesaid process.

This invention further provides an oriented homopolyethene material which has a 2% secant modulus of at least 10 GPa at a strain rate of 2 X 10-5 sec-'; a tensile strength of at least 0.4 GPa, preferably at least 0.5 GPa, at 2WC and at a strain rate of 2 x 10-5 sec-' and of at least 0.15 GPa, preferably at least 0.25 GPa, at 1OWC and at a strain rate of 8.3 x 10-3 sec-'; and a creep rate at 0.3 GPa initial stress of not more than 10-7 25 sec-1, preferably not more than 10 sec.

The following Examples illustrate the invention.

In each Example the oriented polyalkene material used was polyethene fibre produced by melt spinning ALATHON 7050 (ex Du Pont; 9, - 60.1 03 andYn 22.103) at 2800C through a 19 hole spinneret at a winding speed of 150 metres per minute to give a 19 filament 855 denier yarn which was plied 10 times. This yarn was 30 then hot drawn in accordance with the disclosure of UK Patent No. 1568964to an effective draw ratio of 30X.

In each Example approximately 15 metres of the oriented polyethene fibres were wound onto an aluminium spool through which cooling fluid could be passed. The spool was next inserted into an evacuatable glass tube and was irradiated by an electron beam produced by a Van de Graaff generator operating at 2.9 meV and 80 [xA total current. A C060 source may also be used. Test procedures used were as follows:

(a) 2%secantmodulus For the room temperature tests, a 40 cm sample was mounted between flat plate grips lined with polyethylene sheet and mounted on an 1nstron Tensile Tester'. At other temperatures the sample was tested inside a cabinet in which case either a 10 cm ora 20 cm sample length was used. The length used for calculating strain rate was the free length of fibre between the two clamps. The 2% secant modulus is calculated by multiplying the stress at 2% elongation (using the unstrained cross sectional area) by 50 to obtain the theoretical stress (i.e. modulus) at 100 per cent elongation.

(b) breaking strength This is the same as tensile strength and is the stress at break (using the unstrained cross sectional area), again measured on an 1nstron Tensile Tester'.

(c) creep stress The creep stress is the stress applied based on the unstrained cross sectional area. The creep strain rate is so the limiting strain rate determined by a method described by Sherby O.D. and Dorn J.E., Anelastic creep of polymethyl methacrylate, J. Mech. Physics Solids 6 (1958) p. 145- 62. The present measurements were made at room temperature by suspending a load from a 1 metre length of fibre and recording the creep until it reaches a constant value.

3 GB 2 151 238 A 3 Example 1

In this Example the glass tube was evacuated and the contained fibre, on irradiation, was permitted to assume autogenous temperature. Breaking strengths were measured at room temperature (23'C). The results are given in Table 1.

TABLE 1

Breaking strength (GPa) - 1 Extension at break (%) - 2 2% secant modulus (GPa) - 3 at a strain rate of Irradiation is Time Temp Estimate 60%Imin. 0 elolm in (min) rC) dose Environment 10-2 SeC-1 10-5 sec- 1 (Mrad) 1 2 3 1 2 3 20 Nil Nil.95 4 35.22 3 10 25-40 9 vacuum.94 - 34.22 - 11 30 25-55 17 vacuum.90 - 34.30 - 15 25 25-75 35 vacuum.84 3 32.43 6 16 25-90 52 vacuum.88 3.5 31.56 4 18 30 yield point Table 1 indicates that increased doses of irradiation give small reductions in high speed strength but substantial increases in low speed strength.

Example 2

In this Example the glass tube contained an acetylene atmosphere at standard pressure. Breaking strengths were measured at room temperature. Coolant water was passed through the spool to maintain the irradiation temperature as indicated. Samples 2 and 3 were annealed in acetylene prior to allowing access to 40 air. The results are given in Table 2.

