Synthesis, Modification andCharlcterization of Epoxy Resin as a

Matrix Material for Composites

A thesis submittedrequirements

in partial fulfillment ofthefor lhe degree of

Doctorete of Philosophy

in

Chcmist.y

by

Sumcerf, Ikram

Depanment ofChemistryQuaid-i-Azarn University

lslamabad, Pakistan2009

irrra

i"*f I| -.-

DECL^RATtON

thi! is io enit djrt diis distlrti .nrkn "Strdatt, tuqfidton ,xtch.ttbrbdldn at qo,! Bi.t s ! 'rcr! e.idtr ..npod.d, suhnitEd b',tt SM ILN it @@d in ib F* f.m by dE D.Ftrnd. of Ch.misr.r,Quid-i-Azn Univ.6iq, blmb.4 P.ti!|I, s $ljsfying rh. p.niol Equtcm.ir ao,6. degrce of Detor qf

^Aovpttr in Ino4tnL/Awltti.rl Ch.tqtsrry.

flo,yx^ [/"eQ,t

AUm. lqb.l ODa Uni6fty

To

fu'tyQArcNTS

ACKNOWLEDGEMENT

Ihis &knowledgnot is not ody e expr.ssion of ftmal duty but also for hefii.slgntitudc, $slc ed .egad. for tllo* who h€lp€d thsugh oui ny PhD IMh wo*,

Fi6t of all, mud* rhanks to at-MIGflTy ALLAI, iilh th€ we of ny hsn,*ho$ magnminons blesinSs olways tuabl€d me ro ptrive Md psue my Boals

I havc gre€t pl*uc md pnvibg€ to exp6s Dy shc@ gniiude io by dpe.tlble,l@ed ed aferionale sup@is Pmt Dr Mrh@d Mrn.r (Dep6.rndt ofChdinry Quid-i-Azd Univdity). ft ws Eally e horcr for n€ ro wor{ uidd his

kind slpdision. Ht valuoble sugeestiotu. onsrructiv. ditiois, ufailing@@uagdar md supponiv€ aniMe dlighteb.d nry wars of eFmh for mc. I md,nttul to |tot Dr. S.&.wrr Sh.t Chaim&\ (Depsrrrncnr of Ch€nistry euid-i,Azu Ud6ity) for pmviding r€6$y frcililiG for 66ch wo*.

I fecl pl€are in qpBsing ny rhdks !o Di Arsn.d Muoir (Dirto. c€n@I.NESCOM) for his help duins lhis worL

I would like to D6y ny hmble gtuind. io Dr, Rir.! Husrir (Dir@lor, NDC),

DL 8i, Anmd (Pmjar Dir-ror, NDc), xri M. zn+8.4 @rcj@r DiEcro,, NDC),

for lh.ir vihable sussstioN, d@mgd6t dd no6l suppon

Thd*s de due ro Dr. M. Siddiq (Dy.Dn.Cdenl, NESCOM) for fnal pDof teding

I d thanl,ll b ny ftqds dd ollag!6 fo. rhei. nie anitud. ard help, in

wolde de not 6ough ro €xprcss giaritude ro my Imily ncmbd who praysd for nysu4ss c.elesly md dhdrdins mihirg of rlr.ir adl6s su@r.

(suneel, IkI.m)

ABSTRACT

Poj*t h6 b6 djvidcd into rwo bajor parls. In the fiBr pltr ofrhe pq6t disllcidyl.lhq of bisphmol-A (DCEBA), which is olmonly sed in most of the €poxy !€sins

applictions, havina nub.r !ve6g. molsula w.ighr (MJ 375, w6 sFih6ized. To

improve its h*ldnical popenid like touShness, llcxibility ed impact slJdgh for 6e in

high reh atpli@rio$ lit. Fse v6sts. @mposile tukel molor 6ings etc, n w6hodided by in@'?onting the hydbxy rmimt€d poltbutadia€ (mPB) ba\ed prcpolrnduing

'$phoone diisy&ate a . @lpling aCs . Fd thar rten ETPB of nmba

avsage nol€mltr w€ishr (MJ 2800 ws uscd. To in reN lhe @opadbiliry betwed rhe

.toxy r6in anl HTPB pa.ij pold aouls wde inEoducel in th€ laler ro acli4e physicd

ed chdical inhadions b€fwM rhe rwo ph66. The noally nodified DOEBA systmwa wcd eil[ mine ba&d b.rd6d.

FIIR ahd |H-NMR wqc ued ro moniro! tne whole noditication procedue. The rubberpanicl6 sia dd rhci. disi.iburion wft nonitorcd s ! tunction of HTPB onqnation inthe Fsi. s),std using sconing el6tron micos@py (SEM). ft€ nebeicjl, ih€lml sdthmGnehmtd prop6ti6 hav. slbM rhat ihc rtuit€ srqgth, louehl4. flqibiliryed npact streogh ofthe modified cu€d syst.n have bm su.esstu y jno€ded at smeoptmm HTPB or@rdtiotr wirhod lff{ting the intrftnr rhmat ard thmcn6hdic.l stabiliiy ssocioied wirh DGEBA Bin srstd. sone of de mechMielpbpqtid li*e fldur,l $rogl1\ ncxural rbdutu, youg.3 modulus dd @np6ivestEnglh de@ed wirh ioetuing rubba @rce raiioh. Tn€ nodified DGEBA swto h6b@ uad in tne fomularion for f.bn atin8 Kwtd fibE rcinforced omposile v6*t byIlldot winding lehnique in conpden with rb. fomularion containins LmodifiedDGEBA sin. The htds-bd id Bdll of th€ mpodlc veFl shov€d dl.r high€rpre$u€ is equircd to bust lh. nodidcd ontosite cytinder mploing t% HTPB@n@Eat'o ^ @dparcd io the cylitrdd nmufa.iured Aon the fomulalion oniaininsmodified DcEaA 6io, Moravd, tnqc hd bM a d€cre6e in the vatue of snessespoductd in eithd logiodinal or rtuvdc direjon in the nodified @Dposne cytinddboth on dome dd ns cdtral prn phil€ k6pi.s th€ intemal pr6su€ @n$si

Io lL. .ed Fr of tu Fojct . Fvd tigh @ad!. prr@ol. .?dy rrio (PER)

v& .Fli4riz.d lldtiig tm 8*r Valrlnbln r...a!g.dcor lt &L ?o:y !rd!E (r|tld eitl 6 @i@ ad 6 d)tri& h!.d tq! dtu tdG ic,dihrMdrrrt .it!rr6.n (DDs) .!d lrdic n et ehrdri& (NMA) i! difr.Gor v.irhrdio. dd {r!! ndrad ttio8 O.o.trvi!.ric ddya GE ) dd dtdiclhaEob.c!&icrl &rlyz.! (DIMA). Pluzol. b6!.d .Doxy r..i! (!ER) rhopcd q..lkdrtLul d rir@.D.d|!i6l Flpqii. tit |hdl d.gddba idodiG, dotEsito! lr@pdr!ft (Ir[ ald lloE8e & lors doddu a! c.Dpsr.d !o cl)@ody !!.dAorydiB .{. IrOBBr"

Table ofContents

Chaprer I Inroduclon

t.l

t_l

L.{

t.5

Ll.l Fabricalionof ComFdtesCla.irr.rio! ofconp6irB o! rh. B.!€ ofM.tri!| .2. I ce@ic MaEix conpGires (CMC91.2.2 Mdd Mar.ix conpGne (MMCS)l.2l Polyn* Makix Conposile (pMCs)Reilfort.odr in CorFliaa1.3.1 Panicle Reinforced Composil.s1.1.2 Fibe. Rcidor.d Conposil€

l5.l Hiet l.mpcdt@ Epoxy R6jni1.5 2 Ch@terislics of Epoxy Resins| 5.1 Effel of R6in SnrtuE o R4dviry1.5.4 Efl-t of Functionaliq| 5.5 Ellel ofcbss-Linlcd D€Niry1.5.6 Ty"€s of Epoxy RsirsCr.ing Mei.oim of Epory Rsi!,1.6.1 Baic cuilg ag6|51.6.2 Anine C[ing Agents

1.6.4 Acid Curing AgmtsTolgh.dng oa [po!r R6i!.Mlin Work hd Na ldet h th€ rhdt!

I 8.:l Feedb..t fDm p.si Wo*jng ExFri.ne

2

5

5

5

8

t0l0

llla2l2l22

2l25

28

2a

29

29

It

Chapt€r2 Exp€rimen!.sl

2.1 Cenenlconlid.ntiotr31.2 Sy.th6is of Dbticidyt E$o of BnDtoor^ @cE&{)

2.2 I Dereminadon ofEpoxy Eqdvaldl

30

34

34

ti

It

t7t$

Hydroryl valu. Dcl.diDtlio. ot IITPB

Prrprniior of Rubb.r Modifi.d EPolv R.!in

2.4 I Delenin tion ofNCO s ralw i. HTPBIPDI Polvmq

Prat.e8 ForDrtion for F.brigrioo ofCoEposit' qlin'c'sl'roced{F for fil.n.nl Wird g

(icneml Comidediionrsynihdis or Nor€l Epory RBir tirh nigh r&:.8 I l'Fpmrion ol l l2'hldbxtTh.nvl!3{2'helhoxvth€n}))

plopenc-1.l- dioie{l)1.8.1 l,epmrio.of l-phenll3-(2rhvdrcxvPhenvl)-5

-(2 n thoxy PhoYl) PY@olc (ll)2.8I l'Epdrion of I -phe.tl-:l_ (2heinox)"henvl)

-t(2lhydioxy phoyl) py@le (Ul)

1.13.,{ CdeBl Pdedure for Deneilylation of CohPounds {ll&lll)2 8.5 I'Ep.ration of I-phe.yl-].5_bis [(2'. 3'€poxvpropoxv)

phcnyll p'@le (PER)

2.1t.6 Otrjn! olEpoxy vilh Hard€nd

Resulls md Dis(ussion

35

31

37

4l

42

.tl

45

( haprer l

i I srro.tonl amb3i! of ModilFd DGE&{r.l 1 l'TlRand IH-NMR AnalysisofDGEBA

I 1.2 lephotune Diiwyeale(IPDD:l.l I tlldoxy Terninaled Polybuudienc (HTPB)

i.l r lPDl-ll'IPBIPDIlcl*helicPoltmqAralvs'sl. | 5 srructuEl Hl PB Bed Eldbner:1.16 Fl lR SFclrun ofcuing A8.nl

1.1.7 I]TIR Analysis ofcurd Epoxy Resin

.1.18 s.dni.s El*mn Mic@oPy GEM) of Modlncd Epoxv Sv$cms

1.1 rhrmd A.rlyitu olModined. Uonodifi.d Crred R€titu Svtlens

l.l rhemo-ndh.tiol ADVtit of Moditu Dd Unoodilisd Crr.d

1.3.1 Srooge Modulu orCursd R6'r Slsl€Ds

l.lr 2 re d ofModified 4d Unnodified Cftd Resin Syslems

l.l I (ilds 'f.mnion TmpeanuE (Ts) ofcut d Rsin sy$ems

.l,l Mehrnicrl Ar.bd! ofcu.rd Rsln Sy.t€m

17

5lt:l55

53

62

1.5

3,4 I l6 c PreFdi6 of Curd R6in StsGN:1.4 2 Flexu.l PDpeniB of Modifi.d ed UDmodificd SFr6s1.4.1 Cmpcsive Sftrgdr ofcurcd R6itr Systersir.4..r Mice.hdldness M*urehsB olcuEd ltdi. Syst m3

1.4.5 lmp&t Susgth of Culrd R6ii SFl€nsConpori& Ring. An.lFi'Hydru-Bl6r T6r ofcorpoitc Cylhd.n3.6.1 Htd@-BurslT.n of Composirc Cytind.r b6.d or

UModified Epoxy Rain1.6.2 Hyd@Bdsr T.sr of Compo6ir. Cytiid.r b€s€d on1.6.1 Modificd Epoxy R.sin

67

7J

78

80

8l8l

82

95

100

102

85

89

1.7 s:-nrb6ir of Pyn rl. Epory R6ir (PftR)3.7.2 Ch@teriation of l -phdyl-J- (2rhydrcxrlh.nyl)

-5(21rcthoxnhoyl) pr@tc ([)1.7.1 cn@rcriarionof l-phcnyt-3-(2hcrhoryplEnyt)

pr@t. (pER).

:l 8 'rh€nd Sbbility of Cur€d PER R.rtr:.4 Th.mmehui.l ADbri. otcoEd pER R€i!

-5{2 Lhydrexy phetryt) pr@lc (rrD 9l1.7.4 Ch@l.riarion of l-phdyl,3,5-bis (2 -hydroryph€nyt) p,@te (lV) 9j3.7.5 ch@teri2arion of l -phmyl-3, s-bis [(2 , 3'apox]TDpoxy) pborll

90

Trbl.!.11

LIST OF TABLf,S

Amme onng aeenrs sed wilh €poxics, 24

Annydride cuin8 rg@rs us€d wnn e?oxi6. 2jChnicalscedforlhesthth6ismdnodinatonof epoxy(DOEBA). 3lInsrrumals ced for lhe naraial ch&etqiz.tion, 32

Fomdrion ofnodified dd umo<tificd epoxy r6in. 38Pbysi.€l paruer* for rhe 6lmmt windine of omposite vsel. 40

Chemicals us€d in rhe sy.thes! ofnov.l €poxy @sin 42

Difdal fomulations prcpared for rhcmat ed thmGn*hdiet 45

'ftmal shlility pg@.r6 for rhe curd epory fomuladons A-F.

FTIR srEclral datd ofpe fiTpBFrJR spetEl &ta ofpuE N(3nin€thylmi.oFopyl),1 ,3-

5l

55

MqihM d@Dposilion rmpedre ed .he ponion ar 7O0oC.

storage Moduls at di,Ier@t renp@t@ (oC) for diEaor srsmsEilet of conc. of p!€polJda on rdsil€ pmpe,ries

Elti.l of@nc. ofprcpolyhd on flqud pmFrti6.Etr@t ofonc. ofpEloltnd on orprdsiv€ prcpdties.

Etred of@nc. ofprcp.lynd on VHNEfe.r of@nc. of pretotyha on iDpad slrengdl

FTJR spectial dara ofdills€ fundioml groups ofcuEd eroxy, 5j

T@pmo(e of pdqt wcjshl lN for nodifie<r and modin€d 62

62

64

13

79

80

rig.1.lIig 2.1

FiE.2.2

Fig.3.l

Iig.3.3Fig.3.4

rig.3.5

Fig.3.6

ri& 3.7

Flg.3.8

Frg. J.9

Fi& 3.r0

rE 3.r r

Fig.3.l2

Ii& 3.13

Fig.3.r4Fi& 3.15

Fig.3.l6

Fig.3.l7

Iig.3.l6Fig.3.r9

Fi8.3.20

rig,3.21

FiA,3.22

LIST OF FIGURES

Co*linlinS nevork fomed b) rhe cDnEot etox' by m'neFilmql windin8 for the fab.iqrion of conposite v6sls 6d

Coss linling ofPER with diminodiphoyl sulphone (DDS)

FnR sp@itun of prc DCEBA in rrsnision bode

'H-NMR sp€caat dara of DGEBA

FTIR speft ofp@ IPDI in t emnlDe mode

FTIR speln ofHTPB i. tllsmission node

FTIR lpecka o'IPDI-HTPB-IPD| ktqhe 'c

potrmerrl utusmbson

FrlR speln of€poxy retuinar.d HTPB bsed pre.pol)m.r

FrlR speElD of N(t-dinertlylminopopyt)F l,3,prcpy'ocdimine

FI'IR Aerm o{ ctoxy-.dhe nerworkins potymd

sEM mircgraph of rAr 0.19" tB) o.70o (c, Loqo{D, 2.0.. H I pBmodifi€d Cured Epoxy.lmrne s'tshF lTd ol HTPB @nqEsm on the d,mets of pan,ct€ rze ,nmq,htu €poxy.mrne sy$fiTGA e,lysis of ditr@i ydg6 of nodj66 in epory@inc srsd.Ef.ct ofrnpdatue on stodge modulus ofnodiiied epoxy-{nn€syslh.Efled of lmpaorue on ih 6 of nodified etoxy mine srslm.Etrct ofHTPB @nc on gt6s F.tririon tqnpsaluG (Tr),Shain-Std. cwe of te nodi6.d eporyeine s,std.Ultihar€ t nsile shd$h as a tunction ofHTpA onchrrariouvdiadon in Yowg's oodutB witb HTPB in c?oxy-min€ sys@Elibcl ofHTPB @oc. on o/dg. clodgaiio. ofepoxy-mine lys.fl.Ef..t of HTPB @n . on roushnds of eloxy-Min€ sy3r@.Stnin-strain cW€ of nodjfie<! cpoxysine s'sr6.Flexural st .ngrb as a tunction of HTPB in €poxy-min€ sysrfltf€ci ofHTPB@nc. on nd@l modutG ofhodifi.d €pox'.hine

49

5t

53

22

39

55

51

59

65

69

70

1l

72

73

Iig.3.23F19.3,24

Fig.3.2s

Fig. 3.26

Fie.3.27

Fig.3.28

Fig.3.29

fig.3.30

Fi& 331

Fig.3.32

Fig. 3.33

Fi& 3.34

Fig. 3.35

Fig.3.36

Fig.1.37

Fig.3.38

Fig.3.39

Aig.3.4{

ri&3.41

Fi$.3.42

FE 3.43

Fi& 3.44

Eet ofHTPB @nc. o! fqibiliiy of€poxy-miE sysrm. 16

Etret ofHTPB @nq on abpcsile sr€dglh of.poxy-mine stslm. t8vi.k6's Hardnes NMbq (vHN's) s a turdbn ofHTPB @nc. 79

Efrel ofHTPB @no on impersr@gih of.poxy-din elslm. 8tRines mde by (a) w€t winding md (b).pEpr€g windins rsl'!iq!€ 82

Str*6 in loneiMinal di@rion of Modified @hposir€ vsd. 8lSlr€s in Fa$vse dnedo. of modiicd @mposirc vsel. 84

Comprison ofstrBses in cotc in longitudinal aid trmsvee 84

Coipden of str.ss6 produced in longrtudinal dd lr&sv* 85

Str6sa in loryindinal dir*ljoi nodifie<t enposiie v6kt.Str6*s in 6esv€6e dir€ciion in nodified @nposite v€sel.Comp.n$n of sDtg prcduccd r rtr 6rq o, @mposrk Doror rlongtuditral dd r&sv* d'acnon duns hydo-b;{ ksCoDpeie. of stcs in longrrudinat &d tr sve di!6on.Cmpaien of slr6s in nE antn of@nlDsite v6st,3 D q.w of I r 2 -hydror' phenylr-J-(2h.,horFhmvl tspopde- | .l_

lD vicq ol l-phoyl-l t2:hydoxy"h.nyD-5-r2 :mefioxvphqyl)prrel€ ( lt )

lH-\MR "p*Fd dda of t-phtryt-.r.5-bb r2:hldro\rlheh),,pydale (W).

Tlmol hehaqdof rar pLR Hyooo, 1.t (8, pER DCEBA Hyooo,2.5:0.5 | r Cl DCEBtutry906. l : r.Tnmd&havidoflD) pER/DDS. I rtr, PER/DGEBA LrDs, r:t:2(F)DCEBA /DDS,l:r.

86

86

a7

87

88

90

92

96

Lo$ b€hvior o{ (A) PER/8Y906, 3: I2.5:0,5 i1 (C) DGEBA/HY9O6, 3:1.

fB)PER/DOEB/A,H\906, 91

milfriiH:3;ff :iid.#[1,],#j#,*,,,',"'*"'o2;trfiJff'*:?,H 3 iz

o(^) PyER.4rYeo6' 3ir (B) PER/ ro3

s.r.D 3.r

S.tr.3.2S.b.33

Sct n 3J

Sct*15

LIST OF SCmMIS

Fn -ddql o.ct-i|n ft. tr. tFri.ar orbldrcsy hi-t

srdbclr ottPDI- HIpHpDt rd.cid. polrd..Rdidh<wa !l.d.licFtrEA dd DCEBA ro adrdEsrdh..n of l{2'tdory dot}3{24EdoryD!6},1}Fop.D

st nad.d l{h.ot't-l (2ai*q}"hor+t (2.'{.dotypt oyt)Pyr|rDL(tr) -d Irt.),i-3(2,f,.6qyptryt!i(2..|'ldro,,Inqrtst'r.roL (UD

D@.rhtrdo of.ora.lrdr U &d IUPrlpi.doo of!ryDzob .onriitry Aory rarh

52

v

50

89

Sct D.3.5S.t m.3.7

9t

93

L

1.

6,

7.

8,

9,

lolt.t2,

t!ta

DOBBA

IITIBI!:DI

llRDI'S

NMA

FIIR

'g-NtB,sBM

tqaDTMA

TtvPovBN

LIST OF ABBIEVIATIONS

D.efdnDisl,oidyt & ofliDhd-AEld!ry6n-dFlr!4dio

Dbilodblarlo&t@

Foiri.",k ,.dnGrd

Sd@to9 d..nq dc!.o.ttIt@dgdbdicelyr-Dr!.Dic 66uo{..ldlcrl u\z{OL.rdi&!t6F!b!VS.F.1r.o@ry

INTRODUCTION

l.l CompositeM|t€rials

Conp6ire natei.ls e ogind€d mreials rhat d s thre dim€.sio.al

onbinslioD of at l@! rwo chmiqlly diiitMr Mtdials, with a disri.cl inlafa@sepaanng $e @npondrs, crealed to ohain popeni€s thosc cd.or be achi€vcd byey or rh. @mpondt acting .tom. The nG! prinirive @nposnc naldjdsompnsed shaq and nud in rhe fotu ofbn*s for @str4tioro. The nosi visibt€

appliation pav.! ou rcadways in lbe fom ot eiths sr@t and aggrcgare reinforcedPonlmd cd@t or 4phatr 6ncEre. 'nFe @ lwo €lesoris of @nsrirumtmaidials. Tne @nslilu.n! lhat is ontiNou aod is oftm b mt alNays p6dr insreoler quetiry m lh€ coftposne b rmed d dr morrix. Tbe smnd @nsrirDqt $alqhme or impbvB tlE nenoical prcFni6 of thc narix is rcf€Gd ro s tn.reinfo@dl or rcinfoEing phNe, ln @sposir6, the rspedve @mponors rctainlheir identily. A s]4r.reisn produc* materiat poperiiss unavailabk AoD ihei iividul @.situq1 nardials! whjte tnc wid. vtri.ty o{ mar.ix ed sndsthoirg@rdiols allow $e dAiend of the prodlcl or structuE ro ch&s d oprindenbination. UniqDe ph,sical. ch€hical, electiiel ed mahdjcal Fopeni6 ea€hiry€d by onbining pha6 in d6n€d dchir.clle allowing 1h€ {twctoFDar oIinpoved nl:Mds in rm ot tow osr. rs,L'ne ro @mJd, q€+ rdpqatur

Tte efleotiv.nds oi reinftrcinS ph& is dehin€d oy he gon€try or dreErforcin8 ph&. Th. neh&ic.l pmpdi6 ofonposirs @ rh€ tuncton of3hap€ond diDqioc of the r€infoe@dt. M6r onposiic mdo.ls @s{t or selet€dfilld or rcintorcins natdial tud a @nratiblc Bin bindd to obhn rhe specificcbectdisrics dd d*n€d ptupdrie. Tvo oulsrddirs ryp6 of hodd @oposncDaLrials qet for ogrnains sppliqtioB a€ fiba glN-rcirfoEing nalai.l jn apolrqter or epoxy mahix &d carbon 6bq in e epoxy rutrix. Advmc€d onpositeDarnals (ACM) s@h c fiba gldscpoxy dd enphit€-.pory conbharons eb@dba norc ihponmr dt lne dne for hish-pqftude ud oitic.l sttuhral

AppliMlions lbr @hposits @vfl a brcad spatrm iom hobby }its cured at

@n ldFdtre to a<lrdc.d nilitary sd amspae onponais cured al hish

tmp@tues. Pdfomo@ dd pro*sin8 r€qnirsots @ nuch divdsified lik€

their applicltions5 $ a srAtdric apprcach Dut b. talm wh6 $lFring rhc r6itrand cuing agdt lor the sp€cific .pplication.

l.l.l Frbricatiorofconposit€3

continuoN ilmot reinforced pl4tie @ be mdc by ldious r4hniqu6 [2]. Th6e

L Hdd lay-up mctho<t

2 Cold pr6s noldins

3. High pr6w noldins

4. vacum bae molding

5. Pres@ bag nolding

6. vmum injetion molding

?. R6in tresfer holding

3. Fil@dt wtuding

E ch pe6s na ib oM dvdasB atd disadvdus6j thdenne, p,oesel.clion depdds on th€ Esin srsrqn, Eidol1mqq pFdlcr d€siAr prodlctiorqMtilx qulity dd eohonics, Composite pnpcni6 witl vory Mth 6in systd.eiiforceMr ry?e, Einfo{mhr g@n.Fy, fabncario. merho<t, 6bd vollnefiaction ad void more s. In 8osal, a ihe nouldirg tr6su€ is incE6ed, th€

slrogrh ol rhc lmimlc will bc incbed for ln€ sme rt?e of rcinlo'rmor and Bi,

L th. pnent wtt, lil4r.,t Ni"didg pr6 h6 bd u..,t tu thz t bi..nM of

l l.l.1 rihmeDt Wlnditrg

Thjs po6 n p.iMily us.d fd hollow, g6..atly ciule or oval se.iiored

@nPonmts, slch 6 p'p€s [4]. Difqent @nposir€ stnEtudl pans u$d i. may

aionns, milihry dd i.duslrial applicaliohs, m tude by lhis prccc$. Filddtwindin8 may be dry or wel winding ln wct windi4, rhc 6in is applicd duing the

winding s..8e while dry winding ne{ho<l urilte inpagnated B{r.ged oving(l.med 6 prcprcg) leading io. poducr of @Nistmce ohposirion ald a v€ry high

p€rtb@ce. It is a prccBs in which fibas or l!p6 de wourd onio a lotatins

mmdrcl fton a reiarilely stltionary position. The 6bd lows @ dispared tion a

trmlatinA h€ad ar @ntoued m8l6 rcmal ro rbe brlting mdr€l dis. Lay up

compaction cm be @ntolled by the deg@ oflosion nai ained oh ih. fibft or

lape duih8 the trc6s. V&iery ofresins k b€ us€d i.e., €porx polydrei, vinyt

616, phdolic €rc The fib6 re ued sFaigh frm a @l dd ml wovo o. sti&hed

Filudr windins pro@s h6 ney adv4rages, s it @ be lcry fa5t md

thdefor€ @nmical n thod of layinS materirl doM. R6in ontd s @ b.contoll€d by m€tdin8 rhc r6in onto @h 6b6 row thtuuCl nip6 or diB 6dsrucnual ptut€rliB of lminates @ b€ very Sood sincc siraighr ffbd ce be laid in

o onpl.x pattm to march O€ applied loads. Ild€forc, this pmm @ be used for

lhe nduf&tuing of chmical slonac bnk and pip.lin6, grs cyund6, tue

extjnguishd dd bethinS ranks erc.

