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NEUTRON AND GAMMA RADIATION EFFECTS

ON THE VISCOELASTIC BEHAWOUR OF POLY(ARYL ETHER ETHER KETONE)

Captain Danny J.Y.S. Pagé, CD,B.Eng

Submitted to the Department of Chemisw and Chernical Engineering as a requirement for the degree of

Master of Engineering in Chernical and Materials Engineering

Royal Military College of Canada - Collège militaire royal du Canada Kingston, Ontario

7 May 1997

Copyright O 1997, Danny J.Y.S.Pagé,DND

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ABSTRACT

The effects of combined neutron and gamma radiation on the viscoelastic behaviour of two industrial semi-crystalline PEEK grades (VICTREX 150P and 450P) were investigated. Tensile test samples were processed on an ENGELS5 injection moulder, then irradiated in a reactor pool environment, agahst the reactor vesse1 wali of the SLOWPOKE-2facility at RMC, for exposures resulting m dosages ranghg fkom 10 kGy to 320 kGy. First, the rnorphology of the irradiated resins was characterized by differential schg calorimetry @SC), X-ray maction and density meamements. Secondly, the viscoelastic behaviour of the material was studied at three thermodynamic states, m order to define the nature of the structural damage suffered by PEEK, by comparing ts degree of molecular motion with the dose received. Therefore, standard mechanical testing was performed at room temperature, stress relaxation near the glass transition temperature(T$, at 140°C, and melt viscosity above the melting point (T& at 350OC.

Results confnmed that PEEK is highly resistant to radiation, but also demonstrated that PEEK degrades faster under a combined neutron and gamma flux,in a reactor pool environment, th observed in previous work under electron beam or gamma afone. The density increased slightly over the range of irradiation (450P: 1296 to 1299 kg/m3; 150P: 1300 to 1303 kg/m3), while the crystallmty (450P: 24 %, 150P: 27 %), and the thermal properties, like Tgand Tm , remained dected. Therefore, the hcreases in density were attriibuted to transfomations occtmhg mostly m the amorphous phase, which is also consistent with previous work. The viscoelastic behaviour analysis provided the following damage assessnent for PEEK. the amoqhous phase is subject to both crosslinking and chah scission; the eEects of chain scission, on the viscoelastic behaviour of PEEK, are predomhant for doses higher than 100 kGy; tie- molecules, at the crystalline and amorphous phase mterface, are more sensitive and are proue to chin scission under radiation; and,crosslinkmg occurs predoxnhantly near chain-ends. OveraU, this research confirmed PEEK as a good candidate material for applications in nuclear reactor pool environments and for the disposal of radioactive waste.

1thank the personnel nom the Chemistry and Chernical Engineering Departrnent at RMC for their professionalism and dedication to a job weU done. Without the assistance and patience of many staff and fiiends, this thesis, dong with its research work, would have not been possible.

Special thanks to my thesis supervisors, Dr. Hughes Bonin and Dr. Van Tarn Bui, who ûusted my initiative and provided me with sound guidance when required

Mr. John

Perreault, Mr. Bob Whitehead, Mr. Helmut Weiland, Mr. James Irving and Mrs. Lynn Keams, for their assistance and cooperation.

Special thanks to the following technicians, Mrs. Kathy Neilsen,

Special thanks to Captain Jean-François Legault and Major Dave Gosseh for their participation in some fniitfùl discussions.

And finaIly, special thanks to my cornmittee members, Dr. M. Erki, Dr. K. Machildon, Dr.P.J. Bates and my supervisors, who reviewed, challenged and accepted my work as a fùltillment of the requirement for the obtainment of the degree of Master of Engineering in Chemical and Materials Engineering.

lll

Staff Officer, CanadianForces Comunications Command, Ottawa, Mar 88-Jul90

QuaIifications :

Basic Officer Training Course, CFB Chilliwack, 1983

Second Language Training (English),BFC Saint-Jean, 1984

Communications and Electronics EngineeringOfficer Course (Part 1), CFB Kingston. 1985

Basic Parachutist Course, CFB Edmonton, 1986

Young Officer Tactics Course, CFB Kingston, 1986

Communicationsand Electronics EngineeringOfficer Course (Part II), CFB Kingston, 1987

Land Basic Signal Officer Course,CFB Kingston, 1988

Promotion to the rank of Lieutenant, 1988

Promotion to the rankof Captain, 1990

Intermediate Signal Officer Course, CFB Kingston, 1993

Intermediate Tactics Course, CFB Gagetowa, 1994

SpaceMission Analysis and Design Course, CMR Saint-Jean, 1995

Abbreviations and acronyms

ASTM

Amencan standard test method

DSC

differential scanningcalorimeky

rn

Fouriertransfarmed in£rared

CY

Gray (J/W

LET

hear energy transfer

LEU

low enrichecl Uranium

LDPE

low density polyethylene

MPa

Mega Pascal

MW

molecular weight (MW)

MWD

molecular weight distniution (Mw/Mn)

NAA

neutronactivation analysis

Pa

Pascal (N/rn2)

PEEK

poly (aryl ether etherketone)

PMMA

poly (methyl methacrylate)