TABLE 2

Breaking strength (GPa) - 1 Extension at break (l/16) - 2 2% secant modulus Wa) - 3 50 at a strain rate of Irradiation Time Temp Estimated 50%Imin.12511161min (min) rC) dose Environment 8,3 x 10-3 sec- 1 2.1 X 10-5 sec-' (Mrad) 55 1 2 3 1 2 3 80 35 vacuum.83 3 32.49 6 17 18 23 20 acetylene.88 3 32.52 3.5 19 60 18 85 20 acetylene.94 3 35.62 3 24 Table 2 indicates that the use of an acetylene environment greatly reduces the required irradiation dose to achieve a given improvement in low speed strength; and that the effect varies as temperature.

4 GB 2 151 238 A Example 3

In this Example the procedure of Example 2 was followed. The results are given in Table 3.

TABLE 3

4 Breaking strength (GPa) - 1 Irradiation Extension at break (%) - 2 2% secant modulus (GPa) - 3 10 Time Temp Estimated Irradiation Annealing at a strain rate of (Minj rC) dose and time temp 50%Imin.12501.1min (Mrad) annealing (Min) rC) 8.3 x 10-3 sec- 12. 1 X.10 sec-' environment 15 1 2 3 1 2 3 18 25 20 acetylene not annealed.83 3 32.40 4 16 18 23 20 acetylene 30 86.88 3 32.52 3.5 19 20 18 85 20 acetylene 30 88.94 3 35.62 3 24 yield point 25 Table 3 indicates that the low speed strength varies with both the temperature of irradiation and of annealing.

Example 4

In this Example the procedure of Example 3 was followed. The results are given in Table 4.

TABLE 4

Breaking strength (GPa) - 1 Extension at break (11/6) - 2 2M. secant modulus (GPa) - 3 40 Irradiation Irradiation Annealing at a strain rate of Time Temp dose and time temp 500161min. 12501.1min (Min) (OC) (Mrad) annealing (M in) P C) 8.3 x 10-3 sec- 1 2. 1 x 10-5 sec- ' environment 45 1 2 3 1 2 3 18 87 20 acetylene 30 88.94 3 35.62 3 24 18 81 40 acetylene 30 81.32 1 -.42 2 19 so Table 4 indicates that high levels of irradiation cause major reductions in high speed strength indicating that molecular disruption has commenced.

GB 2 151 238 A 5 Example 5

In this Example the procedure of Example 1 was followed but the effect of irradiation on creep behaviour was also determined. The results are given in Table 5.

TABLE 5

Irradiation 10 Breaking strength (GPa) - 1 Extension at break (%) - 2 Creep at a strain rate of rate 15 Time Temp Estimated 500161min.1251161min at 0.3 GPa (min) rC) dose Environment 8.3 x 10-3 sec- 1 2 1. x 10 sec stress sec (Mrad) 2% secant modulus Wa) - 3 1 2 3 1 2 3 Nil Nil.91 4 34.25 3.5 11 1.3 X 10-4 25-90 52 vacuum.83 3.5 34.58 0 19 3.10-9 yield point Table 5 indicates that the creep rate is dramatically reduced on irradiation.

Example 6

The procedure of the previous Examples was followed but the breaking strengths were determined at the 30 temperature indicated. The results are given in Table 6.

TABLE 6

Breaking strength (GPa) - 1 35 Extension at break P/6) - 2 2% secant modulus (GPa) - 3 at a strain rate of.501.1min (8 X 10-5 sec-) and testing Irradiation Irradiation 45 dose environment temperature of (Mrad) WC WC 1000C 1300C 1 2 3 1 2 3 1 2 3 1 2 3 Nil.36t 5t 12.1 2t 5t 6 >.05 1 melted 50 acetylene.72 3 22.54 3 17.32 3 12.17 2 8 52 vacuum.66 4 18.48 6 13.28 5 9.14 5 2 55 1%secantmodulus t yield point Table 6 indicates that there is a major improvement in the high temperature breaking strengths on irradiation.