1.1.1.2 Pr.preg Tecboolos,

PftDrcg is a shortlhd dpl$ion fo. "peinprcg@l.d.' It is fibs or fah.ic.

wbich is slunred (inpFglared) wirh a Gin systo md h6 bd paniatly ,curEd,,

(or ract€d) duing $€ @!rin8 op@iion. Prcpr€g is ats @lled .B-SL8e' , 'Bonding

Shet' or, sinply "Preg'

The substrare 8bs or fabric is @a!ed with a 6in in equipmat calhd . @ater (or

a€attr). Ih. slbsrate is pulled tleugh ! pd filled wilh a soluton ofresin in one or

DoE elvdls od lho th@ugh a seq6e of "melainS b6" 10 a{wrcly @trfol

the d6ir€d 6in Mtdrs The Bin-erualed fabnc is pa$ed thrclgh m ov6 havins

a sdi€s of hp@nu&confolled zon6 to rdove solvcnt md case lbe r€sin topartidly Ercl d iB-sldee.!' It is nGsary lhlt the prcpr€s nNt b. o.ribte dd

drapable, s thal it d 4ily 6!fom !o the shdpe oflh€ Dould. It is funlE dsiEble

ilBl rhe prcprcg pcs a requircd dcgc of l.ckins od .ufficiorly sticky to stay

in pl@ w[m alpli€d b thc nould surfse, d to a prcviouly apptied lar6 ofpFpFa udd diSh plsw.

1.2 Classificstion ofComposltes on the Bsses ofM.trirDepddins upon th€ matir us.d, @mposit€s .d b. cldsifi€d i o nebllic,

mic or polrmqic ruEn onDosites.

1.23 Polymer Mrtrh Cobporit€ (PMC.)

The nost @m@ly used naEix m dials fo. @nposite e polyndic natqjals

baae t[. der'dical prepdi6 of tolyns e inad€qde for mmy shcnml

appliqtioN. I! parti@hr lhen sE@grh .nd stitrr* e low 6 @npa€d to nelal

1.2.1 Ceranic Mrtrix Conposit r (CMCS)

Monolilhic csmics have reaombly high srrenerh dd stiifn*s bui @ britrle.

Thus o.e of th€ ndn objetiv4 of prcducing @r@ic natrix onposiles is to

ihc@e r\€ longhns. Reinfo@enr wilh prnicllales md @ntiruou fib6leld !o

& in@ in touehns bur lhe increse is noe sisnifi@t for lhe hr*. Impo'tb!qmpl6 of CMCS re dmim and da cffic mrtix @nposile

1.2.2 M€td Mrtfir Conpoclr. (MMCa)

In rh* naioials, the nanir or ontineus phe n a ndal d neral alloy, &d |he

reinfollddt or disnlinuoB ph6e is in amd ! qmic Th* mposit€s hdv€

supoid popertis b tnei. \@iofor.d 6u.tcrpans, dd highd op@ting i@perah{€s

lhm PMCq have mn-nalmabiliry and 8'€ata Bislace ro d.gradalion by orgmic

flnids. Tney have Sood condudivity dd good load bering catabiliti€s ed ducliliry As

uual, lhee hiel t€ch naldials we!€ prcduc€d n6t for the adospace indust_y, bul hsve

applications in olher deas such es autonobile engin€s, Tle reinfomeht cm be

ohtiNous, dismntinuous. wniskd or padicllate. Son€ tt?ical nbr€ matdals ued &€

b@4 silimn carbide, gnphit€, alMim and tugsio.

ed smics. lt nms lhat a @nsiderablc bdefii @ be achiev€d by reinforcins

polyn6. lte prccBsing lmp@i@ of polynqic matrix @nposiles (PMCt is low

ald tbqeforc th€ equipmqls Equned fo! PMCS synthcsis trc sinple. For tb6e

Mons lhe PMCS dev€lop€d rapidly dd oon bc@e widely .@e/€d Ior slructure

1.3 Reinforcement in Composites

Thse re nMb€! of woy8 lo rcinfor. conpositB, sone offid e;

r3.r ParticleReinforced Conposite!

Pdtiolde rcinfol\mdr h* dim.nsions thar @ equal in all di@tions. The

shape of r€inforcins panicle nay b. sphdicrl, plaul.t or ire$le in g@netry. In

this w, particls bd lhc mdin load dd th€ tunctior of naLir is load dklriblrion

ed t af6 to the priticl6 I51. As rh. volmc tldio! of thc disp€a.d matdial

inm6, lhe meimicd pop€niB @hing m optimm val!€ dd lltd begin !o |all

[6, ?]. AI higha volMe fizdion of rh. mic nalcrial $e pailcle ste in.ll'$dd the sfucnr of Ihc iturs6ic dohlin b@n6 icgxl& and poous which

deeFd6 the tundiql popcniB of fic @nposn6.

13.2 Fiber Reirforccd Conposttcs

Fibq is ay €lmgried n.tsial srch ihlt the rnio of irs ldeih io irs @s sion@ is l0:l or mo@. Common 6bq rcinfor€.d @mtosits e @mpos.d of 6b6ed a nabi:. Fibe$ @ th€ Einform.lr md lbe main eue of slr68n wnile tne

tutrix elues' .ll the fibes iog.thd in shap. sd trdslen sre$6 b!tw@ tne

rcinforcing fibe6. The ituponst god of rcinforcld-rcinforc€d oohposn6 is high

sFcific stmrtr dd hisb sp@inc nodul$. Th.rc arc !h!ee rr?es of lib@ sy$ms:

Continuou & Ali8rled. Dis@ntinuols & Alierr.d, Disntinuou & R@don.

Fibrc reinforc€d omposites d€ aho knoM s naco-onposites s the

r€infomenr h dispded in the mahix oh a hrcoeopic l.vel 18, Sl.

1.4 Polym€r Mstrices

All thr* tlFs of polF6, dlifusaq rhmoplaid€. dd €ldrohd e Ned

a nalrix for polyndic @nposites. Hovds, thmosdting pol'nd bease ofthen high Dodulu, g@d straeth and sriffns m nost sid€ly u$d mar.ies flrr

PMC s. Tney m noe cist&l to c[oicd alla€t rh6 mosr rb@oplsrie. Anons

th€* epoiy r*i$. phdoli6, pol'€stds, polyinidB .tc., m o@o.. lu rrscumt preject epox! hatix os r .ontirtous phdte tu tte conpasne slsrzn h6

l5 f,poxy R6ins

Epoxy resin is deiin€d 6 a mol@le @nrai.idg ooF thd one epoxide group.

Th. im "cporl' rcf@ to a chdic.l grcup osistinS of e oxyg6 aloD bnd€d to

two .abon lions dut e€ drcady uir€d in eDe way- Th. simplBi .IDxy is a rh@

nflb.G{t ring strucrue knoh d alpha-€poxy' or '1,2-@oxy' or oxirme or

Ths prlducts N elid or liquid wiih iie @6istdcy of horey &d hare lhe

abiliry to r@t vis tt. cpoxy ad-goup6 to smdre rtrceiin@ioml nerwolts

providing rh€ final nstdial wirh ngidity. hddn€ss md lh€ inabihy b renow

The fihal pbduca gad.lly erlibit:

Erend elcai.d Dtropenie

Cood adn*ion due lo F€se of pole grcups

G@d inp@r 6i3l!n€ tud

Epoxy poltmd ws fi6t strth€sized by P.Sc actq thc invdtor of nylon 6, in 1934

tlol. nr. ruine recliotu wft disvdrd by p.CNiln dd Ciba towaf& lhe ad ofWorld We Il inboduc.d polynd p'oducG on rhe ftdl€r I I I I. Moe rhd 22qo0o ioBof €poxies qe now ued enurlly il th. USAi worldwide copaciry is 4OO,OOo tons I t 0l.The steady indeae in mnsmprion is d!.10 th€ hpid dev€lopnot of*vdal tieldr of

applidions. Th6c itrclutle m.inly adh6iv6, lmliry. speial 6itu 6ed in the

€l4aonic indusEy {d aapsulaiirS m.ldi.l €tc. The nosl inport nt epory Dolym6availtblc in thc na*et (noneglt{idyl compobds dc€pted) conpris th. following

tr0l.

I. Amalic di- md polyglycidyl conpoundJ of bhphdolA {i.cluding

advd@6i prcducts), bhphdol-F (honft nixturc), pheiol .ovolas,

cJel novol6, tis(!-hrdrcxt?h6yUaelhme ffi zkis{FbtdutthqyDerhde (Cllo&l ddivdive).

Il, Arcmdic bis€tbylSltridyl .tlM of bisphmlA.

l!1, Aliphatic diglycidyl cihq of 1,4-butm€diol, l,Ghqeediol, n@phayl

slyel, polr?rcpylme glycol 425.

IV. N-elycidyl €tnds of diline, 4,4ldiminodiphdylneiheq hoctduiclcidj 1,3-bis (3-nyd&binyl)-2-hydrcx'?rcpde

V. Dislycidyl6t6ofErrlydophrhalicacid,hqalrdephthalicacid.

vl. Crcloalipbadcepoxi6:3,+epoxrclclohqylmerhyl,l,.L

€foxycyclohe@.aft oxylrt i lll,4eporyrlcbnexy)-7,8-.poxy-2, zL

dioxsspitu l5l udede, bis{3.4.€poxylycbnexttn thyl)adipatc.

Epoxy 6ins have ba usd a adh.siv6 since 1950s due to lh€ir g@d wening

ability, low cue shrinkage. supdioi hechdical popenies dd €xcell.nr chnioel

TL idatized cltmical sEucr@ is shown below od is dte nost 6ily idddfied

checlaistic of oy norc cmplq epoxy ml@le

0)S.vqal of the more @nnon hono@oxies hav€ hivial !md, such as

epichlobhydrin (ll), clycidic &id (IIl) ed glycidol (lv).

(v)( ) 0tD 0v)

Glycdyl (V) is used lo ref€r lo ih€ imiddl @oxy goup, the lme bein8

nodifiei by €thd, esla, mine etc., s@rding b the nat@ oftlr gmup anached ro

1.5.1 High Tehp€r ur€ f,pory Re.ins

Epoxis nadc aith bisphaol-F, bisphool-F &d novol& mixne, or Novol@ epoxy

resin exhibn geally ihprcved choical sd heai Bistdce @6pe.d to Ur nuch more

onnon bnphdol-A epon6. Probably 98% of all @oxies de tc$rld' bisphool,A

epon6- Novole €rDxi6 e norc dF.siv. the regulr €!oxi6. They qhibii highd

tqt disionion rdpqanG, [ie!d glss niNind hpduc T, (both of lh6e etu68 of whd the €poxy b€Eis ro $ftd wirh he.r).

Gmdally bbphcnol.A eFn6 will b.gln to sotm in d€ tmper.tui. regp of 5(]-70oC,

Novolac epoxi.s initially 6ise thh v.lu. by abour 5"C. Morc inponor is what happqs

atove ihis lmp.ratrc. AI epoi.s will rchtrdo wh6 the clqai.d temp@rdes lall

belos rhis Etunion tdp€ratre. Howcv6, Bis Novoloc €poxi6 will @Drine 10 (Wwha expos.d io tmFatlE ofabour 65oc for fw nos. Ans this additional cuirslney smdally q ei$st nd about 15trC (dry @vitumat wilhout ptlblms i 16l.

Botn pnmol oovol& ?oxy Bins (EPN) ed bisphdorF epoxy rBins (BPIER) @prodrcen non a phdol fonaldehy& pberolic r€sin. Th* staning ph€nolic rcsim de

ected wiln Aichlorohy&in 10 ptudw $e linol eloxy resin. The sloichiomel,ry ls€d in

th€ podudion of the phdolic 6in MII influae lhe nncdoMlny of lhe phoolic 6insd offqudly rh. epoxy 6h md. fron n.

1.5.2 Chrr.cteriiticsof Epoxy Resins

A nmb€r of pbFni6 have le<l to npid 8rcwth of epoxy 6is e.l th@ e in ! wide

mae ol indutriB. Considqing rhe liquid 6is, th6e @ low twnry [qui&, whnh

read'ly @nven ro dr themoet ph& upon hixine witn a popd trins a8dt. Thd€ ar€

olher lquid r*ins likc phenolic, poly$tes, aoyli6, erc,. cu.ing in a similtr fshion, bur

the cpoxy resiN hav. d nlh€! uique @mbinarion of ptupeniB, which se dli$ed

Hieh ne.nmical prop€ni*

Hish elelncal insllation

Cood Chdiol Bistane

Th€ @oxy rsi.s de prcbably d€ mNt vasaiile of thc cont€mponry ptsslics. Tne

baic popenies nay be hodifi€d in ndy prrsr by blddi.g of r6in typ6, by *hciionof cuing agals &d by lh€ w of nodifid and fi116. Due lo ih* ch@dqisti6.crbxi6 aaenlly olt pdfom Dct of rh. orh6 r*io tytes in tcms of neheicalproperti6 ed resistec€ to qvircmat degadttion, wnich l.ads ro their wid€ rdg€ ol

Followine de en. oflh. indiorive appli@lioro:

As adh6iv6 for anmn ho.cy@nb shcilG, for bonding toS.rhnpaintbrush bnslLs ed for @n@t€ topping onpou.d.

ii. As body sold€s sd muldng conpounds lor rhe repai! of plastic sd ihe

mel boals, automobilB etc

iii. As ding @npound for fi. flb.ic5ion of shon-M dd prcro-ty!€ mdd5srabping di6, @nms dd roolin&

iv. As r salant obpound in buildi.g ed highwdy @sfudion appli@tioN old

in applistioB wn@ high ord6 of chdicd r6isru@ rc r€qu!€d.

v. As potting dd 6@Ful.tion @npou& &d inp.ee/uhng sis edvmisls tbr el6tric ed dle.tonic .quiPln@t.

vi. As a lmimtin8 r6ins for airlid. Md missile applicdriors, for filmqtwound st'uctus and for toolin8 iixtucs.

E€noe epoxy 6ins b€long to rhc thmosctting clas of pla1i6 having snp{ior

nehdical pbpeni€s dd oursirnding .dh6ion. tlowdd, whd tr€n wirh

sioichion€&ic mout of polldbciioidl Mi.6, ih. hish degr* of croslinkiie nat6epoxy briido The hieh mslinl tLnsiry wc*ds etory's pel strelg0r and inpact

str@grh- nris, in tuq linits iri ue in ndy applidioG eh@ rhe bonded struclue ha

io @@ut r n@hoicd vibdtioB d dDck! n?l. Th@fo.q modifi@tion of epoxy

Gis Do inpove i|3 bond glldgrh hd louShns b impo dt [8j

153 [fi.ct ofR.siD Structure or Rsctivity

The tyF ofqoxy soup dd irs l@rion wilhin lh. no|6de influae rqctiwiry.

Son€ locarios pEf6 !o @ct *ith acid cuin8 lgdtr m. wiih bs6, $ne @qtrmely @tive wnh 6lain c.talFtr, othd litually indt dd eme posss e@d

ovqall @clivity witn nost clas6 of drin! ag.nts.

R@ctiv€ goups otnq lhe .poxy nn8 nay be presot in th. mlfllq nost

omonly hrdrcxyl and olefin gmups dd thei. numbq md lomrion al$ influflce

rhe @.tion €qlilibrim with sp6inc curing 6e€ni md nay reiard or acelqale th€

1.5.4 Etrect of Fumtiomlity

Id epoxy 6ins, @ch @ory gtuup hay havc tuncti@ahy of I or ?, depadina

upotr llE ui4 agent nploy€d lrd th. @cdon @nditiotu. If €poxy Bi! is ractcd

in r!.h a wry thai a syst 6 of tuncdoolity te is obtrin d, tio otrly li!d,

1.5.5 EtTect of Cross-LirL€d D€rrity

BBid6 the ftnctjonality of rhc cin, it is ncs.ry to ttrov how f& apd tn

ixctionrl gowa @ pl&el si@ lhis det€min6 mslint d€6ity. Cbslinlinadmsny hay be <letn€d a rhe nMbd of .ffefile msslinks F dit volme In d€

diglycidyl €th6 of bisphmfA (DCEBA) th. €pory gnups re s€pmted by svoun'ts ($e mnatic ring being oul.d as o.e uil). b othd 6ns, the grcups e€

sep{at€d by 30 10 40 uits. I. g€hoal, shon spocing (3 ro l0 unirs) giv€ riSidity

whcr€a nediun spacing ( l0 lo 30 uils) gives flexibility or softlr6s. Additiohally, ifpole groups m pr€gl alon8 the polynd chdins, the nol@uld inl@ctions betwM

adj{mr chaiN de indaed whicb lhinttely rcd!6 th€ clain fldibilily. Bulky

side grcuF, ech 6 mmtic riags als hinder *Cm6irl Doiior 4d thq.aorc

de6c flqibility. Hae to Frdu@ a givq enns or flenbility, .t a giva

ldpd.turc shorter cbain l€ngtu e r.quircd for e aliphatic-bar€d 6in 6@mpd.d io s mnatic b6ed Bin. Th. €ilcr of irtroducins substirulion on th€

b..kbon€ is goqally lowards lh€ r€dwtion of cros$lirting d€mily.

1,5.6 Typer of Epoxy R6ins

Thd€ Ee two Min cat€soriB of cloxy rsihs, hmely

l. Gltridyl epory Bjn dd

2. Non-Slycidyl @xy Ein.

drmoplanic molaulB wiU r€sult, As rbe stsidlink.d pbducls de ohlain€d. widin a givcn class

inctiohal noleulB Nill provide ihpoved thmal

fiDciioMlity is in6easd, coss-

of epory 6in,0t hore highly

stabilily ud slvdl resistsce in

1,5.6,1 Cvcidyl Epory R6ir3

Epory 6ins ddvd fiom Aichlorohtddn e tcm€d 6 Clycidyl baed r6ins.

Clrcidyl cpoxy 6i6 @ b€ sldthdi@d in senl ways {191, bul most

cmmsdolly importal e?oxy i6iB pr@arcd by @upling epict orohydrin with

naldiah lhal possss al lss two Mctive hydrogo atoms. Thse i.clud€

polythtulic @npouds, mo@ dd didins, oinephcools, h.l@yct,c inid6dd mid€s. sliphatic diols md polyols md din.ric fatty acids. Apprcxinarely ?5%

ofde epoxy r6i6 Mady uscd worldwide @ ddived fon the diglycidyt .rha ofbisphenolA {DCEBA). This mdket donindc. of epory Bins is a resulr of a

onbinarion of rtrei. low 6sr and rd€qdo r€upgiq perfolfu@ in Deyapplieliong sohe ofth. glycidyl eloxy ein ed rh€i. popqriB e gjvei below:

1J.6.I.t Clycldyl Etb.d Epoxy R€si.!

Gltcidyl .lhq epoxis $ch 6, digtjaidyl €rhd oI bbphmol-A (DCEBA) is atr?ql @@ftial epoxy r€sin md str$sizcd by qcting bhphdol-A witnepichloohtdrio in th. pr.ge of ! be s a et2lrst 1201.

Slru.tur. of DGEBA

Th. prcp€nic ofDCEBA 6ins dcpad on !h. vale of n. which is rhe nunbq ofEleaxn8 e'ts amohty lnom s d€gre of polrmqizdtion. Tte nhbq ofGpedng un d€pods on dE noichjonctry of slnrhdt rq.rion. low mol@tdwergnt DCEBA resitu i,.., eloxide equivaldt nas! (EEM) =175_2OO re p.cpsed i!No sr.p actlor s.qude non €pichtoohydrin md bisph@ol,A. T1E fiBl slep isb6Haiallzed @upling of bisph€nol,A ed @ichtorehydnn to yield dnoohydrin.DehtdDhrlogdlri@ of the chloohldrin imem.djlre wirh a sroichiom€fic mourofb6e lads lo the to@ation ofglycidyt .rhd.

Medim to hieh noteuld w.ight DGEBA Gi. @ b. prcrluced vi. &e.la$/,po6s [211. Ite lm "bftfl is daived frm thc app€eee of epoxy 6i! prior toits scprhtior fton watd md pbipnar.d salt3. A low 6tio of .pictdoohydrin ;

bisphenol-A is uei t<i prcmote fomiion ofhish nol€uld wogff r€$G.

Olh< glycidyl{as.d .pori6 includ. b@itut€d bilphtul-A, phml .rd clsl.pory novol4, 8lrlidyl Gthd of phool-hrdrooion norcllcs gltlidyl .thd ofrlip!trtic diolr ac. All rhe mlrdi.ls @ nduflcnf.d by pl!...s sinild ro rh@

d$ib.d for DGEBA cins. Th6! spei.lty r6ins poss 6iqE FbFrri6 rhal

nlrc thd cdPdiliv. wilh lN qposiE DGEBA 6in in p€nicdu applisio.s.

lJ.6lJ BroDi!.cd BLph.lol-A B.r.d Epon6

M&y rppli€tiotu of.pory 6is r.quiE rhc syston ro bc ighion Giskni c,&,

€l.crriol l6itur6. A co'm6 ncrnod of inpming fiis ignition 6i$ane is thc

in@rpoFli@ of lcF.bomobilph@l-A. iRto lt! Gin fomuhtioi [22].

E'

StrrctuF ordislycidi dncr of t€tr .bomobisphool-A

lJ.6l3 PLlol ud C!@l Novol.c Epoly Rdla

Epory nowh6 @ multifiDcdonrl eroxiG thlt qnibn b.rr€r high-ldnPdtlc

pqfoms@ $d chmiol 6is1&e lnd ding a @np.r€d !o DCEBA r6itu.

Borh ph6olb8ld cToxy novolG and tul-bt!.d .toxy Nvolq @ Fodu.cd

ffiidly l2ll. Norcls e pcpa..d by th. eid-qt ltz.d @nd.nsrion or

fom.l&byde wilh.nnd phtul or clwl- Cheg6 in novol4 hol@lf q.ighl @b. nd. by chesrng the dtio of ph@l or clsl io fomsld€nyd.. Eporidration of

th. mrcl$ with .pichloEhydrin tumish6 th. GDoxy novola6. C@l .Pory

rcvols h!v. beit6 dability ed lowa hoiste ade.plion thd ph@lic cpoiy

wlt€E, R=H dd CHr in phcnolba.d epoxy novohG ed cresofbdd €poxy

Ir'e slrcidyl eihc of bisph.nol F, bisl4'(2,3.epoxr?rcpoxy)phqyl]neilhe is

th€ sinplBl n€mbd of lhc cpory iovol& fmily. It is sed prinrily a incti@al

dil@|.' in alpli@liotu !€quinrg a low-vis@sity, hid p.rfomhe 6in s$ln(e.s., elvml-les 6orirys).

156.r"4 Glycilyl Etn n of P!.!ol-Ald.[yd. AddNt

h addnion io lh. phaol @vold, thfr e oihd eFxy r6im ddived tonphml-ddehlde ondcslrion lodka [2a]. F.w oflhe polfuctiotrd r6is have

sc[€d @m@iolizlion bdw of fi.n bidr 6t !o bdrcfit 6tio.

(\,^--OL"r(*"---tNw oppliqlion thar r€qune incrcer.d p.rfomd.c from the epoxy Bin.

padiculaly io rhe el@uooi6, msp.@ &d mililary iodustrid hav. mdc ths€

tt!6 ol Bid ooe attacrivc d6pit€ rh.ir chdv.ly ti8h osl.

ol& ol tne ffnt polytunctional eins is based on l,1.2,2-t€trDlis [412,3-

epox'lrop.xy) phoyll.th&.. 'Ihh rclratuo.lional .poxy cin is pepd€d by the

acid-catalrzed ondtu.don of ph.nol sd glyoxll (eihe€dial), followed by

epoxidation of the Gulting tetia ph€hol with epichlorchydrin [25].

Th6e Esins ae solid and hdve bea pnn&ily $ed a additiv€s in slanddd €poxy

Bh fomulation in which indased hot dbtonion lmFature od improved

clmical cGlarce rc d€si.ed. Tritunciional c!rexy r6ins b.s€d 6 ris!L(2,3-

etor'?rcpoxy)phmyllnefi&c im6 have bd inroduc€d to help .los dre

pdfomde Crdp berwe. ph6ol ed c@l e?oxy novoldcs dd hieb perfome€

meinding ihmopl4tica [26].

1u.,"4"Acid-cataltsed ond€Nation of ph.nol ed htdroxybozld€hld€ €.g.,

salicyladehyde, alIordi the ritudctionrl phaol, wbich tu lhd epoxidiz€d widr

@ichloiohy&in [2?, 28]. Applicalion of ib6e misolid cins includ* advmced

mposils rnd adhdiv€s wh@ lou8nr6s, hor-wcl st @8lh ed eistdce !o hich-

hp€ratu€ oxidltio @ equtud.

l3.6.ri qy.idyl Elh.o ofAlipb.ti. Dlolt

Aipnadc epoxy r6is hlve ba sy l6iz.d by Slyddylation ofdrtundio.al or

polt'tuldimd polyob sEh a 1,4-but..diol, 2,2nin€thyl-1, 3-pmpanetiol

(n6patyl Bly@l), polprepylde sl)@ls, glt@ol ed potldrlhdtol.

o I Pt p.

