6.1 Ing:robuottoo, - f3tEldiasr on blnarry alzturss of as@
aawoundt &re been 0A' oonsidso.&&a Ssltsmatr, For
e m p l e , t n Bhs idenfifiaa%lon or acsrsetreraa tlypes.
ulh.8 twsr wmto&war cara a x e d togsthrsc, usually $ha
&%*-a arPxrLbi) only $he nem%&o pkoraa, %Pgll, $he
ammuafio-IraroCmgia, trane1t;iiJn berarperertiwo aS audh M x w e r p
mrxiss linaarly w&th lrompebltlan ao sr &it& arppoxi~~slUa8, $43
2x11 au& sgatenrra, %ha dopan(2eneo o f tbs g~e1t;fnp: polat @ol
Qhs aolid oa %ha oorql;lor;tt)lon waa bo derriarihed bg the
&mAe+Van Z&w eguatlm. 9
fiow*ver, i n $ha rooenti gmt, n e w $;ygea of phsae
d l s r g l r ~ a h v e bean PouBcZ i t s bSnerrg m b & l ~ @ @ @f @@%I%
~ ~ ~ Z Q S F ~ M I . '*20 %t~bhea drtursas show me aaneetio A
@16~@e (a& B C U I Y ~ ~ ~ W B sr$?Par. l i~~)@~tSok~) i d , esofar rqrs o f oo~poriMonn (ras4lurs aonaenO~crf1 me) even r A a n naimer
Q E J - O O . ~ ~ 111 the p u n @tiate exhibit^) the eltu1aW0 A ghrse.
OenMalsag aus slrtteixtie11 to suah o*n 'inQuseb srnraolle A*
phma (or Andwad A g a h ~ * * ) ~ Oha MO 8raneai$iarr boutlory
ohiaxarste+ietla&lSr axWbfta a rou f o r or a e r ~ n
oomgoeibien wM6h 5, muol%y 50 slaaeP o f the aoaponents 6 .
S . S t i r now known M a t .hhs idlutred A phase is
oberal~ved i n o m 8 o o ~ o s t i f f cm ranee of the sll;xatrola wbw
one aP 4ho oari)onen0a hau, %ha stroagly polar @yam oa:
nlPlra and grwp wMZ+ We o t h r oaapownt bra no eu&
maup. 2hw Lntezaotlan* wtw@en ye-neat Bip~1. m w n t
o f jibe sts'm$Jy poY5s irrolealalts m a t h e XnBaocsdt dip&@
m w n 0 oC the we&Zy paJw raoXcsauZc ssgpem lsu be $war-b
far the aaswgeaae of &e SRduccadl .& pU#a. We nraootbae,
bowever, mntiilan %her% Daaron and 13;~~lard" a d ~ursnrh~"
have Sound $he Anduead A i r r . amat mp0dltt~~ Oran wfx@n
nei *er ooml;rwio~a$ ha# bhe wane o r nttro P*
Pmk 90 OX'' sw@aQad tbti Lseu~ed A phase is
i omrd by virtu, of nx a W & e trmofer intexaacrtion of tho
omponc)ntls o f o b J ~ w y ~ S x t u r e aontaiatng rsWawly ipoXar
a& wmrrkQ p a Z a ~ soZ~c~ul6s. f a szrgih *1x$wes, ahar,$e
em%^ oomrplex t~~mull i~a W o @ pboa between Che
me;ls@ulea of Oh* Bwo kintl6, the hd&lg p o u r a~mt3omat
~ o t f n $ a@ Bbe rPeo*lrt;sr while the o t b r ~mponemt mtl~
fLka ca donor. BvlBow* f a r @%oh an iatararabim ha@ been
XQ@ by riltebrw 4% 81'' who 64t(liaBbd 81f addltioml.
absorption bond nLth negrrfiva dZoh~oic4~1 i n tb@ ~ l @ i b b / ~ ~
Q , 6 . 1 ~ : Phase diagram of the binar systemr 4-n-pentyl- ttenyl-4 *ahe~>tyloxybenzoet~? (7.0. SY) 3 rl.-n-pt~ntyloxy- 4'-ayenobiphenyl ( 5 (IBP). (Reproduced from re f . 16)
Molar percentage of 7 C B
PIG. 6. I b r Phase diagram of mixturen of (2-hydroxy)p-ethoxy- ben~ylidene-pl-butylaniline (OH-EBBA) with 4'-n-heptyl- 4-cyannbiphanyl (7CB). (Reproduced from zef. 17).
sm;rsotnur of aaru aix.tiuraa axhibltirrg, thr iaduo6d A
p&aes. 3EhlP ilajrrxaefion ~ e s ~ 3 t i s La o prw~ng Satanal
atSrsacr8Scm batwrcn blrs J;wl Qgpw of w3@ouhs, en& Ln
turn m n load t a @ha Esrratisn o f a layoxsb
-ti eh~~1?w*barfsU;rso a f Pimaadito pbareerp.
rUll 8iraeucaaral i n Ch6 araeli6r csh~tara (I, X X X
and XV), tihe P pbea %xBibi$Qd by h i & Q po2u: cswounQa
wiXl br d f 81 bll~lgttr vaxicty, hare Zag@%? aperoiayt: b a i w
oona281ar&bly gsbkltao **a a6 aoXsoukar: ~ew%.~* BhSm
alruc)nrr@ ~ X % S Q Y &we to the rWaw arnBip~lrall61 aorre
latiions MbraQen the nri&bawb% aolsoulse aiP fcrsasimf
galax 0 0 ~ ~ n d s r X* binany m ~ t u r e @ a f euch ooa~poundrz
tri* wra~arleX,y palas! eonpournder, it iu found %a *an OEB.8.
tha: Ww bbXatragss amcMo Zm AaJdsralbla u f t k inbus@&
A p&sr2' ( f 1 g . t ~ ) . t i ma bizamr aez,Fraapoatr tc~ nrox~j
twa molcsauhr rerrlrt$hD (La., % ghar), o m grEs ta phaw
b f a m i t t ~ n Ezlw (B bilarw I p b o r f a a raoaahger A phase
( A ~ @and (as dimaurama i o ohgp$a~ x j.27
cbuEsa o l -bhs goXas [email protected] on om bawl, toad fhs @brae
jrmmta* aorpSrx folbrarrticus be Gvrrsn *he Owa tym@ o f
mcliteulee on %he o b b r brPB $a al&nUiorupf inkfura~ars on
thl phyeleal prope~tiarr o f Chr aisl$w*rp. Sar sxia~~ple,
Pwk eB a&'' have obewved s$rens panritiv~ drvhffom fn
pI0.6.2: Phase Eliagram o f mixtures 02 4-a-pelitylphenyl- 4 *-n-ootyloxybenaotlts (8.0.53 with N-p-eyanobetnaylidene- p I-n-octyloxyaniline (On0aA). (Reproduced from rmf .26).
the mJlw @Z dieleotrio arsi@ot*opy (he). A SOIW wwk
per #en$ of i l - ( p m s ~ a x p b a n s y l i ~ ~ n @ ) - p u n - b ~ ~ ~ ~ i U ~
(MBBA) an4 4-ayuuro-4*-7genty%bipMrqjS, {OFlI1] hsr ;Q a e
of 7.7 wbesaara icn ssllat;?le addiMVff raw fayglias or, value a i
9.8. 9Che i a temcb imr abbe aswe o b 8 @ @ ~ i n d@a~l&%iarrr
and *hatlLa 001~01ssllba Of thl O I X ~ \ ~ ~ U @ * "
ALB wa waw i n We pnarPouar ehaptur. mcaatic3-2iks
ahnrt raw* o&zrz t n the mbiw &nSlu.nclari, eon8uct%vity
aarootrapy $o a oonei8rrabLb3e 6tsbegs.t. Xicook &.ti arlE?' have
- w a n d thca el@rrPri@ralL. @ollSuo$ivitp erf %we 2k4atfB 6xy#Pml
#&ra$wea, @xhSbiWw iolXd%ed A p W s s . 2hda resulOar
ahow Waf as)n iua t lv i ty a 8 a ' f ; r e p j the &tw%~3, wnioh
i@ n a w t l v ~ aO Xa*rex aorra@nZretiom o f the po3.ar o ~ o a r l r r t ,
Sraoraaneks end p ~ s i t i v e with inor-iw QonedarpOrw
$ion aP gofax uerapsmmrb. S a g hav@ a%S&bu$e& bhSpr
t o %ha wawfw biilaycsr rlkru~ttture fhe pal&.r ooaponcnt,
the3 & Q V ~ dilt;ow#i~n i f i: alem tihat op@atf&a
raokwlar int~rssotiom ixrPTusnaa the pWs5aar3 p?opr$ieb
of Dhe a5*funsr omroide~ably. #. have a Wdied sevee8X
bt-g agltxtw@s wMkfoh ulxibi t the induced a ph@aro oz 81
w a a o gap betwwn A@ aond induaed phsse,.
avo omponemtie of B e mixZure ware ulri&tie&
aoourataly (ueiw spa ru%~hlaurea Perkin Ebmr )bodel A&&)
fnao en gZarwr dug prmid86 w i t h a ~ ~ u n d @US)@ i?utOpper.
me a x t w e VBB AeaO~4 t@ ?it143 tlraerap5a pbea a& Bzix84
thorowSailg by a~nrmioa2 %tit "~h.rn i t w a a ktapt in
Oh@ &~8rop lo ghaao fcrs a Sew bwm. @ w ; l e wm
%ha $ranraferar& on to a slide wM&e It waa la
lootrapfa gfiaillie. %tr tPhm&ntrioa t@ap@x~hxc~tdl w a r s date*
s&ned bg u a i w aa Hetr0hr bat-@tare8 (FP-92) fa eanjumtion
wiOh r whrlm- aiamercepe. !EM ras$e@ of hear@%* and
oooZing used for Chis p'ixlrp@&o w e ~.Z'/alaulrb. Flaisai.
txaxurltlam wore alrro ceof1rolard wlw di t l i i f e ~ s n t X ~ r
~lsdannbg caelo&lllsl%sr (Be~Um-r D&Eb;?). Ew* o i
QFsnaJ1 tian* p ~ l r varSow &&%%re# wars &SO detomfaald
4sw th. DBQ otubfea.
