peek - polyether ether ketone

8/19/2019 Peek - POLYETHER ETHER KETONE

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Technological University of the Philippines – Taguig Campus

Km. 14 East Service R. !estern "icutan# Taguig City

CHEMICAL ENGINEERING TECHNOLOGY

$%niviual Polymer&Polyether ether ketone

(PEEK)

Submtte! "y#

$el% Cru& "ry%n 'eher S*"+

CHEMICAL ENGINEERING TECHNOLOGY

Submtte! To#

E'(R. E)ER%T* +. +%',-*ES


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T*"E ,/ C,'TE'TS

%. +istorical 0evelopmentI+ Chronolo,-%l E.ent o/ E%rly Stu!e %n! $-o.ere o/ PEEK

II C*SS%/%C*T%,'S

%%%. Structure

III+ Stru-tur%l Re0reent%ton o/ PEEK

%. Properties

%.1 PEEK s. )etal

%.2 PEE3 s Stainless Steel an ,ther Polymers

%. PEEK (raes

. *pplications

%. )anufacturing

1I+ The m%nu/%-turn, 0ro-e o/ PEEK

%%. /a5rication of PEEK

%%%. PEEK Testing 6 *nalysis

%7. Property )oification of PEEK

7. Environmental %mpact an Relate %ssues

7%. )aterial 0egraation

7%%. *vancement

7%%%. RE/ERE'CES

%. +%ST,R%C* 0EE,P)E'T


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18292 The 3rt Pre0%r%ton o/ -om0letely %rom%t- 0olyether ketone 4% re0orte! by "onner o/ $u Pont () 5 4ho

obt%ne! 0olymer o/ lo4 mole-ul%r 4e,ht by the 0oly%royl%ton re%-ton (*) un, both o0hth%loyl %n!

tere0hth%loyl -hlor!e % monomer 4thNtroben&ene % ol.ent %n! %lumnum -hlor!e % the -%t%lyt

/igure 1# Pre0%r%ton o/ -om0letely %rom%t- 0olyether ketone 4th o0hth%loy %n! tere0hth%loyl -hlor!e n

Ntroben&ene eth %lumnum -hlor!e % -%t%lyt

182: 2 In ICI5 Im0er%l -hemtry In!utry5 Goo!m%n et %l5 0er/orme! ml%r e60erment %n! 4ere the /rt to re0ort

% 0olymer tru-ture 4h-h they m%!e by the re%-ton (7) un, %lumnum -hlor!e % -%t%lyt %n! methylene -hlor!e

% ol.ent Th 0olymer %0e%re! not to melt %t *89 !e, C %n! h%! % re!u-e! .-oty5 R15 o/ 98:

+;*92A Polymer o/ the %me tru-ture 4% 0re0%re! .% re%-ton (8) by I4%kur% (7) 4ho note! th%t the 0olymer 4%

noluble n %ll the uu%l or,%n- ol.ent %n! ue! 0oly0ho0hor- %-! % the ol.ent < -%t%lyt /or h re%-ton

/igure 2# (7) Re%-ton 4h-h n-re%e! the 0ro0erty o/ the 0olymer (H,her Meltn, 0ont) by Goo!m%n et %l

(8) A re%-ton 0er/orme! by I4%kur% 4ho note! th%t the 0lymer 4% noluble to -ommon ol.ent ue! /or mot o/

the 0olymer

18:2 A mu-h more e//e-t.e %-!- ytem 4% !e.e! by M%rk 5 4orkn, /or !u Pont5 4ho /oun! th%t l=u!

hy!ro,en /luor!e 4% % ,oo! ol.ent /or 0oly%ryl ether ketone

18;9 > !u Pont !%,ree! to te % knot 4th the ICI 4h-h % /ormer 0%rtner !e.elo0n, other 0olymer 4h-h

-ommer-%l&e! %n! mono0ol&e! to ,%n hu,e money

18;9 2 'ohn Roe (% -hemt 4orkn, /or ICI Pl%t-) !e-!e! to n.et,%te h,h tem0er%ture m%ter%l He 4%nte! to

/n! % m%ter%l th%t 4oul! h%.e % h,h meltn, 0ont %n! %lo be ret%nt to o6!%ton

18 The ICI P%tente! the re%-ton5 0ro!u-n, 0oly%ryl ether ketone

18 throu,h /urther !e!-%ton5 ICI !-o.ere! the Polyether ether ketone (PEEK) /rom the /%mly o/ Poly%ryl

ether ketone A % re.en,e5 they !ene! !u Pont /rom ben, % -om0%ny 0%rtner to -ommer-%l&e! the ne4ly

!-o.ere! 0olymer PEEK


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18=2 – The U.S. grante the %C% for patenting the polymer# PEEK

1889 – Polyether ether 3etones >ere commerciali?e.

1889@ PEEK be-%me %n m0ort%nt h,h20er/orm%n-e thermo0l%t- -%n!!%te /or re0l%-n, met%l m0l%nt

-om0onent5 e0e-%lly n ortho0e!- %n! tr%um%t- %00l-%ton

188 2 1-tre6 /orme! /ollo4n, % m%n%,ement buyout /rom ICI S%le o/ ?+: mllon %n! le th%n @9 em0loyee5

/o-ue! 0rm%rly on the n!utr%l m%rket

1888 2 1-tre6 %-=ure u0tre%m %et throu,h the 0ur-h%e o/ our $3$PM m%nu/%-turn, te %t Rotherh%m5 K

(0%rt o/ the 0ro-e /or m%nu/%-turn, "$35 the key r%4 m%ter%l to m%ke PEEK)

299: 2 1-tre6 %-=ure the Se%l S%n! te on Tee!e5 K5 0%rt o/ the 0ro-e /or m%nu/%-turn, "$35 the key r%4

m%ter%l /or PEEK Rotherh%m %n! Se%l S%n! to,ether 0ro.!e % lon, term u00ly o/ r%4 m%ter%l %n! u0eror

0ro-e n m%nu/%-turn, "$35 the key r%4 m%ter%l /or PEEK


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%%. C*SS%/%C*T%,'S*. Classification 5ase on sourcesA

Polyether ether ketone -l%/e! % % ynthet- 0olymer5 hen-e5 t % m%nm%!e 0olymer It m%!e

by the !%lkyl%ton re%-ton o/ b0henol%te %lt

"en, % ynthet- 0olymer5 t h% %n %!.%nt%,e5 nterm o/ m%nu/%-tur%blty 4h-h b%l%n-e the

u00ly o.er ,ro4n,

number o/ !em%n!

". Classification 5ase on structureA

Polyether ether ketone -l%/e! % % Lne%r Polymer Poly(ether ether ketone)5 PEEK5 % lne%r

%rom%t- 0olymer 4th % re0e%t unt o/ three ben&ene rn, e0%r%te! by t4o ether bon! %n! one

-%rbonyl bon! % ho4n n /,ure 7

The -h%n 4hen he%te! -%n /lo4 e%ly Althou,h 0ro0erte o/ten %o-%te! 4th th ty0e o/

-h%n %re % 4e%k m%ter%l5 !u-tle 4th % lo4 !enty %n! meltn, 0ont5 Polyether ether ketone h%.e

h,h meltn, 0ont5 tron,er %n! t//er th%n other lne%r 0olymer

A5 % member o/ the 0oly%ryletherketone /%mly5 t h% %n %rom%t- mole-ul%r b%-kbone5 4th

-ombn%ton o/ ketone %n! ether /un-ton%l ,rou0 bet4een the %ryl rn, Th 0e-%l -hem-%ltru-ture m%ke PEEK e6hbt t%ble -hem-%l %n! 0hy-%l 0ro0erte #t 4e%r2ret%nt %n! t%ble

%t h,h tem0er%ture B t ret%nt to %tt%-k by %ll ubt%n-e %0%rt /rom -on-entr%te! ul/ur- %-! B t

rem%n t%ble n terl&%ton 0ro-ee

Figure 3: PEEK resin produced through laboratory


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C. Classification 5ase on molecular forcesA

PEEK % em-ryt%llne thermo0l%t-5 the 0olymer -h%n %o-%te throu,h ntermole-ul%r /or-e5

4h-h 4e%ken r%0!ly 4th n-re%e! tem0er%ture5 yel!n, % .-ou l=u! Thu5 Polyether ether ketone

m%y be reh%0e! by he%tn, %n! %re ty0-%lly ue! to 0ro!u-e 0%rt by .%rou 0olymer 0ro-en,

te-hn=ue u-h % ne-ton mol!n,5 -om0reon mol!n,5 -%len!ern,5 %n! e6truon

0. Classification 5ase on moe of polymerisationA

PEEK 0olymer %re obt%ne! by te02,ro4th 0olymer&%ton by the !%lkyl%ton o/ b0henol%te %lt

Ty0-%l the re%-ton o/ 757D2!/luoroben&o0henone 4th the !o!um %lt o/ hy!ro=unone5 4h-h

,ener%te! n tu by !e0roton%ton 4th o!um -%rbon%te The re%-ton -on!u-te! %roun! *99 C n

0ol%r %0rot- ol.ent 2 u-h % !0henyl ul0hone

Ste02,ro4th 0olymer&%ton re/er to % ty0e o/ 0olymer&%ton me-h%nm n 4h-h b2/un-ton%l ormult/un-ton%l monomer re%-t to /orm /rt !mer5 then trmer5 lon,er ol,omer %n! e.entu%lly

lon, -h%n 0olymer

$ue to the n%ture o/ the 0olymer&%ton me-h%nm5 % h,h e6tent o/ re%-ton re=ure! to %-he.e

h,h mole-ul%r 4e,ht The e%et 4%y to .u%l&e the me-h%nm o/ % te02,ro4th 0olymer&%ton