Zl,'1"-'\-.--f "...-A

Tn€ epoxidalion is gdddly @nducicd in lwo sieps: l) The polyol is added l,]

@icnhohy&in h the F*dce of a Lwis acid @ulyst {sl@ic cdoride, bontr

irifluorid€) lo poduce lh€ chlorchydrin inim.diale dd 2) the inl@ediaie n

dehydrohaloeoat€d wirh sdim hydroxide to yicld tbc aliphadc glycidyl €thq. L4w

nol€culf *€ignt 6ins such 4 the digly.idyl ethc of but&e-1, 4-diol tre !*dexclnsively s r€ocliv€ diludts lo tdu@ vh@siti.s of eloxy Bi. sysds Epoxy

6ins bas.d on lons chain diols, such 6 lh. diglycidyl e$d ol polr?rcpylm€ gl,€ol

de ued 5 flqibilizin8 agots to in@6c a thmosei\ €longatio. bd impad

1.5.6.1.6 Fluorin.t.d Epoxy R$in.

Prcpati6 ot nuoriMted digltlidyl erhd bascd .poxy 6ins sueg€st thai they

my otrtitute on€ of the futu. nq cl6s6 of cpoxy Bins [29]. Th€s. .poxy iesim

cm be preparcd by slvolrsis rsction, with nn8 cldure, acording to the followins

/\.-*V\."*.) " " {-r../+.,**1,,Hf1 ?-*'

Th. followinS fluorinal.d diglridyl .rh6, 5-hcfirfl@@pbpyl-1, 3'bis [2{2J-elox)"rcpoxy) hqs-fl@c2.trepyll b.leq illEdt6 lb. stlte of the dr in

This 6in is a vi@s. @louless liouid thtt @nt!i.s 52% flenne It bd l low

slrfa@ iosion. which nal6 it a slpsioi w.tiing agdl for ds nb6. fterqcrility ofthis r6in with minc or.rhldridc curing.gals is @mpaabl€ ro eloxy

!€sin b6ed on bisphool-A md 6ults in a thcnos4 thd hN a low aflllily for wttrmd €xallqt chdiod r$isrd@, Fleriraicd .poxy resitu @ hieltly resisht io

cnmiol od ph'sioal @odidois ..d e us.tul in vdiely of hi8! pdfomm€

applicarios, includirg specialty oairSs ed comp6ii.s, where dEir in€vilable @st

is ofrs€t by then speoial popdties dd lonS sNic. lif..

15,6.1,7 H.ttetdL Olycldyl IDll6 .!d Ad.br

Triainabrs.d epoxy 6iN li*. r.islrlidyl isFlwre [32] 1,1,5-rri3{2,}

.poxy?bpylll,l,5-pdhydod&iF2,4,Grrione t a eud 6in $at provid.s

spdior tlmd, clerri.d ard d*hdic.l popdriB and b r@mddd.d for

Iuinal6, i@lftins vmish6. @tinss &d !dh6iv6. widcly us.d a cuinS !8atfor s?ei.l polydd-bls.d wadr@bl. Dowda coltingi [33], n n dso Eld in

clettonic lppli€rioB oMir8 !o it! rcl6ri@ of oFiol t_mp.rcncy aftd rgjnS ar

ldnpdanc up ro l50ec ed ninihal mk..6lurion on rhdn.l d@mp$irid.

Thc tiieirc rinSont ining Foducr 1,3,5-tiglrcidyl isyeuit. is stnth6i2.d by

8ltlidtnion of cy&uic &id with c?i.hloohydrin.

1.5.6.U arooltc Glyddyl adn. R6luTm @matic gly.idyl miF @ of @mqci.l imponoc. -r1t. Eislttidyl

rdducr orFminophml, 112,3-cpoxypropoxy]F4.[N, N-bis(43{poryPnP/)mim]

ba1ac is. @crirc, low visity cpoiy Gin thd is us.d FiMily a m.ddniv.

!o DGEBA 6is ro inclqs both thc 6r. of ls . tu gla uaiti@ tcmp<.i'@

Ih€ epoxy rBin bs.d on t tielycidyl ei.e ofn€thyld€didilin., bis{a-[N,N-

bis{2.3-eporr?ropyl) minol ph.nyu m.the. b rh. .pory Bin mGt @monlyucd in s..phit€{cinforc.d @hpo.n6 []21.

Ciba-Cic3y is prcd@ing thjs din with lh. rrrlc n4€ of At lditc MY-?20, This

6in with th. @mbinltion of 4,4 nimimdiphdysulphon is th. 6Rt s'st@ io

nat the pdfotue €quims ! 3.t by 0r .ftspe i.dstry dd is th. s|i|dr.d

la.irn whjch odc 6in 3t5lm ae judSed.

1.5,6.2 No!4ly.idyl Epoty R6ltr

Epory 6iB h6.d on eFoxidiz.d rliphtric &d cycloaliph.ric dic6 e t@u dM-glycidyl ai$. ftcsc aliphnic, M-Slridyl .08 Gpory BiB e od y !s.d

in lpdidtioB thlI GquiF b.nd wotharbility ed.l..tricd po!.nica, such a eldd E&ting 6in,@, L' 966d, ctrlo.liphrtic .pory cis e low-vissity

liqli& th!! 6 bc cr@d with rdrydride !o y,.ld thmcas h.vils a hi8h hstditonion l.mF!tuE- Th* .!oi'd6 6 b. PcPat d frD di.G by pdidon{hion of @bonqtton &u!lc bdds [36]. It* didc p|ltlra Nudly etic.rcd b, $m. v{imt of thc Di.leAlda @crid. Tt?idl dopl. of this ds of

cldoaliphltic cpoxid6 k @oxy 6i6 bas.d on 3,4dloxycycloh.xylnclyl-l+

.poiy.ylohqe4r.boxylat .nd 4-!toxy.lhyl- l,29oxycrrlohqsc

1.6 Curi4 M.chinism ofEpoxy Resitrs

fte m6l v.lqble singl. proFay of cloxy 6ia is th.i. .lilily to limfomrcadily fton liquid (c drmopldtic) 1Lr.10 iough h.rd thmos.t slid fom by

chdicd onbinadon eith ding agd$ or by thc aclion of caialysls, Both ffingmenuism noddly i'k plae wnhout thc lvolution of by-produ.rs, Th.

tonFil@ !r which ruing 6.*ion |.f6 ple dcAad! FiDeily o! th. Aeificqi.g .gdr d dE 6r!lys1.

Optihm cu! cy.l6 fo! ey .!ory rrn6i .I! d.rmilcd api.icdlt Th.

vr.i.U6 im[d. @t6E tid of qd.g.aal!, a@l@toB &d qt lysr5" dE ri@tanpdrurc !.hdd6 for B-{r8in& iniri.l @.ad FJ or; {d 0t ifidcion ofth@ frdoB. N@.lly, 4h r6ir Fopqiy is odiniz.d ind.tqdady. AftdoDlimizrlidr th. uqd p6.rie t b 6t Utuh @nditioN th'l yi.ld . d.sinblc

@mbin tio of popdric veioN ui!8 !gq!i' E avAilrbl. for ct$elinliry.?ory 6ii. AlthooSh eq! tha 150 dirg agmB c *rowt! otly l0 o! $ @wi(uy u!.d fo! ov6 90% of0E sl'|m Epoxy 6id polyhai4 to hrd@.4 ctlelidcd, rhFdi|'l6iond elids. rhb polrrDqizllion oeN by e ddidon o.

clhlyric ra.tid. ln thc ddition ddiu! lE @ing i8grt (h!rd6E) @nbin6 eith

rh. @ry |6in ,!d &t ri. cll*lintjns !s6t fq binditr8.?oxy noldul6. Thi3

typc of r*1ion is cdlcd hctdoFolyindizltioE with cJdtric r.&rions, tlte sclf-

polymai4tion oftlF .ooxy is afidccd. Thi3 rqdion i! c{l.d hotrlopolFdizrim.

Although nu.rr k laDM alod tE mclmis of rh. tuin8 Fe* fd thc wi@chs of Nirs $6rs [37!, still wo* onrinG in rhi! !@

FMi6 trafom htlrcd (FTIR) spc.llospy clcctlD! s9ln t6dee (EsR)

spcctls.opy t3El dd luclclr |!.8ndic rtsoMc (NMR) Jpc.tospy I39l ecl!6dy b.ing us.d b 3ndy fi. F.chdtutic dclik of .poxy qi.g @ th.

ml@l[ lcvcl. M.o$..oic adrrictl t chliqu6 rld a dif.6tid s.ming

oldim.rry lao,al l, rnd didcdic r.br!d@ mdum6|rs [42] a e.ll a $ppon d

dyluic n.cl6jcd n lbo&, su.h B losio l brid .nilFi! ta3l rd dyD4ic

3lring &dy*b Fovid. sltitiodl itrfom.lid .bout lh. tincti6 {d .hdornob8yof0E cpoxy 6in sing.gsn ra.rios. Dc?€tdirs UFD dE |pDliqtiq ofu.pndus a|d rhc pred B.d to 6!t ir. diff.(at qbg.g@is @ us.d. The bulk

prepdtiB of dE l!qm3.t @.frer.d bt thc stu.luE of 0|c €poxy ain dd drcuing a8gt! a wll a by th. dr6t of dre E tion b.nEt 0m t44j-

Mdt .?oxy Bin fomulati@ EquiF lh. s of $lvdt!, Mclivc diluat3,

pldicizar fll6, pisrna|t3 .nd lh6. @nnituar! @ d$ .ffet FoFri6 1451.

The epoxy rinS difrd in r€aotiyiry, drp€nding upon whethd n is lminal, inhal o.

ringiituatd. The epoxy goup may ed in or. of iwo ditldst wals: dionicaUy

r9-tlxl

o\.1^..-

Both t}!6 of rescrioN e of impone* io epoxy r€sin l€chnolo8l/. In lbe

dio c nehhisn, th€ epoxy gtuup nay be opoed in vdious fashio$ lo prcdue

N mior Ar aion is { activat€d sp*id, capablc of nmhd Ecrion.

In 1h€ calionic n€chdis, d& @oxy grcup nay be opded by d active

hydogd (i.e.. hydrogo arms which e. Fdedbl€ by a netal, sucb a neLllic

edim) lo prod@ a trry chdi.il bod ed c hrdnxyl gbup. The €tiooic

nehdis nay poc€.d i. . nmba of waF, seh a dt foUowing

f o: HX

,/..\ \.AY

f ii,r*i"-"i

,9H ^ ,9H\c-1"' ' >.-11 +v

/, \ ,/ \XHX

r)

2)

3)

t.

'1" l\l r,/

HX\,/+ c-c \ + Hx,/l \

x/

The b6ic anry agolr mploy.d in lhe spoxy 6in ldhrology de lais blseiinoedic basE pnDary ed s@ndory hincs ed did6. Thc eid €uing agals

nomally us€d i. epoxy rqin i*hnolos/ is carboxylic acid annldrids, dib4ic

oremic &ids, phenols 4d L.wi! acids,

1.6.1 Brslc curitrg rgents

Tne orSmic bas€s. such as tenidy din6 (RrNr) N rpresdt tive offie moE

@cn \ er y?e L.w, \ bes rJrable for rhe cdng of Aox] reetu

1.6.1.2 Inorgrnh Arr.i

Inorgeic bes. such s allali netrl hydoxidd tcact wilh €poiy Bitr a€wding

to the ionic m4iois similr lo r.niary oi.6. Tn€ bG safrl6 e dion by th€

'9H,6,6o

+K"

1.6.2 Anine Cur' g Agetrti

Amjn6 de safllly used 6 cuing aSdts for .poxi6. Tn* ag6ts include

aliphatic mine mMtic min€, ldiary hinc. di.. adduct, alicyclic min€ .nd

lalal cuina mine. Hmdli.S of low mol@uld mss, low vis@sny mine cuing

aemls i. ons diftculi be@ue of their ioxicity [46], !€aclivity dd voladlity.

cycloalipharic dimines. slch a cyclohqe.-l,2nidi.e [c6H,o(NHtj], &d 4'(2-

minopropee2-yl)-l-nethtrlcrrlotqm€-l-min€ e€ lo! viscosiy liquids that

Eact readily wifi epory resios ro give a ih€mosd witn dadvely high slssransnion tmp@tde (>150"c) [42] A'onad. diminq &.lhe lssr !€octive ofth€

din€ cuing agsts, Epory 6ins cured wilh Nm.tic csng agenls e\nibit a hish

slss tr sition lmpqstue ed €xellor chnical resi$dce. lmpodmr tronalic

dimine cuing agdrs ,nclud€ bi{4,mircphmyl) m.lhec (MDA or nethylqe

dieilin€) ed bb (4-mimphoyl) sulpbd. (DDs d &pe@). Th. .biliry ofth*baterials lo .tred cu. lo ! dry B slag€ naica thm uFfin for pepegs.

\-#"\,-"*r*'/*trt -*:\L"*-*-L/II

rr<\--. aH d t-**\.--r"-,/' d d \,,r+\/4_/J dr od \

-"-d\*,^ld4\,-,,*"d\n-r*.'

/ t', 6H\

II

II

Fi8. l I CD${inlins nctwdl fomed by tne wias of Gpory by mina

1.63 Amid6

The dides ulcd in €poxy{€sin fomulltions e acru.lly didepolt@ires@ntaining sufficiqt ftedine hydrcgd to .@ct. The hydsgsB of the midegreu! de Duch hoE slu@iidy ediw .trd cl4lled tqnpqatlG @ r.quircd for !

1.6.4 Acid Curlng Agcnts

Diwboxylic &id such ar th. .rhrdiid6, opa !p e .?oxy rinS and b..ome pan

of the Nsslinted strucrr$ s s 6rd linlaga Conp.r.d with e min d€dsrsten!, the dhydrideq€d Bils show b.tid lb@d Bbre.c b.nd hieh

Lop@t!re p.rfomm.c md inprov.d .lebi.al popdti6, Conmnly u$d

di@borylic eid annydrid. dins asdi inclld. ndhylbicyclol2,2,llh.?r6c2,3-

di@xylic enydtid., 1,2-crdohde.dicdboxylic arbyddd. o! hq.Iydrephtlulic

onydrid€ $d phth.li. a.hyd!i&.

Ihc prcplg.tion st p in dE cro$tiDldlg of d €?oxy 6in vnh d dhtdt de

dtdyz€d by a tcfiiey dire is $ follo$:

o

Th. pbpa sroichiobct y for arhydridc@Fd syst ms is uully delmi.ed by

qpqimdi [a?] b@w th! qclul cuins Eahdjs is cmpliqrcd by lhc rc!.-tion

of s@nd{y hrdsryl sreuF with @oxi& srouls (6t€rificlio.) ta8l. SoDc ofth.inporter dinc &d adrtdrid. cuing ag6ts u.d witb lhc ?oxi6 e lbt d in TaUc

TabL l I AdE tuin8 .a.nts u!.d qrh .tou6

b) Tddhylddmirc.c) llexamtnylmd$mirc,

a) Mebphenyl* didlreb) Dimift diphmyl$ruorc

c) Methyl* didilift

a) DdlylmjroprcpyLnircb) Oletu ond€-polldiGc) Gltridyl.rb.r-poltmic

b) Ndjdnyl pipaeiE

hlenl cololrsr, cuinc fulnlsla) Bomntifluoride-mndhylMln empl.x

b) BooDtifleride-@no.itdollmituconpl.x

TETA

DDS

T,blc | .2 Anhydrid. cuiry .gd! ur.d *i$ @n*.

k) Hex.bydroptnbdict

TMA

NMA

'V.ry uMIt aed b.Me dhan nirg w.

1.7 Toughening ofEpoxy Re6iD8

Thm6er Bils @ highly qo$-linr.di thftfor., tney fon a risid netwonr

which is diDdsionrlly st ble udq difl@l @nditions, having good chdical ddthmal r€sislmce. As a resulr th.!€ poly6@ ae very inpondt dgine.ring

maraials, llmutins fu aql! 20% of th. polym$ ndk€! including 6e incmposiles, @atnss @d adnBive rppli$liotu [49-51]. Epoxy resis de lhmoslswith qn&rdinary adlesion a@mpdi.d by sihPle cw, Spod sfag$, qep

eiston€, nd rolemc., cnmical d$bility rld relatively low sbnnkaga

Adv@lt the poltmd de sle britd€ dd have a hiSh deere of noistsmitivity. Touehoing epoxy BiN eould dloe lho to h. u€d in t|ny addition lolplica'ioB i.clqdrng

'tucn$l rlpliodos l5ll. Thc nain ain ofloughaine of

.poxy cins is !o prcvdt cE r fomarioo sd to 3top th. @k pbpagrtior, This 6be r@nplishcd by ft*ing r lysrm 1hat dbsipaio m.rgy ovq largq ea, Orc

$ch oeilod ot di$ip.ting 6crry wirhoul ca4k fomation i! poltmr d€f@ation. Ifihc bditl. cloxy 6in @ bc nade b d.hm, @k fomlti@ cor be avoided.

For ihc @ks thli have alre3dy fom.d, touS!@ing mehuisr nNt be ablc !o

iminr|te the @ct befor€ fdil@. This @ tE don€ by spr4ding oul @dg:/

Fpoaible for cd.t pbp.gatiotr ovd ! l{gFr !u dl*iating the lcdizod sF*.Toughding of lhmdclitrS pdtms 6 .le b. @hplishod by addinS a

0cxibilid tc' rh. rhfros.l. Addiq a flqibilizd will inde.d inc@e the kJuglEe!

bli it 6d$ io adv@ cfrd $ch a loGing of thc 8ls ttNilio tqtrp€Bt@

(TJ .d nodul6. Anotha h.thod of ioughrd is inclBion of tubbd p&ricl6 into

rh. priney phe. The gDndlry Dbb6 s inptuv. l,h. inpct sftngth eithout

lN in polFtr otha Fopqti6 t521.

Epory 6iB e e.q@dy hodifiGd by dislving in a 3nall Fopqtion (lG

2Cl.) of. Iiquid obbd @!oi.ing ra.Nivc od eloup6 3k[ a cetoxy-tmimt d

eroniE c opolynd (CTBN) [5]l .nd diietdniot d but dio. ldyloniEilc

@pdynd (ATBN) [s4]. ^lthouSh

CTBN dd ATBN olisond e vdy efficiar in

ieptovilg th. t&turc pop6ri6 of .pory 6is brt b.t. rhc @lra mttqial

To .sid d.Grior.rion in th. inh.6r dift* dd sti.ngh erd a Educrion in the

ela-r.Gnion rdF.lurc of lllc 6nr eu@ @8rnqiry pl4!ri6, such a poly

nla $lphon€ (PEs) l55l &d poly.rhd imid. [56,57] have bd us.d ro ptud@

sr$os @ntlining n8i4 du.lil€ p6nicl6 disp6.d in cpoxy sin. Psnicl6 of

dtstallilc polymd, 3Eh s poly vinylida€ I@ride (PVDF), poly butyl@kEphrh.i.t (PBT) drd nylon 6 h!v. bd s.d for thc tough@in8 of6 mmdcmin dftd epoxy 6in. It ha bq reponcd thlt nylon 6 sd PVDF tough6.d

.poxy r4ins !o 6 exrd sinild ro lh.t of CTBN, Th. 6!.rrc toughrs, howdd,

wa i@.d two fold by th. irdBior of PBT ovd thlt rchjcwd with nylon 6.nd

PVDF [58]. Ii hB b.a epon.d rhit both poly.thd ahd k€too. (PEEK) ed PBT

@uld fom cry$ak in thc fom ofhibloct @polyn@ with morphoN PES [591.Ite

nost etretiv. nodiid fo. i.ftaing roughn€s oppald to be th.lribl@k PEEK-

PES-PEEK s)sim, which gave d alnost sinelcphAe stnrture [6!]. V*ious

oboxyrtuinared €lasromdic a.ryloie oligomd have bcm u€d to touenm a

DGEBA resin. They fomd that aqylate oligomds exhibned qtrqnely good

nisibility with $rvotional €poxy r6ins ed cur€d cstinSs exhihit€d

efimcddts n 'mpacl

streogh ompeable lo those of kaditio.ally tongloed

epoxt slstms f6ll A ditfeeni dpploach bs ben tak€h [62] to s]ntnesize two

pollmas, o.e oI wnich fomed a neMork by simult,n@c indep€.d€nt Eadions in

ihe sme @ntainq. Inldcoss linting rcrcriohs w€re elinimt€d by rh€ combimtion

of Ae-ddical (acryla|e) ed ondssaiion (.poxy) polFdizlion. Th€ ne.nmical

prcpe,ti6 oflh€ resulranl slstn inpovcd wh.h the ert€nr ofmol4dd nning wsninint.d dd heltuphe smi-inicrploaloinA polF€r netwo*s (sdi-I?NtNft pmduc€d. Sinild obswaiions wdc rcpon d in rne worl( mming dr.

produclion of nelmgmoN iniapoetoting polynB ldworlc (IPN' of poly

ndny' mdn crylale wirhio . poly din€|hyl siloi&c .hsrom6 [63].

Regd, €Doxy r6in acrylal.d polywthde si-lPNs v* synd6iz€d th**@ cmpltible dd sufiicidtly U€xibl.. A gdt d4l of litdn@ hd b@ devo&d

b Ihe tougbding of eloxy 6i$ vi. pol)'rdhee in@Ipoation s a wd..,pne in a slain€ marix to fom a gnicd or b8rafied IPN [466]. Silolm€

el61om6 hav€ als bd us€d a .nr.criv€ altmarivd ro n?ditional iouelaing

s,$m. For qmple, th€ addnion of rcoh lhpdatur€ wldiz€d (RTU sili@n

rubbd in mout up to two rim6 thar of th. wodifi.d 6in hb b€d ieponed 16?1.

Artnongh some of thse oliSon6 ac quire exp€nsiv€, th6e olison€B eimiscible in the Bin srsl€ms .d tcnd !o ni8rote lo thc oulside. To I@lve this

prcblm, €poxy Bin na ben chmically nodilied wnh tunclioMlly tmimt€d poly

din€tnyl siloxme od poly dihcthyf@"diphayl siloxde olisonds [68].

Rubbs modificaiion of bitunctional a.d tet.atunciional €poxy nalnces by mems

ofblock o-polynd ofpoly dinethyl si)oxde dd poly oxyethylde el6t@6 oi m

anbdndegraned polybut€nc [69] inprcv.d the inpact strdgtb for biibclioml

cpoxy s,316 bul failed for telztunctional .poiy r6in s)stm' Tougbaiq ofcpoxy 6i6 by incluion of mim and tuo panicl6 h6 ben dorc [?0].

within this fiudort $e main objctive is b ioueha epory r€itu by

chmically inorpoEtina hydexy lmiDr€d poly buladim€ (HT?B) inro rhe

backbone of epoxy Bi. and ils ch@laizalion. Ditrffit m€.nmicil poFnidslch a ltuile streed, 0€xul $.de$. @mpr€sivc sr€ierh, inpa!| sFdslh ednim hardn€s of lhe !6ulLnt ststds wdc .ho e$luated. Th€ siatic dd dy.micmechmical pmpenies nsued by tb.s..quipnmts d€ coft€lated dd conclNions

ae dnwn bded on 0E exD..immkl dara,

1.8 MaiD Work end New Idess in the ThesisEpoxy Blns have one main drawbrck: their briftloGs, which shoss poo. toushn6s,

por r*istane lo dack ptopagalion, ed lo* ihtscr stlmsth. TIis inhqml bntd€ness

hs linited th€i appliqtion in rcinforc.d plstjca, matrix resi6 for obposild, ond

@ting9 Th4fm, in tne hst fw de.d6, nuch atrdtion ha bm eiv6 to inprcve

toullnd of t'on6. I! it widely bGlided thal the britd66s of epoxy 6i6 is

Miated wilh lh€n hishly ccs-lintcd sr.ucrucs, which ab$6 isisd6@r moutsof odgy dwing |he lircrw pllBs. H6€ mon of fi€ Gwch h6 b€d fcls€d on

inproving tF danvely por ft&rur€ prcpdri6 of cpoxy cins, eiih* by reducing the

ms-li.ked d6ny of the eroxy n€t*ork or by hodi&ins @mftidly availrlle @oxy

6ins with sondary omponols. This 6emt foos6 on lhe *6.d appro&h:

modiftan8 epoxy r*ins by lsing nodifift. Dtu touehoed epon6, whm us€d anatrix naterill in @hDosite vessh, acts 6 a ndjor slmslh @ntibuting €lm4l edsubsquody hydo-blst pressu!€ of Kelld/€poxy omposite vessl incrcaes

siSnincmdy. As th€ sM.d pan of Geaeh, a novel epoxy resin wiltr big! glass

transition ldFatuq inpmved nodulus dd bertq adhesive prcpatiB at elevated

tdp@twe m slndsizd.

1.8.I Wo.k P.e.ented

Htdsxy' gDlps e relcdvc ro*ads NCO grclp 6 well $ epoxy emnps Pht6icil

blading of tubh6 like erborfminatcd aqroniEile opo\rna (CIBN) may

inpDv. th. loushrs but phe i€p.dtion oe8. Thcrcforc it wa pl.nncd to

i.dF6tc rubb.ry s.gMts of hydDxyrmidr€d polrtuhdid. (HT?B) b lle hais

bekborc of cDory Gin- For ctrdi.rl li!l!8. . oupling.S6t h 'qui'€d

which qlinl HTPB wilh @xy Gitr. lPDl h6 b6 s.ldtcd a a @upling aggtr NCO gblP3

ptlal in IPDI 6 @.r eifi hydbryl gbup of HTPB 1(! fm utthde linlage .nd !tth. sc lim. n tu @cl wifi.?oxid. nng of €poxy Gi, [? I, 72]. I! lh. sd|d plnofth. Fojan ! mv.l pri.@I. bs.d.poxy ci! (PER) wiIh inptuv.d thhd ed $.mon*ndicsl prlldi6 wa syn$6iz!d. Th. lrrth6b wa cei.d oui vir nutli skF.

$nin8 wirh dp FrTsmri@ of l-(2:hydmxy plmyl)-3(2'htalbiy phayl)-prepae

l,3di@.. All the intdhcdi.rB pFdu.ld.t aqy st€p a w.ll a th. fi l Foducts wdchdcldiz.d by difoqt &dydcd t*hniqc.

lJ.2 FutuE Plu.Ic wly dev.lop.d toughdcd .pory wiU b. us.d for calton sd sls 6b6

oEpositd. The hain f(ru will bc on i 6f&irl Fopdti6 blrsr prd@ h omposilc

v6scls, bustin8. @r norylDlosie. K4le aldg pith c{to. ard 8la fib6 will

bc sndicd for @mp.t tiv....lFb.Norcl .pory Bin pill bc u.d fo. onpldtlion eidj difffit mdals sd it3

ch&.Ndizdon by v{ioN .!.lytcrl t@luiqu6.