This invention enables the production of high modulus, high strength homoor co-polyalkene materials, especially polyethene fibres, having not only substantially reduced strain rate sensitivity of tensile strength and substantially reduced creep rate but also significantly enhanced high temperature tensile strength. 65 6 GB 2 151 238 A 6 Example 7

In this Example a 6MeV (15 kW input, 800 watt beam) electron accelerator (ex Radiation Dyanamics Ltd., Swindon, England) was utilised.

Table 7 indicates that the higher power accelerator gives improved properties; in particular, there is a further improvement in low speed strength and highspeed strength can now be higher than that of the control. A preferred dosage range from 20 to 30 Mrad is indicated.

m Zt N - U) :R j LO CO LO (0 CM 0 r, m 1 CN CS (6 C C Ci d C C LO X em 'It r, Lq hz CM m LO c c m qt T CS m qt C) CD c Ci rl: R T m Ck C) 0 C) CD m m Q) Cn r-4 C6 d d d d M m C9 CM N m m CM cc 0-0:0 Z) 0 C G CM C LO (n 't m It m LO X 00 L2 r qc m m m CO 00 0 C6 d C C 0 0 a) M m M m CD E C 0 C a C C1 iz z m m m r r- LO rj) C0 Cz n q) E C C) CO W C> 0 C) 0 ci d La >, CM C4 (n - CM -F-- Q 0 C) 0 Q 0 a) a) a) r r, a) c CD CM m LO z Z CM C9 - C4 7 GB 2 151 238 A 7 Example 8

The irradiation employed in this Example was from the 6 MeV accelerator.

Example runs 8.4 to 8.6 inclusive show that low doses can give modest improvements in properties, particularly at low strain rates.

Example run 8.10 suggests that improvements in properties at low strain rates can be obtained even at 5 much higher weight average molecular weight.

0 C Lg (q 7 rl: r CM c CM c m CD m CM CM qc m (0 CD N m St L6 Ld r- Cd lzi Ld LCS ZO o CO Ci (i nt C9 r- (q rl:

0 C> 0 c> C C C Cn r,: (R c! C Lq T r M M m M M CM CN e) 0,1 Lq R cl cl LO m LO U) LO LO M c cl M m m c CM m - It M CD r, C m - a) a a) CD 0 w W q 00 J L C--NO 06 d d CS 'i Ili j 'i CS CO LW _j CO ?J) Z Cc Q) c: z n IZ 2 M i C0 0 0 0 (D r r_ r r_ a) (D c) (D cj 0 cj cj M to cc (0 LO C 0 0,c (D 00 cq Q):

i c E (D 0 (D (D U 0 cc 0 C) C) M M 0 C m CO 0) r_ a) W 0 (U C) m m m LO m 0 0 CD m m M 2 Q r 0 C) cj (a Q) c -Z Ct CU LO c M r (R 0 Cli N r 4 cl M 'I U R r 00 a? 00 CO 00 00 00 00 OD 00 CO cl CD -m 1 X C X U1 3:

m CD CM CM E C 0 E E cc LO 0 r, Cq 0 r- U) CL 0 U) 0 < TABLE 9

Irradiation Annealing Sample Esti- No. Time Temp mated Environment Time Temp Environment (Min) dose (at 1 bar) (min) rC) (at 1 bar) (Mrad) 9.1 Nil Nil 9.2 17 Nil 25 acetylene 30 acetylene Breaking strength (GPa) - 1 Extension at break P/6) - 2 Tangential modulus (GPa) at 3.1 0,25016 at a strain rate of 50% min 8.3 x 10-3 sec- 1 3.1 1% 3.32% 0. 12501. min 2,1 x 10-5 sec- 1 1 2 3.2 3.2 3.3 1 2 3.1 3.23.3 0.93 5.0 42.3 28.6 22.0 0.294.9 23.8 9.45.0 1.06 4.1 43.5 24.9 24.9 0.74 4.619.2 14.1 16.7 ul r CD CD 0 (D (D W " < (D CD (D CD (D D=r :X M i-n.