PSU

polysulfone

rad

physical dose unit (6.24x 1oL3eV/g)

S

second

SP gr

speci.fïc gravity relative to water

TEM

transmission electron microscopy

150P

lower molecularweight VICTREX PEEKgrade

450P

highermolecular weight VICTREX PEEK grade

vii

TABLE OF CONTENTS

Abstract

Acknowledgments

Vita

Symbols & Abbreviations Table of Contents ListofIllustrations

moDUCTION

CHAPTER 1 . STATE OF THE ART

II

111

iv

vi

viii

xii

1.1 In the Beginning

1.2 Previous Work on the Irradiation of PEEK

1.3 Scope of the Present Work

CHAPTER 2 .THEORY

2.1

Radiation

2.1.1 Interaction with matter

2.1.2 Energy transfer

3.1.3

Doses and units

2.2

Effects of Radiation on Polymers

2.2.2

Induced chemical changes

2.2.3

Impact on macroscopic properties

2.2.4

Degradation

2.3 Poly(Ether Ether Ketone) (PEEK)

2.3.1 Chemical characteristics

2.3.2 Physical properties

2.3.3 Processing

vlll

CHAPTER 3 .METHODOLOGY

0utli.e

3.1.1 Production ofthe test samples

3.1.2 Expainlental conditions

3.1.3 Charactenzation

Injection Moulding

3.2.1

3.2.2

3.2.3

Neutron and Gamma Irradiation

3.3.1 Description

3.3.2 Apparaîus

3.3.3 Procedure

Density by Water Displacement

3.4.1 Description

.

.

Description

.

.

Apparatus

Procedure

.

.

.

.

3.4.2

Apparatus

3.4.3

Procedure

Stress Relaxation at Constant Strain

3.5.1 Description

.

.

3.5.2

Apparatus

3.5.3

Procedure

Standard Test for Tensile Properties

3.6.1 Descnp~on

.

.

3.6.2 Apparatus

3.6.3 Procedure

Differential Scanning Calorimet~y

3.7.1 Description

.

.

3.7.2

Apparatus

X-ray Diffraction

.

3.8.1 Description

3.8.2 Apparatus

3.8.3

Procedure

3.9 Rheological Analysis

3.9.1

Description

.

.

3.9.2

Apparatus

3.9.3

Procedure

CHAPTER 4 .RESULTS AND DISCUSSION

4.1

Genera1

4.2

Density

4.3

Glass Transition, Crystallization and Melting Temperatures

4.4

Crystallinity

4.5

Tende Properties

4.5.1 Young's modulus and strength

4.5.2 Maximum strain and energy at break

4.6 Stress Relaxation at Constant Strain

4.7 MeIt Viscosity

CHAPTER 5 .SYNTHESIS AND ANALYSlS

5.1 Radiation Damage Assessment

69

5.2 Role Played by the Morphology

70

5.3

Error Analysis

72

CONCLUSION

76

RECOMMENDATIONS

77

APPENDICES:

A.

INJECTION MOULDING PARAMETERS

B.

IRRADIATION PROFILE

C.

DENSITY CALCLKATION

D.

RELAXED YOUNG'S MODULUS CALCULAï?ON

E. STANDARD TENSILE TEST REPORT

F. DIFFERENTIAL SCANMNG CALORIMETRYREPORT

G.

X-RAY DIFFRACTION REPORT

H.

RHELOGICAL ANALYSIS REPORT

LIST OF ILLUSTRATIONS

Figure 1.1:

Chemical structure of poly (aryl ether ether ketone) (PEM)

3

Figure 1.2:

Radiolysis mechanism of PEEK

6

Figure 1.3:

Selected temperatures for viscoelastic tests

8

Figure 2.1:

PEEK crystal larnellar structure

22

Figure 3.1:

SLOWPOKE-2irradiation set-up

31

Figure 3.2:

Typical tensile test stress-strain cuve for a polymer

36

Figure 3.3:

Tende test bars dimensions

-37

Figure 4.1:

Density as a function of dose for PEEK 1SOP

45

Figure 4.2:

Density

as

a

function

of dose

for

PEEK 450P

 

45

Figure 4.3 :

PEEK molecular arrangement in its semi-crystalline state

47

Figure 4.4:

Typical DSC heat flow diagram forthe processed PEEK

48

Figure 4.5:

Glass transition temperature as a fùnction of dose for PEEK 150P

50

Figure 4.6:

Glass transition temperature as a hction of dose for PEEK 450P

50

Figure 4.7:

Crystalhation and melting temperatures as a function of dose for

PEEK 15OP

 

Sl

Figure 4.8:

Crystaiiization and melting temperatures as a function of dose for

PEEK450P

 

51

Figure 4.9:

C~stallinityas a function of dose for PEEK 150P

 

53

Figure4.10:

CrystaUinity as a function of dose for PEEK 450P

53

Figure 4.11:

Stress-strain curve at 24OC and Smm/min strain rate

for PEEK 150P

55

Figure 4.12

Stress-strain curve at 24°C and 5dmin strain rate for PEEK 450P

55

Figure 4.13:

Young's Modulus at 24°C as a function of dose for PEEK 150P

57

Figure 4.14:

Young's Modulus at 24OC

as

a

function of

dose for PEEK 450P

57

Figure 4.15:

htramolecular bond occhg in the PEEK molecular backbone

58

Figure 4.16:

Tende strength at 24°C as a function of dose for PEEK 150P

60

Figure 4.17:

Tende strength at 24OC as a function of dose for PEEK 450P

60

Figure 4.18:

Maximum strain at 24°C as a

function of dose for PEEK 150P

62

Figure 4.19:

Maximum strain at 24°C

as a fiinction of dose for PEEK 450P

62

Figure 4.20:

Energy at break at 24°C as a function of dose for PEEK 150P

63

Figure 4.2 1 :

Energy at break at

24OC as a function of dose for PEEK 45OP

63

Figure 4.22:

Relaxed Young's modulus at

140°C as a function of dose for

PEEK f 5OP

-65

Figure 4.23:

Relaxed Young's modulus at 140°C as a fûnction of dose for

Figure 4.24:

PEEK 4SOP Melt viscosity at 350°C and 100 s-' as a function of dose for

,

-65

PEEK 150P

-68

Figure 4.25:

Melt viscosity at 350°C and 100 s-' as a function of dose for

PEEK 450P

,

-68

Table

4.1:

LIST OF TABLE

Power law factor (n) for both resins in fhction of dose

67

INTRODUCTION

The aerospace, communications and nuclear industries rely increasingly on new polykc materials for advanced engineering applications demanding high resistance to radiation. Among the most promishg polymeric materials ispoly (aryl ether ether ketone) (PEEK), a semi-crystalline therrnoplastic which is resistant to high temperatures in addition to displayhg excellent mechanical properties and good stability in both chemically active and radiation environments. These characteristics make PEEK an excellent candidate material for nuclear applications such as waste disposal, reactor components and telescopic tools.

The specÿil mechanical properties of polymers are driven by their viscoelastic atmbutes. The viscoelasticity of a material ca. be characterized through a variety of methods including tende, stress relaxation and rheological tests. The changes in the viscoelastic properties of polymers exposed to aggressive environrnents such as radiation are often an excellent indicator of the ability of polymeric materials to maintain the mecbanical resistance required kom them throughout the lifetime of thek application The viscoelasticity of a polymer is dependent on its molecular structure, defjned by chernical bonds and chah length, but also by its morphology which is dete-ed by the cvstalline and amorphous phase composition and interface characteristics.

The role played by the morphology in semi-crystalline PEEK, during radiation- induced molecula. transformations, is not weil understood. Radiolysis descnbes those chernical reactions occurring in the polymer as a result of irradiation('"'. Radiolysis is dependent on the reactive species created by radiation but also by the fieedom of movement of those reactants. Molecular movement hcreases with temperature as the polymer goes through various thermodynamic transition state~(~'.Molecular movement in

a polymer can therefore be used to study the role played by the morphology during

radiolysis, and also to assess the damage caused by radiation on the structure of the poiymer.

Past research work has concentrated mostly on the study of the effects of electron bea~n(~-'~'and gannna radiati~n''~)on PEEK among other thermoplastics. No research has

been carried out on the effects of fast and thermal neutrons on this materid, especially on bs viscoelastic behaviour in the temperature region close to the glass transition

temperature. In order to assess molecular darnage and to better analyze the specific role

played by the amorphous phase, the crystalline phase and their interface during radiolysis, the morphology of the PEEK resins were characterized using density measurements, differential sca.g calorhetry @SC) and X-ray difnaction. Then, the Mscoekstic behaviour of the polymer was studied at three different thermodynamic states. The

methodology used for this part of the research consisted 6rst to perfom stress relaxation testing just below Tg(140°C) to study the viscoelastic behaviour of the irradiated PEEK, then, these tests were complemented with tende testing at room temperature to assess the

elastic and plastic behaviour of the material finally rheology tests were performed above T,(35O0C) to assess changes in the viscous behaviour of PEEK.

This document is divided in five chapters. Chapter 1 reviews the research performed so far on the effects of radiation on PEEK, and, presents the scope of this thesis. Chapter 2 covers the important theoretical principles behind the interaction of radiation with matter, its effect on polymers and the special characteristics that rnake PEEK an engineering thermoplastic. Chapter 3 desmies the methodology used for the experimental work and the basic principles applied with the various techniques used in this research. Chapter 4 presents the results obtained for the characterization of the morphology and the study of the viscoelastic behaviour of PEEK Each series of results, related to the same studied material characteristic, is foilowed by a preluninary discussion. Finally, Chapter 5 provides a synthesis of all the major discussion points and analyzes the potential sources of emor.

1.1 In the Beginning

Chapter 1

STATE OP THE ART

PEEK was designed in 1978 by Imperia1 Chemical Industries (ICI) as a tough high temperature-resistant cable insulating material'? Since its commercialVation in 1981, PEEK's excellent mechanical stabilRy at high temperatures coupled with its ease of processing has made it a material of choice in a number of high technology applications in the aerospace, automotive, electrical and chemical mdustries. PEEK is generally a tough, semi-crystallinethennoplastic with the following chmical structure (Figure 1.1) (16):

Figure 1.1:

Chemical structure of poly (aryl ether ether ketone) (PEEK).