% ,rou0 o/ 0eo0le re%-hn, out to hol! ther h%n! to /orm % hum%n -h%n F e%-h 0eron h% t4o

h%n! ( re%-t.e te)

Figure 4: Structure of Polyether ether ketone

Figure : Synthesis of Polyether ether ketone via Step!

gro"th poly#eri$ation


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%%%. STRUCTURE

PAEK % /%mly o/ h,h20er/orm%n-e thermo0l%t- 0olymer5 -ontn, o/ %n %rom%t- b%-kbone

mole-ul%r -h%n5 nter-onne-te! by % ketone %n! ether /un-ton%l ,rou0 Thu5 PEEK belon, to % l%r,er

/%mly o/ PAEK 0olymer5 Sometme re/ere! to % Poly ether ketone (PEK) or more m0ly %Polyketone

The -hem-%l 3ormul% o/ PEEK ho4n n 3,ure @ Other member o/ PAEK /%mly th%t %re

-on!ere! /or m0l%nt n-lu!e PEK %n! Polyether ketoneketone (PEKK)5 4hth -hem-%l tru-ture

!e0-te! n 3,ure: PEEK the !omn%nt member o/ the PAEK /%mly /or m0l%nt %00l-%tonThe -hem-%l tru-ture o/ PEEK5ml%r to t PAEK -oun5-on/er t%blty %t h,h tem0er%ture

(e6-ee!n, *99 !e, C)5 ret%n-e to -hem-%l %n! r%!%ton !%m%,e5 -om0%tblty 4th m%ny ren/or-n,

%,ent ( u-h % ,l% %n! -%rbon /ber) %n! ,re%ter tren,th (On % 0er m% b%) th%n m%ny met%l5

m%kn, t h,hly %ttr%-t.e n n!utr%l %00l-%ton5 u-h % %r-r%/t %n! turbne bl%!e It t%blty5

bo-om0%tblty5 r%!olu-en-y5 %n! me-h%n-%l 0ro0erte m%ke PEEK % ut%ble bom%ter%l /orortho0%e!- %n! 0ne m0l%nt


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n/lle! ne%t PEEK %.%l%ble % t%n0ellet or 0o4!er ( 3,ure J) 4h-h -%n be -on.erte! nto m0l%nt

0%rt by t%n!%r! 0olymer 0ro-en, te-hn=ue u-h % ne-ton mol!n,

%. Properties

T%ble + # Key Pro0erte o/ PEEK

%able &: Speci'c Properties of Polyether ether ketones


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PEEK % em-ryt%llne thermo0l%t- 4th e6-ellent me-h%n-%l %n! -hem-%l ret%n-e

0ro0erte th%t %re ret%ne! to h,h tem0er%ture The 0ro-en, -on!ton ue! to mol! PEEK -%n n/luen-e the

-ryt%llnty5 %n! hen-e the me-h%n-%l 0ro0erte

The Youn,D mo!ulu *@ GP% %n! t tenle tren,th ;9 to +99 MP% PEEK h% % ,l% tr%nton

tem0er%ture o/ %roun! +7* C (J; 3) %n! melt %roun! *7* C (@@ 3) Some ,r%!e h%.e % ue/ul o0er%tn,

tem0er%ture o/ u0 to 89 C (7J 3) The therm%l -on!u-t.ty n-re%e ne%rly lne%rly .eru tem0er%ture

bet4een room tem0er%ture %n! ol!u tem0er%ture It h,hly ret%nt to therm%l !e,r%!%ton % 4ell % %tt%-k

by both or,%n- %n! %=ueou en.ronment It %tt%-ke! by h%lo,en %n! tron, "ronte! %n! Le4 %-! % 4ell

% ome h%lo,en%te! -om0oun! %n! %l0h%t- hy!ro-%rbon %t h,h tem0er%ture It oluble n -on-entr%te!

ul/ur- %-! %t room tem0er%ture5 %lthou,h !oluton -%n t%ke % .ery lon, tme unle the 0olymer n % h,h

ur/%-e %re% to .olume /orm u-h % % /ne 0o4!er or thn /lm

Sho4n n both t%ble ( T%ble +5 %n! T%ble ) 5 It h% %n E6-ellent -hem-%l ret%n-e 1ery lo4moture %bor0ton Inherently ,oo! 4e%r %n! %br%on ret%n-e %n! n%//e-te! by -ontnuou e60oure to

hot 4%ter or te%m


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*. PEEK S )ET*S

PEEK %n !e%l re0l%-ement /or t%nle teel5 other ty0e o/ met%l tubn,5 %n! e.en ,l%5 /or 4e,ht re!u-ton5

-om0%r%ble tren,th


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". PEEK s. Stainless Steel an ,ther Polymers

A ho4n n t%ble 75 n term o/ t Tem0er%ture 0er/orm%n-e5 G%m% r%!%ton5 t ret%n-e to -hem-%l5 %n!

0re.enton o/ !menon%l -h%n,e5 Polyether ether ketone !oe .ery 4ell5 th%n to mot o/ the 0olymer5 %n! e.en

to the mot -ommer-%lly 0ro!u-e! %n! h,hly !em%n!e! met%l m%ter%l5 t%nle teel5 4thout %-r/-n, the

0e-/- 4e,ht 5 4h-h !er%ble to %ero0%-e %00l-%ton %n! -ln-%l %00l-%ton

It 5 ho4e.er5 .ery -otly to 0ro!u-e5 lke PT3E5 4h-h 4ll be !-ue! l%ter on5 n M%nu/%-turn,

C. PEEK (raes

c.1. PEEK BUnfille

Th ,ener%l 0ur0oe ,r%!e unren/or-e! %n! o//er the h,het elon,%ton %n! tou,hne o/ %ll PEEK

,r%!e n/lle! PEEK %.%l%ble n heet %n! ro! /orm n n%tur%l (% .ery l,ht bro4n or t%n) -olor (ho4n

n 3,ure ;) %n! %lo %.%l%ble n bl%-k "l%-k PEEK !e%l /or ntrument -om0onent 4here %ethet-

%re m0ort%nt5 % 4ell % /or e%l -om0onent 4here !u-tlty %n! nertne %re m0ort%nt All un/lle! PEEK,r%!e -om0ly 4th 3$A re,ul%ton + C3R +::7+8 /or re0e%te! /oo! -ont%-t

',TEA "oe!eker Pl%t- no4 -%rre 1r,n PEEK 789G Tube Sto-k

%able 4: Properties of Polyether ether ketaone vs- Stainless

steel and other co##on poly#ers


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c.2. PEEK B9D (lass /ille

The %!!ton o/ ,l% /ber ,n/-%ntly re!u-e the e60%non r%te %n! n-re%e the /le6ur%l mo!ulu o/

PEEK Th ,r%!e !e%l /or tru-tur%l %00l-%ton th%t re=ure m0ro.e! tren,th5 t//ne5 or t%blty5

e0e-%lly %t tem0er%ture %bo.e *993 (+89C) Gl%2/lle! PEEK l,ht bro4n or t%n n -olor

c.. PEEK B9D Car5on /ille

The %!!ton o/ -%rbon /ber enh%n-e the -om0re.e tren,th %n! t//ne o/ PEEK5 %n! !r%m%t-%lly

lo4er t e60%non r%te It o//er !e,ner o0tmum 4e%r ret%n-e %n! lo%! -%rryn, -%0%blty n % PEEK2

b%e! 0ro!u-t Th ,r%!e 0ro.!e * tme h,her therm%l -on!u-t.ty th%n unren/or-e! PEEK 22

!0%tn, he%t /rom the be%rn, ur/%-e /%ter C%rbon2/lle! PEEK bl%-k n -olor

Figure .: /irgin ( 0n'lled ) Polyether ether ketone

Figure 12: 9D (lass /ille ! Polyether ether ketone


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c.4. PEEK B"earing (rae# Ketron +P

Th ,r%!e o/ PEEK5 -ont%nn, -%rbon /ber ren/or-e! 4th ,r%0hte %n! PT3E lubr-%nt5 o//er the lo4et

-oe//-ent o/ /r-ton %n! the bet m%-hn%blty /or %ll PEEK ,r%!e "e%rn, ,r%!e PEEK h% %n e6-ellent

-ombn%ton o/ lo4 /r-ton5 lo4 4e%r5 h,h lmtn, P15 lo4 m%tn, 0%rt 4e%r5 %n! e%y m%-hnn, "e%rn,

,r%!e PEEK bl%-k or !%rk ,rey n -olor

Figure 11: 9D Car5on /ille ! Polyether ether

ketone

Figure 1&: 9D Car5on /ille ! Polyether ether

ketone


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In the t%ble 8 ho4n %bo.e5 o/ %ll the three ,r%!e o/ Polyether ether ketone5 n-lu!n, %lo5 the un/lle!5 .r,n

Polyether ether ketone5 the PEEK ,r%!e th%t 0oee the h,het unt o/ 0ro0erte5 PEEk /lle! 4th *9 -%rbon

It be-%ue o/ the -h%n,e n Mole-ul%r 4e,ht

0. %nfluence of molecular >eight on the properties of Polyether ether 3etone

1%r%ton n mole-ul%r 4e,ht o/ 0oly(ether ether ketone) ,n/-%ntly %lter t 0ro-en, beh%.or5 0ro!u-t 0ro0erte5