1.83 F..db.ck froD P.n Worur8 E!p.rl.!ce

In l98q I posl-Sndurl€d in Andyticd chdisiry A@ qdd-i-a26 univGny

l!lb.b!4 P.lds16. ^nr

ny posl sr.dution I joiftd . r€€rch b8.d dg&jzltion

wo*ing on clhicals, sdFis .nd @nposn6 of a.@p|e .nd omdid gndc,

Duilg th. pbdu.tion of @nposite vBs.L by Kdld.4oxy, low bBl F6@ wa a

qitiql ise thn &rs 6 . hotivlriw tovlrds thc d.si8nin8 of the F6at wo*

Simild, d.bordirg of.?ori6 wilh mcldt !r highd tcmpqln@ sls posing a pobldin .!@bly of onporite pdrs for joi'ing &d ifl.8ntio. En@d8hdt and

notivrti@ nn d, boss, suhordidre ed @llagu6 s . key fetd in ny c@h

EXPERIMENTAL

WORK

E4erimentel (PNrt-I)

2.1 CenerrlConsiderstioNAI mDipulaliotu wft @icd out urdd dry nirlogo alrnosph@. N13-

tlinethyldinoprepyl)-l.lpopylde di@in€ (Adldite 20llB) by M/s Ciba,Ciegy

havina a nolml{ weighr of 160.269/mol, iephoone diis@y@ar€ (IPDI) havins a

nol€cule weighl of222.28g/mol ed tunctiotuliiy of2 0 obtained liom M/s siena wilh

a puity of 99% od hydtuxy ltuinated polybltadime with avdag€ Mi - 2800 ohain€d

nom M/s Aldrich, w@ us.d a @ived. Bomo@sol sd nethyl orau€ indicatos

wd€ supplied by nrts Acroeorgoics while phdolphthalein iddicator having 98% puity

wd obt ined ton Riedelne Haan. Bkphdol-A havinS nolsulr weiShl 228.3elnol

ws used wilb a luity of g@!d tho 99% we obhin€d fton N,Vs tu€d€l-d€ lta€..

Epidnoohydrinhavi.ganol@ &w.ighrof 92.5gnol ddpudtyof 980,4waoblain€d

froo ]vl/s n6Mhd. . P@ epichlobhyd.in, pFdin€ ond n€thml w@ obrrined by

dryinS ovd c"lciM oxidc ed c.ldM 3ulphat followed by distillation. All elntioN

wft slaldldiz€d by srordod poc.dF. 'I1E chmicil slrucnr md the 86d€ of all

otbd cbtui..ls & lislcd h Talle 2- L vsios s.ltaical lehriqus w@ used lo tullwthe pr@ahtiotr pd.dw ed lo e.lts Ihe cultinA msldiols rhs pr€p&€d.

Sperrsopic ndhod $ch s FTIR md |H-NMR w@ us€d to follow rhe reidion

involvd in fi. synrhsis ofnodificd cpoxy cin, iG cuing pm6s and the srdt6is ofmvel €poxy.ein. Mchiog poil|s w@ @rdcd on appmtu mod€I9200 mmufa€tur€d

by B6mos1€ad. Ele[o-$mal .ln@td eal'3is w6 psfofted or CENyO odmoldl& v€ighrs w6e det@in.d by v.por prcssu€ oshon€$y (\rPO.) The prni.le

siz€ add dislribution of prcpolynd io th. cpoxy m.lrix wr€ sMied by SEM.

Mechmical propdies w@ sMi€d fron str.s$irnin dala obtained &on fldual, l-loinl badin8 dd tmilc qpqimds, Univ.Ml hsdn€ss ws meNred non nimlaidn*s dprimsh. Dynmic n{hdi.al thcm.l &alysis (DMTA) ws cmied out to

study th€ !-Eldotioh behaviou of iic maiaials, Th€mo sravimetric s$di6 w€r€ mrde

in the telpaature regc of 100'C 10 900'C io get infomotio. abour tlr€ dmal stability

of rh. maraials. Lisr of i66um.nr ued io thc chMctenzarion along wrln mmpay .m€sd nodel is sivcn in Toble 2.2.

l0

T.blc 2.1 Cllnisli u!.d aor th. srrnh€i5 .!i Dodifi.nio! of.Doxy (DGEBA),

i,l,?3 Ri.d.l.d. tllan >999'.

NlOH

rtl

(cll.).Ncl

ttl

t,ttl

HCIKOH

Ddrils of de ch@1cri2!ti6 of th. tucaid! c 8i@ $ fouows:

All FIIR etlys.s w6! nldc in 0E 6nsc of 4004000 mr siiS KBr P.uc!.CDCIr ws u€d s $lv6t duing 'H-NMR &.lFis .t llM tdpdle, r{l chdiqlshins 0!6) @ giv6 dl.riv. ro t.rrdaltylil@ (IMS). For mo|4dd *.i8hrs

dct@in4iod, vlpor p6w oson rry (vPo) wa B.d. vPO tu bti.d d tuuus l.vth.l govos cllegc itr v.!or FB$F of lolution wilh v{ying &nod of $lutc Thc

.pFnh! @Bilrs of t*o cbanb*: orc for p!rc el@t .rd thc olhd for $lution

@ntaining pollma. Eqlilibde b !.lidcd in both .rimbd by diffcotial hatitr&

Fmn t plor of lmM mled& e.idr slutiq .or6ri ion vru .l*nical

difrc6nd, OG moleulu w.ight of uDtroM polynd t dctcmin d. S6ing deron

micd@py (SEM) wa Frfom.d m ln. tt tuFd $af.6 lnt diPPing thc splc i o

liquid Nr io malc rhc Mt6i.l tre bdni.. F@tuld luf!6 w@ sIDncGd wilh gold

M/3Ncd.l-&H.ar 9.(l.4M/tFlul, zg9jto

I

and dl thc maffidts e€rt &e sinS l0 tV voltrgc cl€ron bon. To sidy rhc

sts-sE i! GFr of thc nodi6.d ltoxy-mim @mFsitc n tdiak a . fiDction ofrubbd @ntats in taail. nodq sdB wi[ (q.25 x 5.t-5.6 x 0.2G0.25 m)dih6iN q4 ot. Th. sp€ciM w@ v&um &i.d ovq dsbr !t 120'C b.foca!dt!is, Ttuil.3Eagth *!3 d.lcmincd d dbiqr @nditiN (@fonn.d to r{STM D

618-52) with r .Gtisd sp..d of 5 dntrin Bing Tdm.rlic Uni6d T6ting

M.chinc, UK, Fd high leMry .d prlcisro4 . sitive lo.d cell of lm K8 dpeirypith 1.0 mg lotd da.dion r€$irivily wa ue!d.

T$1. 2-2 ht'tlJ|:lfu ur.d for tlF dqi.l cl'eqiaiod.

FTIR. Spturs (FnR)H'.N@rd M|gdic lol[EEla&nr.l Arlye (cllN!,/o)

M.hinl Poid ATFEn! (np)

soniry Eltu MicmF (sEM)Univqsl Tdilg MGI rF (nS)

Tbd|D8Dvileic Atdta GGA)Dlt@d.l S.siry C.ldir|c6 (DSC)Drodc ThcncrElE i..l Aidte(mM^)v.pd Plw onrctu(vPo)

r"U.rEOL JSM

92oO

5910M35050G231

K.70@

53103

Strnd.d pd.d@ !d fmulr. wd r!.d for c.l@Lliu8 vdioB taail. PrePdii€

ircludinS s!8, str.in, yo6g! nodd$ (3tiftBs), roushnBs, ultjnre le site 3Eagdt

(UTS).rc t?31. ,Ilt..vorg.

of lylicaUy 5{ sratnd w@ dcmi!.d for ad! splcaid Epqtcd wilh dE i&d!d dlviatiotr h tlqunt nodc an*{tda Gpoe fo. ttlmodifcd !d uslodif.d .poxrmirc conPo.itc rulcri.k a fibdi@ of rubta

@!a!r wB sftrdi.d !r dbi6r orlirionr ain8.{sTM D790. supl.s wilh (127 I12.? ' 32m) di|lt4ion s@ F€potld lti v.clM &icd .1 l2dc ovd nidr b.fot

&dysis. Flqurl popdriB litc fldunl 3t4 or fldoil sEtin q dd modulB of

Gl.Jicity in bading mod. E w@ dcrmin d Bing IBEon Univdd T6drg M.cnin.,

IOOKN, hodcl-5582 ibn Nt3 Terdenic UK. nE avs.s. oflrlicslly 5-6 sp@ind

*d dehined for e&h mple od .cpoded with the srmddd d€liarion. Codpresive

stflelh of the modified €poxy-di.c natlix as a tunction ol rubbd conhhts w6d.t mined at mbi6t conditio.s wing Univecdl Tesdng Machine of250KN ftom M/s.

BC TEST TECq (250kN). Cyli.&ical smpl€s sith (25nn l6eo dd 30m dia,)ede

cut ed dried befoG flalrsis ed th. rdr ws p€rfomed @rding lo ASTM D-695.

Avdag* of l}lically fivc smpl6 w.rc t6l.d for @mp6ion &d tb€ 6ultl wd.rcponed with slddad dwiotion. Vick6 h.rdn* nmbq (vHN) wa cdculared singni@hddn* tgtins tuFual mmufa.tu.d by M7s. Ftulq uK. For hardrss

m.Nmd 6t mbi6l @ndnions, filns of unifom lbictns {0 8-l 0 nn) w@ us.d

and ndlmmt ws rrto at fiv€ lo sd.n diff@t poinb. The hardnes of a mordill

ws m*ued by Iorcins { indmla inro th€ surfa@ of 1he nh with a @nslml speed, A

fo@ of 2.94N ws appli€d slowly by prcssing the ihd€hta at 90" inlo the maldial

surf&e being lcsed. Tne indotq matdirl, i. the fom of squm has€d Prrmid dade up

of didond wB Nel for indmlation. Th€ inddlalion rim€ was kePt fix€d (ie, 30

$@n.b) for all spl6. An mpiriql bardnBs nmbd wd tnm calcdat.d by

n6uing ln€ lmeln of tne dia8on.l $bugh ni@@pe anacn€d with $e iNtrmdiThe h&lns wa reloned in the tom of Vic[6 Hardn* Nuba. Izod imPet l6rs

wft p.dod€4 Mrding !o ASTM D 2t6 at tun lonpo.rre with FoddM imp&l

i6ia mchinc (Cmoy) equipped wilh a h@mr. The Iad rt!€ rd N€d a sl4ddtd

nothed (l ftft) sp*in6, held 6 . vqticd sdlevq heM boko by a sinele seing or

a pddulm, dd n@w€d lhe enqgy !o failue, Tne bbw of the hamd struck lh.

spcin€. on $e notch side. Drop hei!)ri ofpmdllum wd Lept 1.,16 melq with a siliking

Hydro-bu6t t€sl ws died o$ uing FEdlov. Inc. hydroslalic l€st equiPddl and

cryog€nic swi6, nodel.mbd FCCTS-IoK. ASME code non Div lllx was 6ed for

dalurion ofhydrcstatic &d hydcbuFtiry b€haviou. TlE ctlinds wd nlled wilh

watq atons with pugirs oui an dd Ba. Shin grug6 ald disPl

in$.llcd on the cylindd for &t acquisnio. dsng l6t'ne" Tlte dttmic Dehdicd

rh.mal arElysis p.rfom.d on th€ @nposne naldials in lh.

l@pmue ruge 50!300"C 6ine Fdkin Elmd Didond DMTA in a bddins nod.

Tr"ical dindsions ol tbe sopl6 wq. 50 hn l48th 8.0 m width dd 2.G2 5 mm

3l

tbictn*. All n6umo$ wft nlde !r ! hearing nre of 2.Chin dd !i a filqudcy

Th@ gnvinerric dolysis (TGA) of rhc spl6 w6 Mi€d our usi4 Psti6 Elm6,

Did@d TGA alpmllls- 15-20 mg of rh. matdid ws tolm in plarinm mcihle ddhanet tim l00pc ro I000pC ar a hclrin8 6l. of 20 lvmin in Nz s6 witb a flow r.te ofsomumjn. B.fo@ TGA ealJ6is all th. sphs w@ prehqt€d ar 9ooc in v&!M lor

50 nin b move ad$rbe{t ooisru.,

2-2 Slrthesis ofDigllcldyl Ether ofBisphetrol-A (DCEBA)

288s (1.0 noh) of bisphdol-A wa nixed with 1,3339 (15 nol6) ol€pichlomhy{irin in a 2L Bi! teidc tuied with €nlx @ndesq ed nechdical stids,

Tne ssmbly wd placed in & oil batb undd nirogm atmosth@, The r@iion nixture

vs stft.d and tbe soludon we hd.d ro r€flu d I I 5'C for 2 hoN ud tha ooled

do$ 60 70'c. 44g (l .I nol6) !.diun hrdbxidc flrk6 wre ddded in l0 eqld ponioG

wnile miftaidtrg the ldF6t!rc in the tugc of ?0{80"c. Ana 6e onplele addition

of cdslic, hstiry alory with stiEilg w6 @ inu€d for ndI half o hou. Anwods250m! ofdistilled watei w6 added. The onrcnt ea qtracted with 30OnL of rolMe

dd dgmic lay€r wa $tdatcd fron !4u68 laF by s.p@ting nmel 1741. Tnc

dgeic l!y6 wa wa$ed with hot w.t€r sddl dme dll il b€ome mtrol, ch@t€d by

pH pap6. nE wcted @ichloobydrin &d rolwn. wa r@oved tun orgeic lars by

djstillation udq vacuM. Thc peducr ohain d wa 6n lly vasm &i€d at 130"C (92%

yield). Analysis: 'H-NMR (3OO MHz, 20.C, CDCI3, ppm)r O = 7.16 (d,4H., -C-C6li6),

6.8 (d,4H" -O-C6IL), and 1.6? G,6Hr, -CHr),4.22 (dd, J=3,3 Hz, 4FId, o-cHt 2.9 (d.

2Hb, CH, of oxitue),2.7 (d, 2H,, CH: of oiim.),3.3 in,2rL, cH of oxnme). FT-

IBrcnr,3010-2850 (w),912 G), 830 G),3518 (s), l4oo.ll5o (s), l6oe150? G),

r245G).

21.1 Detemimtion of Epory Equivrlen.

0-2g (0.53 nnol) of epoxy r6in w6 w.ighcd in a 250nL mud bottom fl&sk by

a&ltticrl b,le@. 25nL of pyridinium chlorid. slution w6 added vilh the hclp ofpip.ne od sw ed util rhc 6tirc smpl. w6 mplerely dislved The @i@b wft

rc{lued for 25 Dinuid 6ing hating ndilc and mlgnetic sti@. Tbe slutiotr {s@oled whjle k€ping @nd4d in pl!e. 50nL of nethdol ws adled rhmugh the

Enu ondos uine calibdrcd lp.(.. Tt. ondosr w6 thm movcd md Mcrion

nixlrne w6 lilraled in th. sme round bonon 06k srritut o.lM metheolic NaOH

using pndolpnthalein d e iodiqlor lill th€ pint end poini Titdiion for blett w6 also

caried oui uins the sme ptucedurc (Fa 2.3)t?al.

ot(A - B) (M) (0 0r6)

wntrq A &d B ffi millilitrs of NaOH for bldk ed sdple, resp.ctiv€ly. M is the

moLmryoI\rOH Md 0016 BmnLcaurv.lcnrw.iSh'of oxygen inerds

Epoxid€ eqdwldt = l94e/nolc,

Hydroryl Valu€ Detarminrllon of HTPB

(vL- vt(M)Hldtuxyl vahe (frmoyg) = (2.4)

ris (0.62 mol) of HTPB w* wciehed i, . 500mL sloppded @ni€al flask ed5.0nL ofacylaring .gent wa add.d. (Actlating lgdt wb Fetded by dislvinS 2.sg or

paE tdMe sulphonic lcid in 200mL ofdn/ lc€tlte in 500nL ofgla b@tq. Finrlly

l5ml- ofacetic &hydnde es ldded dd nix.d ihc mdre elulion w.ll) Tne 0st vst€or h a wot6 bath sl 50!2"c for 30 ninui6. 2.0hL of dislilled w!t(. 2.0mL of 75%

prridilim elutio. ud 25nL of b.lh. ws lho add€d. Atid @nplete nninS fsdbps of phmolphlbalein wb add.d ed titrat d ogdinslo.lM donolic KOH solulion

fion @loules io the fi6t tinge of pinl @lour. Titration fot ihe bl$k w6 al$ cui€d

our followilg the sme pbedue (Eq. 2.4) [?4].

Sdple r.ight (g)

W!ft, Vr dd v, d€ th€ volun6 of KOH elution ued for blar! md smple,

6p€tiv€ly. M is lhe shdgth of KOH elulion (0.1M), Hydioxyl valE of HTPB wd

tinin€tricauy deremi.ed to be 0.?2 mcq/8

2-4 PrepNrrtion ofRubber Modified Epory Resin

20g (0.090 Dol6) of IPDI rnd 80e (0.029 nol6) of HTPB vft chls€d i! I L Bintdda Th€ lid wd prolely clos.d &d phc.d i! d oil bath. Th€ nntE v6onriNoldy $ircd ed lhc tarpdrure ws rai!.d to l30oc ed t€pl @nster for iwo

ho6. Due to high Hctiviry of is@t@tc group with Oc noisnr, lhe ection e6tri€d out mdr d.y nitrogft atnosthd€. Htdrcxyl group (OH) of mPB readed with

isrmale group CN=C-O) of IPDI lo Dodu@ urcilee linlc. Rmrining @.tedNCO crcups wn€ delmin.d by thc proc.duE givo in sedon 2.4.1. Aft€r a senes ofdpdinars. ir wa foud ilat 53% NCO lroups wft rmained ureet€d anr two

hous stiEing at l3o'c udd inen atmosph€r.. Analtsis: 'H-NMR (3oo MHz, 2o'c,

CDClj, ppn):6=?.5 G.2H!, -NHCOO),5,17 (m, J=l2Hz,2Hb, CH=CH).4.30 (d, J= 5

tlz,4t1", O-CHt, 1.09 (s, l3Hd, ring-CHt, 2.03 (d, J=10 H2, 12IL, cHl ofnnd, l.6lrm. )H'. CH ofrinSr.2.4 rd.4H. Ch: auch€d bNCO, Fl-lRd l720{sr 22oo(t.

laa5 (n), l3s0 (m), 3431 (w), lel (w).

Anwlrds, 800s (2.13 mol6) of DGEBA r6in wde add€d ud rhe lmpsatN wd

nis€d widr th€ addition of 5srn ofrdra butyl '@onih

chbn{b d r cahlyst in sn llponions. The addition ss o69l.t d dll dF rdpdtue of nixnr ws 145+ fc. Tiathe tenpdatue 6 nmha incrcls€d io 200"C, whft n ws kepl for nexl ndf m hou

wfth rhe mnsla visomu sdnin& This Gultcd h thc fomad@ ol IIT?B-DGEBA

petolynd wnh nMbq Nq.8p nolaul& weighl (MJ of 1553 6 d€tmin€d by

vEpou p6sw omon€try. B.for. odn& the prEpoly66 wa 6fihd dilut€d with Pu€

DGEBA io gei natdal v&ying in HTPB oicditation hnl with sme Prepolldd

@nposinon. Anallsh: |H-NMR (300 MHz, 2O'C, COClr, ppn): 6 =7.62 (s, 2H,. -

NHCOOI 4.49 dd 4.19 id, J= 4 Hz. 4He, CH: in NCOO ring), 5.?0 (n, 2Hd, CH in

NCOO ring). 1.58 (m, 4H., CHl .tiach.d to ldiary oitrogd) 5.a0 (n, 2Hr, C|=CH),

7.l3ed6.36(d, J=6.5 Hz, l6Hri,Ctl ofC6H.). L6 G,24tli, cminal CHr in DGEBA),

4.29 (dd, J=3-3 Hz, 4H,. CItrO id DCEBA) 2.89 (n, 2Hr, CH i. oxim€). 2.?6 (d,

J=3H2, 4H, cHt in oxi@e) ppm. Fr.I8r@ r: I ?49 (w), I ?23 (n). 967 {s), 913(n), 3033

(s), 12,t6 G), 2874 (w), l4l I {m), r 641 G), 1456 G).

t6

2.4.1 Determination of NCO'3 vrlue tn HTPBIPDI Polyner

2gn oflhe HTPB-IPDI smple sas takd in a tiuation n6L zsnl- solurion of2.0 M

di-n-butyluin€ sd 20nL oflolueic wde addcd, (2,0 M di.n'butylmine ps prep{ed

by dissolvihS l?2ml of din.burylamine in rolude in 500nL voluherric nak). The

mixturc ws stin€d for l0 ninuies Thd 2l2ml of isoplopool dd lw d&ps ofbrcnocresol indicalor we!€ added. Solution s.s titrated osinsl shdtrd 2.0 M Hcl

elution ftom blu€ ro lisht yellow €od poinr (Eq. 2.5)[74].

2 (1000) Gmpl€ wcieht, g)

w1'@, M is the sliqgth ot HClin moUlit ed foud to be 2.01M.

volue of HCI used for bllrk dd s6ple, r€spedvcly. NCO valE wsfor UTPGIPDI lelehclic polynd.

(A - B) (M) (|l r.l5) ( r00)12.t

2.5 Pre-pr€ Formrtion for Frbricrtion of Composite Cylinders

The pr@res v6 fomed sing the Keld49 fibrc obbined iion DuPom a trcmto'mor haqns rh€ Gl.tE ddia vriu. a3,o. dffiny | ,t4gm',

'ntme cNle

$mslh 3000MPa, tensil€ noduls I l2opa od 2.4% elongition 3t h@! [75]. -rwo 6in

fomulatiom vft prcpated .no . s6i6 of .xFino|atio. lo gd ih. pE?rcg wilh

ndjnM shelf life ed otns pDp..rid lilc 3hw sMglh ed lacki.6s. One

fodulation w6 bas.d on unodifi.d .pory 6in ed thc othd wN based o. nodified

epory 6in wbile all othd @nt nts wdc k pl @nst nl 6 shoM in Toble 2.3. Uni-

dir*tioml lape pcprs n&bioe {s Bd io pr.pe trcprcg laP with lomm width {d0:5m-0.l(tnn thickns. A sp@iall, dsiglcd ptet@g nlcnine w6 tumished with

cEl box- r€sin balh rcllers. ed a e.i6 of ov€.s. Kevla fibd non $e cr€el box thal

supporld the Ke{d spooh w@ trelted at 120'C by t sing tluough e ovo to rflove

the nontd€ od oy sizing matrial, ftc fib€6 wd€ otd pa$ed lhmugh a omb before

sakins in a resin bath to sepmt. ihe fib€E for better inpregnalion. Fibss w€r€ pssd

throuCl rctaiing iolleG in the Bin bath at a speed of 455 artmih sherc the fib€rs w@

37

Tible 2.r Fomularion oi nodificd and unnrodined emxv sin.

Di@ino diphmyl sdpho@(DDS)

l5

Uni{irctional bpe FetEg h4hin. wa u.d lo preparc Fepcs tat with lomn

*idth and 025m{30m thicklB. A sD@ially ddigE d PrePrc8 mchin€ wa

h@ished with @l bor cin bath. oU6. md r si6 of ovm Kevltr 6b6 lion the

cEl box thdl supponed $e K4ld sDoob wse ra&d , 120'C by p6sins lhmush &ovd ro @ov€ d€ noistw sd sy sizing Mtod. The fib€s se€ th4 pNed

rtrolgh a @nb befor€ ealinS in a rdin balh to se?aat€ dre fib6 lor belld

inpregnatior libds w€E pdsed through rclaling sll6 i! l,rt€ r6in bath al a sp.€d of

455 cnthin wh@ fte 6bos wde soaled thooughly. T1E 6in bath ws followed by fie

vdtical bd llal ontroll€d dr€ r6in contdl! dd @ove my dtra resin ftom fie laPe

Thc bs nad bd adjust€d lo scr 30 to 12 % cin odqri Tbe irlly inprcglal.d nbds

wd6 pNed fmngh a si* of ov6s tefl al a l@psoie of l2Gl4{PC wn6€ th.

F@rcg @hed sbge B sd ws @ll4t€d d th. otttira spools 6ng rclee ptps Th.

spools w* lefl d llm tenF .n[. fo. No hod to 8d lhc ddirEd taclinGs &d tho

3loed in t@ ot 5l0oc ro be used 6dhd in filddl windin&

38

2-6 Procedure for Fihment Wlndlng

Two 9?6 of prcpr.g a di*us.d in setid 2.6 w* us€d for lbe 6bnc.rim ofmF6it cy'ind€B. Winding ws dorc on +db 6lmat winding D!.bire Th.

bachile wa @bputa nhaiqlly @nEollcd &d hiehly dionared Washaue b,rdrelof Equir.d sie w6 tult tudG Aom $d ed bolss. Ii ws tna lined wirh a rubhs

latq to avoid dy poosity &d lo fit ihc dcairn of cylirdq upo! which ihe epoxy/Kwlar

!rcpreg t4e w$ woed. The m.cl nc hs nsy pds lite oel thai supponed the

9r@rcg qbls, and a cdiag€ thal mov.d horizo .lly ed woud the iop€ upon rclaline

nandrel. Since th. tuchin€ va conroll.d by codputer opddring eftw thftfore the

onotatio ofth€ rape, eSlc .!xl i4rion wa cdctully adjlsl€d erd k€pt onsr&t fqboth mdin€d ed mo.tn.d fomulalions. CADWIND softwde w6 us€d fd tne

v6sl wtudin& Pumeld ofrhe vinding Eachin. ws6 adjBled $ givo in Table 2.4.

Frg 2, I l-rlmor w'ndine michrn. fo! ves*h ed cylinder.