The special properties of this polymer can be attriiuted to its chemical stnicture. The aromatic ring is the domhant component in PEEK's composition, as shown above, and is mostly responsible for the strength, the high temperature and radiation resistance of the material? The ether bond provided by oxygen in the backbone contnbutes toughness and fiexhility. The Iast feature, is the ketone side goup which provides some degree of intennolecula. spacing, reducing both the density and glass transition temperature

(Tg= 143OC), and also contnbuting to the toughness of the material by increasing the fiee

volume. The repetitive sequence in PEEK's molecular structure, alIows aystaliization to

Occur, enhancing both the strength and the chernical resistance. Detailed characteristics of

PEEK are provided in Chaprer 2.

The potential of PEEK for use in the nuclear and space industries was identified

early and research work was initiated by Yoda in 1983 with the study of the effect of high

energy electron beam radiation on the structure and physical properties of the polymer'g'.

ïhis effort was the initial thrust on the nudy of the effects of radiation on PEEK mady in

four areas: morphology, them1 properties, gas evolution and mechanical properties. The

source of radiation most often us& was high energy electron beam radiation and on some

occasions, gamma radiation.

1.2 Previous Work on the Irradiation of PEEK

In the mid 80's, Temey and Slemp fkom NASA studied a number of polymeric

materials targeted for space applications. including PEEK composites'n. The scope of the

research was to shidy the effects of thermal cychg and electron radiation on the tensile

and shear properties of the studied materials. Materials were exposed to 1 MeV electrons

at a maximum dose rate of 5x10' rad/%(5xlos Gyh) for doses up to 1~10''rads (1xlo8

Gy).

An inrrease in Young's rnodulus was observed for the AS/4 PEEK and graphite

composite. This observation confirmed Sasuga's et al. research done in 1984''L',who

studied the degradation of tensile properties of both morphous and semi-crystalline

PEEK, among other thermoplastics, exposed to high dose of electron beam radiation.

They observed that the elongation at break and the tensile strength decrease and the

Young's modulus tends to increase for doses up to 50 MGy.

In 1991, Hegazy et al. investigated the effect of gamma and electron barn

irradiation under vacuum on the gas evolution of several arornatic polymers at doses up to

25 MGy. The two types of radiation seemed to generate comparable damages to the PEEK rnolecular structure. Crystalline PEEK yielded less gas under irradiation than amorphous PEEK"~),and disphyeti better resistance to gamma radiation due to the presence of crystais. CO2 and CO gas evolution showed that the ether and ketone groups were the most affected by radiation, however the evohitioa of H2alSO attested for the occurrence of crossiinking which is the creation of new intermolecular bonds. From this work, Hegazy coocluded that aryl ether ketone linkages were seen as exhibiting a protective effect aga& radiation(13)and proposed a radiolysis mechanism for irradiated PEEK as shown in Figure 1.2. Furthermore, Hegazy et al. confirmecl, by ushg DSC, that PEEK creates crosslinks under radiation below its glass transition temperature('? Crosslinlsng was attri'buted predomkmtly to the amorphous phase between the crystal lamellar structure, which increased T, while Tm and the crystallization temperature (Tc) were lowered.

Yoda obsemed that amorphous PEEK suffered enough defects to be unable to crystallize after receiving doses of 50 MGy. Reduction in crystahity and of the rnelting temperature were observed upon recrystallization after the material had been exposed to an electron beam radiation dose higher than 10 MGy. Yoda also ob~erved(~),following electron beam irradiation at room temperature up to 50 MGy, that the average crystafite size was reduced by 15% while the c-axh of the orthorhombic czystal ceii structure of PEEKremained ddly affected.

Vaughan et aL observed that PEEK aystals are slightly aEected up to 66 MGy. At higher electron beam doses changes are so important that at 260 MGy only a small fkaction of crystals can recrystallize(? Vaughan et aL proposed that the formation of intermolecular crosslinks above 260 MGy can occur to such an extent that no rnelting is possible and no endothemi can be detected on DSC. However, Maction patterns and transmission electron microscopy (TEM) would stiiI indicate some local ordering in the form of lamellae that could be associated with the crystailine structure of PEEK?

Vaughan concluded that cross~gcould occw to such an extent in the amorphous

phase as to prevent melting of the remaining crystals.

Figure 1.2:

Radiolysis mechanism of PEEK as proposed by Hegazy.

Sasuga and Hagiwara proposed a highex electron beam radiation resistance for

amorphous PEEK than semi-crystalline PEEK based on dynamic relaxation results. They

observed important variations on the material relaxation behaviour at the y-transition (-1OO°C), p'-transition (40°C), @-transition(140°C) and a-transition (180°C). They

suggested that the disintegration of tie molecules at the amorphous and crystahe interface would explainthe lesser radiation resistance of semi-crystalline PEEK(''.'~).