(5 ) p'-aitroplxanyl-pawaaOf 1.~ltg$ennwbe (81EJW)B) w i t h
t 2-~a~%y)-pl.tho~Ben~yJ,ide~~~-p~~brit ylr~nilfsu, (O&BIIBA)
a d (&A) p ' r s i - @ ~ Q & @ ~ p p c ) y ~ n O b i p b ~ y & ( 8 WB) with
p-bu~ojypha~l-(p~~porttyr6ry)be1~10*td, (4Q.09). 8 008
ww bzmgh* &am PQIIPgSBa-a &@he -6 u5.d ulthoul,
iur$hor purif io&bi~o. 4D.03 aM3 OIIImBA ware nynbh-
riasd ig our ehamlrrbrj SaboxaSwy rMia the %haOB elurrp3.e
woe )ainBXy @at to oar by Bxel. ~c f ;r .@lf fh ,
%he ahntakrral i'orxiube o f a l l %be aa.qparad@ are 4 h e a 1n f16.6.3.
pbuarars &&&warn of t h e ~ . aixhbufes fa rhoPm i n ti$, 6.4.
lgPOCtf'l ham aha a.trrow3.y pol= nfwo ow8 $COW rad rxhlbits
r pa~~%iaSly bilicml* A phatee w i * layes @wow 2', +iS2L, whem R ~s tha ra%eauler. ~ e w t h . 0 8 - ~ B A Bn~m
er&y a t;f@ phma~iar sye kai (~*RiBlt@ a pranourred
&srimrra la We &4t bapmdaxy, indll~nilllvs o f apn ln$uoed A
gh&a*+ B e malr i i a Pbe il.4 boundary i s obaraevad $OF
wdiw aonoentlra.fricau (d SUP PEP t h ~ ~ B f a r aamp~aan~.).
%!his with naerorat, rdlrlier obla*sratlons re@ ~ t g * ~ , la,&). 8-x O ~ C B ~ ~ A ~ A ~ R OUPV~ i~r a180 m x ~ & t l ~ l ~ a by tRa b-ES borndarn ada be men fzw t fw Murgara.
Plore ixlt/e~@rxtdw;lg, 'th# b,B ' b W s c y e s A i b i t ~ ta w a E
Mole percent of NPOOB
FIG. 6.4: Phase diagram o f mixtures of NPOOB with OH-EBBA (sys tern I ) . K stands f o r the crys ta l l ine phase.
briiaea mimimum for a aornyoaition rieh i a $hs B - 1 ~
p a @ aoaponant (~',?49 Q.C IOW0B)r $ha% the
fbp0~rrrrt;urs rangee s f oeslcllo%w% b a t m a 6h6 A and E,
B rnnd T phase@ are Perlsly narsew. PPw N g h s ~
proentrrges of 0SmBA (>74&)), $he ialrfwm arsrlzibier
~ n l y ttba lu p W e .
( i i ) 19ixburrrrs a$ 8 OOZI and 4Q.M --- m a 1 *- me
@we Qiawraar of $hh i%riil~~%oaia @hwa Sn iQ.Q.$$. B am hta $la@ sffowl31 poXac oyana, em3 (group while ncr euch
s$zoa@ly gobr esoup~l m e prraent; in 40.05. 8 QciB a&$-
bier, a pw$iorlXy b i l a y c ~ ~ & wk%h hyer sgaatn((t
cJ,O .4 k . !&A@ ag~lPl~ra cPZeo axMb50s a well 4aZineB rmxi-
mm ae weU a& a adaAxnu1~ An $hr A 4 treun~$tlea bounaery.
Em@% il~ i# ucrkhprhil. soapwinas aha g b r n &$amam o f
ily~tem BIB a& r f (Pligw,B.4 aria fi.S)* ~vaura the two dlagraroa
i% Am &em sht i n egtateaa i t , ths tsnilenoy $0 farm tlho
iaQu~tc& 4 pRwe i e meh aWoxig.1c dhdan &a @*Sera Z. Xn
the formr, bha d Naaa wit#$@ up? 50 o o q hi& tap~pratukux?ca@
and naw %he peak, i f t~bhnaiozai, diccletlZy tro eke ia ; ia~oyia
yhrislar. Qpl t h e o%er hw&, $he p e a i a r .t_haa Swluoed A-ti
bow&dlry ef: ~yalialn S i d auah lea@ ya?onwnosd and l ie@
wU. belw the &-I *~rtwttia& b ~ ~ n d a u r g r fhilp asam %he%
the ind;erwtiom respons ib le ' f i r act &&d?ao$&~#r cf .Wd A
phace asr.6 meir rstronger i n @x@%ul IX Wan &A a r y ~ t a ~ X.
Mole percent of 806R
BIG.6.5: Phase diagram of mixtures o f 8 OCB with 40.05 (system 11). K stands f o r the crystalline phase.
m a L probalg. a oomepurmoe of th. LPterar hydmrgl
group is C)&SB&. A8 B meaurB o f thir ozit3~rfiif~m4, We
arcrsmm ~~rucahian batwaeh Q*Nli,A ULQ IlrP06B oolcalrleo
i 8 Xfk@Zj f o be la*rqer th&arh %ha$ bofwron 4Q.05 an8 8 0GB
aolecaulee. "EBur $be a@u& a;l,nten*a.tilon ex$^ s%~ryomfb3e
for the lrndoorrd A phase fm aye war f t a 611P1021.~~ qhdifl i n
eycsdsm i f . Xn aystrra XI, bha m&aX~lua in $ko A43 bodurry
w o w @ $or a airture aoNirlniag d B ! $ $ o f EP O(W &&Zg me B Q ~ X S ~ I I 5a obtsimd Zw dl OQ~~QISISIOII SLBtir&$ cJ5tlC1Y;k 83 OCab.
POT 96TY high piBfQ@Xx6@((S.. @f IC)rOfS, th attxtu~et~ ahcw
an& t b s I@ pliraae.
b.mg*saturcl an4 a q o e l C i on ara lirtad i n W Gli. I .
we Piad that i n eyetern X1 the obseswd rand oabaabrd
w%l,uer of euteaESu tewer&$urare we suuaX while ti2
@-%em P I , the obb&@m@Q WTW @ff %hebie euttaaClrv fiemar- xabu~h i n r Lower SFia %ha ea30uhLsotertP rducs bg Bbolnt "PO. En bo&h the ~*uyar$war, fho ckrrPemed faallwa Qf wte@lrlc
aclnoeaCrotianro cf the polar ooullpmnrle (am23 a d 8 O@l
ase Xessl $&&a Oha rsorreaponopiq ca2au2utM ohuluba.
fPclnrllw 4evic;8tlom Leva bean feu?& i n rorlidlr i%%u&frre
on @pt.k,w rxhibLfiin(t iMuocrb A phaare. r7 m e wag arr?iee
ua h v q oae2ouli;atisd @M efttrswip o f W(B A 4 t w a f -
t i ~ a fmm J389 ewvaa. %'he rrrsuL%~fr wuee pr@asnW for
apvcsra X in flly.6.6. Zd &a SxcbemsUq G L ~ nete $hat, t h e
&&ape of Shi r owvr ira wary aSlPlibt ta tXlllC OX TAR, Q X k b
bieiag lo laruhrn for a oo~pprnirlo~ whfeh a&@@ exblblfe
tw wim An %ha firrive ~ O U M ~ Q . ihw~;tlrrr, the 4-48
0.rauaXtien f a olmoal aa~c\o& wc8er i n o h m c tfeir for hba
@oapori%tun aldzibitin@ tka aiaLrow~ i n ah@ glerrtle bcunaarry*
x very @i&ZSBr bxe& S1ZE IOU& D c ~ 8ysyatew IZ, Cnca @atropy
ot: A-SL brmtipiiaa xurew: W a mxhm hSng very eauelr larglox than the h i ~ f m a t Y&UQ 5P GYP tea P. XS i b X n t e l ~ ( b a U ~
to note that i n haw .tho r r y ~ tala, campeaai tionas e(~rr.- spending ~4 rn ol;entals in Gks 444 bouMnracss irtrvg
Mole percent of PJPOOB
PI@. 6.6: The entropy of the A-N t rans i t i on of crystem I as a function of compositicm.
gmhaz e 0.91. mi@ WCSQ iiii hi~hffar tbaan mt rayortrrsd by bhrs, PIQkafZaLan ~hewy,'' r;la*, 6 0,837 for
aeolpnd oflev H trarmitioars, %Irb oncae sagatn ol@u~J.y
shows that %ha int6~aationa rcraapunaibjre bar a 4 iwu~rad
saeatfc phase i t n r'Z a n swh %h~-h0~1(1
$a sjetsnli X I X t &@ anppropsS,ate %to stexlli~n Zbt
BuLlr eO &%I3' haare a.Ou82eb 2he M $=ml%iorn %n%h&lpy
or ia iunatisa ef ompwgtion in m d + % w c s a t EBBA md 14 0ts.