Duing dE prces, slools of pr.prc8 lap. support d by a @l md thrEid€d murd

1ft56 bs w@ uwounded with a 3p..i6c Ltuion ed dire.l€d on the @iae€ of lh.

winding ba.hine thal woud d. rapc upotr rh. bllting n&drcl 'gdil8 to th. FFdeEftd pros@ins. NMbd of h.li.d lay6 ws L@i wa folo*ed by l[rcimnd or nop layas. An6 th. @npldion of witrding p|oc6 the @npoele smr.nr

l9

donS Mlh n rdrEl @ mord ton thc windi.g D..lire ard plaocd inro ''

ova dpop.r cuils cwle ie Iodc for thr. t 2dC for I hi, l.{r'c for 2hr ed 6lslly l6{PC fd3la, cpcctively. Aftd wing, nedrcl wr6 reDoved @etuIy ed th. cmpdiiecylindd wa kka ro lh€ hydro brBt L!t, Final didela oI tE eylind€s ws n*!rcdlo bc 518 m and ovqdl la$n wa 828m,

Tahle 2.4 lnysi€l Frar66 for lh. fil!@l *idils of coqosir. vel.F.2nR@ mnhtEAngh

2

3

5

1

8

t0

ll

m2

t34

t3l

215

20

Nm20

2A

20

mmm20

20

t5

l5

l5

t5

t9.o

!9,5

!9.9

39.3

40

23

Experimental (Part-II)

G€neral Considemtions

(r)l-(2Lbydroryph€.yllq2"-methotyphcnyl)

I -M€thyl-5-norboma€-2,liiqrhoxyli6obydridc {Nadic m€rhy' arntsnde, FY906)

havi.g a molml& vcight of I t3.l 859/nol wa obbined fron |"'/s. V&d@ Lrd.. wilh a

puity of 98%. Diuinodiphmyl sulphoo. (DDS) hlvins a moleul{ weight of

248.30e/mol, dd a nnctionalily of four, ws obiained non M/s. Flula sith a pujiy of99.5%, Dgltlidyledd of bnpbenol A (DGEBA) wilh o nolr lms of 375 dnol,equival@t weighi per tunctional golp E6 = I g4dnol md a value of dispqsity i.d€x n =

1.0 was sFtnaized in ou laboratory as pd pocedue givd in pan I, s6tion 2.2 o-

hydloxyac€lophoorc having s hol& mss of 136. 148 8/nol md o-n€thoxrtffoic ocid

having o mole m6s of 152.l4?Enol with puitiB >99% w6e oblaircd fiom t'ls. Flula

ed w€r€ us€d 6 reived. SoDc othd chdicals ls€d in port II re shom in Table 2.5,

TIIF w6 dri€d ova sdiM bcMph@arc, poi'siM hriory butorid€ w6 purifi.d

by sublimdion *[ile DDS v6 @rsrallizt.J tn c.t@ol. Chdm.E izdiN w cMi.d

out 6 pruerluw Eiw it e.1iu 2.1.

2.8 Slrth€sis ofNovel Epoxy Resin with high Tg.

Nd bieh tenpmtue Bister pt@ole @ntaining €poxy 6in (PER) *6syni!€sizd slarting Aom the pcpdlioo of @mali. diketone @Epoud lrtrough

nodined Batd Vs ol{me r€d&8€n.nt, which ws lhd @nv€ned inlo dtcPoxy

lhnugh a senes of st€ps. The srndEti. routes along with chmical €qutions d€

ddcnb€d unds the followite sub heddin$,

2.8.1 Prepantior ofP.oPanFl, 3-dion€

112'-hydrext?hdyD-r{2"-metlDxy!bqyl) Fopdel. liiorc (D wd pEpdcd by

nodiied Batd vatalaM lco|mgmdl 6 @pon d dliq [76]. Puifi€tion w6

@ied out by rerrstallizatiotr uins obelltc ctnmol. Anal'sis: Elmdral tnoltsis of

Cr6HrO. 270: Calc.: c 71.11%, H 5,18% Foud: C 71.25%, H 5.?270, |H-NMR (3OO

MHz, 20pc. cDclr ppm): F 1.64 G, 0.8 H! cHr, 3.9G, 3Hb oCHr, 4.61 G, 0.4n .

-'.CH=), 6.80.?.14 (4 4rL Arlt), 1.A-1,55 ln,2*, Ar III1.12 (dd, I H,, tu-H), 7.98

(d, lHi, Ar-H),5.12 G, lrid, phaolic), 15.60 G. lHL, oolic) ppn. FT-ltum-rr 3!74 G),

1292 G),2976 G), 160? G), 1568 (m).980(w).

Tablc 2,5 Chmicok lsed in thc slnthBis of novel €poxy r*in.

\/"

n""AoA"r,

".cfox

.., o\

M/sFlurclm 98rh

M/sFluk arlyliel

2.8.2 Prcp.ntion of t-pheryl-3- (2'-hydrort?henyl)-t{2"-meihoryphenyl) pyrarol€ 0I)

]-ph.nyfl- (2trdsxr?hdyl)-5-(2'h.rhoxrdmyl) priel€ (ll) ws pr€pdedby

tle crllo@hdeNsrion of Fniteione (l) in n utral conditiotr. 27s (0.1 noh) of l{2rhrdrexy phmyl)-3-(2'h€thoxy ph6yl) pbpsel, 3iion€ (I) v6 dGsolv.d in 20OmL

of tbsoluie ethaol dd t.l€h in a 250nL thie.n*ked flsk fitted with a dropping tunn€l

sd a wat€r r€flu .ondds6. the ssobly pas plrced on a ho1 plare wifi m6$elic

niffi. 10.89 (o.lmol.) phdyl hyd@ine w added drep wis i! a solmim ar 55"C. The

niil@ wd hat d lo rcflu fo 7 hos. The elv6t Da rdoved ud6 rcducd

p!$sure ed tne mdni!8 visus r6idle w6 cr)5talliz.d &on absolute dh&ol(Yield: 4?% mnpoud (II) md 13% @npound (IlD). Analysis: El€mmlal malysis ofC,HrNlO: 342:Calc.: C ?7.19%, H 5.26%, N 8.18/q Found: C 77.91v', H 6.397q N

8.62%. rtt-l.IMR (3OO MHz,2dc, CDClr, ppm): 6 = 3.41G, 3H., -oCHI,6.8l(s, lH,

PyMl€ H),6.87(E lH, Ar-H),6.96 (t, lH, Ar-H), ?.02(s. IH, Ar-H), ?.0? (r, lH, Ar-H),

?.24-7,14(n.8H, Ar-H), 7.66(dd. lH, AFH, J=?.8H2, l.5Hz), 10.98G, lH6 -OH). FI-

Ituhr:llOO (1,), l25lG), 1023(s), 1588 (s), t59? (w),3053 (h).

2.83 Prep.nlior of l-phetryl-! (2'-meihotyphetrylF$(2"-hydroryphenyl) pyrrzole (Itr)

A 500mL tltren€ck€d t dk fitted with wdd Enu @ndcner ad a &oppin8 tumel

es .hdged witn ?g (0.I mole) oI l-(2lhydoxy phsyl)-3-(2'hethox'!hoyl) prop&e

l, l.dio@ {I) diselv.d in 2mDr of rhelule elheol 20nL glacial aelic scid 8$arlded io rhe eluli@ ed 10.8A(0.I mol.) of phdyl hydE n *a induccd tleu8h

dDpping tum€l to rh. r.aciion fldk. Th. mntw wd heatcd to reou for ? ho6. The

slval ws .flov€d unds teduc.d p6s@ od the dixlutc obtained vs purified by

@lumn ctunatosnphy EinS sli€ g€l dd lolufte d e €luat. Resioiemoc

@hpound l-phoyfS- (2lhydmxt?hayl)-5{2 helhoxt?hdyl) prrel. 0l) wG

elurcd 6Bi foUow.d by l-phoyl-3- (2lm.0Dxyphdyl|5-(2ahydmxt"hmyl) pJ@ole

(lll) ITtl (Yi€ld: 35%@npoud Un) sd 23% @Dpodd (II)) Ara]]sis: Elmotal

malysis of cdlrN:qr 342: crlc c ?7.r9%, H 5.26%, N 8.18%, Foud: C ?7.81%, tl6.50%, N 8.08%. |H-NMR (3OO MHz, 2O'C, CDClr, ppn): 6 = 3.95 (r 3H". -OCHt,

5.56 (s, lHb OH),6.83 (t, IH, tu-H}6.98-?.10 (n\ 4H, Ar-H),7.13_7.39 (n! 7H, AFH),

8.14 (dd, lH, Ar-H. t=?.65 Hz, l.sHz) pptn. FrlR/6r: 3062 (w). l2aq G), I028 (n).

1588 G),l59l G),3030 (w),685 G)

4.1

2.8.4 G€neral Pro.edure for Den€thyl.tion of Compourdr OI& I)Dihrdexy @npoud wd synth6i2cd by dh.rhytari@ of borh onpoud I sd III

*pdely or tos€tha N a nilturc by sing foUowing poc€dw

l5.l5g (o.lmole) anlydrcu alMinih chlorid. *a dislved h SOnL of edeethioltalen h a 250nr oEd botioo nal 6n.d wirh a cflu @ndelrg. The IIsk ws plac€d

in & ice batn od wa sdded. ,{ $lurion of 10.26g (jO molc) onpound (lt-I|I) in60nL of dicNorceth$c ws add.d and srided at O.C od tooc for one hou. The

@cion mxtur€ wa rhq hstcd !o r€flq for eolh€r two hous. AtNards, ir wspoued into water, acidified with dilur€ HCl, md ihen dhaded wil! dichlorcelhme. Tne

orSaic ldyer ws slDl@ wilh distilled waie!, dried ove! !.htdroN Na:SO{ filleEd &dtnen evaponted to leave a crude malsi.l. The prcdud t-ph€.yf3,5-bis (21

hyd&xrlhflyl) ptr@le (lV) ws obtain€! by rle Brystslization of Bidue usine

dichlme$m€ [?8]. Analysh: Elddral ealysis ofclHrNro:328: calc.: c ?6.s2 zd,

H 4.87 70. N 8.53 %, Foud: C 76.76r/r, H 5,76c , N 7 .4ry/.. 'H-N'MR (300 Mu2, 20.c,CDClr, ppm): 6 = 5 16(r I H. -OH), 6.8'{.98 (n, 4H, ArH & py-H), 7.05-?.l0(n, 2H,

Ar-H), 7_2J-7.35(n, 8H, tu-H),7.61(dd, lH, Ar-H, .,=7.81t2, 1.5H2), l o.82G, l H, .oH)ppn. Fr-wm r: 3303 G), r 59? (s), 3051 (w). l24l G). 6s5r*,.

2J.5 P.epantion of l-phcnyl-3, tbis I(2', 3'-epory"ropoxy) ph€Dyllpyr.zol€ (P[R)

l-phdyl-1, 5-bis [(2, 3repox,?opoiy) phqyl] ptr@le i.e., ptrdole b6ed epoxy

(PER) w6 synlh*ized lion @mpound (tV) usihg the tollowins prccedue.

32.88 (0.1 hole) l-phmyl-3. 5-bis (21hydrcx4h€hyl) ptrdole (tv) ad lls,75g (1.5

mol€) epicnbrchrdrin w@ placed in a 5OOhL loud bottm ibE naked nast fided

Mth a wata e,u o.deIg dd a n.chdic.l sriftd. Tne ambly ws heared tc,

reflu fd 2-hoN in m oil bath. Th. tmpdrtur€ ofde r@ction nntw wd ,educdt 10

55"C &d l3-2e (0.33 nole) of elid NoOH w4 add.d in fou €qu.l ponions duling !psiod or 60 niNl6. 5bL of wotr w6 lddcd to tne Mction mntu€ sd wd frlrbqstiEEd for 30 mirul6 ar 30"C. Th. org&ic ldlq w6 v4hed with dinilt.d wale li|ln€urrd ond ltle slvmts w@ Mov.d undd r.duc.d pI*m. Analrsis: Elddral

6alr3k of c,?HaNo!: 440: Cal.-: C 7 .6tyo, H 5.45yo, N 6.36%, Ioud: C 71.41%, H

6.147q N 6.84%. jH-NMR(3oo

MHz,2o'c, cDcl3, ppn): d = 2.8i(m.4rL. {H-o-),1,6(o, 2Hb Oxi@ CH-o'), 4.38(n, 4lL, ,O-CH,, 6.8(s, I lr4 py-H), 6.89-?.4? (r!r lH, Ar,H), t.68 (d. lH, A'-H),8.21(d, lH, Ar-H). FT-rtucnr: 9lO (n),856 (w), l5S9

G), 3054 (s), r2,ro G).

2,8.6 Curlng of Epoxy wltb Hlrdener

The synthsiz€d ptr@le cpory qi! wa cui€d wirh rwo difraat hlrdod bes.d

on rilydrid€ ed dine i.e. nadic methyl mhydnde (Hy9O6) and

diminodiphdyhulfone (DDS), which {. monly us€d for the cui.g of €pory cinsThe plopos.d @selinling tEh.viou of

"pory Mlh DDS is shoM in Fi8.2.2 Net pER

€poxy ond its bl€ld sirb DCEBA w6 u€d wirh 1ry906 od DDS in difBotfomulation by p€ighr s snoM in Tabl. 2.6 ro rchiw€ th. oprinu vat@ in lem ofhigh cosslinking dehsity ed mqinm th@t siability. Table 2.? shows lh.mlsribility p@nete6. Fq DMTA sn|di6 hpl. widr din6si@ zo'h x s Orm x50mm w@ prcpared by machioi.g. Machining olsmpl€s cued wnn DDS ntrddd wsnot po$ibl. 6 the n.raial ss so britde lhd ih. spl6 w@ brckd dujng machinine.

Tabl. 2 6 Dilf@r fomDt.lim pn!a,!d for $.mr and rh.m-mch&ical dudics

BcDE

PER+ftCgBA+HY906

PER+DDSPER+ficEBA+DDSDGEB4+DDS

l:l

T,blc 2.7 Tnmd shb nJ pdfrm tor rh. c,rEd cpo(y tomuanob

ftnpcrotua oJ w|shr tos (c)20% @6 s0p/o 7V/e

E

133.123_31

2l.tl423.5

426.3

336.1 4{7.4 432.5 45t.1!27.0 165.a 394.4 404.229a.a 3213 370.5 390.9345,0 4414 4a3.2 450.0t49.0 3?5.0 407.5 4t7.3164.4 136.1 405.1 4ll.1

45

ry.22.Gat riqof PEn. eit! i+i',""et*.'| d$d. @r,6)

4

RESULTS & DISCUSSION

R€sults and Discussiotr

Sin€ tne cd€h ha bd dividen inb iwo najor p.n| Pan-l ed II, daling wirh

tne nodiffation of omonly used €poxy !6ins like DGEBA ed rhe sthrhesis ofthmally slablc novel e?oxy Eim, rspe.drcly. All thc rBults obrained fron both parts

ofrhc wo* e gjvm b€low.

PART-I

3,1 Structural Atraly3b of Modified DGEBA

Modinotion of DGEBA by H IlB bsed elsione! io rhe naio .erwoft of eloxy

m'n. sysld 's

very @nplicaI€d pcs. Tle wholc pbcdua srafiing ton rbe

p!€pMlion of sianing naldills like DGEAA dd prepolyner 10 ils in@rpomiion into rhe

Epoxy-mine neiwork wd monilord by Fouio Tmsfom-Lii&ed Spatrospy (FIlR), Fomadon of DCEBA IPDI-HTPB-IPDI telahclic polynq dd cpoxy tmin.redHTPB-IPDI ela$oh€. wd thm confift.d byjH-NMR as w€ll. Scdning €l€cr.o.

hicrospy (SEM) wd ued io study ihe surfee morpholog/ ol the nodilied epoxy-

Fist studying rhe sp4ln of monoie.slmctanrs ed rhm mphasizing 1he cnmg*takd pl@ in the FrIR Md IH-NMR spata of lioal el6ton6 follow€d sysha,ric

3.1.1 FTrR and 'H-NMR Amlyst. of DGEBA

FIIR sDetrm ofdjgly.idyl dha of bispnaolA {DCEBA) hs bd shoM in Fig

3.1. DCEBA compriss two pafis. one is bisphsol-A dd oltls is €poxid€ ring. The

absorprion bsds in FTIR sp4hn in the turge ot 301 0m I to 285&n r @n6ponds to

ih. altm€tric md sJrmeri. sr€ahi.g vibrarions of aliphatic CH honds. SrmdeFic

sfieiching od bodiog vibhtios of the oxhme iing in DCEBA app€sed ar 9 | 2cd r sd830cd, rBpatively. The lR p6ls obwed b€tw@ l400cmL dd t35oml@Gponds ro th€ symerric atrerhing of the sflinal CHr gnups in lhe bisthdol-Apan ofthe DCEBA. OH stmmedc sberchins vibddons d€ obsru.d ar l5l3mr. The

alsrpion bdds appared ba*ca l6o3d' and I 507cm I is aliribul€d b the symenic

nra.rirg vibErior of rlE dMic C{, whne

stetching vibBtiona.l bdd @ obswed at 3o33cb-l

lh. aremriic C-lt &d pb6yl C-O

dd 1245m', respstively.

['

,]\

n4l'ilu

Fi& 3.1 FTIR lp@tu of te DCEBA in ffiision no<te.

Deiaih ofjH-NMR sp{hal data of DGEBA havc bem shoM in Fig, 1.2, In LH-

NMR sF!trun, two rloubla pe.Ls a!F.r.d due to th. phoyl prorotu i... dc ai 6 6.8

pprn d@ to ph6y' prerons clo$ ro rtE crh6 ti.trse dd one a! 6 7. t6 ppn d@ lo $ephdyl potons away iion the ethd li.kge. The fom.tion ot cpoxide gmup w6@nfimed by the pea@ ofdoubl€t ai 6 2.9 ppn dd mulriplet al6 3.3 ppm due !o CH,

ed cH poroB of€rond. eD!!s, Gpcrively.

3,1.2 Isopho.oneDiisocytuate(IPDI)

FflR spesuh of DDI hs b€ shoM in Fig l-l in ullMin ne moda Thc b&djobwed at 1462m' ed 2270sn ' tr. du. ro s,6ocsic and srrmerdc shelching ofi$cyaale Sroups, r6pativ.ly. In IPDI th@ e iwo tt!€s ofi$cyMat€ groups, havins

diffffit @tivity. h onc nitroga is indirtty on ch.d wirh lhe ring ca$on drcugh

CHi gbup i.e., primary i$cydlte grcup whit€ in olhd .irrlgm is dircrly aft.ch€d wirh

48

.dbo p6di i. ihc ring i.e., r@ndary i$cyeat€ gFup. S@ndr.y istaatc eroup nmoF Maivc lhe prinary io&rar& gDlp [79-8 U.

I

l1.Fd.2puG.Ffu

Fig. 3,2. |H,NMRrp€oEald.taof DCEBA.

Th. CN strdchilg t!9hci6 |nqc&E a!p.&d at 1456 o'nd 1360 m',n3pcdirely. Tllc per d 1705 d_' is due b d. caionyl greDp in IPDI

3.13 Hydrory Tdmil|ted Polybutrdiene (HTPB)

HTPB a b. sjrth6iuld Bils lhc fc hdical ocdmi@ s shoh in s<tme 3.r-

FTIR sp€ctrun of ET?B ha b6 shoM in trlmisrion mode in Fig. 3.4.

01,

Fig 3.1 FTIR spelr. ofpe IPDI in rcnjttan . mod€.

02.

01,

CH.-CH-CH=CH, + OH'

HO-CH,-CH=CH-CHr'

20H

Ho-Ctlr-CH=CH-CH;

I

(n.1) C H,=CH-CH=CH,

HO(CH,-CH

HO{cHr-cH.cH'CHri + (CH,-CH=CH-CH,),oH

Ho(cH?-CH=CH-CHri,fr -OH

S.hde3.l. F e ndical h*heis fd rhe syn0!6is of hldrcxy tftinat d polyburldj$e,

cH-cH,in

50

Btuad b&d a! 3155m ' app@ dE lo $c plffie of teminal OH sir€tchilg, while

th. pe.t due io C=C atrctching ,.ppes rt l645mr. CH .liphadc slr€rching a!'pe6b.twm lol O.nr dd 2855m r. C-OH bodins ad defomarion lppa at l44oc6 r dd

Fig 1,4 FTIR spesa of HTPB 'n

r.Mision nodc.

Nmbd av@ee nolql8 weighl (Mi) of HTPB w6 Ioud to be 28oo uing vapou

T'ble I lFr-IR spehl dab ofpft IIIPB

n'?t' .r t t.df,

F@iMt sturi of H|PB Typ.ofnbrotu',Y**-h.,|^T

GH

HC=CH

30t0-2355

5l

3.L4 IPDI-HTPB-IPDI T€l€ch€lic Polyner Ar!\a:sHTPB wa rerctel wnh IPDI ro produce uelho€ linlage s shown in schde 3.2

lPDl wd alwdls latm i. .xB ofthe equidold niio belwd NCO gnups of IPDI edOg grouF of HTPB. The @ne.lmrion oi IPDI sludi€d ws l6t , 20yq 24r/r 6d 121/"

w/v Mth cpd to HTPA rh{ @d6!ond to 2:l:2.5:r;3.0:l dd 4.0:l nol6 of\COgrcups pd nole ofolt gtuups in IPDI &d HT?B, Bpectively. The nold dlio 2: I ( I 6%

e/v of lPDl with cD4i !o HTPB) ws 66iddrd id..l s it @utd lav€ one NCO

goup fte€ to !€acl Mrh one eloxide srcup of epoxy resin. in rh€ seo.d step of@cion,

* ,o+t'\ "itt'"'\"eo'

13ot2hB

H3c

.n.

H cH,3

S.hde 3.2. Synrhesis of IPD|- HTPB-IPDI ret*helic pollmd.

Using FTIR &d iH-NMR tdhriqus moniro&d rhe roctiotr of ETIB sirh I}DI lofom lelshelic lolyms FTIR speinD of iPDI-HTpB-tpDI polynd we t*d inralMission nod€, FiE. 3,5. Tlt. p€t in rhe FrtR sp€.lM appcared rr l?2ocmlindistcs the fomalion of uFlbee linlagc betqea HTPB ard IlDt. Ibe pert du. !o

wctad NCO s is al$ pffit ar 226OcmI, while in rH-Nn4R the NH eDlon ofu€tha€ lintag€ app@d ald 7.5 tpn dd o doublct appeded at d 2.9 ppn d@ 10 fou

H

52

potos in 2cH2 cnach€d ro air.ogd. The p€at appa.d !l 164t m ' in FTIR sp€trur€D!€€nk d€ Ebon-@bon doubl€ bond.

Fig. 1.5 FTIR st*!a of IPDI-HTPB-PDI teb.h.li. poll,ld in [omisbn node.

Tbc !€adion ot utr€acled isoolMt€ a@ups o{ IPDIHTIBIPDI t€lechelic polynd

wilh the €ponde gouF of DOEBA, s slFm in shde 3.3 ws invBtigar€d by FTIR

and rH-NIvR. Th. fonatioo of oi&olidon€ linkaee in eloxy mimt€d HTPB bas.d

finol Gl6ton6 h mndned by sing both techniq@s, Tl& cheerdistic p€a! olcadonyl aoDp app.&d ar 1749d ' and l?23d' { FIIR rnal}sis dw ro oxelidonesd ur.rhue lintag€, Bpedv€ly 6 shoM in Fi81.6, The bdd appding.t l,l45m'is alrribuled to i!. C.N linkag€ ir ox@lidonq No p.rl app€trcd in FTIR spellm at

226ocr'' @@pondins ro NCO r eristmenic $.aching indiotins th€ cmpldiotr ofthe rcacrior. wlilc in TH,NMR rh. doubl.t at O 4.49 md 6 4.19 ppn dd multiplel ar 6

5.70 ppD appsrcd d@ to hu prcio$ of2CH, GrvinS AB sysrn) dd lwo prctoN of2CH in oMlidone nng rBpetivcly. While lhc fomarim of lwo reniary nnrogm

were @nfimed by the app*&ce ofmultipler at 0 3.58 ppn by $e 2CH poton an ch€d

5l

",flr-4*"'*--i4*+

\+*=-lk"d^-,1

1*."^=t"

Sahdo3.3. R6.tid b.tva t.ler4ic polrha .!d DCBB,{ ao !yrtb..tr. F€lollda,

Fig 1,6 FIIR !pc.tr. of.pory rdminat€d HTPB bls€d pa-pobds.

Tle pars oberyed at 967d_' md 9l3m-' @.ttributed !o the slE!.hin8 and

baditrg vibfiid of cycl€xile in FTIR spelruh. I! |H-NMR spectrr4lhc CH ard

CH, potoff of.poxide appclrd !r 6 2.89 pPn ud 6 2.76 ppD. cl'..rively.

Funati.Ml stu,ps oft deher fte.ofibntion WMnynber(cn")

3.1.5 FTIR Spectrun of Cu.lng AgentCom@idly availablc N (3iin€thy'dimprepylll, 3-pbpyla.duhq oliphalic

minc b8€d hatd66 ws u.d fc ln. tuing of nodifi€d ed Modifi€d .pory 6id.FT|R sp6rM of pue hard.nd q6 ratft in rhe fr.quoc) roge ot 40G4000n sslDwn in th. T!bl. 3-2 rnd Fig, l.?.

Tlhle 3.2 FI-IR data of pe N (3iinclh,lui&prepyD-rJ-Fopylm.dimirc

C N CNHR)

SyB Shbnins 3210ct300 (Bood B!!d)NH lracbi4 ll30

NH d.fomlion 725sl! iohing I I55syn da.hinB 2915-2470

55

i". r*'*"

-"t I

1u1r",\'\:

Fig.3.?. FI-IR sp*Fumof N (ldinefitldinopropyl),1,3-prcpylmedimi!..

The pqts app@ing doud 345ocnr cor€spond lo s'frnetric shetcling oI NH,grcup. Per. a$@in8 ar 3330cm' .nd 725m' @ otribured to rhe NH stittcb ard

d€fomalion cpecdvely in s@ndey mine ( NHR), whil€ C N lhet hing vibFrio.

3.1.6 FTIR An.lysii of Cured Epoxy RelinEpory-mine neiwort w6 p.oduced by tui.g diglycidyl did of hi+hdol-A

(DCEBA) with (ilin€ihylminopopyl).1.1-Fopyldedimin€ ar l20oc/2ni ed losicur.d aI l45qc/lhi- Duing thc prc@ of cui.g, rh€ eporid. rings of th. DGEBA deopd.d by -NH? tu cliona.liry of hddad rBdting in the fomation of $re dimosional

retwdt slstds. Atrost alt of rhe primey oi!6 de rhs @nvsr.d inio Gniary

din6 in i!. final cur.d podu€t. Mosr of rh€ @oxidc nrgs dsins th€ pr@s of cuingal$ disapped.d a shoM in uble u.3 od Fi& 3.8. TIre srrmeric md sFm€rricsI. lcting vibritiotu due to cyclooime !r gllmr md 87odn I cp€riv€ly, wtich

ould be scd in FTIR sp@trum of pu€ DGEBA (Fig 3.1), @npl€tely disapp..red i!lh. rp€d.q of 6!al €u€d st:rd s slDM in Fi&J.8.