%n! 0er/orm%n-e

%able : Properties of Polyether ether ketone rdaes


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e ue! mole-ul%r 4e,ht (me%ure! by &e2e6-luon -hrom%to,r%0hy) o/ *59995 :59995 %n! *:5999,


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M%ny %0e-t o/ PEEK 0ro-en, %n! 0er/orm%n-e beh%.or %re rel%te! to t rel%6%ton -h%r%-tert-5 4h-h h%.e

not 0re.ouly been re0orte! Our rel%6%ton tu!y o/ PEEK5 un, % 0%r%llel20l%te rheometer5 !emontr%te! th%t %

l,ht n-re%e n mole-ul%r 4e,ht -%n ,n/-%ntly n-re%e the rel%6%ton tme# PEEK+; e6hbte! rel%t.ely

lne%r beh%.or5 %n%lo,ou to rubber2ty0e rel%6%ton (ee 3,ure +7) Ho4e.er5 PEEKJ9 %n! PEEK;7 h%.e %t le%t

t4o !//erent rel%6%ton re,on

e -on!u-te! rheolo,-%l tu!e un, % -%0ll%ry rheometer n te%!y he%r mo!e %n! % 0%r%llel20l%te rheometer n

both te%!y %n! !yn%m- mo!e The bro%! r%n,e o/ he%r r%te /rom thee e60erment en-om0%e! -on!ton

rele.%nt to PEEK melt 0ro-en,5 e-on!%ry o0er%ton5 %n! tre rel%6%ton In the entre he%r2r%te re,on tu!e!5

the he%r .-oty n-re%e! !r%m%t-%lly 4th n-re%e! mole-ul%r 4e,ht (ee 3,ure +8) A!!ton%lly5 !ouble2

he%r2thnnn, beh%.or5 %n%lo,ou to th%t o/ l=u!2-ryt%llne 0olymer5 !tn,uhe PEEK /rom m%ny other

0olymer e !etermne! the !ouble2melt he%r2thnnn, re,on o/ PEEK In lo42/re=uen-y re,on5 t -%n be

%,ne! to mole-ul%r rel%6%ton %t -ryt%llne nter/%-e %n! rel%te! to the !ouble2melt20e%k 0henomenon o/

PEEK

Figure


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In umm%ry5 un!ert%n!n, the n/luen-e o/ mole-ul%r 4e,ht on the PEEK therm%l5 me-h%n-%l5 %n! rheolo,-%l beh%.or5 %n! 0ro!u-t 0er/orm%n-e 4ll be ue/ul /or o0tm&%ton o/ 0ro!u-t !e.elo0ment A!!ton%lly5 both

0rm%ry %n! e-on!%ry -on.eron 0ro-ee (u-h % ne-ton mol!n, %n! e6truon on the one h%n! %n! %nne%ln,

%n! 0ot20ro-en, on the other) 4ll bene/t /rom th 4ork Th re0reent one !re-ton n our -ontnun, e//ort

to better un!ert%n! en,neern, %n! h,h20er/orm%n-e 0olymer ltm%tely5 the !e,n o/ h,h20er/orm%n-e PEEK

-om0ote 4ll be o0tm&e! be-%ue o/ %n un!ert%n!n, o/ thee mole-ul%r24e,ht


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PEEK -on/orm 4ell to the -on-e0tu%l 4orl! o/ % t4o 0h%e em2-ryt%llne 0olymer5 -ontn, o/ %n

%mor0hou 0h%e %n! -ryt%llne 0h%e Sml%r to em2-ryt%llne 0olymern-lu!n, utr% h,h mole-ul%r 4e,ht

0olyethylene (HMPE)5 the -ryt%llne -ontent o/ PEEK .%re!e0en!n, u0on t therm%l 0ro-en, htory

The -ryt%llnty o/ ne-ton mol!e! PEEK n m0l%nt ty0-%lly r%n,e /rom *9 to *85 by %!utn, the

-ooln, r%te !urn, /%br-%ton o//lm5 -ryt%ll&%ton o/ PEEK -%n be ,re%tly re!u-e!5 reultn, % ne%rly

-om0letely %mor0hou m%ter%l

. *pplicationsA HPLC A00l-%ton

PEEK h% be-ome the ,ol! t%n!%r! /or HPLC %n%lyt-%l -en-e %00l-%ton !ue to t 0urty5 h,h burt

0reure5 %n! -hem-%l nertne %n! ret%n-e It %lo ret%nt to or,%n- %n! nor,%n- ol.ent

Chrom%to,r%0her .%lue PEEK /or t tren,th5 /le6blty5 %n! e%e o/ -uttn,

Pro0erty o/ PEEK eent%l /or th %00l-%ton#

• Purty

• H,h burt 0reure

• Chem-%l ret%n-e

PEEK (0oly ether ether ketone) tubn, h% be-ome % t%n!%r! tem n the o0er%ton o/ m%ny HPLC ytem It

-on.enent5 ne60en.e5 %n! e%y to !ent/y the ntern%l !%meter Ho4e.er5 ome -%re nee! to be t%ken to %.o!

0roblem %o-%te! 4th PEEK tubn, .

Mot re.ere!20h%e HPLC %00l-%ton 4th ytem runnn, %t -on.enton%l 0reure (Another %!.%nt%,e o/

PEEK th%t t e%ly -ut to %ny !ere! len,th 4th % m%ll ,ullotne2lke -utter -ont%nn, % r%&or bl%!e "ut be

-%re/ul not to -ut the tubn, by l-n, throu,h t lke you 4oul! 4th % 0%r o/ -or > th -%n blo-k the lumen o/

the tubn, R%ther5 0n-h the -utter %n! rot%te t %roun! the tubn, untl % ,roo.e -ut %ll the 4%y %roun! the tubn,

The tubn, then -%n be n%00e! %t the -ut5 le%.n, the lumen o0en A 4th SS tubn,5 t 4e to run % /e4

mlllter o/ ol.ent throu,h the tubn, to 0ur,e %ny 0%rt-ul%te m%tter le/t /rom the -uttn, 0ro-e 'ut -onne-t the

u02tre%m en! o/ the tubn, to the HPLC ytem %n! turn on the 0um0 /or % mnute or o

An %!.%nt%,e %bout PEEK tubn, th%t t e%ly !ent/e! Mot m%nu/%-turer -olour2-o!e the tubn,5 %

ho4n n 3,ure +: The br%n! ho4n ue re! to -o!e the 99982n (9+82mm) %n! yello4 /or the 999:2n (9+:82

Fi ure


19/58

mm) ! tubn, Other 4oul! 0rob%bly 4orre! %bout the -olour le%-hn, out %n! -%un, 1 nter/eren-e "ut

ome -hemtQ l%bor%tory !! e6ten.e tetn, %n! !! not /n! %ny e.!en-e o/ 0roblem 4th e6tr%-te! 0,ment

/igure 1


20/58

Alo5 %lthou,h you -%n ue PEEK /ttn, 4th SS tubn,5 !onQt try the re.ere SS /errule -%n 0n-h PEEK tubn,

-loe! or / o.er2t,htene!5 -%n -ut o// the t0 o/ the tubn,

" Aero0%-e

PEEK 0%rt-ul%rly ue/ul n the %ero0%-e /el! /or t 4e,ht In %n %00l-%ton 4here t4o ,r%m -%n m%ke %

!//eren-e %n! 4here 4e,ht !re-tly -orrel%te! to /uel -ot5 l,ht4e,ht PEEK tubn, u0eror to t%nle teel

PEEK m%t-he %lumnum n me-h%n-%l 0ro0erte5 %n! more ret%nt to /lu! u-h % hy!r%ul- /lu! Thn4%llPEEK more /le6ble %n! knk ret%nt th%n %lumnum tubn, PEEK -on.olute! tubn, %loue! /or t %br%on

ret%n-e 0ro0erte5 to 0rote-t .ulner%ble 4re lo-%te! n %re% 4here they -oul! be -ruhe! or e.ere! PEEKQ

tren,th5 4e,ht5 %n! he%t ret%n-e %re !e%l /or th %00l-%ton


• L,ht4e,ht• Stren,th

• Chem-%l ret%n-e

Aero(0%-e en,neer( re=ure l,ht4e,ht m%ter%l( th%t 0r o.!e 0ro-e((n,

/ le6 blty5 re!u-e m%nu/%-turn, -ot5 %n! 0r o.!e !ur%blty n h%r(h

en.ronment()PEEK 0olymer h%.e (u--e((/ully !(0l%-e! met%l(5 tr%!ton%l

-om0o(te( %n! other 0l%t- n % ,ro4n, number o/ %ero(0%-e % 00l-%ton

be-%u(e they %re e6-e0ton%lly (tron,5 nert5 %n! nher ently /l%me ret%r!%nt5

%n! -%n be e%ly /%br-%te! nto t,ht toler%n-e 0%rt() 1ICTRES PEEK 0olymer (

h%.e been o// -%lly =u%l/e! by m%ny %r-r%/t m%nu/ %-tur er ( %n! -%n %lo be(u00le! to the mlt%ry (0e-/-%ton MIL2P27@+J*)

PER /,R )*'CE

St%blty %t Ele.%te! Tem 0er %tur e(

M%ny %ero(0%-e -om0onent( mu(t en!ure -ontnuou( lon, term e60o(ure to ele.%te!

tem0er%ture() PEEK 0olymer e6tremely (t%ble 4hen tete! %,%n(t other -ommonly kno4n h,h

he%t ther mo0l%t-

Fi ure


21/58

Se.er %l ne4 PEEK 0olymer ,r%!e( %n! -om 0oun! %re %.%l%ble to m%6m&e

me-h%n-%l 0ro0erte( %n! m 0r o.e mol!%blty)

+igh Temperature R esistance

$ue to the (em2-r yt%llne (tru-ture o/ 1ICTRE PEEK 0olymer me-h%n-%l

0ro0erte( %re m%nt%ne! 4ell 0%(t the ,l% tr%n(ton tem 0er %tur e)

3,ur e +;# Yel! Str en,th % % 3un-ton o/ Tem 0er %tur e / or

PEEK Polymer (

/lamma5ility

1ICTRE PEEK 0olymer 0er/orm( e6-e0ton%lly 4ell n re(0e-t to /l%mm%blty)1ICTRE PEEK 789G L;7 129 r %te!