%he ;afix$aiure e%h4bite inBms& A plaareeb fax Q00pWitl~)XW
rangin& tmao nr %e# t a 60 & of B &)QIt. "Ehs heat cE t rm~lil-
$lw reanoh% a ranarir#raa valua for tb oomyroi:f t i o n arhioki
we have nuwurrd tlrcs %lraqcara%urca vwiuUerm@ o f
the ZIiryer rlpocaingrs i n the A i t @ r irnd o f tho @ m o t i o 34ke
ahwe s oraib~ i n Oha B pbt le @%@@a .Fie %@, IOI? vwSwue
a m m i t & ~ g i ? l a$ ay8tm6 X em3 XI. %he rbi:ulrx~ are @ham
i n Eiw, 6."Ptt 6.8, BePoTr dlscruiladw We rchznlra a f
our clxy@rlmn%s, w bxibflp teoiaU %he #&rXller werk by
BtnaeZarm, s t alZ6 i s h ~ M2wrvtt rrrllwwed t ;E lO ~ a x e z slpea62n& iarra or
fousrttSbn i?rP u~e~~wi&iatn Sn Y P ~ ~ A A ~ % G T @I 4-a-pexi :~pZph@w1-
4"mn.-o,2tyJoxybon-ti(4 (8.0.51 aru! %-pcy&na'5ernwI::d~)rw-
p~- lm~oeZylnxye~~st l la~ (m0aj~ ). The ILay~3r ~"~u@Anhf ySotOEOd
WePna* @soarpa;~ihien i n t&;hla aycXidtzu i@ ahwn i n f*,6*9.
FIG.6.7: Layer spacings of mixtures o f NPOOB with OH-EBBA as functicms of (TAN - T). Phe numbers against different symbola indicate the mole percentage of NPO (IB .
r-. ---.-.-.7...-.-..- - L D Q
o o a , o - = t - ' c ; c u . i & , 4- 5 c o r - w
I I I I 0 - CQ @ ; x u 4
0 0 cT)
X
><
x
x 0
0 X
e X
a 0
0, - X S -
0 @ X a
0 a @ X
0, cg X 4 e s" 0 X .~.. Q) -
0 B X
1. I 1 L - . A CJ Ln
0 o a l
PI
; 8 4 (U
; 5 3 al
4.4 9 (d
ol el 0 id4
- ~ 1 ' 5 1 0 .i
0 a * P I
0
$3 4 '2 k
- $ I - $33 a'
+k, 9"; id
a PO P) (d
!l rn CI R
0 if* CV C ; : a o
(U w g f ! a .rl 0 .al
rn &Z +r 2 R ' t!
Q il's 3z (dn a, 14- 6% .. co . \O
cs' m c.4
y UI 6 u ! m d s r
0
AB $lie, paraenwm P ~ X O&WA 2n $he nix lwe , $8 lmwaaed,
Bk.@ Jayi~lex t i h i a h are3 deamarsea olmorra l in.at~%y up Co
a'bou.t $a# ~ o U A . Whrn B h i a l S a ~ i 6 a ex&rapolmOad CO
11e t o %;ke maLeauZorr
Ienlgth a% GWQA L obtakmd. B\r$ &arlnrra]l
%ha% a n l;he moirtbure &a laom SO: (bi( BoQA %he
rgaoinlg l a b r ~ w a a *$Etita ~ k ~ ~ p l g r ~ p p ~ ~ ) @ ~ h i a ( $ B b PlSlOyar
vurlw of 611001 m 6h8 8.0.5 oawmbroltiarr, f a Qlronipxsed %o
seize. It Pa i n t w e ~ t t n l ~ , tro notlo@ &at the inklluarb
rnmuli~-acissaatfo * ~ & m i Z l o a allicw PIOX P c48polrStion
w i t l a 5O. l CLGQA. ZYroiadW atlrtlSlar trmdls am be a@50& era $ti@ $$a haas% a fuddr4 Lrg ua, %%pa vaxlatf urn oE layer
srp&aisgo with ctow+oaftf us are &how& Psi fi&,u,C. 811; (81128 6 , l l
als BX 0-011 x~bat lve tarq98mWre TAR - f r 2.5% fcr the
@yo teas I a& Xf re@@e@$Avdl>y. Bhd aOoJ~cular iea~%;karrr o f
bhar f e w ~owmlada~ saPaulra%etrcab unlw ::@fanif: madcl3ar arsr
24*0 ( I m B ) , 281.2 (@&=&A), 22*9 1 (@ OGS1) mrJ *
24.6 A (40.09). U$l .ng thesw &at;&, wa sw Chat t b layer
I
Z
-- I J-LL-LLL- 8.0.5 CBOOA
Mole fraction
pIG.6.9: Layer spacing p lot ted against compositf on for mixtures o f 8.0.5 and QBOOA. The spacings corre- spond t o the temperatures represented by a dashed l i n e i n f i g . 6 . 2 (Reproduced from reE.26).
FXG.6.10: Layer spacing (ti) and the r a t i o o f the layer spacing t o the molecular length ( d / l ) Plotted against composition f o r mixtures o f system I.
F10.6.11: Layer spacing (d) and the ratio af the 1.ayer
spacing t o the molecular length (d/k) plot ted aga ins t cornposiiion L o r inixtures of system I1
QoaPpaasnOi h m b o a snonoxwagrrr dm& P l t l ~ ~ s f ~peOL603
I x l mmmen% wAm marulba an lat;hrrx: bynbem. j6 Ckr%w-
baortiona a% ga-T 1 ;"?*5*cmhov B M b (di.4.) rra.tio vlxrjlee
nrmoa*Xy firom a wine namim2Xy Iaatns Wcus ona for -%#
waEd.y pobr a e R $ w n t %O d Ire3 i n *bhr oarm ab pure
RPOm in mgertsam I and Oo ~ 1 . 4 2 An %W @me o f s Oills i n
cryrsbsn 5%. 4M P raa;luft& oS grCIQ19 @bnB 8 OQB @ear. wZ%h
atrrXpt2isr msrrswaraenZle, 32,114
PPSnima Jln the ph;plll~o d h m a ;ta&io;sr%e t b t Aa ma A,
(5.a.. imhoad arrsarnf;i@) N a e m y urot: 'be atruaaraXky
Bm1%2ilblla ( i n solare owe@ 14 i c r iounb ahat tliha A* pnsue 26 arnd the 5nBua.d A ghnm ox% iar;liarrkblrr 1. Hwevepr, t;hr
aoaxiotenoo o f botrh We b&sohod@r m d ismrorroX%@uXar?
&peelea far [email protected]& nhMs -Qa dbe dntma, srj tradf-
oat& by a aarrkinuou8 v@x4ation i n PaQbioe @xms~PltP.
BW*F@ OU% aw PO@@ &bZbl* A4 I d l t ~ ~ g l k t $ t 4 X I .
wib &pgmfrttln er oolFm~~o&rion c;%,waJpoP18$n$ $14 tho ml.rn2mm
isr $he A 4 b s w u r y gr%koa a.$ Auhas f ~ i d a s . B3.a 44.x b:rour$h% out
crlsarslgr S n ffg.c",,l&!,. m t h . ~ ~ , %he aqtna.$.on trclsP%claan$
gnemmeio w 1 f A Srincsseaear (PE % w p ~ r . a h r ( ~ . far 4nx &v0n
Mole percent of NPOOB
PI0.6.12: The thermal. tlxpanslon ooeffiolent o f the layer spaclnga of mfxturea o f D1900B with OH-EE3EBBA at Ir,, - T 5 2.5".
oclmpw19toa ia tMla s%gim. On obbex hnrnd, swrh
a tmm4 16 ruaO very BQIB~&UOW l a 8y0Ci.m rZ * W
rt9xlbube P U S dl5iwraae i n 'lrghaviow batwwn ithe tun
ap t - t a the large dlifocsaoa fa m e o$l?eas#lr o f tho
In%moSeoulnr iatu#toofttoa* betwwa Qhe oaapoarrnbr ttl
t M 4wa orno&, Ae 4ilaour66d ear l ier , ah% i n b O ~ t 4 0 n
h d w ~ ( ~ ! n Q&8 b * ~ ~ l l & y paU8 6\ld wa&Q polar
moSaa;uIe.*a ii aekat iveu we& i n isga9aa X, w&n2r boauaao
of fhe larttertcl hydror~tJ. g m g ,1'8-=BA aa;L@@uks, wrd
psrhapa bPljt @Ugh%J;Y higbrr am istrraa95on mw%y
wlriah &ve@ r l a e $0 onbJipralaJ, c)arr*latiiam botneoa fwo
m l s a u h r , Oerreeqwntly, She
t q e r r a t u ~ r i m solsod, Ifirob2~ tit10 b$eraal s x ~ l a ~ r
ooeS5lcSe& US b y e x a p ~ ~ ~ l i f @ osn be (~amibex&Ze a6 w6
[email protected] i n uhptex ZEX i n ihe @%so @i 00aylsudla j&&
bulky l*tcrrorl t%$uenle, m4 &wthrt $he a6roolg5y
goleer-m&U g a k r wirs o m craatlg b~eal t up aXlow&ng
SWOB noJeo~Xes dre ~ Q X D a w e aatigaraU@l p S r s axid Otnsa
the Zhamal erpanerion omocriPPaSenO @&a Be vc*?p la;sr&%. XC
o m &&so be acbdl t h a t f o r aanpoarStlonar m a r PSalmw,
fhrsro oxr Wixw BIWm raQILeouX@a ;ror irswazlg QE-mBg wlcroule.