1.3 Scope of the Present Work

Past research work has conceneated moaly on the study of the effects of electron beam and gamma radiation on PEEK in vacuo or in air. Previous work on epov and polyimide composites clearly demonstrated that the mecùanical properties of the studied materials were more sensitive to neutron radiation as opposed to an equivalent physical dose of gamma radiation"? No research has been carried out on the effects of fast and thermal neutrons on the mechanical properties of PEEK, especidy in a reactor pool environment. Since PEEK is known to bz a radiation-resistant pober, such information may be valuable to assess PEEK's potential for employment in nuclear reactor or applications involving neutron radiation.

The mechanical properties of poly-mers are dependent on their viscoelastic nature. The viscoelastic behaviour of polyrners is best observed starting from their glass transition region up to their melting point, where both the eflects of the elasticity provided by molecular conforïnation changes and the Mçcous flow created by chah segment movements, takes place. In order to ver@/ if viscoelastic changes could be observed foUowing irradiation, a series of stress relaxation tests were performed on Vradiated polycarbonate and polystyrene for doses between 10 kGy and 100 kGy at temperatures going fiom (Tg-20°C)to (Tg+20°C). The best temperature region, providing for the optimal observation of stress relaxation and the repeatability of the results with a minimum standard deviation, was (Tg-10°C)to (Tg-3°C).

Consequently two grades of PEEK, 150P and 450P.were processed in the form of tende test bars and irradiated with a combined neutron and gamma flux m the pool of the

SLOWPOKE-2 reactor facility at the Royal Military CoIlege of Canada (RiMc).

ïhe

studied dose range was set between 10 kGy and 320 kGy in order to identify early degradation in serni-crystalline PEEL and also to mess molecular damage before the occurrence of significant morphological changes. The morphology was characterized with density measurements, differential scanning calorimetry @SC) and X-ray diffraction. Then, the viscoelastic behaviour of the hdiated resins was investigated at three thermodynamic states as demonstrated in Figure 1.3, with stress relaxation tests conducted 140°C, standard tensile tests at 24OC , and melt viscosity measurements at

350°C.

24°C

Tende

140°C

Stress Relaxation

350°C

Melt Viscosity

Figure 1.3: Selected temperatures for the three viscoelastic tests, and, the impact of the phase transitions of PEEK on its Young's modulus and thermal properties.

2.1

Radiation

THEORY

Radiation is radiant energy emitted by a radioactive substance. Radiation can be divided in two groups. Fust, particdate radiation which consists in moving matter

particles, me electron(e3, beta(P), neutron(n), proton@) and alpha(a) particles'*). Then, electromagnetic radiation, which consists m energy photons, like gamrna and X-rays. Radiation propagates through the environment surrounding the source and transfers 3s energy to the various media in its path, resdting either in absorption, dissipation as heat or ionkation which is the formation of electncdy charged radicals. This research, is mostly concemed with the most damaging process, being ionization. Ionization &tes physical changes in the imdiated medium that may potentially affect its mechanical, electrical and chemical propertiesB). In assessing the potential impact of ionization on the macroscopic properties of the irradiated material several factors must be considered mcludmg the composition and the density of the mednrm, the energy, flux among and other characteristics of the ionizing radiation

2.1.1 Interaction with matter

Nuclear reactors produce a large variety of radiation. The nuclear reaction is initiated h the core by the spontaneous fission of Uranium-235, and leads to a series of interactions producing radiation in the fuel rods, surroundhg water and reactor vesse1

materiah. While electron, beta, alpha particles and heavy ions are attenuated rapidly, neutron and gamma radiation can interact with mataials fàr fiom the reactor core. This radiant behaviour is the redt of different interaction mechanhm between radiation and matter''').

Photons ionize atoms through three miportant energy tramfer processesRO'. Fifst, the photoelechic process,(21"4)where low energy photons (< 0.05 MeV) interact with a tightly bound electron fiom an huer shell of the atom and causes one electron to be ejected out. Second, the Compton scattering, m which a higher energy photon (0.1-10 MeV) interacts with several atoms, each time scatterhg off an orbital electroq which goes on to ionize more atoms. Compton scattering ends when the photon has decreased its

energy low enough so that the photoelectric process may occur. The thUd process is the pair-production, where a photon of energy 1.02-20 MeV, converts ts energy in the presence of an atomic nucleus to a positron-electron pair, which proceeds to interact with more atoms and rnoleculesN. In most cases, Compton scattering is the principal radiation interaction mechanism for organic polpers. Overall, photon energy deposition tends to

be fairly unZorn

within the irradiated material.

Neutrons ionize atorns along their paths by ejecting electrons, but also collide with

fast neutrons (1-

2 MeV), mostly produce energetic protons fiom the collisions with hydrogen atoms which, in turn, interact and cause farmore damage than the incident neutronN. Neutrons of thermal energy (0.0253 eV) cm ab be absorbed by other nuclei which then become unstable radionuclides and undergo nuclear reaction or further radiation deca$lg). This type of reaction cm induce radiation that canremairi active a long tmie der the irradiation exposure is completed, especially m metals. Again, in most pure polymers, induced radiation is short-lived, because the radionuclides generated by C,O and H possess short half-lives, and decay ~alywith the emission of beta and gammii-rays. The end result of neutron radiation is the generation of recoa protons and heavier ions, producing a different

and produce energetic recoil nucleus by hock-un process. In a polymer,

geometrical distri'bution of the energy deposition which tends to concentrate damages along specific tracks and in more localized sitesN.