%t +8 mm %n! h% % Lmtn, O6y,en In!e6 o/ *8 %t * mm th-kne(( %n! 7 %t

97 mm th-kne(() Thee / l%mm% blty -h%r%-ter(t-( %re nher ent n the m%ter%l %n!

%re %-he.e! 4thout the n-lu(on o/ %ny /l%me ret%r!%nt m%ter%l( (u-h % h%lo,en2

b%(e! %!!t.e() In te(t( to me%(ure (mok e 0ro!u-e! by the -ombu(ton o/ 0l%(t-

m%ter%l(5 the !%t% (ho4( th%t un/lle! 1ICTRE PEEK 0olymer h% the lo4et .%lue

o/ 0e-/- o0t-%l !en(ty o/ %ll the m%ter%l( tete!


22/58

.

ToEic (as Emission

1ICTRE PEEK 0olymer 0ro!u-e( .ery lttle to6- ,%(e( 4hen -ombu(te!) It

0ro!u-e( m%nly -%rbon !o6!e %n! -%r bon mono6!e u0on 0yroly(() 1ICTREPEEK 789G h% % to6-ty n!e6 o/ 9 (MO$ NES :+*) 4th no %-! ,%(e( !ete-te!)

Coeff icient of Thermal EEpansion

The n-lu(on o/ /ller nto 1ICTRE PEEK 0olymer re(ult( n % re!u-ton n the

-oe//-ent o/ e60%n(on to % le.el 4her e t -om0%r%ble to met%l(5 thu( %llo4n,

!re-t r e 0l%-ement o/ met%l -om0onent( 4th 0olymer2b%(e! -om 0onent 4thout

%ny rk %r(n, !ue to !//erent%l e6 0%non)


23/58

1

3,ur e +# Coe// -ent o/ Lne%r E6 0%n(on n 3lo4 $re-ton o/ 1ICTRES PEEK Polymer 2

"%(e! M%ter%l n Com 0%r (on 4th Other Common Aer o( 0%-e M%ter %l(

Strength

1ICTRE PEEK 0olymer h% h,h 0e-/- tr en,th -om 0%r e! to met%l() R en/ or -n,

4th -ho00e! ,l% or -%rbon / ber yel! (tren,th2to24e,ht r%to( th%t meet or

e6-ee! thoe o/ -ommon %ero(0%-e m%ter%l() Contnuou /ber r en/ or -e!

-om0o(te( m%!e 4th % 1ICTRE PEEK 0olymer m%tr6 h%.e (,n/-%ntly h,her

(tr en,th %n! (t// ne

3,u

r e *# S0e-/- St

r en,th o/

1ICTRES PEEKPolyme

r 2"%(e!

M%ter%l n Com 0%r (on 4th Other Common Aer o( 0%-e M%ter %l(


24/58

1

Chemical R esistance

PEEK 0olymer h% e6-e0ton%l re((t%n-e to % 4!e r%n,e o/ %-!5 b%(e( %n!

hy!ro-%rbon( n-lu!n, Cet / uel %n! hy!r%ul- /lu!) So%k n, PEEK -om0oun!(

n

:9C (+8J3) hy!r%ul- /lu! /or +5999 hour( le! to le th%n % 8 -h%n,e nnomn%l 0ro0erte( o/ ten(le (tr en,th5 ten(le mo!ulu( %n! ten(le elon,%ton)

E.ECTR%C !%RE "U'0.E *'0 TU"%'( C.*)PS

PEEK 0olymer h% been -ou0le! 4th % 0r o0r et%r y (l-one o.ermol!n, 0ro-e(( to

0ro!u-e % r%n,e o/ 4r n,5 tubn, -l%m0( %n! (t%n!2o//( th%t !el.er (,n/-%nt

4e,ht %n! -o(t (%.n,( on the ne4 "oen, :J: %r -r %/ t)

A!.%nt%,e#

• Oe,ht re!u-e! .eru %lumnum

• P%rt -ount re!u-e! by -onol!%ton

• M%ter%l -om0letely non2-orro(.e %n! non2-on!u-t.e /or ue throu,hout

un20re((ur&e! &one)

Figure &4: 5iring and table cla#ps #ade fro# PEEK

Poly#er


25/58

1

%)PE..ER ".*0ES

1ICTRE PEEK 0olymer h% been u(e! to re0l%-e met%l 0ro0eller( %n! m0eller( n %

.%rety o/ %ero(0%-e !e.-e n-lu!n, ol -ooln, (y(tem %n! .entl%ton (y(tem

/ %n u(e! /or lo4 0re((ure %r !el.ery n hel-o0ter() They -%n be !e(,ne! to 4e,h

mu-h le th%n met%l -om0onent(5 h%.e le nert% %n! re!u-e the hor(e0o4erre=urement( o/ the motor( u(e! to 0n the bl%!e)

*ir craft oor hanles

Oe,ht re!u-ton 4% 0%r%mount 4hen !e.elo0n, the

Arbu A*J9 Th n-lu!e! !oor h%n!le (y(tem) PEEK 0olymer 4% the onlym%ter%l to ur..e the Ar butet 0ro,r%m /or !oor h%n!le() Com 0onent %ren e-ton mol!e! %n! h%.e -om0le6 ,eometre( 4th numer ou rbbn, %n! lon,/lo4 0%th

C%ble Te(

e! /or bun!ln, %n! (e-urn, 4re %n! -%ble( to the %r/r%me) Lo4 motur e

%b(or0ton o/ 1ICTRE PEEK 0olymer en(ure( the !men(on%l nte,rty o/ the te( o

they 4ll not 4ell %n! !%m%,e 4re nul%ton)

Figure &: Environ#ental control syste# #ade fro# PEEK

Poly#er

Figure &6: 7oor 8andles in ,irplane

#ade fro# PEEK Poly#er


26/58

1

C Chem-%l Pro-en,

In the -hem-%l 0ro-en, n!utry5 PEEK -hoen be-%ue t nherently 0ure %n! h%

outt%n!n, -hem-%l ret%n-e nlke mot met%l5 u-h % t%nle teel or %lumnum5 PEEK-%n be ue! n lon, -ontnuou er.-e %00l-%ton 4th .rtu%lly no le.el o/ -ont%mn%ton

ntro!u-e! to the -hem-%l ben, 0ro-ee! PEEK h% been ho4n to out0er/orm /luoro0olymer

4th t e6-ellent /%t,ue ret%n-e %n! ,ener%l me-h%n-%l 0ro0erte


• Inherently 0ure

• Chem-%l ret%n-e

• H,h -ontnuou er.-e tem0er%ture (8993


27/58

1

+ip *rthroplasty

Th !ur%ble m%ter%l %!!ree the nee! /or ne45 lon,er2l%tn, !e,n /or youn,er %n! more

%-t.e 0%tent E6-ellent 4e%r ret%n-e %n! e6-e0ton%l tru-tur%l tren,th m%ke t %n !e%l

-ho-e /or h0 -u0 th%t u00ort bone2-oner.n, -on-e0t

PEEK2OPTIMA e%r Per/orm%n-e o//er %n %ltern%t.e lo%!2be%rn, m%ter%l to met%l !e,ne!to %!!re met%l on -on-ern It /e%ture % mo!ulu ml%r to hum%n bone5 4h-h re!u-e tre

hel!n, %n! le%! to m0ro.e! 0hyolo,-%l lo%!n,

PEEK2OPTIMA e%r Per/orm%n-e %--ommo!%te both t%n!%r! %n! ne4 m0l%nt /6%ton

te-hnolo,e It r%!olu-ent %n! -om0%tble 4th -ommon m%,n, te-hnolo,e Th %llo4m0ro.e! .u%l%ton /or 0l%-ement %n! 0ot2o0er%t.e /ollo4 u0 n the month %n! ye%r %/ter

ur,ery

• S-reenn, tet %n! h0 %n! knee mul%tor tet n!-%te th%t e6tremely lo4 4e%r -%n be

%-he.e! %,%nt met%l %n! -er%m- -ounter/%-e

+

• An %-et%bul%r -u0 be%rn, %,%nt % 87mm -er%m- he%! ho4e! % 4e%r r%te o/

%00ro6m%tely +mm*


28/58

1

Knee *rthroplasty

In 9+9 more th%n ;95999 knee re.on ur,ere 4ere 0er/orme! n the S %n! Euro0e Th

n!-%te th%t ome J o/ %ll knee m0l%nt 0ro-e!ure reult /rom /%lure o/ the nt%l kneem0l%nt A -ontrbutn, /%-tor to thee /%lure !lo-%ton5 4hereby the rot%ton%l %6 l0 out

o/ t ,u!e5 re=urn, tot%l re0l%-ement o/ the m0l%nt

Hn,e -ontru-t m%!e /rom PEEK2OPTIMA Ren/or-e! %n! PEEK2OPTIMA e%r Per/orm%n-e

o//er u0eror -ol!2/lo4 ret%n-e % 4ell % !menon%l t%blty !urn, the !e.-e l/etme (+8

ye%r) -om0%re! to tr%!ton%l hn,e me-h%nm th%t ue HMPE5 4h-h ret !lo-%ton In

%!!ton5 the PEEK2OPTIMA 0olymer h% % /le6ur%l tren,th ml%r to the -ort-%l bone5 thu

re!u-n, tre hel!n, %n! m0ro.n, 0%tent -om/ort It 0ro.en bo-om0%tblty %n!