M t h e r , for t h e e oompoobtiaaa % and A* a t r w W a r
ooexdst arng tho A 4 4rcml0ioxl has a sr@en& or?der oharaeter.
&@ a ro@uZt, %hs %hemX emawioa QwQIIIQIJB~~ rirtairnd
l t ~ ~ p o . -Xu6 fsr g m o s &$ion aBom t~ tho .Ila;Enimm in the
phase PlounBwyr
(a) 9iW~io d i e f 6 ~ t r i 0 -- ~ t ~ n a P ~ b @
%he bewex~rrhwe ~NistA~n* OS $he grlWlpsaX
&ierfso*tslo romtents (a,, utdL ad) in Oh6 A oad I
phsrarea and sic i n tlPa im9ropic gfesrar ww8 waat%wed
Zoac +onrime @ye tern and am @hwn i n fim.Q.13 - 6.22.
Xa tM oasee cS puxe Pt , both e,, ma c,
ahow a daere~cae as OM rample $8 oacXsd aemsca Tm
I Wr t a w & a re ;in braad a(glec*n@at w i t h
slarlbicas maasulPs~(ent* era this o o ~ ? p o u a d , ~ ~ * ~ ' IWOB h a
PI mkXg flrdll order A 4 tzeura2'tion (Pig.bi.6) a d the
inarrsarre of &, , olad br@rascn, olt cA caa the aueqpla f a
5ooleL.d i a tha I ph.8. prob&&y rnaann that thgl w*i-
par&2e2 oocmh;slliw So no0 WaEy sucl* w i t h %mperrature
i n %ha A glPOilo aMj, $he v&~Iatiw a re ementt2a11y itetw-
ariaod by that o f tihe os%ent&tioml cxdox. 'Ehe ." t,, * 21, c *aSw iacrrmaer, vh$b tlsageratux@ Pn ma
PB phace, Pnsioslrtint~ boxr*mr@nai% demaa~a OP anti-
pwaU6L 6oerelation;o (u ascuawd in abpturrrr fXI an4
SV), & phs foqer~t;lPm 101 nrire6 i n the i~lotropfa
pkuasre, E ~ , , exhibtOa a bmad arariaaur, w i n Ctue $a a
deoreaiae in mtigarsr1le;E. ao8seLar;ionr, sti highar s w p e
=*we@. Xn Wo nrlxture ccn%ainiw 9rJ.ap BPWB, as tho
~)mgile ds aoobd, t,, doareasale lhiaighfZy aomsr Znaa
(.25&.6,14), atitam a broad iniaiaunr ma4 then inamauaea
aZigM1y l a the Zoc*rx barnpeatwe zmga QIP $he A pha#or
lpI0.6.13: Sow frequency dielectric constants (measured a t 1592 HZ) of NPOOB as functions of relative temperature. m e vertical arrow on the temperature axis indicate8 im.
BIG. 6.14 : Low irequency dielectric constants (measure8 a t 1592 H5) of a mixture o f 90.2 .inole per cent of RPOOB with 9.8 mole per cent of a-EBBA as functions of re lat ive temperature. The vertical arrow indicates Pa.
€ 1 1
22
20
-
-
90.2 -‘---T 9.8 % '10 OCiEBBA NPOOD
18 0
10
I!,
-
--
- E
G IS
s-- v - - -- - -+-- CL -*--- v--
e* rolaatm pxaaticafiy aoaraerpnti i n tlls A pha*ct.
2 a(laln laareewer with fi
whiah i r &as t t a a deotwrr i n anDfpw~tlr1, m~ra la$ iom.
91rmi9ar .tixea&a a re obrsarvrd in t;&Q ~ ~ 6 r s r k x z l . vari*#cn
of 6+, Jn the s%x$wre oantialxping 76.88 #Par38 (fa.&. 19).
?4& B M B (oorm@~;~ondlw $0 %tibe ~ i n f e u a i n .the A-IBt
bouMharrg)Cffg.B116), 7 2 k r m (fis.8.17) a d 67$1POo]i
(il i&.Q,S&). &a% it flnc imQ.*rerstltag t o note tha t fos
D%uarrr mtrtkre* e+ inarernaw wi%h deoraaao of trartpcrraaurr in
-hhs A pbaarr. %?Mipi o m ba eass31gr undurautcob i n terff5 sf
the tmllslssr I n tb swrbe~ (1S atsong2y pobr?lwe&ly g o h r
P I O ~ ( P O E ~ ~ l i l i ~ ~ ~ a t $he gxpenoe 09 Use antSpa~knl2el
**<XI&%JP P Q ~ X BLQ36QUbE PIE@ * d$;dtU&w Cb8
Qharge-Drensfar oamplexca iil w e for&*, A t i s @Pear tbt
Bhe trMef9*"r% poSwla&iilty and bsnar re, erkruulOD inoreaae.
Aa ean br sewn lhroae 4hh d 9 ~ 0 ~ 1 l e . &a ds&rra oS @&ancb
m n t f n eI WZW) itte)rw#bs wZCb Xnomooiw %onoeatr@tiara.
o f Of2-SBg. Lehira waka i~rh~wrr ahob a w e auarbss o f
eOatpl@larr~ as* re-d Wk* ia@mslSs OE--A
maldaull*#. Pox &ear aawsliitf om 5 va2tae inwewear
ali@tXy as ths Qi@m~riatwa U1 l o w r a l in Che Bi aa8 d
p h o l r ~ , daasewss v%;eg 62&helg as the ts@oratura
is r a i e d I n We itrotropla itbllPIar "Eh8 aurrplllka peak.
olaeu'vadl i n #war TM w&aw i%m the start?% tmdeoy
of like dkrro.lot t o o~icsn* hamofrgyisrallg i n ZSrr A p b a e
BI0.6.15t Low freyuenoy dielectric constants (mauured at 1592 He) c f a niixtwrr of 76.8 mole 5 of NM)OB with 23.2 mole $ o f OH-EBBA as functions o f relat ive tempe- rature. The vertbal .arrow indiaatee Tm.
74 O/. N PO0 M -I-
26 "10 OHEBBA
FIG. 6 . I 6: L w frequency a i e l e c t r i c constants(mea~ured a t 1592 H Z ) of a mixture of 74 mole per c e n t of MPOOB w i t h 26 mole percent of OH-BBA as funct ions of r e l a t i v e tempe- ra ture . , The v e r t l c a l arrow i n d i c a t e s TAN.
72"Io NPOOB + 28 "10 OHEBBA
FIG. 6.17: Low frequency Bielectric constants (measured at 1592 IIZ) of a mixture o f 72 mole 7; of NPOOB with 28 mole % of OH-EBBA as functions of relat ive temperature. The vert ical arrow indicates Tm.
FIG.6.18: Low frequency diel.ectric oonslantt: (measured a t 1592 Ha) of a mixture of 67 mole b o f MFOOB wl-th 33 mole % of OH-EBBA as functio:le of re lat ive tempe:rature. 'Phe ver t i ca l arrow ia;~i.oates TAN .
r ~ r t w e e aowoaiuma)) i n the nemboipho& of
Zn aiatures biaouslaed sa far k ehwa a p o z i ~ v o
*mp a* %x. ~fowevcrx, w e ~ a t a u d e ~i the jurpp
beareaem with 1aQrrsxor of @%m;BA ooa@omst. Swh
j w a b v e beon abseplved tn uevwa2 earlier si$udrtar f6.97
wUeh are naw well Wemtood (as dieowa.d i n ahepter XV)
aa srisial3; i r a r a a dearerne An tihe mnber af arntiparallal
gta&s, Wi6b tihe r e s u l t tbt the sIf%clDlvta aontribu%ion
a t Ch, Qipolax w w p a 6 1 Me paJw aaolrraules t o tho
d io l aa t r i c EIonatanli i e enherwed.
Ere remulta far a BLIx%Ure 00nt$r;b&w 54,5$ WPOOB
ur)nicrh i r a crmp@s$S;2oa aePw %he IP&X~F$U@ i n %he ~'4.d barulbarr~r
&fa shown i n Pi&.6.19. %he %eaycrlral4ust3 $8 dcrcsreiured, a
vary smaS;e d$sreass@ Sn c,, orralue l a bbmnlbfved mar ta.
But r , show5 a lager jhung new !Em I'~stl% 8,. on8 e*
lnamaea with Bmra&as of %csmpcaratuco i n %Pas A p b e .
%64se rasa&t;e are nore prast~urcsaad An ra enixiSurlra c o n t @ U n g
44.6$ NPOWI9 wlaoh Pa even ~Zetsrrar %o %he -1- (fLg.6,20).