M X (D CD (D CD (D c) CO CD :3 (D 3 0 Ch r (D (n =s = M m 0 =r 0 r_ 0 0 1+ 9 0 C) (D (D < 0 > =r (D W Ei (D 0 (D CD (D (D rj) (D W 0 :3 rL (31 00 c) m rl.) al N) CJ 00 OD 9 GB 2 151 238 A In conclusion, in accordance with preferred aspects of the present invention, it is found that the creep strain of the irradiated homopolyethene material of this invention, at 0. 3 GPa initial stress, plateaus at typically less than 2% and remains substantially constant for more and 105 sec., usually for more than 106 secs., from applying the initial stress. It is also found that, with irradiation at 6 MeV, the breaking strength, both at high and low speed testing, of the irradiated homopolyethene material of this invention is not less, 5 and is preferably higher, than that of the untreated fibre. It is further found that the tangential modulus of the irradiated homopolyethene material of this invention at 2% strain is not less, and is preferably higher, than that at 1% strain.

Claims

1. A process for the preparation of an oriented homo- or co-polyalkene material of improved strain rate sensitivity, which process comprises subjecting the oriented homo- or co- polyalkene material having a weight average molecular weight Nw) -- 350, 000, a number average molecular weight (-Mn),i 5,000, and a 2% secant modulus of at least 10 GPa at a strain rate of 2 X 10-2 sec-' to a high energy irradiation of a dosage of at least 1 Mrad and not more than 60 Mrads at an elevated temperature in vacuo or in an inert or sensitising atmosphere.

2. A process according to Claim 1 wherein the oriented polyalkene material comprises a homo-or co-polyethene material.

3. A process according to Claim 1 or 2 wherein the oriented polyalkene material comprises a homopolyethene material.

4. A process according to any preceding claim wherein the oriented polyalkene material has an Mw 100,000.

5. A process according to Claim 3 or4 wherein the oriented polyaikene material has a 2% secant modulus of at least 20 GPa at a strain rate of 2 X 10-2 sec'.

6. A process according to any preceding claim wherein the high energy irradiation is effected in vacuo or under an argon atmosphere.

7. A process according to Claim 6 wherein the high energy irradiation is of a dosage from 15 Mrads to 50 Mrads.

8. A process according to any preceding claim wherein the high energy irradiation is effected in a 30 sensitising atmosphere.

9. A process according to Claim 8 wherein the sensitising atmosphere comprises a gaseous polyunsaturated hydrocarbon.

10. A process according to Claim 9 wherein the hydrocarbon comprises acetylene.

11. A process according to any of Claims 8 to 10 wherein the high energy irradiation is of a dosage from 35 M rads to 40 M rads.

12. A process according to any preceding claim wherein the irradiation temperature is from 30Tto 1200C.

13. A process according to any preceding claim wherein the irradiated material is annealed in a sensitising atmosphere.

14. A process according to Claim 13 wherein the annealing temperature is from 40T to 120T.

15. An oriented homo- or co-polyalkene material of improved strain rate sensitivity whenever prepared by the process of any preceding claim.

16. An oriented polyalkene material according to Claim 15 which comprises a homopolyethene.

17. An oriented polyaikene material according to Claim 15 or 16 which is a fibre.

18. An oriented homopolyethene material which has a 2% secant modulus of at least 10 GPa ata strain rate of 2 x 10-5 sec-'; a tensile strength of at least 0.4 GPa at 20T and at a strain rate of 2 x 10-5 see' and of at least 0.15 GPa at 1000C and at a strain rate of 8.3 x 10-3 sec-'; and a creep rate at 0.3 GPa initial stress of not more than 10-9 sec-'.

Printed in the UK for HMSO, D8818935, 5185, 7102. Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.