The level of damage caused by radiation depends not ody on the quantity of the energy deposited in the material but also on how concentrated the energy deposition is, resulting in fiee-radical pairs along the path taken by the energized particle or photon'2). The destructive potential of radiation is assessed in temis of hear mergy tramfer (LET) which is the amount of energy deposited per unit length of the ionization trackCJ"', expressed as dE/dx For example, gamma-radiation has a low LET of 3.5 keV1p.m in

water, whereas energetic protons and alpha-radiation have a high LET of 53 keV/pm in water. Since fast neutrons can generate several recoil protons along theù paths, they are

also attnbuted with a LET of 53 keV/p m water. If the incident neutrons have energies

lower than 10 keV, they are attributed with a Iower LET of 7-10 keV/p in water'lg).

Another important factor is the abildy of the radiation to penetrate the irradiated material. Gamma and X-rays can deeply penetrate polymers, as opposed to electron beams or alpha-radiation which are strongly attenuated, resulting only in suface effects(*). Conversely, if an irradiated sample istoo thin,less than 1 nim, the radiation goes through the material, for the most part, with little interaction with the medium. Therefore, the dosage for thin specimens cm be large@ overestimated? In nuclear reactors, protons or alpha-particles generated in the fûel do not &se beyond the reactor core. However, fast neutrons can travel much fûrther and induce high LET recoil protons when they collide with hydrogen atoms in the materials surrounding the core. Therefore, nuclear reactor radiation can combine both the effects of high LET and deep penetration, and produce a hi& concentration of radicals throughout the irradiated material.

2.13 Doses and units

When measuring the effect of radiation on a specific materiai, not ody the energy and the type of radiation rmist be considered but also the intensity of the emitting source. Those parameters dong with the distance fkom the source and the radiation absorbing properties of the imadiated medium are used to measure the absorbed dose. The SI unit for radiation intensity is the Becquerel (Bq) or 1 disintegratiods, the energy of the particles is expressed in eV or MeV and the absorption properties are r;hacterized with absorption coefficients. The Gray (Gy) and the rad are the most commonly used dose units to measure the amount of energy transferred by radiation to an irradiatecl material(".

1 Gray(Gy) = 100 rad = 1 Jkg = 6.24 x 10"

eV/g

Other units are also used to express the chernical yields of certain radicals or chernical species, produced by radiation. Among those, is the G value, as defincd bel~w('.~*).

G = number of changes1100 eV of irradiation G(S)= number of scission!100 eV of irradiation

G(X) = number of cross-linksll00

eV of irradiation

The dose descnied above is the physical dose which is based only on the energy absorption by the mediun In biology, ceU fiinctions are encoded in their molecular arrangement. If the radiation energy deposition is diffised. most of the damage caused is of a rninor nature and self repair mechanisms can re-establish the original molecular code of the celL Concentrated energy deposition creates major darnagesc5) beyond the repair capability of the ceil, therefore killing it. For that reason, in biology, the physical dose is multiplied by a quality factor to give a biological dose. That quaiity factor is based on the energy transfer capab* of a type of radiation which provides an indication of the cell

killBig potential based on the type of radiation. The resultmg dose units are the Sievert and the rem

Like living ce&, poiymers are also structureci with long mlecular chains. Although there is a siniilarity between polymers and biological systems with their sensitivity to the nature of the incident radiation(2),a quality factor system is harder to define for polyrners because they react differently to irradiationdue to their wide variety of molecular structure.

2.2 Effects of Radiation on Polymers

Polymers are being used increasingly in environments exposed to hi& levels of ionking radiation. The properties of polyrners, such as elasticity, light weight, strength, resistance to corrosion and formability are ideal for use m the space, communication, electical and nuclear industries. Ionizing radiation cm alter the molecuiar structure and macroscopic properties of the polymer~(202? It is mostly the levels of chah scission which is the breaking of macromolecules, and crosslinking, that determine the extent of the degradation of those properties. Several factors play a key role in predictïng and understandmg the behaviour of polymeric materiais under radiation. Some of them are the molecular structure, the crystallinay, the density of the polymer, also the type, energy and flux of the incident radiation, just to name a few.

The ionization of molecules is the initial step in a series of events that lead to

Irrelevant of which pdcular radiation interaction

mechanism applies, as described m section 2.1, the prirnary consequence is the ionization

of the affected molecules. The absorption of energy causing ionization depends sinq>lyon the electron density of the material. Therefore, the Hiitial radical species induced by

chemical changes in the material.

radiation are distributecl m a fâirly random mer m the material, concentrated along the tracks of the penetrating radiation. Ionization occlils by the ejection of a high energy electron Eom the molecule (Equation 2.1) in the fkst 10''~ s following the interaction with radiation. The ejected electrons ionize Mer molecules (Equation 2.2) until they become thermalized about 10"' s Iater. Then, mtra atoniic spur activity goes on for another 10"s and radiolysis species start to migrate and mteract with other moleculesW. Excited molecules (Equatiom 2.3 and 2.4) may undago radiationless decay to the ground state, with heat being released, which may result in a siificant rise in the temperature of the materials mder high radiation flux'20'.