Par tM@ aorn@ocaiflan we we %a$.%% a ntrmg rduQt1an i n
a h , an& t, an ata asrrgrrce $.@ aoolad di4oacrci~l5 ktnro. "hb
m y bee atat.tffibuEeCt t o the dlat~% th% Ma haat csf A 4 Qmml- %%en l i a r qu i t e X w ~ e far Chi@ aoa2aai%Lcsn ( f . i g .b*b ) clad
eke rcaaar.i@n%atioa& iar&csfr pwmeb@s o m btr expsacEwd OB juplp
$a a higher value in the A ." IIhQ ~ ~ O ~ U W I C I in E,,
5 4 . 5 % NPOOB
4 5 . 5 '10 0HE;BWA
F30.6.1'3t Low freyucancy d i d . % C t r i 6 eonatants (mmeured at 1592 He) of a mixture of 54.5 mole 16 of NPOOB wiW 45.5 nole psrcent of OH-El3M a B
iuno tiona of relative temperature. !the,
vsrtioal arrow Pndlcatars TIUJ .
fIG.6.20: Low frequency d i e l e c t r i c cons t an t s (measured a t 1592 H1;) of a mixture of 44.6 mole 8 of NPOOB w i t h
55.4 mole $ of OH-EBBA as func t ions of r e l a t i v e tempe- r a t u r e . The v e r t i c a l arrow i n d i c a t e s TAN.
partirly aua, t o aca, imndeoay of tb 4iireotw t o prefer
hono?$*aarotr@ oligmraenb la thia oempwitioa Ewe . Wowetaat,
th6 @%rangy pour-wee-3 pelar rlwlsoulsx pa&@ atlouP4
Be very Xw(l* fax: theas oa~yoalt ioar , rhiek we aloee
50 the acaxikw i n the p1l)maare bouldarg, and %he g e m w n t
bIpaXe lnoawrnte o f the ir&it$$ural mleculae BeZon&ng t o
auczb paertrn fu l ly eanbribute te a ,, w n U k i n th. #me of
pulp#' oQ" an%Zliprnca1142 HPWB wliaioube Sn whiobr mwe Is
a : :4rtiaX wmarna~crtien of the dipel4 m m n t . ESUrtlbr,
Ihs ohrge lclrsa~nsf@r cowlex &sir@ illnomare with d e ( ~ r % a ~ e
cP tempomturn. Ikhucl to fld(Pma6~ crubstisaUa2ly as the
ciratt~m 'la! Zweead Sn ths A phmae. a& atao imxcrmrs w i t & jhglearaebr?@ o f t(~~1plauutwe rs aSready Qi trousrsed f o r
&he :?rp~cscl%loaa having & higher aonaen%r&*&oss. of BPOOB.
Fur %ll%at% oawesi0iaaa, (aXa@e ilo tkdo ~ X I M ~ I P i n the A 4
buundsry), na jurqg, is obsurvrrd ia ralw af THX. 2hLs
i n r t o tho r~l la t l teXy BI)B~U stunber of onatrprallbl
palre An tach CmpasaiUennr.
%%Oh itlltme~ 4e0zewe BP BtYOQka concen%t&f2ua
(30% BPOOB, .tig.b.24), the 4frm$otr; ob&&rner& Em %ha 44.611
I,PFQOB rir-re (pet T e ~ a pronrricmoed ~d w&@m Wdarblg tho
inrarsaae a l 6, W A ~ B l~ ru l r i ng o f aesapeZ&&tur@ beomem ~ 6 a k r
FI'I0.6.21: Low frequency die lectr ic cronatanta (masure8 a t 1592 ~ z ) of a mixture of 30 mole 6 of NPOOB with 70 mole yb of OH-EBBA a s functions o f re lat ive tempe- rature. The vert ical arrow indicates .
%!tie grXmipS dicllsa%rio constarm%@ o f OE-EBBA are
@hewn i n fig.B.22, Am o m bo men f r m the Eimplsrr
OR-mBA fbao l f hoe o eem2;ra9tva diealers%rfo maalrerstmpy,
as tb$ ne t dip@%@ isomnt o f %i% m ~ l c s t d a art&ea a lasgi?
&wm$ka wit ih t h e X0mr8[ mi&. rl iracrc9aa~os and a,, & e ~ ~ e a a @ e I,
wibh dtncrraae el: tsnpwatwxre. t sew4 ria deoraaars
almost linawlly wiiih i i ac raaa r~f tcbm~?~lra@~.. AX1
OhracPr fxendo @on be Wass tood i n tarmss 05 Bhe Wrsr
and Hoi@s's thwzy ((POI)@ e h a p t e ~ fY) ahl app2.fed .to a
a a ~ e u n d with n@&atiVQ A@.
2he 8iaXmt;xle enlrsa%roplbarc nf a U %be @ A % ~ ~ c ( B B ~
thtiit we have &a;udia@ nra osXJ.sates& fn 13L&:.6,2!9. TB b
quf te a l s a ~ t h a t t h e BrsrqjiarraLurc~ vns&% t ian BZ Aa;, i n
tho n phase i r s qui,t@ &ilbZsvcsrr2: Eor corapa8ltSnn~ o l m e
.he cthe c a i r n i m ~ ~ a , dn %ha 4% h~indbap:~ camp=@& t o t+aacf@
@Y.@eai¶ $8 %he mxtmw.
In sarngor;SCfom e l w e f e t ho rPinima, WL8 A-kl
O~waf tSon is war~k euaB hema the ameoflo ordor laareme61c
( ~ b the t e m ~ x a t u r e 26 Zowena la %ha A phase with a
corsa~gcn$fngb inorease i n Ula dipolerr aorrala%%an fraabor
i n the laycrrsd s t ruc tu re wh&h tend8 t o to . mrs WWM oaqaneaae fax xry lnwc~raaae i s t ,, dun t o
r.frram&or ahawe BrmrZer int%rr\ati 0x18 end henoa 6 ,, does
not PnerePurs weh a2 Zower C ~ W ~ I F U ~ U F ~ B . iS#no. AL
BIG.6.22: Low frequency dielectric oonetants (measured a t 1592 Hz) of OH-EBBA as functions of re lat ive tempe- rature.
TN I ----T
6.23: Dielectric imisotropies of mixtures of NPOOB with OH-EBBA as functions of relat ive temperature. The numbers against different symbols indicate mole peroentages of NPOOB and the arrows indicate TAN.
8eareascbar at lower Bsmp%rraturoe.
Sear the whtatuar % x i Dhe pbed boundmg (W.9&
8wet8 arr M.B$ PO^), tihe A 4 $rannai*iaxa h a a*roag
fisrrb order @naraelrax&~Ue@, m d &nosrras* tn tihe
ua$ipara%Zel d&alor assrelation oierabors would P e a %a
a wxw w l t r h r jump of e,, (iiip.6.1'3 dr ~ i g . 6 . Z O ) aart
$&a A-I3 $ra&xaartlass. The j u q la the arictntlatiar&
a&er pormta~r r~uld 2erad t o 8 de(~r(b~r$i(l l a EL aldro
at %hi@ ;,ufLnd, 3u+, ,a@ the ~ m e a c ardw f s afseaiay
i . Z TdavrS i'ku %i@~ar3 )rat t r u y rauali w&L% a &Ether
1av4a~ii?, 3: tim~@xnt;um. %Q i m m s a f n %he number o f
@ h u r @ ~ Urwaf@r paire: wrjulJ la&& %o 6413 Lnaran8Qt 09 a,,
due t e t N amra ~ f f e a t 4 v r canrrfbueisno o f RC9, d i y o b e C
ira mch , ~ l r r , sffeut q p a w s . t o be 8trongger than
tk.,,%: Pnarcsc s o f E, Q u ~ $0 %ha inosaaee i n tb $mn@vw~e
golurSet4bi2lt,y o f the @ohargcs tranr~fsx g d r s m d Aa
aebcqmlly $ns@$l~_&@ wi%h 4(IsaMcosiae af f;6niyb~abm. We
& l a d ;:@it$% auk fwa comlsuu~!X Setatweat (I) %he arfxture
u i t k 74," h,m n lawsr vallir o f Ab %an *a$ fioi
th6 iaf-cfusc w l t h 72% BPEIO'b in the 1 phacrcc @load t o 'Pat
(19) fC01001u~~e C F the 0pp081be variation o f ~ c r r ~ t h $ a p e -
roxt~ara in %la@ A p%nse of %ha mkxtures viOh 54.5 $ IPWB
oolaprrd %a ~dxturas, with higher x?.srcm$agea of lilPOOB,
ah aoffieleolaly low teaapom%~%~erli, $ha 4o-r M e
~e m h e s bhm aany r r l r b r e s c i the Ipi$Pex typcr.
Z t i r a l s o intecalartlw t o oo*paaa thr arrlasumd
m1ueB a t ac ond 5 of the ezix.ture0 wiPh the aozlx!e-
~ p p o n w nmbem ~a1~u;La tad en We barris o t lrrn a&&itive
l a w of fhla tgpe AS* * PI ncbl 4 P2 AS^, where Pl 1,
s o l e fratrtion o f tba fwret c~oaponont, e ta . gbi*
results sara d o r m i n fable 6.2.
Xb i r elear tht a~m~aa/48~ Ja - x f b n
unitj. ( I n a p e e m a t witti ~clonr, erer~ierr cbsclr*lntima1'~
anat lslorsatam with inexeaafw pereclmtagtr af CXH-BDBA.
!&As i s rpcinly be~murre ths pmbablllity sf brreaklng up
of aatf psrrs le 2 cacjaoiatdanr M0wiaan gtm)OB moleaulabl
inezvsure~r with inareomfalp peracrntaoes o f C)H-mBA rmolsoultass.