bot%blty n m0l%nt%ble !e.-e 4orl!4!e 0ro.!e %/ety5 lon,e.ty %n! re%ur%n-e to

0%tent %n! ur,eon %lke

Figure &: a-) 8ip i#plant #ade fro#

poly#er(left) b-) 8ip ,rthroplasty by PEEK


29/58

1

Shouler *rthroscopy

PEEK2OPTIMA N%tur%l /e%ture me-h%n-%l 0ro0erte th%t %llo4 rel%ble uture retenton /orknotle uture %n-hor Commonly ue! n the l%ter%l ro4 o/ % !ouble2ro4 rot%tor -u// or n the

Gleno! /or SLAP %n! "%nk%rt re0%r5 knotle uture %n-hor %llo4 ur,eon to 0er/orm

0ro-e!ure /%ter %n! re!u-e the tme 0%tent %re un!er %nethe%

• The n%tur%l me-h%n-%l tren,th o/ PEEK2OPTIMA 0olymer h% ho4n rem%rk%ble

0er/orm%n-e n lo%!2to /%lure tren,th (3. A. Barber, M.A. Herbert, C. Beavis, F. Orro; J.of Arthroscopic and Related Surer!; "ol. #$, %o &; #''&) Th 4hy the m%ter%l

-ommonly ue! /or h,h2tren,th %n-hor

• PEEK2OPTIMA 0olymer %llo4 /or m0le 0ot2o0er%t.e m0l%nt %ement 4th no

m%,e %rt/%-t un, @r%y5 CT5 %n! MRI m%,n, metho!

• Com0letely bo2nert PEEK2OPTIMA 0olymer re!u-e the 0oble rk o/ 0%tent re%-ton

to % !e.-e m0l%nte! n the bo!y

• PEEK2OPTIMA N%tur%l %llo4 /or ,re%ter !e,n %n! 0ro!u-ton /le6blty /or ne-ton

mol!n, %n! m%-hnn, 0ro-ee5 en%bln, !e.elo0ment o/ m%ller m0l%nt%ble !e.-e

Figure &.: a-) knee i#plant #ade fro#

poly#er(left) b-) knee ,rthroplasty by PEEK


30/58

1

%. )anufacturing

Poly(%rylene ether ketone) (PAEK)5 u-h % PEK5 PEKK %n! PEEK %re %n m0ort%nt

-l% o/ h,h 0er/orm%n-e en,neern, thermo0l%t- !0l%yn, % un=ue -ombn%ton o/ therm%l

t%blty5 -hem-%l %n! ol.ent ret%n-e5 ,oo! me-h%n-%l 0ro0erte o.er % 4!e tem0er%ture

r%n,e5 ,oo! /re ret%n-e %n! ,oo! ele-tr-%l 0er/orm%n-e

b-)

a-)

Figure &.: a-) Shoulder i#plant #ade fro#

poly#er b-) Shoulder ,rthroplasty by PEEK


31/58

1

Thee 0olymer -%n be /%br-%te! by -on.enton%l te-hn=ue5 u-h % e6truon %n!

-om0reon mol!n,5 %n! -%n be %00le! % m%tr6 ren /or h,h 0er/orm%n-e ren/or-e!

-om0ote The T, %n! Tm .%lue %re uu%lly %mor0hou 0olymer %n! ube-t to %tt%-k by

ol.ent5 PAEK %re em-ryt%llne 0olymer %n! there/ore ret%nt to ol.ent5 4h-h %

-rt-%l /%-tor n %n %ero0%-e en.ronment Ho4e.er5 be-%ue o/ ther -ryt%llnty %n! the

reultn, nolublty5 to,ether 4th meltn, 0ont ,ener%lly %bo.e *99 !e, C5 thee 0olymer

%re %lo !//-ult to 0re0%re 4th u//-ently h,h mole-ul%r 4e,ht unle e6treme re%-ton

-on!ton %re ue!


32/58

1

PAEK %re ,ener%lly ynthe&e! by %n %rom%t- nu-leo0hl- ubttuton re%-ton o/ %-t.%te! %ryl

!h%l!e 4th %rom%t- !0henol%te n % !0ol%r %0rot- ol.ent5 or by ele-tro0hl- (3re!el2

Cr%/t) %-yl%ton o/ %ryl ether

1.2 Synthesis of PolyBarylene ether 3etones

1.2.1 Electrophilic Routes

In +;@5 "onner J

%t $uPont 4% the /rt one 4ho re0orte! the ynthe o/ 4holly

%rom%t- 0oly(ether ketone ketone) (PEKK) by 3re!el2Cr%/t %-yl%ton Io0hth%loyl

-hlor!e or tere0hth%loyl -hlor!e 4% -on!ene! 4th !0henyl ether un, ntroben&ene %

ol.ent %n! %lumnum tr-hlor!e % % -%t%lyt (S-heme +) Ho4e.er5 only lo4 mole-ul%r

4e,ht 0olymer (nherent .-oty5 I1 W 9+J !L


33/58

&

re%-ton %re -%rre! out n the 0reen-e o/ %n e6-e o/ %lumnum -hlor!e n non2b%- ol.ent

u-h % +52!-hloroeth%ne5 !-hloromethene5 or o2-hloroben&ene The nolublty o/ the 0olymer

n thee ol.ent lmt the /orm%ton o/ h,h mole-ul%r 4e,ht 0olymer S0e-%l tre%tment

uu%lly re=ure! to m0ro.e the melt t%blty In ome -%e5 ortho2%-yl%ton %n! %lkyl%ton o/

%rom%t- 0olymer -h%n %lo o--ur

The lo4 -ot %-! -hlor!e5 u-h % tere0hth%loyl -hlor!e %n! o0hth%loyl -hlor!e5%re 4e%ker b%e th%n 757Q2o6ybben&oyl -hlor!e %n! more !//-ult to %-t.%te by AlCl* The reultn,-%rbo-%ton- nterme!%te %re more re%-t.e %n! le ele-t.e to %rom%t- te5 4h-h le%! ton-re%e! ortho2%-yl%ton !urn, 0olymer&%ton

Polymer&%ton n the 0reen-e o/ % l%r,e e6-e o/ AlCl* -om0le6e! 4th % Le4

b%e5 u-h % $M35 LCl5 !methyl ul/one5 0yr!ne or % 2methyl0yr!num -hlor!e5 4ere

re0orte! by '%non et al to 0ro!u-e -le%ner %n! h,her mole-ul%r 4e,ht 0olymer %t or belo4

room tem0er%ture+5+*

The Le4 b%e -%n -om0le6 4th AlCl* to kee0 e6-e AlCl* n the

oluton The -om0le6 %!!u-t -%n be !ol.e! n % non2b%- ol.ent5 u-h % CHCl or

+52!-hloroeth%ne The 0ol%r -om0le6 oluton %lo n-re%e the olublty o/ 0olymer

-om0le6e th%t le%! to h,h mole-ul%r 4e,ht 0olymer Mot o/ the 4ork n th %re% 4%

ubmtte! /or 0%tent One o/ the e6%m0le n lter%ture 0ubl-%ton 4% re0orte! by 3uk%4%

%n! T%n%be p2Pheno6yben&oyl -hlor!e 4% 0olymer&e! n the 0reen-e o/ e6-e AlCl* %n!

0henyl ether -%00n, %,ent n % oluton o/ $M3 n methylene -hlor!e to ,.e PEK 4th

+*: !L


34/58

&

+5*2b( p20heno6yben&oyl)ben&ene 4th tere0hth%loyl -hlor!e5 %n! +572b( p20heno6y2 ben&oyl)ben&ene 4th o0hth%loyl -hlor!e (S-heme +*) Th 0er/e-tly %ltern%tn,-o0olymer o/ (eta %n! ortho 0henylene ,rou0 h% h,h T, (+@@ C) %n! lo4 Tm (** C)54h-h !er%ble /or /%-le 0ro-en, %n! h,h he%t !e/orm%ton ret%n-e

Poly0ho0hor- %-! -%n be ue! % % ol.ent to 0ro!u-e h,h mole-ul%r 4e,ht 0oly(ether

ketone ketone) Pre.ouly5 I4%kur%+@

re0orte! the ynthe o/ PEK 4th nherent

.-oty o/ 98 !L


35/58

&

PEK 4th %n nherent .-oty o/ +** !L


36/58

&

1.2.2 'ucleophilic Routes

The nu-leo0hl- %rom%t- ubttuton re%-ton n.ol.e ue o/ %-t.%te! %rom%t- !h%l!e %n!%rom%t- !0henol%te The ,ener%l re%-ton ho4n n S-heme +8 In ,ener%l5 % tron,ele-tron 4th!r%4n, ,rou0 u-h % -%rbonyl5 ul/one or 0ho0hne o6!e ne-e%ry to %-t.%tethe %rom%t- !h%l!e The re%-t.ty o/ the h%lo,en %re n the or!er o/ 3Cl"r Ty0-%lly

0ot%um -%rbon%te ue! % b%e to %.o! the !e re%-ton o/ %lk%l met%l hy!ro6!e+;

%n!!0ol%r %0rot- ol.ent u-h % $MSO5 $MA- %n! NMP %re utl&e!