56

r'l'

\[

.l0m 2500

rJ,i

t,ir, l

'i,

il.

'tI

\iI

3S0 2000 l$0 5@

Fig 3.8 Fr-lR spdra of erory-mine nctvo*ing potyns.

St one absrption b.nd at 3415@n dk ro -OH d..rching p& ate obwcd, Noproni@t r€al tor prindy N-H bord s& obld€d in the specrru indioiinS thal

almost rll of N-H imaionaliri* hav. h.a us€d up in op€ning tne .tory nngs ofDGEBA. The lbsorytion beds al 3o39mr ,nd 2966mrmpood to th. srrnmenic

shdchirS of-C-H mnatic od alpnadc, cp€crivcly. P€a*r app.&ed in fi. absorption

mge nom 1608-1514@ ' w6 de !o C=C (dh.tie) st aching while a Fat appsredat 1246@rindicadng th. symaric sE rchjng vibmtion ofphdyl-C-O. FrIR dara is

Tablc3.1FI-IRdrboidlficE tundiddgbupsofqerpoxy-€lN.ndf,off

OH

2990-2870

3.1.7 Scrtrrirg f,lectron Microscopy (SEM) of Modified f,poxy

Morpholos/ of rh. mldiar, sire and distribution of the elslond paniclB dd to

sme extot rhe nalue oI bonding betwso th€ nrtrix ed ibe.lasrohd panicles weF

sudi.d by sming elenon nim@py (SEM). It@ are howw6, so mjorpoblds wbich & en@ulered while studying polyndic maFnals uing this t@tuiqlq(i) a almst all polynd &e p@r eldicll ondudoB (€xc€pr @nducting potlm6),crDrge is dpidly blild !p whq th6e &€ bonbad€d Nith hlgh s6gy cletron hes,ThG chdge buildiry l@lB in itu8e disronion, (ii) potynd e Fon€ to d€8odltion by

high 6a€l)/ inpirrins €1etu6, quing anef&t !o arp.s. FiEr preblo w6 iackled by

6.tine these ml€rials with onducrin8 natdials tike gotd dd seond hy $ing lopadgy elaoon b6 (5- 10 te\?)

SEM oicosralhr of ihc fractued surfae of modified epoxy-flin. sysiem havins

dj,tdt proportion of elaromd or tubbd i.€. 0.3 E1%, 0.? M%, I O $a% dd 2.0 *'r%

e shoD in Fis-3.9 (A-D). The cl4iond lppqrcd $ distinci prnicle in epoxy-minc

nelwork. Thes€ nbbd panicld wde cl*rly obs*ed to be homogm€ousty dGpsed in

tn€ .poiy-dine DaEix. The di@ctq of tlE plniclc ws in lbe rmae of 0.2 jrn ro 2.6

pn. Althoud bouddi€s w@ ior lery slwp bur still rh€ panictes app*rEd as disiincr

@3rituats wiib *pant boudri6, which @nfm€d thar rhde was l6s .bdialint r.dion beiwq th€ two @mtirusrs. BoudqjB w€r. @npmrivety visiblc

sQd.ting the two phas6. Th. di$rs.d nah!€ of rhe bounddies obsfled i. lhenicDgftlh nay bc dle b rhe phJ6ical irl@crion (hydreaa bonding elc_) hdwm t*ophaFs, It ncN ihar fie polr goups thar had b*n ins.fied in fi€ tubbd ch.ins i.e,€roxide groups, OH-sroups and NCG a@!ps najG rh. prcpolymq @npatihtc to l&ge€xldl with the n.ljix @iing phFisl intddcdon rhat 6sisr the honogdsusdi$riburion of nbbd pani.l6. Du. b rhc F*ne of hinal epoxidc sreup nosr ofthe pr€pol,ftd ould b@me the pdr of th€ roi! poltmer chains d@r6ils O. nmbdor dislincl panicl€s rbar coutd be qpet€d, 6p*jally ai to{d conmtdlion ofpft?ollmq. The parl ofdc prepolynq insdr€d in nain pob,na chain is suss6red to b€

nainly responsibl. for cheging irs nechoiql ed lh€monehdiqt Drooerties.

Ac@rdine h lhe SEM resuns 6 shown in Fis. 3.10 thc panicl€ size in@ed *irh the

incl6cof rubbd @nrots in rhenrdx

Fig. r.g SEM micrognph of (A) O3a/o (B) o)a/. (C) Loo/o (O) 2.0% HTPB nodinedCured Epoxy-amin€ sysleh

. hitially the ef€cl of elGtomtr ooenlrdtion on tbe pani.le size ws lery smdU bur

atd 0.t M% th@ wd a slep ircline sugg*1ing rhat rh. rubb6 pMicls.gtglom@tc

ehd ils 6n6rr.rio. qc€.d.d @nain hl!. Md had pmnomc€d .fler on particl.

didei6. Alnosl $c sde b.haviour hs bd reponed in $e modiicltion of apoxy

res6 by rubbcr pafiicles [32].

HTPA conc.{tg)

Fig. 3.l0 Efrqr of HTPB @nq!.dion on did€ra ofpanicre sra

E

3.2 Tlernal ADilysis of Moditied rnd UDn'odlfied Cured Re.irsSystems

Modifi.d ad modificd cpoxy-@in€ srslm wqe sodi€d uingtrhoStuvin.Fic aElysis. For lhir purlo* rhin filns w@ cut inlo v.ry sall Die6dd maltsis wa @ied od up io tmpdlrm of lOOooCi at a n@dng rat 0120 Klminundd ined (Arson) ahospn@. All rh€ smpt6 sq. drj€d at IOO"C udq vaam for24h b€fore dalrsis. AII the condirions for @lrsjs wG kept @Nr..t ro tind our th€.ffcd of .tsbmhc @nrdb on lhe $md sabrtrry of n&n €poxy.mrn. srrlm

Thmal degrad6tion benrviour of all the sdples baving dillq@! prcponion ofrubbs hd bd enpd€d in Fig 3.1I wnh lne modided polFd. Th. goe.l r.6d ofpl@lJ6is for all the smpl* includine Modifi.d slst@ e 3inilr showing o.e slep

degndaiioa $aning witb the w.ieht los tDn aloul 3OdC uD to about 5OOt. I w6indi*lei that thc hehaical p.rfomda hs bm inpoved by addiog elstomq or

rubbd. bul it h4 no advdk efre.t oh the inhdenl thmol st bjtfty of 0r epoxy,mine

thmoser Bin. Tnis .d b€ aunbured to the facr rhat the thm.lly less $able rubhd

@nlds dc very nall in q@riry as conpdtd lo rhe marir sysrem lo affer irs thmFlnalility dd tudly rhe tubbq @ntan midt bave bq ,en o6k€d by rhc n€rwdtof thftally slable €poxy-minc n@orr. A gndual snall d€.lte in weight from 200

io 250'C 6 6. attibud ro ihc wolltion of absrboj ooist@ iEpped i, epoxy-minen€twoik dd w€acted p@soB. Ttre qft very snall chmgB in pelMt weicht tosat vdioB lmpmlu6 wirb in@6ine dbbq @nhrs as shown in Table 3.4. Thevmalion an th€m.l srabihy, hiSnd rnpdtm cmot be eftlor€d wilh in(i6ine

360

5t

r.hp.6r!o fc)Fis. 3,I I TGA bslrsis ofditrahl %ages ofnodif€r in

6l

Table 3 4 Tqlp€6r@ ofp.@r weiehr los fo' rbdified a.d umDdidot !yne6.renryntwr .fveght las (c)

343 2

155.3

'!57.2

351,3

362.1365.2

3352372.1'!14.\

3938333.6

333.1333.2

Tablc 3.5 Mdinum dedposnion hpdre a:d ch.r rnio. a( ?o(fc

:170.1 359

How.vd, lh€ che .onL.ts aftd rh. @mpl€r€ prblr3is ofthe tupls al SO(fC 8@son dqqsing du. ro the d*qs in ca6on ro hrdtugo 6lio or d@sing em$icorlols with incking rulb6 prcponion in rhe polyDd s shoM jn Tlble 3.5 Themdifth aic of d@mposirio, Qtcularcd frcm lhc pqt of oE ditrcMrjd of rhe TcAcwe lbr qch fomdalion o{ (modided ,nd 6odi6€d sysr@ N snoq b Fq. t.9.Thft $ a dar6e orody abod 5'c sojr8 froD wodified b noditied c'5,; edlhft is vhibly no ch&ge at 0E peat idpenrure (TB) ar veoB tubb{ p,oporrjoB.

3.3 .

Tberm-o-mechatricat Aoalysls of Modilied and UnmodifiedLur€{ Kestn systema

strdgth dd phFicat betavim wifi resped b rmp@oft ot noditied Md@odjfi€d stsrens w@ nudied uinS rlutomdh&i€t oatrsis by nssuring sb6sehodulul los moduiN &d d&pins fador io .ctation wirh tqnp@i@ s srv6 belo*.

62

3.3.1 Stonge Modulus ofcur€d Resin Systens

'ntc stong. modulus (E ) d r frctio. of imp@ne, dd ditrcrine in HTPB @rdlfor epory min€ cur.<t nln is shom in Fig l.l2 for all ohposnioN of nodified dd

:l

!6

r.mp.Eroo (oc)Fia. 3.12 Eflar ofldpa"te on iomac no<tutus of modifi€d epoxy srst@

All the stslohs showcd siDile bchlviou md th.n nodulw ddear€d wirh

n@sng tempdat!rc b€low lhe glas rdsition rmpaatlre. Howevtr theE was a wcltdeincd t6d in rh€ vohs of $oEae modutN with inc@ins of HTPB contenr,. Sbdgcnodulus of h@t epoxy-@in€ sJst.m hs rlE highst E value di my rmpsarue betosfi€ Slas Fesiiod thps!r@. This @ b. a$ibuted to rhe ircGed c,o$link dosirywitn bw ft€don of movhdt availrbte to rh€ chains. Vah6 of slo.age nodulN ar

vdious tapmtuB b€low glds lrMsidon rmpd.nre h.ve be. shown in Tabte 3.6,

6l

Table J 6 SbEgt Modulus ,r dtrffir rernpcBruc fcr td drfim iyr.csb0se Modutd (E) .t Ditramt TenperM

45('C) 55("C)

3J.2 Tsn 6 of Moditi€d and Unmodlfled Cured R$tn Slstems

Th€ los bchaviou in tems of ron O fo. dodifi€d sd umodiied s$ld 6 !ftndion of tdp@iue hN bem shown in Fig.3.ll. Fo, vis@elstic materidls litepol)m6ic nar€dal srrain ta$ behind the srr6s, 6 6n*ponds !o rhe phe dgl€ b€rw€dthe .l'plid drrdic defomtion dd 6potu. o{ the nal6i.k. This Dhe shin inDMTA qperimmr ir qpt6scd a dmpi.s ptus, Th. 86 undd tle tln 6c@c ar

3rN tes'to! tmprarue (TJ is o m6w of tite da$/ di$ipared dujra ilE dyndicn€ch@icdl dp€.imar dd povid€s valubl€ infomotion rbout the vjsmus parts of 0r€

wple Tm 6 shows v€ry @urately tne phe rmsition, pani@hly itF novhol oflnc cqt.in pans of rhe polyno noleul€ wh@ ir is lin@ly lEated betw€a rwodnpaaturc qrm6. All rle cw6 in FiE 3.12 e vsy sinit& in sh.pe MagdM. oflh. rer 6 cwa incM.d wnh inqdina mout of HTPB. The Feition of ilr slstrs,hon, hoeevo, on $e tenp@lue &h w6 not nuch oltered. It inllierB $al thepoFnies of the polJds mltrix @ not chmg.d. Conpdns tne nodifi.d ed@odincd systm ir wos obw€d rhol nodili.d €poxy,mine sysl6 hs highd valleof lan 6thd wodifi€d srsrd_ ti @ be arFibur.d b rhc facl dl.t hign nolal&w€'gnt prerElFq irs€fiioD jr the nain @xydine.dyork f&ilirar6 iis mobilirytroud tbc giae rmition terp@tur. The rubbq parriclB pr.sr ,n fie srstd ahohindd thc clos p&king of chains dd rcsbi.t tne fomation of cros-linting in thatpamtul& @. As a BUh rh. dMp,ng otthe hodifi.d sy$m In@b.

50 60 70 30 so 1m

rompfttu'€ (oc)Fig. 3.l3 Efrect of tmp@rure on t& 6 of Dodified €poxy s'srm.

3.33 Glais Trcnsitior Tempe.rture (TJ of Cur.d R$itr Systems

'Ibe gla tlsition tqnpdtuE (T, of the tuEials b6€d upoa modified .rdmodi6.d syst@ a turctio. of mPB conte.t e snoM in Fie. 3.14, Th€ o.€t ofgl6s Fu'iDn odts a siincml chdge in the phr€icol popenies of the Dollna. A

SlNy polFo l@s6 its stiffies dd hs ! ladocy to 0ow above Ts. In g6enl, Tr qbe d€fin€d s a lmpfrtw al which efarilely Lozs molmles of polthd in 8lssysrlte heomc fre 10 mlale and tresLte lt wa foDd ou rhlt T, of 2% HTPB no<tificd

s}alm 's

aboui 6'C lowE s @nparcd to lhe Lnmodifiel natrix. The gtss rusnionlmpdatue (TJ w6 obw€d to be invdely elaled with HTPB orcaEatio. ih ih€

modif€d .!oxy-@ine s,slm. This @uld be qploin.d hy ratirg inro rc6ur lh. tevolm€ concepi. Th6e is a vdy srull cheg€ in rhe glss rrsiion rmpsaiue at

vdio6 rubbq @nGtdtios in rhe no<tifid sr6lqn 6 strm in Fig L t 3. Fno thmal&d dmm{nmical dar. ii is infded rhat inprov€d n€cheical popeni€s 6 be

-0.3%-0.7%-

1,Oott

- 1 .s%2.0%

65

aclia€d by nodiryins the s)stn with HTPB ba&d dstm6 witho havi.E signifi@ietr€ct on the lh@al and thmomchdlcal propeni$ of @xy-dine sysrn

0.0 0.5 1.0 1.5

lig. 3.l4 E,lei of HTPB @nc. on cl6s hdsitDn tdpelaruG (Ts).

3.4 Mech.nical Anal'sis ofcured R6in Slstcms

cood ni$ibihy is g6d.lly requir€d for lhe implovdent in nshai@l prcp€nid

whm ! sy$d n nade ofhm rh& onc @nrbndl. lt de?€n4s upon O. inrerflcial

adhesion, .atur€ ot intdacdo.. size of rle par.icles, dislribution of ohc pbde ioto

&olhd, €te Thu the ovdall effd ol filld or buehcning agor or rei.forcing agfti on

lhe n€cheical prcFniB offie @mposn. is dst@ined by rhG @nbined €flet of all

lhse frclon. SignifiMt cheg€s have ben obsw€d ih l!€ nccheicrl popstiB thor

w@ d€tmined lite rsile prcp.nj6, n.x!rdl, tzod inpacl ed Victa s bddns by

64

63

:ar

E00

56

3.4.1 Temile Pmperties ofcured Reiir Syitems

Str6s-slrain n6um6ls in tne imil. node wde pqfoft€d, ac.ordioe 10 ASTM

D 638-52, at 25"C o. aI smpl6 !o ktuw rh€ efccr of HTPB bs.d prepotyDd

@nmt ahon on lhc eroxy-min€ syut m wh@ the tensil€ force is applied on the

malqial. All ln. @pl6 l@ dried ar 120'C udd v@m ovaisht b.forc dalrsis.Frcn the $ress-stnin cw€ fo! v&ions compositions of epoxy-dine shom i. Fig. 3. t 5,

dl otha Lneile pop.ni6 lik &&he seEg0i. loughr6s, YouSt noduls, &d€loq3tio. .r bEal w@ calolltcd,

_ 0_1%

- 0.3%

- r.5%2.O%

Elonl.tion ( L)

Fig. 3. I 5. Stes-SFAin lNe of lle nodified epoxy-minc systen.

fi€ str*-sioin cw6 followed rtic su€ g6.d hcnlviow. Eacn cws q be

divided, i.!o tl'e rcgions depddiog upon th€ phr{iel behoviow ofmatdiols. Tbe ,isllind pofi of ihe cwc i.e.; up ro abour 2yo strlh is ln. elasric rcgion of rtr @rdial,qh6€ th€ d€fomation produccd in ths @tdal by applying force is @mibtq Th€

s€nd .wcd Egioi i3 catled Ihe ielding rsiotr wh@ the ch.ins in rhc mtgial st delflovidg ed de third pan is the ptsric rcgion, whi€h rcpr.srs rhc pcmdmr oir.vdible defomrrion of the narnial udq q!€nol appli.d foe. Followins stio$

67

giv. the Blltl oftqsile $rmgth, elslic modulu, ed strain at breal 6 detmined

ftom th€ slrds-strain c@es od u€ snoM in Table 3.7 alorc with sto.Lrd deviation.

I rble I ? ElTer oIoffidon of pEp.lytu, m brl. popql'scorc. oj Te.tilcstenqth Md ElonAzhon yons\ M.dth.s foryhres

36.15+2.14l992.t5rll.t6 1099+10.?41256.10+08.39 6947+09.16192.50+10.50 150.0014.381t53.55141.50 211.46*1.361093.3824.94 244.5+5.40990.540+27.65 25t34+4.02963.650*10.06 237.07+5 t6

3.4.1.1 Ultimale TeDsile Stretrgth ofCured Sr3rems

The vdidtion in iiacrue srqsrh a ! tutrction of HTPB @n6rdim ir €poxy-

anine syslm is shovn in Fi8 1.16. Tbe uldmaie slragth or tasil€ st ength is rhe

n4@ of 6is1a!e ofmataial to the puluns fo@ &d is cal.'rlaled sin8 Eq. 3.6.

o.6)

Whm, o is t@ilc $r6gth al brcal Ws is a breatin8 load, dd ,\ h the odgiM!

msFsetiond aE of the @ple

FEclu. sh@gt' of modifi€d slstm obwed in cse of n@r systd is 3l.izMPo.

This low strdret! valu. of €poxy-mine stsid is due to its iniddt britldBs. Mosr ofth€ e@tic epoxi6 cr€d wnn @natic didine have loa 8ictuc odgy od th. cmkb produced al low str* volle. The frerwe strdgdr ofthe syslm ws in@s€d by the

.dditi@ of prepolynd 6 shown in Fig 3.16. Mdidd v.l!6 i.e, 42-44Mla w6e

achiev€d whq 0.1-1.0 % HTPB w4 incoQoFled inro the epoxy-di.e sysrm. h €m h€

anribrt€d to $€ lncree in ia.tue osgy ad rcsishn@ io the dact prcpasation whafl.xible HTPB pd1s e intmdlc.d to rh€ brittle srsrd. B€rond L0% ddition ofHTPB

advwly affects the tdcture slragth ofth€ Bulting ststen, beqse HTPB itselfis low

slurgtl nlIsial. As ih. p*6l:ee of rubbqy sc8o41 indc$ dE Glltine mdaial

acquires i.t€m€diat. Fopdti6 oI6orh rhe ompondls Bulting in the d€c6. in

ultina& sthgth of !h. tuqia],

68

31a?Eg3E

HTPB conc{%)

Fig. 3.16. Ulrimare r4ile sE€oe1h 6 a tuncrion ofHTPB onqnation.

3.4.1.2 Young'3 Modului of Curd Syst€ns

YouS\ nodulus ol$ t oM a nodulu ofelaricity or srilln*s h6 b€e. plort€d in

Fig l.l7 s a fuclion of rubbd onentration ih th€ nodiicd e?oxy-ahine sysim.

Youa's nodulG is the mrio bcrv6 srr6s od rcvdiblc shin np ro rhe limir ofpbpofiiona|ny. lrs ulu€ is as$ciated with ntmolecular or i erchain i.rdrclions.

lnitially thc addition ofody 0.1% ofHTPB in tbe stslm lowdld its tdile modulus by

abont ?00MPa sho{n by a st€e! decli.e in the sfi of rhe curu. in Fig. 1. I ?. Tbn najor

loss of sliiInds is anribule<l !o rh€ hcl rhat Dosr of0.l7. high moleuld seighr epoxy

temituld pFpolrrd addd to tne systd .hdi.dly r€ded wirh oine cDi.E.gotdd b€@e the pan of min epoxy-dine systd. Th€s nexible noleculs i. the nain

chain edue tne @selinting d6iiy dd inc]qe rh. &e volmq which frciliiai6 rhe

chains mobility Funha i.t oducdon of HTIB bosed prepolFtrs showed less

oNidmble effect on rh€ valu. of Youg's nodulu 6 bost of lne prepolym€r o@upy

lh. spac6 bN6 the chains Foducins rulb6 particlB md indcGing panicl6

dim€t€r foming two ptse sFt€m with spdale bounddi*.

a

E

E

Tnis phenommon has aho b€d supponcd by SEM csults in chapter 3 scrion 3.L6.

Thlt is why lhe cfrEt of HTPB @n6F6lio. on rhe value of Yods s Dodulu b.yond

0.l% up b 2.0'l. HTPB sd obwed lo bc l6s Ae tooMPa

Fig. I l ?. vdiarion in Youg s nodulu wirn 8'fPB in epoxyeire slsld.

3.4.13 EloDgatioD rt Break of Cured Sy.tems

WiEre, l. is lh€ ori8'nrl disl@e belwed the sEug€ narks. I is lhc distmce belweo

th. aause DdlG at my line. dd Al is I - I..

Th€ efdi of IIIPB @ncdration on th. dudility or o/0 €lo.sation in epoxy-mine

syslm is shown in Fig,l. I 8, The ductilily of the m dial Ns found lo be increas.d by

in@ing dbba @ntenls ir thc mlting Draial. Th. .l@gation of woditied "!oxy,min. s):td w6 1.7% at bral and thd€ R6 .a9id in@ in ductility wnh rhe

dddnion ofHTPB, ininally. Up ro 0.3% HTPB @ncolrltion th@ vas d steep inctine in

This prcpdy explaitu rhe dudiliry oa the Mt€rial will dtmal .ppli€d foe edwas calculated from d€ sbB$snain orye usirs !q. 3.?.

. = Al4. = 0-L)/L (t 7)

70

i]t. ductility cwc 6 shom in Fig" 3.18, whde O€ duciility ofresulfins matqial qched

ro 5.5% sirh 0.3clc HTPB i@4D6rion.

Fig. l. 18. Etrel of HTPB onc on o/dAe elongotim of .pory-mine stsld.

.9

P

Beyond 0,3% 10 2.0ql. HTPB odoLs th€ incr.s. in ductility of mat€rial sN@npmtively slow sd th. 6nal duclility ofmatEial qched 10 3.7% b€foE lh. fiileof naldial by rh. rtpli.d load.

A! already discss€d in cde of rqsil. noduls, dt low€r @n@nddons high

noleulu weighr epoxr |miMt€d HTPB b6ed pc.tolrmq chnically r.acr. vilirume tuing a86t and b@h6 p4n of nain epory-hine netwo*. Th@ nqiblemoleul6 i.lh€ main chair e mlnly r.sponsible Ibr in(,6e i. rhe dudility of lhe

r6ulling mardial by reducing ile m$linkjng rl€Gily md feiliqring rh€ claitu toslidepGs ah othd. Funhs inr.ortu.rion of ITPB bs.d FepolFd hld lirde €fid on

0E vslue of ductiliry of rh€ systm d nost of $e p!€polrm€r oeupie{t dr spa€s

bawm ihe chaitu prcducing tubbs prniclB having litile efei on lhc ovasll physicnl

,.t'"--'-''l-"T

/

I

1l

3.4.1-4 Tough nesr of Modiffd ind Utrdodllied SysteEs

TouebGs is . llr..sc of rh€ da$/ . nltdial d dt'$rb b€forc n bqls. Uililcduodh, thc toughBe v.lue ira6d wiln hc6i.s ITPB 6nt nts dd at6attaining a maind value n sbried declesins d shown in Fis 3.19. The tousnness

val@ incfued Aon 3lMPa in Modificd slsrdn ro 245MPa ad 25lMPa in dF

nodified srstn wilh 1.0% ad 1.5./o HT?B onlals Bletivdy. Ir shovs llDr thc

toughn€s of bntde epoxy-Min€ systm in@as€d 8 io 9 tim6 with l.oy! ro t.5%

introductio. of HT?B bas.d prepolynd. Howwer beyo.d L5% lhe value of roughne$

t

ar0

Fig 1.19. Efer of tfi"B @nc on tousbnd of @xy-minc slsrm.

si6a lolshnds rePG@ts the d€rgy require lo ruptw a mal€ri.l ed it var@

dep€nd upon $e valu6 of modulu, Ddimm streneth ed elongrtion at b!€ak thftforcils wlue is m6t iftpon&t whil€ el@ting dsi.6ine m!'rdial in sp€.i.1 oppliatioN.

Tbe ira€se in touehes by nodirying 0E cpoxrd,nc srstm wirh rubhd oni6cco be altributel to the i roducriod of fl€xible tubbflv lafi. Rubbd @nrhls rdov.dlhe inhmt bri @6s 0rus r€cisring the.r&k jniliarion wiih ttr€ alplied exlwl foM,

/:---=\--..'

72

whil. initirl shdgrh of the mtoial ws do6cd. Rubbd panicld rhar wd€ wcklybond.d to th€ €poxy-min€ sFcm srancd rgelon€dtins at hjeh 6n6Ealion ofpicpolymd, s supporied by SEM Bulls, *hich in Eaed the ductiliry bul darced rhc

norlulus dd ttrile strogih io & exldl dEl advhely afrei€d lhe toughres,

3.4.2 nerrr.l Prop€rttd ofModlfi€d.nd Urnodmed Sys..Di

ndlEl prop6ti6 of mtaial w@ d.r.mincd by.pplying fde o dlc sple in

thFpoint bmding node uDg ASTM D-790, .r 25'C- t ad w6 al'pli€d util rh! sFain

v.lE rc&hcd lo l5%. Sns{lnin cW6 obtain€d a snoM in Fig 1.20 wha th.

m!16 w@ tdsred in llex@l nod. s . tunclion of |rTPB orqnation.

srdn ('.)Fig. 1.20. SE*Srajr cutu of dodif.d epory.dim s'51d.