R+ +

R

-

e

radiation

radiation

radiation

R+ (ion) +

e

I

R* (excited state)

R*

Although excited molecules can trigger dnectly chemical reactions, the predominant mtennediate outcome is the creation of fiee radicals (Equation 2.5). The foxmation of radiation-induced fkee radicals is similar to chemical radicals except that radiation-induced radicals are not fod in randomly dispersed pairs but rather in localized sets of pairs within tracks. The localised radical concentration can fàvour recombination reactions as opposed to reactions wah other chemical species present in the polymer. The radical chemical species resulting f?om ionization remain active for some iime and induce various chemical transformations in the polymer at rates dependent on

both tïme (dictated by the rate of diffusionand the concentration of the reactive species) and temperature (dictated by kinetics based on the Amhenius equatim) (2).

Radicals in a solid polymeric material are not as free to migrate as a liquid or gas(l':

the radical lifetime can thus be very long, up to weeks and months. The amorphous phase of a polymer is more Milnerable to degradation than the crystalline phase, because in the amorphous phase, the fiee vohme is larger, therefore hcreasmg the mobility of fiee radicals which cm propagate degradation more easily. The crystalline phase is tighter. Radicals caught in the crystahe phase either stay m place with a long half-Me, or transfer their reactive sites, molecules to molecules, untLL they migrate out of the crystal into the amorphous phase(". For th reason, semi-aystalline polymers generaliy have a better resistance to radiation than glassy and amorphous polymers.

2.2.2 Induced chemical changes

The initial ionization, resulting from the radiation interaction with matter, is distniuted randomly. The radiochemistry that follows is more selective. It is caused by the transfer of energy of f?ee radicals, ions and excited molecules and attacks relatively weak chemical bonds. However, m radiation-resistant polymers, that energy is entrapped in radiation-resistant functional groups that undergo efficient non-reactive decay to the ground state'? The extent to which a polymer is chemicalîy transformed by radiation is primarily determined by its molecular stru~ture~?Weak and strong chemical bonds along the chab detamine the nature of the reactive species induced by radiation and also the most likely chemicalreactions to fo~ow(~).

Durmg that stage, some bonds and chemical groups are more vulnerable than others and easily react with the radiation-induced species. The most radiation sensitive chemical groups kiclude COOH, C-Halogen, -S02-, -NI& and C=C. On the other hand, among the most resistant groups are the methyl group and, mparticuIar, the arornatic ring which can trap the energy transferred and undergo efficient non-reactive decay to the

ground state'? For that reason, aromatic polymers cm be 10 to 100 thes more resistant to radiation than aliphatic polymer~(2).Although the C-Hbond is not a radiation sensitive group, it plays an important role due to the fhct that it is a major component of most polymers. The bond scission liberates a hydrogen atom which isthen transferred arnong several molecules creating radicals of lower energy that dl play an important role in cross~g.

Radiation-induced chemically active species can react in Mirent ways resulting m structural and rnolecular weight changes. The first change is crosslinking which increases the rnolecular weight. Crosslinking can eventually result m the formation of an important network which radically alters transitiontemperatures, chemical and mechanical properties of the rnaterial? The second change is cham scission, where fkee radicals recombine with low molecular weight molecules, which causes a decrease in the overall molecular weight of the material. The general properties of the rnaterial are altered but in a more gradua1 way than crosslinkmg. The third change isthe creation of low molecular weight products

resulting fiom ch& scission and followed by

These products are usuafIy gases such as Hz. C02,CO and C&, but some polymers with particular structural groups may release other gases like SOz, inthe case of polysulfones, or HCl for polyvinylchlonde(? Such small products impact on the overaU molecular weight and create smaU gas pockets in the polymer which reduce mechanical properties. The last induced chemical change is the actual structural modifications by the appearance

of new bonds creating new chemical groups or the elimiriation of existing ones. Such changes can alter both chemical and physical properties of the polymer.

the abstraction and recombination reactions.

An appropriate mixture of both sensitive and resistant groups in the structure of a polymer can lead to interestmg behaviour under radiation, like the promotion of mt ermolecular crosslinking? For example, irradiated polystyrene fom primarily two types of radicalsBq: the first radical is produced on the backbone temmy carbon; the second type has a radical site on the ring at either the ortho, metha or para position. The first type can interact with a simüar radical to fom a crosslink or it can react with the

second type to also fom a crosslink. For aliphatic and aromatic polyesters, the tee radicals occur primarîly on the carbon or ring adjacent on either side of the esta group. A similar behaviour is expected with carbonate groups although they are more sensitive to radiation than esters. For aliphatic chahs, fkee radicals occur primarily on ternary and secondary carbon because methyl groups are more difKcult to ionize. The ionization of polyethers occurs prmiarily on the carbon on either side of the ovgen, however breakage of the ether bond cm also happen.