Qonasqueaf.ly, th. grw can azora egfeatLraly aonfri-
burbr t o t ,, . As oan he earrily area fropa tXra dfagrwr
6.13- 6.22, e,, of ntlxt;ursa ip muah hllmt an
addiDive l a w wcmld have given (Jusb1e 6.3)* 'Eh. a, m l u e
do@@ no$ al.we V Q E ~ muah beW\s.sn SPWB m d ON-=&& and
herrare does mot ~ofitribuit. such t o the Beda t ion o f Oh@
a b ~ ) ~ % zaf Lo &ma uait$fe ~rah @hew5 mjPUII wMah
are gxwcrtsr tha one by d 3 *2@ A
(Oomparleon af OralculrrrSFIa and observed vtnlwbs of e ,, cat lSgX - Ip = 5* for M ~ ~ O U S &%we8 61 Syu tw f
rc. 3
2084
a a ~ a
agd f6,SP 4O,OS of nysfea Xf wMah i s ololore to bhe
1Sirax&nw of Ghe bBI browi$ lm boundary. ILM xe@ulto
a l ~ ~ s h ~ a i m fit~ig.dr24 are b ~ i o a J y r a i a S h ~ t o
thosm fox tu olfkt3.a~ cpaapwftrlon o f lap4an X.
Pho dieleotsio disgerclti on wear meewed up t o
$9 . In fi@. 6,294.99, we have pls*lred the
dieZectrio lore rY, ar f ia~Pi ion of frwuenoy at d i f f r
and &%u drlrur+o w i t h
9.B& 26s am3 4i9.5P of EsH-mDI. llor dhr reZLxOuce aon-
talainglt 94.5$BPMB, ths m~~lkcwromnt8 i n 4th P atid A
pluarrsla are @how reparapte;lgr (figa.6*2& aura 6.29 rcrrrpeo-
tiue"ly),
BC al l *he aryatarrtrs @ k \ b k d i t h e ;pa& tsalur of
6 decnaaes w i * inaxe(OL10 @f %ewesotwo whtle t h r
m1axa-t;ien f;Fe.iurncg (iR) given by drhe aserxSDnra ral~, of
, inor@auear. The pw& m3w of kf', Booreaeeta relowly
with teaprraWm ta 4hr I ghrrse, rn8, mare segaitPly i n
We lt &wo, reaenfidlly r e f k c t i q g %he *orirflon of
aoLe-Qclcs pzot (t$, r e , a!, ) i n $he a w e of
HWOB Jw shwm i n i'ig.6.30 for a few teaopera%te@.
btXus Taw i r e i ~ u a w g p e r t of" the p h t Zie@ an a
BIG. 6.24; Tenperature variat ions of the low frequency d i e l e c t r i c constants of a mixture o f 63.5 mole 56 of 8 OCB with 36.5 mole 56 of 40.05 (measured at 1592 Hz). The arrow indicates TM.
I l3 I yk. 6 3 . 5 % 00CR- I -
'I 2
-. 3 6 . 5 ''0 11).05 ... '% . U, E,,
L. -+--. --..*,.-
11 - .
Frequency ( H z )
3'16.6.25: e;*, as a funct ion of frequency f o r NPOOB. The numbers against the eymbols indicate the temperatures i n O C .
Frequency ( Hz)
FIG.fi.26~ t?:; an a function o f freciuency for sr mixture o f 90.2 mole par canb of IPO[B and 9.8 mole per cent OK OW-EBBR.. The numbera against the bymbols; i n a i c a t e the temperatures i n .C.
. .. ~ ~~ ~ ~ ~~~~ ~~ -~~
NEMA1 IC .Sh fE(~ l ICA 74 "1, N P OOB
FIG.6.27: E:*, as a func t ion of frequency f o r a mixture of 74 mole $ of NPOOB with 26 mole % of OH-EBBA. The numbersagains t t h e symbols i n d i c a t e t h e tempe- r a t u r e s i n OC.
100 K 1000K 10,000 K Frequtzncy I Hz)
B16.6.28: Frequency dependence of c:; at; variow tesuperaturea (indicated aga ina t the symbols) i n the nematic phase of a mixture of 54.5 mole $ of NPWB with 4.5.5 mole yb of OH-EBBA.
Frequency i t-lz )
k'llD..6,29t Fxrrquency depenaence o f e# at variuus temp* ratciran (lmlfo ~&..ct;cd again8 t Blf far en% symbol@) In the nmectlc /i pha:ie, of a mlxaucts of' 54.5 mole % of N*GBR w1t.h 49.5 uols 6 oL' &i-mUA.
PIG.6,30: Cole-Cole p l o t for E,,- ela ax at ion in the oaae of NPOQB. The numbers shown against t h e various symbols i n d i c a t e the temperatures i n OC.
~ ~ J Q ~ C O ~ Q , O h r e are crbnoid.r&ble devfotZoB s1t
hi@az Irryubmies. P h i r r w u l t l ~ e i n yu J l t a M o e
agrrrwat with aa aarU%r ah5y on $&& appegotud by
Bafm cr* and tndfootera a hir&h%r fra~ueaap sslaxr
tioa. me latter ~ ' e m a t i o a p ~ d ~ i b l y br OW@
t o bh. hi* f l r e ~ u u r ~ ~ p rrhoulbw found I n W e e,,relrsrra%ion
af 7411 sad 7 Om by BuP:1 et iPl* ha@ b r a &WE&-
butiad by $!tea t~ @ p r s t i a l mwiea2aUm wiSRln ehor$
cazng:e ~urBar.8 glroups oulQ h t a r repcaauord i n a numerioal
oerlaulaeftsa oa the bsasia t3f ia aodel ~ 3 j : Brmfaan a63ti~11.~'
az~zrcthar gotarEbXe 0s3.gin fox? the rho\ll&ar Utt@ i n $he
l ibra t ica i i l &a4 reasllantrat;fsnal sotion o f the tsfutsr
vrraao digoXe aPamsnf oP the w%er g x ? ~ . This rr~lfaxatlan
fre.puenay lie@ ~BIQ ,-J 97 S%e aocrordinlif t o mlasamcl.e 3191.
'Phe h t t r r aontribulrtola cs~n be a%pected t o beeem more
il?por@nt whea the orieolatZansdZ or4dsr garaiea.ter ds@raasea,
an5 %Meed las oien be @@an i n E&,b.SO, the high ire~uttrrray
d@vlatiiane iran Ohe aualoXraullar p lo t a r e &me obvlcuar
st hf &her aaamperaWEurss.
ba de@@rdbrd in caEirjptcr IP, the re&arslt&on Clm
isi @$van bg the b$(rwtiot~ S~ m A %np(w/ltST) uhere
tM 1/2nfR, w m q + % i a %s t o t e1 ao%ivatlan ~~lergy
&ere a Zo We nttmaicr gatentilrl, e(l 1s 8br aotivr;rtim
rnex?r(jy due %kt ~ ~ B O O U ~ eifa'oata and A is er oom0ant.
gggvoa a Uvls Ska slope QE whish f e the arraSva8ian
encatg~r. A ploG 0f la SR vrr. far NPOOB irs given i n
fi#,B.31 and Wtu octiPaCion energJe6 l a A and I pkusces
The valugs braadly sllreo w i t h the@% oPtOak~Q by Batrr
ar t BLP* 34
Eke QoZff-CoPs plot Tmr @e aixetlre wlth 90.2%
BPOMt3 i a rahm Zn ifg.6.32. h a p a , +e~hua, i r ,
aaUg2gRtXg Zowrs B R m i n puPe PPmB ( S & B ~ . 6.'1K)jr IPh. Oola,tr-
Uole p l o t am be bettes fL.bted to asrsai@koXota at
hunpstraSures. But (110~iUwsbh beviotjlans are a m at
hl@;hcsr Cw.@erafwes ant4 at h&br irss&usaaiee. Tba
sotimtfctn eaexgg (Zig1.6.9?5) i n $he A ghaae doae not
elrango moh ooagaared to a t o f pus* (-beb.bla 6.4)
but; that; i n Ohe I @am ehawa e m Jn~~eklisl~,
&st OoXs-Cob pplaba, for Wa ~lfxture wilbh 74s
#POW arm @horn in fAg.6.34 and a m Broadly ~ r a a i p l i l l x !
f a tholire ol tile ~ ~ @ v i a u BBPflux81. Ilhu sa'tilvahtcja Prrurg
(fi&,,6,35) of the A phase A6 ~ I i g M l y M&%r $baa $hat
ef 90.2& a&%tu~rs, while *hat Par the H phaarc 16
oomidwabX~. In%a6idr tho #aktvalrion enar$y of the I
gaPuiaa -8 the &w,eLm&.we (SBJOle 6.4) ~ O P $hie ~ X ~ M X O
whjt& ctarxaagondil t o tb* aitti.mm la *e glns60 bs~nbart.
BIQ.6.31: Plot of in FR against 1/T! i n the uase of NPOOB where fR is t h e frequency corresponding t o st;, peak. The vertical arrow indicates (P@.
BI0.6.32: Gale-Cole plot for IS,, -relaxation i n the: case o f 90.2 mu1.e percent of HPOOB with 9.8 male 6 o f OH-BBA at three different t emperaturea i n 'C.
90.2" Io NPOOB 9.8 "lo 81dEBBA
3 i f ag:::altm:,:l f o r s aufx1;ura of ki
9b.2 ~ 0 1 0 ;it of ISPUOIl with %.& molr, ii, 02 ;II-BI3Ii.
The v e r t i c a l arrw indioatan PAN.