Tt. belBviou of sirds*Fain cW6 for dl th. @op6ition of nodificd .!oxy-

min. syslds wa sme b thqe wa. sigrifi.dl clwE€ in lhe cwe tl ddy poinl athe tubbd @nlmls vdi6. The fl*ual moduhs, ndual slrmgth fld nexibiliiy wdcqlculatcd fion this rylcrl slr€s-strain .w. od wae labulared in Table 3,8.

e/o-I30!6n

iF 1_5%

-.- 2.Wo

73

Trblc I 8 Efrcc of @lcum of Flpol'tu 6 Iqunl po!<ri6.

CM olturpob@ Flqunl stE3tn HqEd Modd6 Fhnbihy

o.l0,3

1.52,0

0,62Ll2t,t21521.58t.611.73

62.0199*2.l5

4.5528!r.21

,38.3r511?,86689.695*10.43

3A2.1 ndurrl Sccrgth ofcurcd R.rh Sy.ae|'rr

Fldud 3aa|gth sa .d@l'ld aing Eq 3.8 rnd ws plotttd a . frb.'ion of HTPB

@t6Eaiion in cpoxynin. ly3tcD a 3hoh in Fi8 3.2 | .

(t.8)

wh6!, or t flqlDl 3tqslr 0E ft!.nr point, Lot lau$ ofthc sppofl 306, b.

3d d is rh. *idth &d 6iclnd of0E lp@iDa !t3p..riv.ly.

NTrl dc, {*lFig 3,2l. Fldul 3E6grh s . findion of HTPB in €Poxy-min. .y!lqn.

Et,l6

Contary to l@il. st@gth tor nodifi.d &d Umodin€d sys.m a di$ussed in

s&rion l.4.l.l rh,l i.da!.d !o cdrdn val@ ed tha ilrt d de]6irg 6 rulbd@ment in &e srsrqn in@.d, int6. Ehtidship w6 ol,sv.d h ce of flqural

srrdath wid ETIB- Th. nqur.l sLdgh of th. lystcm w4 found to h€ d@s€d Nnrbbs o qt in lh. nodified s'std wa g6d@Uy inopoBled. Its v.lne d@s.di_on 62 MPa to l8 M?a at 2.0pld HTPB @ncddition. Sine flddal sddeth dep€nds

upon the intdnol@ule o! inteRhain iotqactions, oridtdtion ed packins ofnoleculd

chaiN in polrrdic natoials! thftfoc prebably in@rlorarion of nbbd @nt@ts

ddeased $e ovo all m$"liDk dmny of th€ @oxy-mine neiwork Bdting in the

d@e ol flqural st eneth of the nat€dal,

3.4-22 nexural Modulus

Lite tdile moddu, flqud modulN d€.@cd s tubbd @l@ls i]m.d in

nodin€d epoxy-dine st$d a shoM in Fig, 3,22,

3

Ea

iTPB.o.o,{1{)

Fis. 3.22 Efrd of HTPa @no @ tdual nodulu ofnodif€d epoxy-mine s]3rdn

Ir3 vahe wd <tec@.d by a3tMPa wilh th. in@rtor.ti@ of 2.0% ET?B. The varu.

of 0qud nodulu in.hstic rcgion wB dwats sd|( tho rdilc nodulu for dy

75

oiposiion of €poxy-hin. ststm. It sulg6is rhd rhe d.fomalion produc.d in

modificd or lmodifi.d €pory-hio. n.tdial is 8r*l.r in 3-poinr bdding Dode thetdsile nod. whd tn€ s. mout of fo@ is appliqd in elDtic Egjon of a 3ystn.

Fl.xibihy rcpr*nr $. @6ibl. d€fomadon wha & qtn.l foG is .pDli.d on

d sp6in6 in l-point bddi.g modc. h iddiotca ort n@r ofd. asSy sppli.d lo lh.

s,srd k disipar.d dd @n!qt.d inio lin.ric d68l'. Fl.xibiliry of.poxy ditu st5rdt cdoidrcd sing Eq, 1,9 [83].

-lll

3.4.23 Fle b0tty

(3.e)

vr'hcr€, Es is dE fldurd trbdulLr L is thc l6glh of. spl..d w a.d t & the

*idth &d thictis of! spl. 'tspetivcly,

Ins.nion of flqibl. HT?a b.s.d €?ory

tmiet d prcpolymq siglnfiMlly inc@s.d 0!c tlcxibilily of culting st!r@ 6 shoM

inFis.1.23.

orc. on n.xibilily of nodificd cpoxy-dine systd

16

E-

Fig.1.23. Etf@r ofHTPB

An opii$M valu. of fldibility is .lw6rs r.quir.d in m6t of i.\. aDpli@tions of

halerial lite 6olinss, sslets !tc., io r6in c4ct i.itialion whd .xlmol foB is

applied in $c fom of cyclic lod!. Th. lpplieriotu of ho of Aoxy-dii. stflmhlve bd linir.d by lb.i! non-flqible b.haviou. nqibility of €poxy-mine srstm

be.de double by nodiryiie wnh 2.0plo.ulbd @ntdt ed iis !rlu. incBed to 1.78

tmN-' Aom 0.62 lmN'. An alnosr lin6 Glaiiochip wa obwed betum n€xihility

ed HTPB @.tal in th. .poxy-uinc stsid.

3.43 Codpre3slve Str [gth ofcured Redn Sysaenr

Complsive sE6eU d86 rhe alility of mtdi.l lo 6in rhc tuhinA f(revdue of @ipBsivc a[a!$ d.tcnds upon rhc Ns-lint ddirx Nhadc chdacl.r

rtd p&kine ofch.is in polyhdic m.rcrials ed is slculaftd 6ing Eq. 3,10.

(1.r0)

whd., o" is c@p6ive sE68$ lt flilw poini, W. is Ihc ultimt lotd .pplie4

dd A" is origjrcl msr€dional !d of d splq Conptsivc strdEth of th. nodiied

rld Modifi.d .pory-min. srltcm ar 25"c is shoM in th. Tlblc 1.9 ed Fi& 3.2a.

Tablc 3.9Efld of @!@tntion of pcpoltfa on @nPldtivc popdn6

cM. oJ Papoltqn Pi) conp*iE SEl3!' (MPr)

LitG tldual ffigth @hpBive sdagth ale .Lqes.d lin@ly with inlfu in

HTPB @n16ts 6 sboM ir Fig 3.24. ConpBiv€ s$ddn of llModified .pory-mine

syeto ws ob6d.d ro b. ll2,l MP!, ehi.h d.tus€d. by 68 MP! by in@tponting 2-0

% HTPB 6ntent! in th. systd. Compcriv. s[arih of 0.3% 0.7vr, I V/q | 5% atd

2.0 % HTPB nodif€d €toxy-mirc s,std ws obw.d to b. I lE.7 MPd. 116.2 MP.,

93,9 MPa, 85.7 MPa, ?7.? MP.. .nd 68.1 MP!, c!..livGly The d.tfu in

30.10.,

1.0L5

17

enpre$iv€ srr€nelh @ be a|tribuied io ihc dcclcac in @s$lirl dsity ed inqsein fldibl€ aliphalic ch@ctq in gulting nodifi.d .rDxy-eihe systd.

Hrrs4, tx)

Fig. 3.?4. Efet of FTPB 6nc. on @mpBsiv. strdEth of.Poxy-mift systdn.

3.."

3.4.4 Micrchrrdngs Maruremc s of Curcd R..b SFtems

llordns is fi. sislare ofa mddidl !o loc.liz.d &fomation Thc tcm 6 arplv

ro d€fomation iion bdding; @tiing, inddr.don or sdlching ln most Pobrqs, tbe

d€fomation @6iderEd is plslic defomtion of th€ su'f@ For elslon6 dd $repolyrtrm, hddnce is defined s thc distan@ io .l4li. defomatior oflhc surf.@. Th€

Vick6 hlrdn6s tsl melhod orsi$s of indoting lhe tsi nalaid Mth a didond

indat€r, h the fom of r nghl ptdid Pith a squd bsc dd e eele of 136 degres

hetwen opposite faes eubjeled b a load of I 10 100 kd Tn€ tuU load is nomallv

applied for l0to l5s@nd!.

To salu& th€ hddress prop€riy, nico hddh.ss h€suem@t were pqfomed on

both modified dd modified smpl6 .t 25'C, usi.g viclGs mico hardness

indablion md the results se shown ih Fig 3,25 &d table 3 10 s a tunclion of mPB

sncanadon, Hardness is conddeed lo bc a lelative pep.rry 11 is a @npld

@nbinalion oftlne abshte popdti6, TbFe arc dpress.d in uniis ofstrds (foc pq

78

un @) ed $r.in (ch6gc in logrh F un hgfi), eldic dodulB (sE6e

tevdbl. sF.in), ield scqsrh GE6s ro eue r tuinm Ftudl chese) edsF.in-h.dding dpeny G.ir in lrs F mir pdlMot ch&gp}

T.bl. 3.l0 Efel of onmtr.tion of rrllolFd m VHN.

VHN

1.5

2.O

l3_910.3

a.x

t.29

'nFfor!, hs'dns nau@6r pFvidd a nas of mdui.g @rbin tufl@

@hricd ptoFnie rucll s E (.lstic d Youg s tDdulu) ad ultind. sts.

Fie. 3,25. vick6's HrldtB Nnbq (VHN 3) a . tuncrion of HTPB on .

ThG mo6l wid.ly !@pr.d 6nc.d of hltd|B is poblbly th.l of Bisrhe to

inddttrid. bu may de irclu& mtch 6i$ane .nd Flloud ciliaE t8al- UL.

0.ru.t nodulc md tc.silc modulB, h{dcs ofmodifild srstd wa ale foud ro b.

dqssd d!. io rhc i@rpondon of eft ptltolFd @ 6t3. Vicka's hddn*

19

nmba dds!€d Aom Il.9 ro 2.? from n6r sy!r@ to 2.@,4 modifi€d systm. Vslue of

vHN eRalq tnm 5.0 is Nually r€qlir.d fo. most of @xy applic.tios tlat m b€

a€hiw€d by ooditins epoxy dine systd with about I 0 % HTPB mlats.

3.45 lmprct Strergth ofCur.d R.ir Systems

Impact slr€.slh shoss the ehld@ of nrtdial lo sudd€nly applied load or foc.Inpact slMgth of a rutcrial is ! ompld prcpcny md d€!€nds upon the stiFn6s.

louehn6s. fl€xibiliiy md leld sl@ngth of maidial as a whole. The 6ul1s of idpdct

slr€nsdr bar€d on ASTM D256 h.!€ ben plotled ds a tun tion ofgTPB mnt€.t in loble

3.1I ddng 3.26.

Table l.l I Eilect of @nentration ofplepollm€r on rnpact shdgur.

I23

1.01.5

Oie of the r€mtr belind nodiftrng €poxy-min. molqial wa ro ibpnE its impacr

srraslh. Inpact srogh ofn@l .poxy-di@ polFs wd ? lt)lm, whi€h wd doubled

by nodi$ing ine s'std Mth HTPB @8tdls. Ihpact slrdglh wd olwed to inc6e

lin@ly wilh incMing mPB @ncdtaiion up to 1.0%.

A1 l.l) % HTPB onlals th. vrlue of impel $re!E1h wd loud lo h. 'l23kj/mBeyond 1.0 % of HTPB the inpact $!€n8b maincd alnost onstal wilh a verv liltle

deviation md rerched 10 4.5!Jh wh.n 2.0 % HTPB co ents wft inol?onted to the

ssi@. sd€ effecl hb bin obsepcd in the n.t€rial pr.pded with 4 epoxv Bnnodified with hld&xy rminaied poly (buladi4._acrylonirile) dd b€sl inpacl Bdbbave be@ ohrained [8]1. h d b. anribuled !o th. f.ct thal HTPB nol4d6 act 6 a

btidge b tne aek whjch is ptoduced by aPPlyng suddo force .nd tmd to srop the qack

prcp.gatior but berond ] O % HTPB @nldls, tgdomdtion of rulbs t2k6 ple lo edtal that n prc<tuce a s€pml. dohditu ehicb hG vdy liidc or no etred on rne oYa all

physical Ddforl@@ of modi6.d sr3ld.

30

E

Fig,3-26. Etr4r ofHTPB @nc on InFct sfdeth of epoxy-mre slslm.

3.5 Compo3ite Rings Anrlysis

The .ings made up ofwcr Pinding dd pF!rc8 *inding w@ pht6i..llv exdined fi,r

rheir apper&e ed intq lmitr bondinS. Thc n.gs madc bv wer windina show€d

slamrion ir th€ imd lalm havirg no bond-abiliiy, while ours I.tG wft 6udich€d dd ! lot of 6in w6 wsied s well duing O. pb6ing Tlis M dE to lhe

ldion on nbF duins winditg vhich .xp.l th. t6in nlh iMd Dan&.I io the or'ld

surfae. On the otho bsd th€ ri.s: fomed ftoe pEFeg *(e cl@ at th€ surf@ dd

snowed qcUdt i.td.lminr md int Fflddt bondiry wiil eay ed cld witrding

pFess s shom in Fi&3.2?. Thaetore the uifomiry of lhe 6it @ntmls 6uld nol be

achi€led by the w.t windinS poccss.

3.6 Hydro-Burit Test of Composite Cylinders

1.0 % HTPB rodiffed epoxy r€sin was *lcci.d 6 d otiinw rubbd oncqthnon

vith good n€cheiel and fimhl proPerri.s fo! the fabricaiion of coiposite vessels

uine filmmt-windins t€chniqu€. Htdrc-busl t$t wa pdfomed. uine ASME c.de

8l

Div. IIx on both Modifi€d ad modi6.d cyild63 to Lnow thct stqtgth lo be us€d in

its n6r @mon appli€iiG. Nmbd of hclio.l ldyds, hoop l6y.B, whding m816,

rcirfotlmot (Kalu) dd Ning cycl. wae k€pi @sknt !o trow $. efrdt of rubbd

@nt6is us.d in h4!ix fomddim m thc n ch!tric.l prep.ni* ofonPdite ctlindd

Fi& 3,2? Piisr tudc bt (.) e.l wilding &d (b). pEpcg winding l*bliqE

Th. 6ull3 obtain d am lydrc-bNt lest fo. unodifi.d and hodifcd cvltudd

indic.t€d thar Oe bst !6sw i!@sed fron 102 bG to 136 bds with the addiiion of

I % ETPB to tr n.tiix nalqid. Th. d.t ilcd r.sult! @ s fouos.

3.6-t Hydro-Burtt T.st of CoDpoclre Cylirder b.t d o! UrmodifiedEpory Rsh

srr6s otodu..d on the suf@ of Mpotite cttind< 3 ! tunction of hldm

6tu in bu hs b6 shoM i. !is. 3,28 i! longirudiial dn@tion Al 2@ pr63w no

s1r6es wq. obwcd but s the htdtu-pca5@ i!]m€d th. 5r6!s v@ pmduc'd

boih in th€ dotr sd 6lr€ of the ompo3it€ sttuclw The 3L.$ rtlu. itr hoth pdts of

de cylind.. ind6!.d lilarly will in@ing pBre bul the tt*6 Fodued itr [t'.loft sw gana fie i! 6!q Il ildieLs that dom n lrc vuln6$L ro srr*th!tr 6td prn ofth. ctliidd. Thc cylindd ffltlvDpt!€d tl 102 !d Prc

az

e

The finrl valu6 of ssse poduced at 102 be p6@ in dom. atd @lre wd

obwed 1o b€ 3 I MPa and 2OM?4 Ggdtiv.lv Sres poduc€d in bod pqrs ot |he

onposiie cylindd i.e,. done md 6trc in tmsvde dtelion aF shown in Fig 3 29

The b€haviour of cylindo in t€m ofsrr6s6 produc€d in trmsvelse di@tion is @€ sin longitudinrl dir€cion 6d slowed lind bchaviou with the incrca. in p6s@ bul

the slr6s produc€d in lrms!€tr dn6rion is vdv largc 6 @hP&.d to &al in

lotrsitulinil di@tion. Fo. qmple th€ sEBs ptoduc€d in mtre i! lluv* dir4tion

at 20,.lO,60, 80 &d IOO lm plsw w@ l8lMP4 l53M?4. 5l I MP!" 606MPa md

?02M?a s cmrdEd to 6MPr. loMP6, l4MP!" l?MPa od 20MPa Bpalivelv in

lonsitudinal dit.clion. Wtiile the sitdses produc.d i. tbe done of composite cvlinds aa Bult of hydrc-b6t l6t in tesv@ di@tio! at 20, 40. 60, 30 ed 100 ba pRssure

wft 248MPa 4llMPa, 54?MPt, 662MP. sd ?44M?4 rsFcliv.lv 6 onp{ed to

6M!4 l2MP!, I ?MP." 241!0! dd 3OMPa cp.divelv in lonSrtudinil diretion

lo.gitudinal dt.clion of lmodified ompdite vsel.

8l

T

6

Pm{t-)Fig, 1.30 Conpaison of sE€s6 ir logitudi@l and Fmsv€Ae <Irecdons.

Pt-d{B-Fi& 3.29 Str6ss itr Fdsv6e din*tion in modificd ompcit€ v6el.

Th$€ obwaiioB shov thal snlss! prcdued in the dtosie cylindd inFesv* dir@tion e ddGl 30 rim6 !ra1d thd thai Foduc€d ir logiMinrl<liclion a shom ir Fig 3.30 {d Fi& 3.31 .

Xor

84

Pe6(r*)Fi8. 3.3 I C.np&ien of st 6s in longjtudidal and truvde diFtion.

3.6: Hydro-Bust Teit of Composite Cylirder bised on ModifiedEpory Resh

Conpositc cylindd bas€d on L0% HTPB Dodifed rein fmul.tion cdled nodjfied

onposile cylindd ws ol$ flb.i€led sd r6r€d by hrdrc-bNr qpdindt by rh. mep@edw€ followed ftr umodii€d @mposite cylindd, Ttr eddal betaviou of both

irF of cylindd {€ @e but the 6nal srlbilny ol llle nodified ohposne siracrw€ is

SBtr tho modified @mposite cylind6. The bchaviou of nodified mposir.cylindd in tn of its n@bdical prop€ni.s on don€ dd 6trc in $o dire*ios i.e,.

looSitudinal dd trNv@ wft studied Md rlE r€sulrs de snoM in Fig 3.32 ed Fie

3.31. The srr6s v.l@ in ddiv@ direrio is 34 b 35 dm6 gr@rd lnd tongiMinal

dir.ction 6 shoM in lig. 3.34 md Fig. 3.35. Ir indicals rhar dmas€ io the cytinddmostry o@!$

'n rmverse dn4don whd ir is i.rhauy pBsuizcd. sinildly. ihde is

ar@i6 defomarion on the doh. s @mp!r.d to the mr{ pan. Onc of dE !!eNbchird tne gRra defomarion on dome of the €ylindd rhd jts @ral prd is tlbr hcljcol

85

hr@ only @va the don. wheM on the 6he both hoop dd helical lay6 de

tr..uE(B-lFig 3,32 Srr.s in lotrgliu<lind dire<tion of hodifi€d @mpo$te ve*I.

Fig.3.33

Pn*FlBz)Sir$6 in tmv* dil@6n in modified ohposn. vese.

6

E6

Fz

at

Ft-{r (B-l

Pi& 3.31 c<dprlrd ofrh$€ b lodsirldi!.I d rsee.r. dirarie

Fnrr (lrt8it. 3.35CdFrisof*rsoFltDdintt d@of-.droiii.red.

87

wlta all tE htdro btlat l6t reulis w.rc cmpE€4 it was obln€d thai when rnore

toughdcd ed dorc inp..t Eistei hodi6.d DGEBA wq u.d in lhe fmulstion ofFin sy$d ro 6b.ic.t the @mpo6ile v*d, @oFtativcly ls itBg s@ prcdlccd

ed mE pla@ wa rcquir€d (33 b6) io bl61 th& u.mdif.d @npci& cyli.da

st u.nae s snoh ir Fig 3.36. The elo.gatiod ofnodined cin ind€aed 500 tin6 edir f&ilitared th€ elongation of Kdld duinS pr*suiation ir htdo.bust t€si.

=.@

Fig 1.36 ComFns of rDlg ir l[€ 6rs olonpciE vNd.

88

PART-II

3.1 Synth€sis of Pyrazole Epory R6in (PER)

In lhe scond pan of dre prej{t a nov€l p}rdole bascd €poxy r6in (PER) wirb

ihprov€d thmal ad thmonechdisl pop€rti€s hs bm synlh€siz€d. Th. strth6hha bm cfiied out via nulti slels. slcnin8 wilh lhe pEp&.tion of l{2lhydrcxy

Phdyl)-3(lhcthoxy phqyl)FpDFncl, 3niore (D- All the int m€dilr6 prrdlc.d rr

d€ry step a well 6 the Snrl poduct, ede chd.'diz.d by ditremr Mltlislrechniqu€s. Derail ot the .lard ohlin€d is suhFriz€d s follows:

3.7.1 Chu.cteriz.tlotr of 1-(2'-hydrornhoyl)-3-(2'LnethorTphenyl)-

prop|le r, Sdiore (l)

l{2rhydrcxyph6yl}l-(2 Lnethoiyphdyl) popdel, l.dionc (I) v6 prepd.d by

nodified Bals Verlatamm rcaction d shom in eh@c 3,4. Yield ws 63% ednelline poi.t wa r.@rd€d s 78.5-?9.0!C.

Schne 3 ,1. Sy.rheisof lr2lhrdor) pha) r-J12 :nerhoxlThdJ lr-prcpane- l, J{,one (1,

89

FIIR sletrun shovs rwo F3tl at 3374 m ' ed 160? m ' de Io rhc srmeEicstr€tching of OH dd C=O gloups p6qt in rh€ cmpound Th€ appddce of sinelei ar

63,99ppnin rH-NMRnaybessiCn€dlo lH of OCHr grcup. Singlerari)5.l2ppm

Md 615.60 ppn @nfims lhc F6a@ of phdolic and @lic pbrotu in rh€ 6npou4Glctiv€ly. Elmoial an lFis dara rcvc.is rhe p@qtlge of @!on ord hydmAa ro be

7l ,21 dd 5.72 rBpetively, which is in good asreddt to rhe calcullt€d valn*. Thr*.dintrio.al slrucnr is siowo in Fis. 3.17. Tne oxygh pre$r in thc k.ro OH ddOCHr grcup h6 ba snoM s cd bdls.

3.7.2 Charrcferizriion of l-phenyl-3- (2.hyd.oxyphenytf5(2,,-nethoryphlnyl) pyrazole 0I)

Cycl@nd@tion @tion of r{2ttdexyph6yt}l{2'tedoxyph6yt}propeeI, 3{ion€ (l) sitn ph@yl htd@ine in $c neunal nedia I€a& ro rh. fomadon of l-ph€.yl-3- (2rhydmx}?nqyl),5{2 Lneitoxthqyl) prrml€ (rr) s shown in schd€l-5 wilh ihc yield of47olo and n.p 120"C. Ctrbotr I in onpound (I) is nor€ et€Eophitic

lh& @bon 2, In n€utal m.dia, nitnso 2 b morc nlcl@Dhjlic, rhmfoie it anacks moE

Fig 3.3? 3D slnDiue of 1-(2' -hydrcx}lhdyl),3-(2,hclhox}?hchyllprop&e I , 3-

dion.(l)

90

eldrcphili. carbon Euliitrs in the fomaiion of @mpoud (ll) in notal @ndirio6.

FTIR sF.rnm showed dE alerprion ba at 3446hr,3258 m-'dd l25l olcorcpohds ro oH, =C-H dd {4C cp€tiv€lr Two sinsleN app*ed ar 6 3.41 ppm

md 10.98 ppn in |H-NMR due to pmrons of OCHr &d one proton of OE soup,

Eld@Ll &altsb dala 3lbws the paqridg. of cdbon, hydbsE! dd niEogo i! the

obpoud !o be very closc to the c.lcular.d volu6. Top dd sidc viry of Egjoisnd l-ph@yl-l- (2!hydext!hdyl)-5-(2'Lnethoxy!h€nyl) plr&ole (lll) is shoM in Fig. 3.38.

schdc 1.5. Synlhdir of l -phdyl-3 (2lhtdmrr?hqyl)-J (2'h.doxy phdyl) pr@l€(ll) ed l -phdyl-3 (2hdnoxy phdyl)-5(2 Lhydoiy phayl) ptt@le (IID.

3.7.3 Chsrscte.iatlotr of l-pbenyl-3- (2lme.hoxyphenyl)-5-(2,,-hydroxy phenyl) pyr.role (IID

I'phoyl-l- (2hcthox4hart>512lhydexy phdy') pr@lc {lll) w6synlhaized by the sction of l-(2rhydoxt?hdyl)-3.(2'Lme$oxr?hayl) ptopan6l. 3-

dione (l) wilb ph@yl hydr&ine in s &idic nedid, wior $e ield of 15% ed n.p ofl4{rc.In &idic m€dia litrogo 2 of ph@ylhtdpine g.t potonaled dd bom6l6sneldpbilic i. ch@dd the nirroas l. In rhjs 6e nitrosd I will @t with M€el€nophilic clrlon I which rBdts in fomadon of@mpound iIID. AU lic F-IIR, NMR

md elddt3l malysis data is i. as!€mot ei$ ih€ already rerorled work [85].