'ohnon et al re0orte! the /rt %ttem0t to ynthe&e PEEK by 0oly-on!en%ton o/

b0henol%te 4th %-t.%te! !h%l!e un, $MSO % % ol.ent %n! N%OH % % b%e H,h

mole-ul%r 4e,ht 0olymer 4ere !//-ult to obt%n !ue to the -ryt%llnty %n! the reultn,

nolublty o/ 0olymer n $MSO To -r-um.ent the olublty 0roblem5 Att4oo!+

%n!

Roe

ue! !0henyl ul/one % % ol.ent to obt%n h,h mole-ul%r PEEK (S-heme +@) The

0olymer&%ton 4% -%rre! out ne%r the meltn, 0ont o/ the 0olymer to m%nt%n olublty

1-tre6 PEEK 4% -ommer-%l&e! by ICI n +;J un, th metho! At h,h tem0er%ture5 !e

re%-ton u-h % ether e6-h%n,e %n! -le%.%,e be-%me m0ort%nt n!er -%re/ul o0tm&%ton5

h,h mole-ul%r 4e,ht 0oly(ether ketone) -%n be obt%ne!


37/58

One o/ the m%or !r%4b%-k /or th ynthet- route the e60ene o/ /luoro monomer 3or

!h%l!e %-t.%te! 4th -%rbonyl ,rou05 le re%-t.e -hloro monomer /%l to 0ro!u-e h,h

mole-ul%r 4e,ht 0olymer S!e re%-ton u-h % n,le ele-tron tr%n/er re%-ton 4ere ober.e!!urn, 0olymer&%ton o/ !-hlor!e

To !e.elo0 % lo4 -ot route to PAEK5 e60en.e /luoro monomer %re ben, re0l%-e!

4th %-t.%te! -hloro monomer

$-hloro monomer 4ere %lo 0olymer&e! 4th b0henol n the 0reen-e o/ /luor!e %

0romotn, %,ent@

The /luor!e on 0romote the !0l%-ement o/ the -hlor!e te to /orm

more re%-t.e /luor!e te5 4h-h re%-t 4th 0heno6!e %non to /orm h,h mole-ul%r 4e,ht

0olymer The nu-leo0hl-ty %n! olublty o/ 0heno6!e %non n-re%e! by %!!n, 82+9 mol

0h%e tr%n/er -%t%lyt u-h % % 2%lkyl272(!%lkyl%mno)0yr!um -hlor!e:

The re%-ton tme

to obt%n the %me mole-ul%r 4e,ht 4% re!u-e! u0 to 8 /ol! -om0%re! to the un-%t%ly&e!

re%-ton

Kr-hel!or/ %n! -o4orker ue! trmethyllyl%te! 0henol to re%-t 4th %-t.%te! !/luoro

monomer5 u-h % 757Q2!/luoroben&o0henone5 n the 0reen-e o/ C3 to 0re0%re 0oly(etherketone) The 0olymer 4ere 0re0%re! n the melt 4thout the ue o/ b%e %n! ol.ent The

.ol%tle !e 0ro!u-t5 trmethyllyl /luor!e5 -%n be remo.e! %t h,h tem0er%ture


38/58

1.2. Solu5le Precursor*pproaches

$e0te the u--e o/ ele-tro0hl- %n! nu-leo0hl- route5 h%rh re%-ton -on!ton %re uu%lly

re=ure! to obt%n h,h mole-ul%r 4e,ht 0oly(ether ketone) To %!!re the olublty 0roblem5 e.er%l

oluble 0re-uror %00ro%-he 4ere re0orte! to nt%lly 0ro!u-e h,h mole-ul%r 4e,ht5 oluble 0re-uror5

4h-h -oul! then be -hem-%lly mo!/e! to remo.e the olubl&n, ,rou0 M-Gr%th %n! l%ter So,%h

n!e0en!ently re0orte! the ynthe o/ oluble h,hmole-ul%r 4e,ht PEEK -ont%nn, 0en!ent t2butyl

,rou0 n the 0olymer b%-kbone (S-heme +;) t 2"utylhy!ro=unone 4% 0olymer&e! 4th 757Q2

!/luoroben&o0hone n $MSO %t rel%t.ely lo4 tem0er%ture (+:9 C) Polymer 4th nherent .-oty

u0 to : !L


39/58

Keley et al *

ue! the -y-l- ket%l o/ 757Q2!hy!ro6yben&o0henone to 0olymer&e 4th

757Q2!/luoroben&o0henone n $MA- %t +89 C (S-heme ++9) The 0olymer&%ton

0ro!u-e! oluble %mor0hou 0olyket%l5 4h-h 4% =u%ntt%t.ely -on.erte! to PEK by %-!

-%t%ly&e! hy!roly Sn-e the 0olymer&%ton -%rre! out %t lo4er tem0er%ture5 PEK

4th mnm%l !e/e-t tru-ture -%n be obt%ne! by th 0ro-e Com0%re! to PEEK 0re0%re! un!er the uu%l h,h tem0er%ture -on!ton (!0henyl ul/one % ol.ent)5 PEK

0ro!u-e! by th %00ro%-h !0l%ye! e6-ellent 0hy-%l 0ro0erte5 e0e-%lly the h,h

!e,ree o/ -ryt%llnty %n! h,her T,5 4h-h n!-%te % un/orm lne%r b%-kbone tru-ture

In +;;*5 P%n!y%5 Y%n, %n! Gbon !e.elo0e! % ne4 0olyketone ynthe b%e! on the

nu-leo0hl- ubttuton o/ b( 2%mnontrle) !er.%t.e 4th %-t.%te! %rom%t-

!h%l!e "( 2%mnontrle) 4ere 0re0%re! /rom %rom%t- !%l!ehy!e n h,h yel! by

Stre-ker ynthe The -onu,%te b%e o/ the 2%mnontrle %re 0o4er/ul %n! ele-t.e

nu-leo0hle5 4h-h -%n re%-t 4th %-t.%te! %rom%t- !h%l!e to /orm % -%rbon2-%rbon bon!

Polymer&%ton o/ o0hth%l%mnontrle 4th 757Q2!/luoro0henyl ul/one n %nhy!rou $M3 %troom tem0er%ture un, N%H % b%e ,.e % oluble h,h mole-ul%r 4e,ht 0oly%mnontrle


40/58

1.2.4 ,ther Routes

*. Car5on@Car5on Coupling Routes

N-kel2-%t%ly&e! -ou0ln, o/ -hloro0henyl ,rou0 n % !0ol%r %0rot- ol.ent u-h %

$MA- 4% re0orte! to 0ro!u-e 0oly(ether ketone)*@

$-hlor!e -ont%nn, ether %n!

ketone lnk%,e 0olymer&e! n the 0reen-e o/ Xn


41/58

%%. /a5rication

th the !e.elo0ment o/ A!!t.e M%nu/%-ture (AM) 0ro-e5 the m%nu/%-turn, o/ PEEK 0%rt

4th -om0le6 h%0e h% been tu!e! b%e! on the Sele-t.e L%er Sntern, (SLS) 0ro-e J5 ;Z The

metho! %t the e%rly t%,e 4th more 4ork to be !one on the meltn, %n! -ryt%ll&%ton % 4ell % theknet- %n! tme2tem0er%ture beh%.or o/ the 0ro-e Mot.%te! by the m0ort%n-e o/ PEEK -om0onent

n /uture en,neern, %00l-%ton5 4e n.et,%te! the ue o/ %nother AM 0ro-e n the /%br-%ton o/

PEEK -om0onent

The m%k2m%,e20roe-ton b%e! Stereoltho,r%0hy (MIP2SL) %n AM 0ro-e5 n 4h-h

0roe-ton m%,e %re 0roe-te! on 0hotoent.e ren An llutr%ton o/ the MIP2SL 0ro-e ho4n

n 3,ure +% The m%k m%,e -%n be !yn%m-%lly !e/ne! by % $,t%l M-romrror $e.-e ($M$) +95

++Z 4th m-ro mrror th%t -%n turn on or o// % 06el In the MIP2SL 0ro-e5 % *2$menon%l (*$)

mo!el o/ % !e,ne! 0%rt /rt l-e! nto l%yer o/ 2$menon%l ($) m%k m%,e The m%k m%,e

%re then ent to % $M$ %n! 0roe-te! on % l=u! ren ur/%-e The 0hoto-ur%ble ren ele-t.ely -ure!%n! /orm one l%yer The /%br-%ton o/ ne6t l%yer ,oe on %/ter r%n, the X2t%,e The bul!n, ob o/

the !e,ne! 0%rt /nhe! untl %ll the l%yer h%.e been bult

Figure 32: An llutr%ton o/ the MIP2SL 0ro-e %n! %

bottom2u0 0roe-ton etu0


42/58

3,ure *9b ho4 % bottom2u0 0roe-ton etu0 th%t -%n be ue! n the MIP2SL 0ro-e In the

etu05 the l%yer th-kne o/ the 0%rt -%n be 4ell -ontrolle! !ue to the -ontr%nt -urn, Ho4e.er5 the

e0%r%ton /or-e bet4een the t%nk %n! the -ure! l%yer -oul! be l%r,e Xhou5 et al. +Z tu!e! the

e0%r%ton /or-e %n! 0reente! % t4o -h%nnel t%nk /or the bottom2u0 MIP2SL ytem The !e.elo0e! t4o