2.2.3 Impact on macroscopic properties

Chernical changes induced by radiation also impact on the macroscopic properties of the material. Those changes are due primarily to the simultaneous occurrence of crosslinking and chah scission. The yieield of a polymer for each reaction is dictated by its structure and morphology therefore respective G(X) and G(S) are difFerent for each material. For crosslinking to predominate, yields require to be 4G(X) > G(s)'~'. Since both chin lengthening and shortenhg occur, the molecular weight htiution (MWD) wiU tend to widen. However, ifscission is largely predorninant, the MWD narmws dovm to a decreasing MW average. Crosslinking can also alter thermal properties by increasing the glas transition, crystallization and melting ternperatures, while chah scission achieves the opposite.

A polymer with a tendency to crossluik increases its viscosity until the formation of a gel and then adopts the properties of a themosetn' which is a polymer that does not possess a rnelting point like a thennoplastic. The polper becomes harder, stronger and more brittle. Polymers prone to scission decrease their viscosity, become sofier and weaker.

Structural changes cm also decrease the crystallindy of a polymer, thereby reducing its strengd2? Crystal defects caused by radiation can migrate to the surfàce of the mal resulting in a reduction m the crystal thickness or size. Crystal defects also create coloured centers by the entrapment of electrons and ions m the crystal lattice, inducing a colour change m the overall appearance of the polymero. For example, this radiation-induced coloration is responsible for poly (methyl methacryhte) (PMMA) tuming to yellow and polycarbonate tirmingto green after irradiationRo!

2.2.4

Degradation

Environmental conditions are very important when considering the darnage perfiormed by radiation on materials. When contaminants infiltrate or corne in contact with the polymer during irradiation, the impurïties scavenge polymer radicals and the crosslinking process can be severely disadvantaged as opposed to chah scission and the polymer degrades very rapidly. Chain scission is the primary cause of degradation in a

polymer, however degradation cm be accelerated if inrpurities, like water, are present in the polymer by terminahg reactive sites by combination with polyrneric fkee radicalsB8). Also, extensive oxihtion cm occur deep in the materia1 if it is eqosed to air during or after radiation.

Oxygen reacts with fkee-radicals generated by radiation m the miuiner shown below (Equatiom 2.6-2.11). Due to its high diffusivity and its reactivity with radicals, oxygen greatly impedes the radical reaction pathways that occur in the absence of oxygen and force reactions into primarily oxibtive routes. Peroxides can also be formed and cm breakdown into more radicals and propagate the creation of other peroxides. This cycle can increase considerably the amount of free-radicals in the polymer structure and greatly accelerate the degradation process40:

The presence of water during or after irradiation can also accelerate the deterioration of polymers m the same maaner as oxygen does, by propagatmg Eee- radicals, as shown belowR8'(Equations 2.12-2.16):

+

-

H20

OH* + H,O+

H20 -

radiation

H202, HZ,Ha , eq

H20 - H20*

radiation

(2.13)

(2.14)

2.3 Poly Ether Ether Ketone (PEEIC)

PEEK is a general-purpose mouiding and extrusion materiai, in both natural and

reinforced forms, with many high perfiormance applications"? Typical industries using the polymer are the electrical (cable, insulation), automotive (bearings, piston skirts), aerospace (structural components), oil (valves, pumps, seals), and chernical industries

(compressor valve plates, pH meters).

fdy, are engineering plastics increasingly in demand by high performance polymer users.

PEEK and new polyaromatics korn the same

2.3.1 ChemicaI characteristics

High molecular weight PEEK can be produced by poIycondensation under anhydrous conditons of a biphenyl and an aromatic dihaiide, in which the halogen atoms can be activated by carbonyl groups. The polymerization is accomplished at a temperature range of 200400°C with an aromatic sulfone solvent'? For example, 0.1M 4,4- difluorobenzophenone and hydroquinone are condenseci up to 320°C in the presence of diphenyl sulfone and anhydrous potassium carbonate. Of course, mare complex fonns of PEEK can be produced by chging the reactantsB9'. One major constramt of PEEK is that it is a dficult resin to manufacture because of batch procedures and insolubility.

PEEK has no comon room-temperature solventS. Concentrated sulfiuic acid dissolves and sulfonates the polper. At higher temperatures, dilute solutions of PEEK can be fabricated Li hydrofluoric acid, trifiuoromethane~onic acid, or dichlorotetrduoroacetone monohydrate, and in phenol 1,2,4-trichlorobenzene, a solvent system used for gel permeation chromatography of PEEK. Benzophenone also produces a stable hi& temperature solution. PEEK is highly resistant to attack by hot water and stem up to 280°C at 18 MPa and for 3000 hours with almost no sigdcant degradation"? PEEK has a high oxidative and thermal stabiiity. This T a consequence of the molecular structure, which allows substantial electron overlap dong the molecuie. Its melt is thermaliy stable at 400°C for over one hour m the absence of air. PEEK is also non-flammable without retardant(3o!

2.3.2 Physical properties

PEEK resin is gray and normaIly crystahe at 35% with a density of 1.32 g/m3. PEEK's mechanical and chernical resistance properties(l" are highly dependent on its

crystallinity, which can be reduced or degraded by the presence of ortho and meta links in

cham versus para W. PEEK has a glas transition temperature (Ta of

143°C and a melting temperature (Tm)of 334°C.