Pf* Wt-4, B.WarBaodn, 3B. bePOhnml and B Oaasparoux, J.&r FQ1. @, GJ+4Q (1979).
r f . $Won smB X. Jsnoarjr , in n8vanaaB i n Liquid QsyrfdU baaaroh and AJaplicraZbonc?a, EN. br $.a~~ar]E"ep.~pu~~on 0 X i 0 ~ d (JRBO) ~ 4 2 2 8 ,
ArJ *&e(pdbePDW, J.Ye&t~"s~e%, J *Pr&le-nt @.rS.&k?~~y and A,wosla;p, J, de Pm. a, f?b (19Tc31,
J 1 ~ l , a r a a ~ , msoi filer., a, &~o3 (*925).
100 80 60 4 0 20 Q Mole percent of N POOB
PI0.6.48: Composition-dependence of the re la t ive croe.8 over temperatures o f the conducti- v i t i e s o f mixtures of HPOOB w i t h aA-EBBA
boundimy, aatysoisarlly rzO lwsr tsmperatwes ( w e ZabZe
6.5). 99h iaaB fht the A-8 1I1Pawition i t s r a w vssk fir 'kb eompoaiM@a ~orr@*;golrdiw %o tb asliniaun% in the A-l4
Bclun&cnsy ronld blsao~ro ~kronger on eibhtx bAr12~ of thiia
a@aposAti~a l t a rmalJloctaS in the @ro@a aer te~twaturcrs
(ti!%) OEf the conduotirltgr adnaotrcjgr. Ae @sen tn
fia.6.2r%, - 2&a shows a rftr~aw p ~ a k fas Wa colagc
lpE t l o o e@1~msgondl~ q140g ( i h ~ aPntre\sr& irn the, A 4 bounctary,
&$me the crmobicr Ulsa rrhmh ~oitm&e wber ilucdt.uetians
eura vary straw 2n fbir, Baa. eve13 rjt ts*rpora0uuce@ fw
FIG. 6.478 The ratio8 o f the principal oonauctlvi t i e s
uR a,,/uA o f various mixture5 of NPOOB with OH-EBBA aa functions of! r e l a t i v e temperatuzc. The first number srgulnc t each ~yrnbol. ie the mole peraerit;+;s of NEOGU and the second number the moan s p e c i f i c conductivity
9 x 10 (oh. cat)-' at 76"U. The ~ P - C O W @ iNl ioate TM.
~rainly beoau*. of t he peuliarr m g s 0 f eha *..H boum3or~.
dlurtthcrr, r a mntloaed 113 ekrpter V, oR dsm&rs on fhe
arstuss and osncbur&.ser$lltan of 1411a oooadwting fmpuxl t teatr
th* velw ~f oEZ $ e ~ ~ ~ ) r a l l y @afw up S f %I& medi~1m h a
h&@ow o ~ ~ n b u r ~ ~ i v i f g ~ ~ ~ * ~ ~ BW erondiuatbg Smp~dhPaa
i n o w saraplea a re ~~nknorn, QM 221 f1&.6o47 wys W V ~
giosa tRo +&usa of %her meion apeoffie mn&uo%4fiiretty
rta4ist1, I! * (~*,/&)a" wwra L*/A 4blr rpfemtrke~l para-
maor of *he or32 urn b e ~ r a t a r d irm tkls moeurcob vn2ue
of the caqaoi$ame a%' $he mpty ask1 srnd l a OZ1$ aearourb&
aonduaCivi$y t P dha aadbua is i n t M Sarotrolplu gherar, o r .. a a (a,, + 2a,,)/rt tl SC i s fn $he Pd p h ~ e r X t is a h a r
thsrt BIQDB bat a anrah tnhi(sfier v d ~ e ei 5 a m OEt-mnA, tiho
sairtwera hating itam lnhrrme&S~ate ralurrcp.
Ma o m szranotliae, a fow fe&(bu~e*: (i) Undwebbarndly,
qR iaxlrr sore ahbsig3.y i n 8110 cssw where fhe A-H *ran*$-
t ian i a aZ $is@$ W o l r ahacbte$*r aolrmrad t n @he cmes
whcrrsa 1% b e a raoonB ordax ntPCura. (i l l) B O ~ a a d o range
of eclrrtlrooZtlw~ (baetwmn 76.rsP t o 44.6$ PPWE), aR verSlua
ahowe a broad ~lniaow st - T r? 32*cand @tart@ -*as- -. a@ hbe tharpca~ektux~ &a Zowe~*d f ur.thor, *I@ 28s probably
connaated wlth deox@e*s o f fa t o very lcw v~Pua@ fax?
7L O/o NPOOB + 26 '10 OWEBRA
FIG.6.45: 'fernperatore variations o f the prirmiperl conductivities of a ~ f x t u r e of 74 mole per cent of NROQB with 26 mole per cent of OX-EBBA. The vertical arrow indicates TAhi.
BIG. 6.44 r Temperature variations of We principal
conduct ivl t iee of NPOOB. The vertical ar8:row ind i- cates TM .
b~csonSag atir ire a few dspp~eeio &@ova a@ A@ t o
be expaabed 43b44 ( l o r an latrobuo4lan r n ~ 5dt~arnerlrion of
om1iatr m@mMlr oa ocnriluativtty asP;acples o s UauiQ
otgettallar, isee obg~tsa: V). A@ d5awatacsd Ln the psovioua
ahaptor, i n ir$e A pbrrae Iam~ 0an flow mom eorsfiy i n
$he plaraa 5 f the layer@ FIB- pw@fl(ti(t~Jar to tha
P ~ B ~ O I P . 1Eh.reiox6, the ooadurfAvlBy ga*gand$aulw te
$he Birwdor ( Q ~ ) f s @eaPttT thpa Oh* aanduotlvit&
w a l l e l $c CW d i r m t o r (a, ) An *he A p h w . a,, axh&b&ta, 'jump* a$ Q fox both 1S?OW (f&,B,44) at63
tihe Poi%&- wj;th M*QC 1A1P041) (15&.6*46), %his &@ 6 ~ ~ d
by the fa#$ tbt A-8 Braneibion hare a S i r r t order
@hwcahar fn both esasaos (f5~.6,&).. r3n the @$bas
W d , a*, lPorZlo slrerply up to In b.0 aaate ole fhe
mix$we with 74P 11$00B aanil -XI 181*10 off l n $he I 'Phase
(iig.B,45), ralaar the A 4 l i s m ~ i t i o n i r n Zhfs. o ~ a lr
ilraord of saoond mdar aWasateE, Ca OhQ o t b r ha%&,
a, ma?i a6 nrpoo%hly aoraelr gM far oXT the a ~ o @ i $ i o a
rs$urtied, Fkl@ dlfferencsa fa the vsrxSat1 oasr o f a,, ud
a, bar slremtg Wen disguardl i n ahap$ar Q i n t e m a of
Ohrr p e w a U o n proosealr due $Q .the iamrXa$ i n $ha A
p h @ e whioh aon%ributes tio e lowering o t o,, .
sat50 uR 6, , /'a, uu o h o ~ fo r a l l the rgtrtclaclri e a u a e q
a,, in t hc Y ~JIDM OQ@IQTO& %Q that in t he A p b n r
lea&# t o ta Lower reitlvartLan W I D P ~ i n Cha Sef$er
pk;r*rr.s a d (b) pearslue &af&usnlas a$! s a i ~ o l r o g l a
piaoLSnff @iZea.O6 h atre X $&@MI.
JCnt3e.d ia UpaGhs 2 , $he omnllsrQ &ifisranan
bntmea Ute aobivttbl~ln ener&gler of ths A a& N pha~sa
oemre Zor tihe nlxturn w l O h 74 mol. par om* bi IOh"801Fb
r~olLrrly brraelr rn Of ?ha &OW vdue 1'13 the IB &an@ s Ilru*ha% r
*a w e Rave ~ . * 8 earLi6r (I&& .G.X2), Wkbhin ainOzam k&a
$be asxilaw* %@emal ~Z~MIIW aotrff&ai.nQ QZ Zayar
apwroiq. Am we bbhiaeunrb i n ahspaor 1V, hi maah a
oarz *he axrlootXopin J J ~ ~ & L Q ~ BIB l e a s e i f e o t l r e kt
lmrrnix @he srafioRtXon anargg i n t he A plaaecr. This
ocu2.d a lno oon.trllpu%@ $a a reduoaiaa Sn tho diiiersnrsc
i m Ln*cltavrtSoa an*sgStt*a be$mr*n tZI. A snd W phssos of
thtra rix%wnr.