-h%nnel !e,n ho4n n 3,ure *+5 n 4h-h h%l/ o/ the t%nk -o%te! 4th % P$MS /lm 4hle the

other h%l/ h% no -o%tn, The e0%r%ton /or-e bet4een the -ure! l%yer %n! the t%nk be-ome mu-hm%ller by mo.n, the 0l%t/orm /rom the le/t -h%nnel (e the -h%nnel 4th P$MS /lm -o%tn,) to the

r,ht -h%nnel (e the -h%nnel 4thout P$MS /lm -o%tn,) be/ore l/tn, the 0l%t/orm u0

Figure 31: A t4o2-h%nnel t%nk !e,n /or the bottom2u0

0roe-ton (etu0)


43/58

In th 0%0er5 4e n.et,%te! the t4o -h%nnel !e,n /or the /%br-%ton o/ ,reen 0%rt o/ PEEK

-om0ote e %lo tu!e! the ntern, 0ro-e %n! m%ter%l 0ro0erte o/ ntere! PEEK -om0ote

0%rt The 0%0er or,%n&e! % /ollo4 An o.er.e4 o/ the PEEK /%br-%ton 0ro-e !e-rbe! n

e-ton The ,reen 0%rt /%br-%ton b%e! on the MIP2SL 0ro-e !-ue! n Se-ton * The

ntern, 0ro-e 0reente! n Se-ton 7 Se-ton 8 0reet the tetn, reult on .%rou m%ter%l

0ro0erte o/ the /%br-%te! 0%rt 3n%lly 4e !r%4 -on-luon n Se-ton @

2. Process ,vervie>

Sml%r to the /%br-%ton 0ro-e o/ PXT -om0onent5 our PEEK /%br-%ton 0ro-e n-lu!e t4o m%or te05 ,reen 0%rt /%br-%ton %n! ntern, o/ the /%br-%te! ,reen 0%rt An llutr%ton o/ the

0ro-e ho4n n 3,ure * In or!er to ue the MIP2SL 0ro-e5 -om0ote lurry /rt 0ro!u-e! bym6n, PEEK 0o4!er %n! 0hotoent.e ren The PEEK lurry houl! be m6e! 4ell n or!er to/%br-%te ,oo! =u%lty 0%rt A/ter the lurry h% been 0re0%re!5 the ,reen 0%rt 4th !ere! h%0e -%n be /%br-%te! un, the MIP2SL 0ro-e A m%n -h%llen,e n th te0 the re-o%tn, o/ the PEEK lurry

4h-h -%n h%.e % mu-h h,her .-oty !ue to the %!!ton o/ PEEK 0o4!er 3n%lly5 ,reen 0%rt %re

ntere! /or %-he.n, m0ro.e! m%ter%l 0ro0erte The -h%llen,e n th te0 to un!ert%n! the 0ro0er

ettn, o/ the ntern, 0ro-e u-h th%t the /%br-%te! PEEK 0%rt -%n h%.e !ere! m%ter%l 0ro0erte

The 0re0%rn, o/ PEEK lurry m0ort%nt It !ere! to h%.e homo,enou lurry u-h th%t the

/%br-%te! 0%rt -oul! h%.e otro0- 0ro0erty The PEEK 0o4!er ue! n our tu!y PEEK +89P3 /rom

1ICTRE Co The 0o4!er n 0her-%l h%0e 4th 0%rt-le &e o/ 79 [m The 0hoto-ur%ble l=u!

ren ue! n our tu!y SI899 /rom En.onTe- In- A 0re-on 4e,ht -%le 4% ue! n !etermnn,

the 4e,ht r%to o/ the PEEK lurry %n! % trrn, m%-hne 4% ue! n 0re0%rn, the lurry An e6%m0le

o/ the PEEK lurry ho4n n 3,ure 7


44/58

The .-oty o/ the m6e! lurry n-re%e 4th % h,her 4e,ht r%to o/ PEEK 0o4!er n the

m6ture hen more 0o4!er %!!e!5 the m6e! lurry 4ll h%.e % h,her .-oty A--or!n,ly 4e -%n

-l%/y the PEEK lurry nto three ,rou0

(+) Slurry that can flo>A hen the r%to o/ the PEEK 0o4!er n the lurry le th%n :85 t ober.e! th%t the lurry -%n /lo4 to re/ll .o! !urn, the re-o%tn, 0ro-eB

() Slurry that cannot flo> 5ut can attach to ippe surfaces >hen ta3ing out# hen the r%too/ the PEEK 0o4!er n the lurry bet4een :8 %n! **J5 t ober.e! th%t the lurry-%nnot /lo4 by tel/ but -%n %tt%-he! to ur/%-e th%t %re !00e! nto the lurryB

(*) Slurry that cannot flo> or attach to ippe surfaces# hen the r%to o/ the PEEK 0o4!er nthe lurry o.er **J5 the m6ture ml%r to 0%te It -%nnot /lo4 or be 0re%! out e%ly3urther5 t 4ll not %tt%-h to !00e! ur/%-e

In our tu!y5 4e %lo /oun! th%t the trrn, o/ the m6ture be-ome r%ther !//-ult 4hen the 4e,ht

r%to o/ the PEEK 0o4!er %bo.e *: It 0oble to re!u-e the lurryQ .-oty by %!!n, -hem-%l

oluton u-h % o0ro0%nolB ho4e.er5 the m%ter%l 0ro0erte o/ the /%br-%te! PEEK 0%rt m%y %lo be

%//e-te! by the %!!ton%l oluton e only tete! the PEEK lurry by !re-tly m6n, PEEK 0o4!er

4th l=u! ren n our tu!y A better lurry 0re0%r%ton %00ro%-h !ere! /or %-he.n, % h,her

0er-ent%,e o/ PEEK 0o4!er n the m6e! lurry n the /uture ree%r-h

. (reen Part /a5rication

3or e%-h ,rou0 o/ the lurry 4th !//erent .-ote5 4e !e.elo0e! -orre0on!n, m%ter%l re/lln,tr%te,e n the bottom2u0 MIP2SL 0ro-e

.1 /a5ricating green parts >ith slurry that can flo>

3or the lurry n the /rt ,rou05 4e ue! the t4o -h%nnel ytem th%t 4% !e.elo0e! /or l=u! ren

Sn-e the lurry -%n /lo4 by tel/5 the /%br-%ton 0ro-e!ure n bul!n, ,reen 0%rt ml%r to the one %

0reente! n +Z5 4h-h ho4n n 3,ure *7


45/58

.2 /a5ricating green parts >ith slurry that can attach to ippe surfaces

3or the lurry n the e-on! ,rou05 the lurry -%nnot /lo4 /reely on the P$MS ur/%-eB ho4e.er5 t -%n%tt%-h to !00e! ur/%-e e ue! % mo!/e! /%br-%ton 0ro-e!ure % ho4n n 3,ure @ A/ter the bul!

0%rt %n! the 0l%t/orm %re mo.e! r,ht4%r! to the -h%nnel 4thout the P$MS /lm (Ste0 b) e mo.ethem !o4n by % -ert%n !t%n-e d %n! !0 nto the lurry (te0 -) The %tt%-he! lurry on both bottom %n!!e ur/%-e -%n brn, -ert%n %mount o/ m%ter%l th%t %!e=u%te /or bul!n, % ne4 l%yer Althou,h the%mount o/ the m%ter%l %tt%-he! to the !00e! ur/%-e re=ure more e//ort to mo!el5 t ober.e! th%tmore m%ter%l 4ll be brou,ht u0 / the !t%n-e d l%r,er In %!!ton5 t 4% /oun! th%t the !00e!

m%ter%l -%nnot be e.enly 0re%! out on the P$MS /lm 4hen the 0l%t/orm 4% lo4ere! to /orm one l%yer

th-kne (te0 /) In or!er to /ll the 4hole ,%0 rel%te! to the ne6t l%yer 4th lurry5 %n %!!ton

rubbn, me-h%nm ue! n our /%br-%ton 0ro-e!ure A ho4n n te0 , %n! h5 the 0%rt mo.e!

le/t %n! r,ht to better 0re%! the !00e! m%ter%l on the P$MS /lm


46/58

3,ure *: ho4 % 0%rt th%t 4% bult 4th %n! 4thout e6tr% rubbn, moton 3or % l%yer 4th % b, %re%5 the

l%-k o/ m%ter%l 4ll -%ue !e/e-t n the -ure! l%yer Note th%t % 0re.ou l%yer th%t 4% n-om0letely bult

4ll %!.erely %//e-t %ll the /ollo4n, l%yer The %!.%nt%,e o/ un, rubbn, me-h%nm th%t the

m%ter%l -%n be 0re%! out e.enlyB ho4e.er5 % !r%4b%-k th%t m%ll /e%ture on the 0%rt -oul! be broken

!urn, the rubbn, mo.ement

. /a5ricating green parts >ith slurry that cannot flo> or attach to ippe surfaces

3or the lurry n the thr! ,rou05 t -%nnot /lo4 /reely nor %tt%-h to !00e! ur/%-e Inte%!5 %!!ton%l0re%!n, /or-e %re re=ure! th%t -%n 0uh the lurry nto the /orme! ,%0 rel%te! to % ne4 l%yer In our

e60erment5 4e ue! % m0le !e,n % ho4n n 3,ure *J% /or 0uhn, the 0%te2lke lurry In the

!e,n5 4e /ll lurry n % -loe! t%nk th%t -ont%n the 0l%t/orm n!e A ho4n n 3,ure *Jb5 the

lurry 4ll be 0uhe! to /ll the re,on rel%te! to the ne6t l%yer 4hen the 0l%t/orm mo.e! b%-k %n!