9l

iis 3.38 3D view ot l-phdyr3' (2rhydrcxr!h6yl!5-(2 h€thoxr ph6yl)

Ptd4le 00-

FTIR daia ws.lnosr sue lor borh r,\. Egioismm d alEddy discN.d io eciion

1.7,2 ahile in cNe of |H-NMR dotr a linl! difle@e in sp.ctrum fq iwo @mpounds

(u) dd (uD va obw€d. A sirsl€t duc io pror@ ofoH srcup i! rwo regioisond i.e.

l-phdy'-3- (2rhydrcxr?hqyl}5{2hc0Fxyphdyl) prr@lc(ll)ed I'phdyl-l- (2!h.rnoxphay)-5-(2"-hrdrexyph6yl) p'@ole (IID app€.cd at 6 10.98 pprn and 6 5.56

tpm, rBpelively. This doM6€1d shii of the pe.k nay he arhibuted ro the pcd.c of

inrmoleuld bydo86 honding in th. 6. of l-pheyl-3- (2rhydrcxt!n6yl)-t(2 !ndhox}?hay') prr@l. (lI) betw6 oH sDup dd adjMi -N alon of pyMl€ring. Du. lo idic hindtuG in 6e of 1-ph6yl-l- (2rde6orr?h6yl)-!(2q

hrdor'"hat) pt@ol. {lID, hydrcgd bondi.g is not posible rhdefor phdolic

prclon r€$nate ar 6=5.56 ppn. El@stal eallsis of @6pound (lll) having noledldweighr 3429 showcd cart'on, hydrcsm sd nirrosa val$ !o be 11.8%.6.50% ad8.08%, Bpedvely which e .lnosl cqud to the fiorc.iql $lu6 6 well 6 to thc

92

lolue found for rcgioiend l.phdyl-3- (2lhydrcxphayl)-5124nd,\oxphmyl)

3.7.4 Ch.rrcteri4tlonpy.uol€ (I\,7)

The dmelhylation of mmpomd (l!) dd {lll) *ii,h anhydoN alminim cdonde bd

to the fomadon of l-ph6yll,5-bn (2lydsxyphayl) p,@ole (lv) 6 sboM in

sh4€ 1.6, wnh n€lring poinl of202'c &d ield 0l?6%. h FIIR dar., a brud pqk ol

3lO8 cn-r wds ssigned ro OH stlmedc sfetching. The absoe ofpeats due to C-O-C

s@dric @d slDnerric srelching @nfimed lhc dmefiylarion r€action. Two

*pmle sigtuls of OH pDlons *de obw€d d 0 5.36 ppD dd d 10.82 ppn in rH-

NMR. This cl*ly dislinguish€s b€tw€6 non,hydrogo bonded dd hydmga bonded

phdolic pototu pr6a1 i! lne noleul€. Siflilulx the pcal due 10 OCHr plotoN w.s

dieppet€d in lh. ompound (I9- Petdlrge valB of cdboa hldbsm and aitugavffi fo$dro 6e 16.76r/r, 5,161/a md ?.4Cr./. s d€t€d.in€d by elm€ntal dalysir which

ws in Sood agrmot to tbe calculated valu6. Fis. 3.39 sboss 'H-NMR spectral dam of

l-phenyl-], Sbis (2 Lhydmrypbetryl)

0v).

schftc 3.6. Do.thyl.tim ofompowds n .nd lll.

I o0l)

o9l

l4 rt 12 3432I

rig.3,39,|H-NMRspGct4ldataofl-ph..yl-3,s-his(2rbldsxypbayl)pFlzole(M.

3.75 Cb.rrccrizrdon of l-ph.Dyl3, rbis l(2', 3'-€por)"mpory)ph.ryll pynzole (PER).

R.adion of l-phdyl-], 5-bis (2lhtdextlh@yl) pylelG (w) wilh thG qc6s of€pi.hlorohydri! led lo the fomation of .poxy doivativ. l-phoyf3. 5bis[(2', ]r.loxt?opory) ph@yll pFele (PER) a shom in $hd. l-7, baving mcldng poinr

134l4OoC snd 94.0% yi.td I.Ile 6nrl podld % ch@r6iz€d by FTIR, rH-Nl\/lR.

.ldol.l &16lysis, avd!8. noldl& w.i8ht ac.

Almse noldl& wcight ws 471 s dei@ined by !?O nedod, sho*ing lhe

oligoddic dte of th€ cin whil. rhc .poxy .quiwlor s delmi.cd tilrindicillywas 321 e/eq. FTIR spNta of the r€sin showed. Absorplion beds ar 9lO mr ed 319

cn r @n$pondins b ttu sFelchins 6!d bendins vibhlion of cyclooxneB pr6dr in

.tory cin (PER). |H-NMR spe.ba cldly indicat€d th€ plMe of alycidyl grups in

PER. by &e appdece oimultiplets .t i 2.85 ppm ed. 6 3.6I ppm due to four porons

of CH: md two Folons of CH in oxir&e ereup rcsp.clively. Psls dE to phdolic

porns ar 6 5.56 ppn dd 6 10.98 ppn in mpoud (Iv) diepped indidins rhe

+Ntl

(tv)

Schn. 1.7. P!.p@tion of pyraole sniaining eDoxy r6in.

3.8 Thermrl Stability ofCured Pf,R Resin

Tnmd stability of PER rsin cud wilh two difimt hfiddd i.e. rry,906 dddidinodiphmyl 3ulphon€ (DDS) e shown in Fie 3.,O rnd Fig. l.4l Gldtiv€ly in

compmson wlh 0r. convdtionally Bed DOEBA Bh Th€ TCA rcsults showed rh.t .odoninery cxisicd betwen DDS &d HY-906 in w of th@61 siabilitv whm u*d for

dr. uina of PER 6in. Tn. cur<t PER 6in ns srvm .xacdy de smc mour of cbd@.lml at 90d'C dd valuB of naximun de@mposnion t€dp@lurc wnh borh hsddeG

o

PERo o

95

e sue s epBmted by fomdado. A sd D. N.3t PER cured with EY-906 show.d

gr.ctd lhmal stahihy ed clE @or6t a onpdcd to n@i DGEBA cured pirh IIY-

906 a 3hon in Fis 3-40. Sinildly n6i PER ofti wi$ DDS slDwed g@rr lhmalst hility dd che @nre s th& neat DOEBA N€d with sm. prcponion of DDS sshoM in Fig. 3,41. Th€ gredtq mout of chd ponion in ca. of c!red PER show€d

Erqr.r C/H rtio atd Dorc Nhaiic chaticrd th& culrd DGEBA.

r-e..-n fclFie. L40 Thmal b.bavior of(A) PEtuHY906, 3: I (B) PER/DCEBA/

HY906,2.5:0.s: I (C) DGEBA/HY906.3: 1

Th@ is a ditrffi@ of aboui 80"C in the tenpfrrw of w€ighi lo$ for the se€mount of.le@npositio. in PER s @mpeed io DGEBA regdrdl.s of rhc hardodNd for wiry, Tie sysron Mrrioing m€ dout of pER hircd with DCEBA crcpGored by fomularion B md E showed i e.6.di.re prop.nies in rh of tneir

themal behaviou i.€. tnei. rhhal slabiliry lies in-berwq n !r pER dd DCEBA.

sug86r.d Inr $c themal silbility is tinaly relatc<t yirh 1he .fuut of pER in rhe

3'"!--a

96

5@:,

Fis. l.4l Thmol bebavior of (D) PER/DDS, 3: I (E) ?ER/DGEBA/DDS. lili2 (F) DCEBA/DDS. l:1.

3.9 Thermo-merhanicd Atrrlysis ofcured Pf,R Resin

Th€ gRls amaic chmctd md rhmal $ability suggesis d indese in slass

trusit'o. imp@n@ &d modulu of cur.d PER Bin 6 @npared io DGEBA. TIE dqudd thc t n 6 al th$ tituitior ldp€n@ is o m@m of rh. 6ds/ disipr€dduing de dynmic ne.hmic.l qpdimmt. Tm 6 shows v€ry acMrcly lhe phde

htufion tdptratue padi@ldly th€ bovmmt of c4rain pds of the poltf€!noleuld whq it is lir@ly hared. Lnss behaviou oflh@ 6in lomuhtion i.e, A, B

&d C cu.d wnn tne sm. hddenq i.e. HY-9o6 is shoM in Fi&3.42. Tn.mofrelhicalprepenig oflh€ slst€m cued wi0r DDS 6uld not be found b€qw lhe Esin rued wirh

DDS wa too bnnl€ to @t a smple requned lor thmohehmical ealysis.

The glN q-dsition tdrp@nE OJ r.to fron $e pet ofun d of th. s!€d PER

r€sin baed on fomulaton A wd Ioud ro be 167.4oC. Olss ndsirion hpmrure ofmia r6in syslm based on fomul.tion B qs found io b€ 94.1 i.e., gr€ors by 22 oC the.st DGEBA srstqn. How.vd the loss value (ran6) of hot DGEBA hlvins fomulation

c is snalls thd PER b6ed systds (i.e. both neat dd nixed fomulation) which

suSaeis tn{ ls 6ngy is dbsitat€d &d 16 novddr of fr.edon h avaihbl. ro th€

polymd noleule in ce of PER Bin sysr.tr .t the talp@tw cloe ro glNhdsition tmpfrtue. A1 dy tdpdatur. tn€ lo$ faclor of PER bosed @r.d resin

srsto is salld ilrd curd DGEBA sysLm.

The ndimw loss no.lulu vrle ofrd PER r€sin culd wilh HY-906 was fodd to

bc 54?M?a qhile that of.edt DGEBA cued with thc ame hard.ner ws lo!.d lo be

r69MPa N shoM in FiE. l-43.

r.nE -Efc)Fig 3.42 t ss bch.viorof(A) PER/HY906,3:l

HY906, 2.5:0.5:l (C) DOEBA/HY9o6,(B) PE&'DCEB,d/3:1.

Sio6g€ nodulu ofPER Gsih systm !t Md tdnDdiw w$ knoqn ro be ?.t4opa

and sho*€d a v.ry lidle d€vi.,rion till l4dc &d lhd sl&t€d d€.@ing riIh inclle in

ldp@tuE d shoM in Fig. 3.,r4. The n€ar DCEBA syltm bscd on fomuladoo C 6ad

3 siodse modulw ofjut l,66CPa ar mm rempmlue ed sbncd loosins ils valw iutalovc tlO'C. The sme behlviou w6 obw€d in ce of 6in b8.d otr fomulation B

lhat hls a v.ry Sood initial sto6s€ nodulue value bur showed very tuly dq€sc whathe thpaatu. {ceded 40qC.

98

i ""

E

r.h'.dE ec)Fi& l.4l LisDodulN m6EEd I trz of(A) PEMJY906. 3: I (B)

PERTDGEBA/ try906. 2.5:0.5: I (C) DCEBMIY9O6, l: L

r-F.--ec)Fis 3.44 slorase nodulus n€surcd ar I Ez of(A) PER/HY906. I rl (B)

PER/DGEBA/ 1Y906, 2.5:0.5: I (C) DGEBd'HY906, 3: l.

I

CONCLUSION

Epoxy !.sins de mong th€ nost le6atile engineoiog matfral9 ft. rouddiog olepoxy r6in, DGEBA Nith htrltuiy-lmidled Dolltiutadicne (mPB) {a su@stully

mduct€d, A chdicil li.kigc betw@ the el6lomd dd 6b *a ddelop€d by

dplotlng isphoone diiecynale (IPDI) s a couplinS agot lo strth.size epoiy

tmimted HTPB baet prcpollmd. Be6r€ onng. pr€polFd ws dil ed hy addition

of pw DCEBA, to pr€parc Darerials diffding in elrsrone @n@taiion, but vilh lhc

sme prcpolFn mposirion. AlihouSl fr&trc touer'n6s alorg with inpact sEdgrh,

ndibility md tosile slrdgth ws improved succ$stully. sme problos l€mined

uNlv€d. For €xmplq t lowq modulu, lowa omprBsive ed nqunl srogl,tr wdobaded i. the mt l€s.mh.

The mat€rials pEpdcd with on@kations of HTPB vtrying Aom 0.11/0 ro 2.V/o

hav€ bm i6led for dif.rc.t neheial, th@o-mccheic!.1 dd themal plop€nies.

T61 6ultl showed looplo ind€* in inpad s[6grh, 200% itrc6e in n€xibilfuy, 80070

in@ in louelrn6s, &d d slidl incM. in ulrinare r6sil. strasth. Othq n*hdi.alpropeni6 like n€xual slrdsth de@d.d by 60%,.ontressive sl!€hsih by too%,

youg's nodulB by I00% &d Vickcls hardns by 2007q Thmal $ability of dr.

slco w6 nor nuch affet€d by loughding DCEBA sing HTPB 6 a hodifiq lris is

beaue or vry low @nchlrotio. of rubb6 particlq s @mpared to h.in epoxy dinenenvork syslm. Oth6 ihemal md lhmo-nech&iql prop€rli€s lik slss iruiiiontempeatur (Tg), stone. modulu old ls modd6 daltls *irh inc|6ing nrbb.r

Howw.r I % HTPB hodified systm vas sel4t€d s oprimm $n@rration for blsi

ln@Gnehdicd prcpqd* for practic.l appliqtios lite Kald-cpory onposite

T!€ conposit€ v6sl fabri@ted using nodided DGEBA r€sin sysh required 32

ba norc pesu€ ro b$i duins hydrc-bwl 161 Om wodified 6in fmdaiion.Due to s@metry, dons of ln. vset wdc norc wtndqbt. ro defomrtion 1ha ns

cmtai pan, Pwatage .lonsalion of modified @oxy in(eas€d by abolr 500% which

Iocililaled the elonsation ol Kald wirh €mci6r load tonsfer mong iI€ fib6.

100

The ndly sFth6ized pti@le ont inina @xy 6in (PER) hs g@rd thm.lshbiliry, ala r.Gitior lenpaarw (Tr, ed srodgc & los modulu rh& @Imonly

$e<i DCEBA sin syslm, lt q6 tried 10 cw wilh rwo ditr@t hed@€s, mine b8ed

&d arhydride ba!d. DDS is rct sitablc cEi4 lgot for rh. rcwly synrh6izd t'oxy6itr. DDS is moE brinb a conpd€d lo NMA du. to tne F€ene of domaric lings in

dE stndw. Slnrheiz€d PER Gin ale @nlais nSjd mric moi€ry, ihdefoE cuin!of PER Mth DDS Bdrs i! morc brinl€ n rwdk sylrd. Hoe ir is rcr $italle scuing agot of PER. Du€ to prehe of Eorc ngid Nmdc p.ns in PER. its thn.lsnd Ihhcnehmicd pbpdti6 e b.ttd s @mpd€d ro DGEBA r6in ti is

@n ludcd rlEl th€ NMA cutld PER cin @ h. usld 6 a mFix mrdiat fd llirn

r0l

REFERENCES

L Cne4 W.M. T\ Y.H. Li, P. W&& C.Z. Zhou. T.Y. YeB, X.P. J Conpasites

S.ie"ce and Tec,,olog. 2wt, 67. 2261

2. Cmpbell, F.C. Manthctunas Prccesses hr Adw,ced (hnposites, Elscyier

At!w,..a Techtulbg), UK 2004,t2

3. MiliEry Hed Bmt. MIL fiDBK-754(AR) 1991,6-1.

4. Chim, T. T.; t6s!p, E. E.t Pn, L 7th Natioral T.chni.al SAMPE Conlcrenu,

Society for lh€ Advmc@sr of Mlt€rial od Peess Engineain& Covina! Ca.

5, .IosE, R. !. I"ttuductian ta Pollne6, Cn p6 & H^ll Lrd. Publ. N€w Fer{,ECIP, t ndon198r.

6. Glffi, R. H.; wilt6, C. L. Polrd. Sull 198,'22.527.

7. Annad, Z.; SNd, M. L| wse, SiMdk,l. E. Pobner 1991, \1, 4523 .

3. Kardrd. JlDrel, L.T,t Mote.. 'ci.,

rqa3,260,7a8.

9. Gaon, A. Polyner CMl lg8/,5,25a.10. Feldnd, D.; Bdbala!4 A. Syntt b Po\mut: Teh"iques hop ,4pplietioE,

lsi et. Chapnm & Hall Publ. U(,1996.

tt. IJncJr, H. Introdrctior to lndBbial PolrrcB, Htus h)r l. Muich. t982.

12. Potttr, w. C. tp&ld, {€r,6, Spnng6. Nw York, Ny. 1970.

13. May. C A.r Tmal<a, C. y. Epat, R$k Chcnistry and Tuh,otog, MtcelDekl6. Nq York, NY, 1973.

14. B,q, R. S. Epoxy !6in chdisry, Adv. Chm. 36. Amai€a Chmi€l Soci.ry

washinBon, DC l9?9. ll4.t5. HolA. K. A. RAPM Rc!. Rep. 1990, aa.4.

16. Bhuiya, S. Adhikdi, B., Jouml olApptied Polrnt Sciercc. Wiley pdiodicals,

Inc,2003,90r 1497.

l?. B6sn, W. D.; Hsroa, D. L. Rubbq I:ouehcn n nasftr, Adv. Chd. Sd'Amdicd Chfl. Sc. wdhingto.. DC 1989,222. l9l.

l8 Rifl. C. K. Rlrr.f Crdn T..hno!,9as.5A.622,

19. Feld']m, D.; B&bd!ta, A. Stnthdi polrdcrs: Tcchiotogt, proptti\,Awli.dio6 1996.

102

20. Tda*a, Y: Okad4 A.i Tomiz*a, L Epory Resi$ Chmxtr, 6d Techtolog,

Mdcel Dekkq, New Yort 1973, 134,

21. G.6le,S O. US Pakrr 2456408. l9,t&

22. Dooblim, G. A.j Schmid\D. L US Pate 4Mar4t,rt17.

23. Gleenlee, S. O. USPalc,r2s2lSl2,1950.

24. Danboh, E C.j Fes, R. M.: M{. Kwiq A. K.: Sn€?€rd, R. G. Jr 1Il t g.

Ch.m. 1953, 45,2115.

25. Schw4na. C. c, USPatent28060l6,r9s1.

26. HowtlDme. K. L.i HMn,F.C. Epory Relin ChcniltrJ, It, AC Slrposi@ s6ica

No- 221, Amd. Ch@. Sft., Wshin8oa DC l9&, Cno er7,135.

2?. Schradd. P. C., U,S Par€,' 4394496, 1983.

28. Ks.aym4 K K, US Par.rr ,1390664, 1983.

29 cnifi$. L R. Chehtc.h. 19a2, 12, 5,290.

10. Kllrl.lye; d al. ./:r ,4&d /u"!*, SSSn, Sd. Knin. 1965, l, 72.

31. Cnfiith, J. R. US Pdt nt3819410,191s.

32. Budnowski. M.t Dohr, M. UJ Pak,l 3288?89, 1966.

33 Sein, A. .t.i Rciib<g. J.: ScnNta, !. M. lnterratio@l Odnot Mux.happijOampa, 1975. AB, lJal262-

34. Reinkins, N. H.tBard, B. P.; Casrnd, F. J. USParc,r 29s1825, t96{.

35. C.lvin, T. J.; Chdudhdi, M. A:King. !. J. Chen. E g. tuoA. 19E5, 8 (t ), 45.

36 Ja,hn, H.i Clwty, P, t/r19, Rsihs ChenLgry and Te.A"otost, Mrel Detls,Ney York. Chaprd ll,1973,653.

37. Toal<{ Y.; Mika, T. F. Epoi:f Resi6 Ch.nktrr and re.hkologt, Ms@l Dekter,

\a Yoik. l97!, Chapl€r I, 135.

33. cupta. A.; Cindiogl\ M.j Couhd, D.; Lie& R. H. J Appl Polym. S.i.19|iJ,28,1011.

39. Gupt . A.; Hon& S, D.j Moamin, J.j Cineioglq M. Chenorheolosl ofthetu&tfi"s Polyne^, ACS Synpoju S€ns no. 22?. Am6, Cho. Se,Wahin8lor! DC 1983, Chaprq 5. 81.

40. Pnn , R. B. Thertul Characteti2ation of Polynqic Md,ta&, Academic Press,

Nd Yo* 1981, Choptd 5, 415.

103

41, P6sini, P.; ldbone, M.j Niolais. L.i Api@lla, A. L]rpl. Pollm. Sci.lg8.4,

29,2083.

42. Zut6, W- X.i M&KriCh! w' J.; SclDeid6, N- S. Chenohcologr' ofThdnovuinA Poltr1t6, ACS SFposiw Sqi6 No. 227, Ama. Chm. Soc.,

Wshinslon, DC r9&3, Chaptd 14,

43. Ems,J. B,iCillhM.L K J Appl. Polyd 5.i.$A3,28,2567.

44. Fi$hd, M.; Lobse, Fr Sdttid, R. MlrlmMl. Chen.19a0.l8l,1251-

45. Kie'4 .,. l.r Abms, E.. Hnnttg, !. P. Ihe Epo, R6in Fmtlab^ Trcini^s

Md,@l Socidy ofPlstic Indu$!y, Nw York 1984, 309.

46, Borgsted! H, H.i Hine, C. H, Epat, Resi$ Chenhtry and Technolost,Mtcel

Dekld, N€w Yo.k 1973, Chaptd 12,69?,

41. cnale, US Pate"t 2160944.1956,

48. Amld, R. J. rod P/6rts t96:1,4t, 149.

49. Cddall, E. W; Mih, w. Cteno .olosr' of mqndeting Polthut, ACS

Sybposim S€ri6 no. 22?. And Chd. Soc, wahington DC 1983, Chapla

50. Odi{. G. Phncipls ofPolym,izan r, 109, lrd €dition, John wiley & e6. N.w

51, Friel, J. R. P,rte.scr'ence an,l Technolosr', Pnri@ HiU Ptr, Nq J6.y 195.

52. Mc. Carry, F. J. Id&r i. Ctoslin\z.l Gl6s, Polyrcc, Ptu€edilles froh ACS

Ruh6€r Dvision l29ih Metin& PlF No. 86. 1986,

53. HMgi et t). Me.huis6 oJ T.uChening Ihendd RdiB in rotAhan.d

Plasn s- 1, Am€rcie Chmiql Soci.ty, Wshjngon, DC 1993, 35.

54, Mc Gary, F.J. I Willna, A. M. Tough.nins of@ Epo4 resjr, R68 8 M JT, R68-8

MIT, wiley l .r sciae, Nq Yort 1968.

55. Kunz S. C.; S!yE, r. A ; Asi.t, R. A. Potrca lta2,21, 189?.

56. Raghava, R. S. P,,@elirss o! the 28th Nanonal AMPLE Conlbmu, |@a, Cl,.

1983.36?.

57. Buctnalln, C, B.: Partrid ge, r. K, Polrner '9a3.24,6J9,

104

58. Girbd! A. H.r Bu.trlafln. C. B. akturiol Chen. (Meoniol Symp) 1991, 45,

249.

59. FrigioE, M.E., Mei.,1., A.iffi,D,J E rcp@ PorM Jo@.199a,31.t02t

60. Kih, ,. K.i Rotr.trslr R ,E. J. Matd. S.i. 1992,27,16l,

6f. Kubord., K.: Y€., A. F. ,lrru. T@t. CorJ. r93, |,3790.

62. B.nthi.. A. K.i Ch.nFdi, P, N.r ,h!, v.i P@dy.b, v. N . s. Rubber Toleha.d

Pla.6, adv&6 in Ch@bt y Sci66 222; ahdi6 Chcniol Scicry:

W$hington, DC 19E9.

63, Tongh$al, R. E,i Thm r D. A.; Sp6lin& L. H. Ioqn,a atd Enule@ otPl6ti6t /l.lr@et in Ch.^ist,y Sqi6 154, Aiditu Chcnicd S@icty,

wlshiugron, [€ lt4 206.

64, v.5dt, R.i Cajlilq l.; Tuy, G,i Rust}, I.r vi& I. A, J. ,.lrpl Polyn, &i.1994,

68,lll,65- W.r& H- H.i Cha! r, C, Polyn. E4, S.i. r9t5,15, ld,6a,

66. Hlmi, H.; Fcllthi. S,i B*d,M, J. Appl. P.ly . Sai. 199E, 10, 2@t.

6?, We& H. H.i Chd,,, C, J. Polr . S.i. 2|'i)0, 42, 290t.

6E. wMilq E. Lt Pi@, O. R.i Polnsr6. K, E.i S!m, J- c. x!rr?. CrttTe.hnol lYl4,52,911 .

69. Yo*8rris, E.M.i Eis!, N, s. ,r.; lru, c-; zhilt6, Ci Mccdqrh. ,. E. ,ldv.

P.Un. Sci. ,945,72,79.

?0. q z@ sDng v.Ho!, J Jor@l ofconP8ite Ma@izts,2007 Attzol

?t. wd{h.ng shi[ cha-Chi M- MA Jd.chos Ym& H68{c Chd, J..rd'elof rlppl i ed Po I r ne I S. iene, 199 l, 1 3:21 39.

?2. Bhbirt S., Adlri}'i, 8., !, JM@l o! Appli.d Polyrcr Scie"e, tlx)3,90:1497

13- Kain,F. T8ting oIMetab, F@z SoB (P\4.) trd. LlhN l9!,15.74. H.nry, tEi rii!, Neil]. H6d B@t o! Epoty R6iB, Mcciw-Hill hc Nd

Yod( 196?, (2)12.

75. Pd6, s;t-, Ha'.lM oJ co,'port6, Ch.!tu tnd H.ll Engl.nd l99t, (2)208

?6. Alna4 R,; Zi!-!fHaq, M.; Duddat. H.i Sr.f.ri*, L.i Si*owsld, I

Mo@tsh4k lt Ch.^i.. l9Yl, t2A,6t3,

105

?. Ah.4 P; z..d.lIe ltt.; (tr4 N.i x,td, N. ll.,l|tdd@ J s.L h4, lgx'2(3),193.

78. }tod., r'r; Niddd., K.; Fqii, KIriiN,E" J. ot, Ch6 l'0"45'4215,

?9. Hddr ra; rri6i UB r4lAi q.i PIpd, s. P..t fttd Jd h'A lr0'2t(l l), 3019.

E0. Bi.b, N.: tta.lc., It.i Md!.tb.t, U.;,RitEW. Db Wcwtubb.bt Ct we

r'la, l9(E),18,$.

8r. Hdd4 K-; Xrtdi Ue P+?.., S.|.J. Polr* 8.1P@1'C r'at'z5(lz\ 1n.

E2. vcr, L P. S,i Vd.i!, D. R; Cdl., W. !,: r.; R.gina S' v N. ,dor€ ttPobwr Talwbat ttt4 2r(r\25,

83. K|in l, C.i @ula Ai Ti!€, T. P.btu 1rt.4t2,31,%9.

E4. &wr. P. r- Itdd&ol of Ple Tst r(ttt.lt,bry,6 sdldic Ed T..L

Ilbl uK l9.l.E5. !dd-, S.i Cirdr lvt J. tnl W*t*rrt a'39'1159.

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