(r 1 dt&u&ivity Btudiasl *--*.. - _. . ...--_U
Tba priacrigrrl aondua%%vitlea (a,, and @a) W f
t t t ~ ~ s r~l9~0b~~:i'b;~ttve o ~ l i l p o ~ % t P m ~ B F ~ &awn i n fSlg.6.
b .44 1 lj .46. (~a l s haw naxawdrad, onn&cao.t;%wlx2t%ecoa i n 821
Phtr syabtaaarr aentioacsd earAisr, buS w1.y t b c e m p n -
rnatotitve diaft.scuaa err& presents4 haze.)
wotirsrtion ereaw in fb B phaes i a S o m ~ t t
Pop the nrlxrwe omm~yorobiw t o tb asrlatsnuar i n fbs A-8
houn8&ry. &is, A@ pxo'bobLy a aomeawnoac. of marby
errconr?l urctep A& .Itm~riai+~&on Pn *irr Oarr (f&g.is,b). me
lf ghcrsa w 5 1 1 have awongt ewtloede lib ahor* rawer @rder
in thLs eats* wbicsh l e refX@obQn &a tihs law aa82tatlon
oea~@g of th t4 phlahrrrsa. 14 wa have dJLactueeed in ahaptsr X V,
loyer'$nan(8 3arabs Zo a Zewurfnqt of e~lca &aUva.f;iaa emrar.
w i f n a-r byi~teulnr uiauwse8 la crPLar@%r IV. thr
tac+s,fu uktfci~ (9aagg:Ier LR O ~ B O team 02a0 am lwsr la
Xtia A A,;pa@ t k ~ a in tihe h @harP~r usApia 01 %hi@
&phenan@n,rtcan himrf~ lpcaalg diutauesrad i s ohaptu: XV Sa terns o f
(a) a r~lctanG WB)S)~F~ of MwarLt8 mef &%w¶danliE pnatarding t o
trhiah the l W g @ ~ % @ ~ . p l t r C L t ~ ~ @ Y b l f i ~ $ & @ Q ~f Qw ~ P ~ Y u @ = $
mo%@auPas
oontsibtbu0c alaao~$ enfflrely ta the obomed BSels~trl~
rehma3ior o f *he pplx(iUl~"~t~. %hw th81 ~bflwtlQa inOx@dtfJO
ln the sroltZveacS~~ enas?@ of "U1. ratxd\ors cPaaparzaQ t o
ShaD o i pwib BLBJ?ae?B #howl& b6 a,tPrZbuted Oc the for~p~~pFien
pafre. %hi@ &n%em~%tcwt l a slwo m~poasstibt
far $ha Zarge mbw0Soa of %he rehsatlan ira~uanoy
ttlilekE in Clzrs aiaWzus (oar *able 6.5). Zn order %o
perrtkcipa%e In t&@ r s l ~ ~ a e i o n procsars, aars % W m maofeau;lla
haa ta ettMr aarrry 9hfiha QE-mBh aaoI@aal@ lttlt?~ +waxdch i t
tnw famed a noJ,~auSl3ht omf12@1; sr brgl+k &wlly Er D ~ P thar
@&re &3lur$he??, );4@ QaZcs-Oole ~ 1 0 % ~ 8hww .t'h& w.l; Lower
$rrrpora-tura@ thr minturars &&a%@ awy ILCPP~J f~o la r o
Ikbga rsXsJcxaS-iaa (Eig.B.36). 2 k ~ c 13% @hior$ r a q e ocdrnr
efbt?@$e fll 5WPClaB-QmBlb gaatca do n ~ t la84 t s mg tatlifl
tn the h i & Smquea~y P Q I J S ~ . & %PA Sempaa;e&kdrsd &4
lnesreoscpd, B@M BIFO~-P~WIJB p&a arc ame el wrd Zurlsnalyr,
the orlsnap.atianar2 ord@r @lxr~)a@C;c.~r dalarpitarrte thus
~l~-mtsmien%aclrn9a motion lo%ter vfb(lbXa 3n %b I&,, r.oaursmn* ant? the high ,he kuatmy h X i i a rwln
ao%iaeorbZa.
FI4.6.43: Plot of In fR ye. l / f in the cam of a mixture of 63.5 mole per cent o f Ei Om with 36.5 mole For oent o f 40.05, where fR is the Smquenoy oorresponaing t o e:', peak.
PIG.6.42: Plo t of in fR ve. I/IP i n the case o f 8 OCB, where fR i s the frequency corresponding t o E:; peak.
The ver t i ca l arrow indicates Tm .
sas-tiexr B1SpoL6 ~;aancPnP; &&i to tha $otI&l dLp~?ols laa~~ont
et2 the latoXeerule and @vea r i o r %o a h&br peak value.
LPha acaavo.kion ansrgbs aala~XerOefl frsm i n JiR Wsr. 1/%
p&c;%e (Ylgas.B,4.r? and 9,411) oaso l l r te8 in table 6.4 &ow with the ds%a o f sgstea 1. %ho saaLrati on enmrgy ig
the a p m o is rrsnrcrllex than in I phonn in B OQrB
&#o. Xa the am9 o f She x&ftlPe of 8 Oegl w-l* 448.03
(i1&,6,41) the 1301s-0oZe plo* ina o aeaioXrr~116 with
tb obn$re 1gln$ ora tao e:, ax%# P i y a* %@war *UD~D-
xrait~ra~. AIC bigXle~ b i t r ~ c r a t u ~ ~ ~ the o$nICw r.E thra e i r m
b r # ? o tier ~ Q Z W tber $2, oxie wbkela ~ ~ S Q P P ~ Q S P re1axa-
Won Snvo?lvdng a i;listrlbutlon o f reXuaLion %Ams. 4 1
Ia$@e&, pplot of 38 SH v~a t/T (i$gyl.lS14J) &ma no*
f ield s straight Zins lae La @&es rtdilass, bltO a 3fae
cumnd auoh %h&t $ha ~a%hfoaiotl&tn @te@r@ whie r du r~ 0.43 eY
rat tlrrj, Mshekt tawrxaltlrrsr in the A ghnas cmSllnuoualy
SI"PO@B 69.5 350.0 63 .S %3% 36.6 2050 51.9 1600 47 .a 1250 41 cQ PK)O
- - - - * - L - - + " _ * * W - - U - L - * _ - - -
% c s , a $ a ~ w ~ * W P ~ f r . ~ n w ObI-BBO 64.4 3a5a
63.0 27430 Q1.B 2IlOis sac % 21,a 51.6 0 5W 4'1.1 1 aso 4s 920
FIG. 6.41 : Cole-Cole plot f o r 8 ,, -relaxation in the caee of a mixture o f 67.5 mole $ of 8 OCB and 36.5 mole S& of 40.05. Centre of the semicircle corresponding, t o 20.7'C l i e s on the E:, ax i s while t h a t corre- sponding t o 78.8'C l i e s below the E,', a x i s .
FIQ.6.40: Cole-Cole p l o t s for &,-relaxation i n the case of 8 OCB a t 44.5'C ( o ) , 65.1 'C ( 0 )
and 70.7OC (x).
Frequency ( biz)
FIQ.6.39: st*, aa, ti funotion of frequency for cn mixture of 63.5 mole % of 8 OCB and 36.5 mole $ of 40.05. Ike numbers against the symbols indicate temperatures i n 'C.
Frequency (Hz)
FIQ.6.38: Frequency degenderlce of he, at various tam2e- ratures (inaicated againnt tha symbol^) in the case of 8 OCB.
FI0.6.57~ Plot of i n fR va. 1/!C i n the case o f a mixture of 54.5 mole $ of HPOOB an8 45.5 mole $ of OH-mBA, where fR 1s the relaxation frequency. The arrow indicates Tub
PIG.6.36: Oole-Cole plots for e,,-relaxation i n the aase o f 54.5 mole 8 of NPOOB with 45.5 mole % of OH-EBnA drawn a t ilif fcarent temnperaturss ('C) Indioated a ~ a i n a t tho symbols.
%he Oole-Box@ plat: i s r s atxhb.ur* with 54.38-
Wmm whiah I* lotr re 6r& %be oowoaS4ion aosr#rt?ya3lt8iw
t o *ho mr&im t n We 6-31 bowdarry i o a9barn in fig.b.36.
"Sh. 116 with la amlolnt le 1.. mu very a~:ooB iaakc%Oiw
$bra% a eir@a rcshxafhoa ahlurxatarimse the tr?rblag%E@&nw
lPhe Pmquanr~y o f tiha e:, psiak at r*, Ma i. d 248 KlXs far
the 54.9 $ Prixtuce while A t ik% d 900 &Hr $o;c pure IJWOB1,
"XYhQ aativatf on smlpgy Sa the A p h r o he@ LracsocloeB
o~intsidambly for %hi@. arlrf\u"e (IrLg.6.W. &&%a 6.4)
00~0g(?~rd ta %a$ pure irlPW.
%$38 @la%:. ~f &@I~at%10 lan@ (e?, ',l W ~ ? R ~ R tmyuanoy
for 8 @ad btc Axtnrra wZ$h YI?i.l)d aaX 43.05 one whcwn
Ln f i g @ . 6. M 6.39. 3Chc 6% ',@Qs vtalsle geniazally
&@orease@ w l e k imseees of %crm~srstws, axerept i n the
xaixtuxr. the @t peak &I% lonerell a f th artuppercrboled temp*
ruat;ur* a l 17.!JbC. We oannart rule out Zhe pbeatfbility of
ia partial ~ f ~ s l u l l i ~ a b f o n &ul?ing %ha experrfrult; i n %hie
~~~~ &@ 1 ~ ~ l @ X % a i a 3 n &QQNBIM~(~S (by;) [ @ @ f i ( ~ ~ ~ n & i ~ , %to
*ha pa& values of gwe 1 arf, mrious tsarpex?er%mcss ar*
ZJo.E.eb Is3 t a b i e 6.9. Gola-GaZs plate Ew them tyy8hg~11
am tabam in i&@.6,4Q w& 6,4t. Xa 8 Om, the @ole-
OaXe plats ~@k~fQPPafe@~ F%ae peak F a u e of 4*, i f r
d 5 . B ab tha kiowsttt; demarku&tur@ whhh i@ wBb lower that in BPOQB (9ag.6.30). %he lattmr crnatpm lkhe
BIG.6.35: Plot of in fR agaimt t / ! t for a mixture of 74 mole $ of HPOOB with 26 mole 46 of OH-EBBA. IWe vert ica l arrow indicates TdlJ .
A1PeiFrarris-iicrw@81R E.Eegdir, F.Bandr%ks~; era& W, l X . 4s Jeu, Yeas ~ J B , s, GI-93 (1975).