/or-e

A--or!n,ly5 % mo!/e! /%br-%ton 0ro-e!ure ho4n n 3,ure *; A ho4n n the

llutr%ton5 the lurry n the en-loe! t%nk 0uhe! bet4een the le/t %n! r,ht -h%nnel 4hen the

0l%t/orm mo.e! Cone=uently5 the lurry -%n be enure! to re/ll the le/t -h%nnel 4hen the 0l%t/orm

mo.e! !o4n to /orm % ne4 l%yer Note th%t there 4ll be -ert%n .o! ,ener%te! n the t%nk !urn, the

bul!n, 0ro-e Th be-%ue the 0l%t/orm mo.e! u04%r! by % l%yer !t%n-e 4hle the tot%l

.olume o/ the t%nk /6e! To re/ll the .o!5 %!!ton%l lurry -%n be etm%te! %n! %!!e! nto the t%nk

!urn, the bul!n, 0ro-e


47/58

3,ure 79 ho4 the bul!n, reult o/ ome tet 0%rt b%e! on the !e.elo0e! 0uhn, me-h%nm A

ho4n n the tetn, reult5 the m0le %00ro%-h -%n enure the un/orm 0re%!n, o/ the lurry on the

P$MS /lm /or /ormn, thn l%yer (89 [m ue! n the tet)

.4 Cleaning proceures of green parts


48/58

Com0%rn, to the MIP2SL 0ro-e /or l=u! ren5 the -le%nn, 0ro-e!ure /or PEEK lurry rel%t.elymore !//-ult !ue to the h,her .-oty .%lue o/ the lurry The 0ro-e!ure 4e ue! n our tet n-lu!e/ollo4n, te0 4th %n e6%m0le % ho4n n 3,ure 7+

(+) Remo.e the 0%rt /rom the 0l%t/orm %n! ,ently -le%n t 4th % o/t 0%0er n%0knB

() Cle%n the 0%rt un, %n ultr%oun! -le%ner /lle! 4th o0ro0yl %l-ohol /or +9 mnuteB(*) e %n ele-tr- /%n to !ry the 0%rt %n! remo.e %l-oholB

(7) e % bruh to -le%n %ny re!ue %tt%-he! to 0%rt ur/%-e

Ste0 ()2(7) m%y be re0e%te! / the 0%rt h% ome h%r!2to2-le%n /e%ture u-h % !ee0 hole

4. Sintering Process of (reen Parts

The lurry2b%e! MIP2SL 0ro-e -%n bul! 0%rt 4th the !ere! h%0e !e/ne! by -om0uter2%!e!

!e,n (CA$) mo!el In th 0%0er5 4e -%ll u-h 0%rt 4thout he%t tre%tment ,reen 0%rt Sn-e the

/%br-%te! ,reen 0%rt m%y not h%.e the !ere! m%ter%l 0ro0erte5 4e tu!e! the ntern, o/ ,reen 0%rt

%n! rel%te! m%ter%l 0ro0erty -h%n,e

PEEK % em-ryt%llne thermo0l%t- 4th the ,l% tr%nton tem0er%ture o/ W+7*oC %n! themeltn, 0ont o/ W*7*

oC In -om0%ron5 the 0hoto0olymer ue! n our tu!y (SI899) h% % ,l%

tr%nton tem0er%ture o/ @+oC A--or!n,ly5 the he%t tre%tment 0ro-e!ure 4e !e,ne! ho4n n

3,ure + 1%rou ntern, tem0er%ture r%n,n, /rom 99oC to *9

oC 4ere et on the tem0er%ture

-ur.e $urn, the ntern, 0ro-e5 % /urn%-e /lle! 4th ntro,en 4% ue! to %.o! o6!%ton


49/58


50/58

3,ure 7*% ho4 %n e6%m0le o/ the bult ,reen 0%rt %n! the rel%te! ntere! 0%rt (ntern,tem0er%ture %t :8

oC) 3,ure +*b ho4 % et o/ ,e%r th%t 4ere ntere! %t !//erent tem0er%ture

r%n,n, /rom 99oC to *9

oC Com0%re! to the /%br-%te! ,reen 0%rt th%t %lo ho4n n 3,ure +*b5 the

!menon o/ the ntere! ,e%r !o not -h%n,e mu-h untl W*99oC hen the ntern, tem0er%ture et

%t *9o

C5 the ,reen 0%rt hrnk ,n/-%ntly (W9)


51/58

A !-ue! n +7Z5 ntern, % 0hy-%lly -om0le6 0henomenon5 4h-h reult n numerou

tru-tur%l -h%n,e m% %n! ,n/-%nt m0ro.ement o/ t me-h%n-%l 0ro0erte The ntern,

me-h%nm n-lu!e both ur/%-e %n! bulk tr%n0ort The nt%l t%,e o/ ntern, m%nly !e0en! on

ur/%-e !//uon $urn, the t%,e5 there lttle hrnk%,e In -ontr%t5 the nterme!%te %n! /n%l t%,e

o/ ntern, 0rm%rly !e0en! on m% tr%n0ort A ere o/ 0ro-ee n-lu!n, nter0%rt-le bon!n,5

ne-k ,ro4th5 0ore -h%nnel -loure5 0ore roun!n,5 %n! 0ore hrnk%,e 4ll h%00en !urn, the t%,e

The tet reult % ho4n n 3,ure +*b llutr%te th%t#

(+) hen the ntern, tem0er%ture \ ;9oC5 ur/%-e !//uon !omn%te the ntern, o/ PEEK

-om0ote The ntere! 0%rt %re !menon%lly %--ur%teB

() hen the ntern, tem0er%ture *99oC5 m% tr%n0ort e6t n the ntern, 0ro-e o/

PEEK -om0ote A--or!n,ly5 the ntere! 0%rt 4ll hrnk ,n/-%ntly

Sn-e l%r,e hrnk%,e %re un!er%ble5 the ntern, tem0er%ture n our m%ter%l 0ro0erty tu!y %reet /rom 99

oC to ;9

oC

%%%.Testing

5. Material Property of

Sintered Parts

5.1 Tensile

test

5e conducted tensile tests on the sintered parts- %he tensile testing syste# "eused is a K; 7eben *icro %ensile #odule that is sho"n in Figure 44- %ensile bars"ith standard shapes and di#ensions that are re


52/58

%he strain!stress curves generated fro# the tensile tests are sho"n in Figure

46- %he >oung?s *odulus values of the related parts are sho"n in %able 1- t can be

observed that the PEEK co#posite after sintering beco#es stronger yet #ore brittle

than the green part-


53/58

5.2 Hardness test

8ardness tests on the sintered parts "ere conducted using a @AK5EBB hardnesstester as sho"n in Figure 19- %he scale of the hardness testing results is 8@F- %hetesting results are sho"n in %able &- +ased on the results "e can see that thehardness of the built PEEK co#posite is aCected by the sintering te#perature- naddition the sintered parts are harder than the green part- %hey are also harderthan the part that is built in photocurable resin- n addition the hardness of thesintered parts generally increases for a higher sintering te#perature "ithin ourstudy range-


54/58

5.3 Scanning electron

microscope images

, 8itachi 'eld e#ission scanning electron #icroscope (SE*) "as used in capturingthe #icro!scale i#ages of both the green and sintered parts- Figure 4 sho"s aco#parison of the captured SE* i#ages- t can be observed that the boundary of PEEK particles is obvious in the green partD ho"ever it is dicult to distinguish the

PEEK particles in the sintered sa#ple (sintering te#perature at &62o for 1 hour)-

%his veri'es that the initial stage of sintering based on surface diCusion happensduring the heat treat#ent process- %he surface diCusion can be bet"eenneighboring PEEK particles and bet"een PEEK particles and photocurable poly#ers-


55/58

%he developed additive #anufacturing process includes slurry preparation green

part fabrication and sintering- t is found that it is hard to generate #i=ed slurry

"ith #ore than

39 of PEEK po"ders in the #i=ture "ithout using additional che#ical solutions-

8ence the developed fabrication process "ill only be suitable for fabricating

co#ponents of PEEK co#posite instead of pure PEEK- %hree diCerent recoating

strategies have been developed for PEEK slurry "ith high viscosity values- %he

developed approaches can also be used in fabricating other types of po"der!resin

#i=ed slurry- 5e de#onstrated that the sintering process can i#prove the

strength and hardness of the built green parts- n addition the sintered PEEK

co#posite parts can have better #aterial properties than those #ade in

photocurable poly#ers "ithout any PEEK particles-

%he *P!SB process can fabricate co#ponents "ith co#ple= shapes-


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peek - polyether ether ketone

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