Glass Transition Temperature & Crystallinity of

Polymers

6.1 GLASS TRANSITION TEMPERATURE

Introduction: The glass transition temperature (Tg) of a non crystalline material is
the critical temperature at which the material changes its behaviour from being ' glassy'
to being rubbery Glassy in this context means hard and brittle while rubbery means
elastic and flexible.
An ordinary rubber ball if cooled below - 70°C becomes so hard and brittle so it
will break into pieces like a glass ball falling on a hard surface. It is because of that
there is a temperature boundary for almost all amorphous polymers and several
crystalline polymers only above which the substances remain soft, flexible and rubbery
& below becomes has brittle and glassy.
Therefore the temperature below which a polymer is hard and above is soft, rubbery
and flexible is called glass transition temperature (Tg). The brittle hard state is known
as glassy state and soft, flexible, rubbery state is known as viscoelastic state.
On further heating, the polymer (If it is uncrosslinked) becomes a highly viscous
liquid and starts flowing, this state is known as viscofluid state, the transition taking
place at its flow temperature Tf
I 1
I I
I I

Glassystate \I Rubber or Visco-elastistate \I Visco fluid state

I 1
I I
I
\ Tough plastics and rubbers
\ I
Polymer me ts
Brittle plastic I
I
I
I I
I I

T9 _ _ _ _ _ __ Tt
Temperature
(Glasstrasition (Flow temperature)
temperature)

Fig. 6.1: Change of state with temperature in polymeric material .

. phase changes (me\ts) into liquid phase is
A temperature whioh crystalline sohd
~allcd Tm.
 turc and
rne• uua ·- · •
.. n tempera
Table 1 Glass trans1t10 d polyrners Melting
of sclccte
Glass transition temperature Tm0c
rg°C ternperature
Polymer · 146
-125
Poly ethylene (H.D,P.E)
Polypropylene - 13 208
(a) Atnctic -8
(b) Isotactic
Polymethyl acrylate
3.
Potymethy/meth acrylate 105
4, 1(,()
(a) Atactic 38 >200
(b) Isotactic 105
(c) Syndiotactic -24
Polyethyl acrylate
341
5. 97
Polyacrylo nitrite 264
6. (f)
Polyethylene terephthalate 250
7. 50
Nylon6 270
8. 50
Nylon6,6 36
9. -73
10. Natural Rubber
43
11. Ethyl cellulose 3<X>
49- 478
12. Cellulose triacetate 700
53
Cellulose trinitrate 310
81
l3. Polyvinyl chloride
THE VALUE OF GLASS TRANSITION
6.2 FACTORS AFFECTING
TEMPERATURE (Tg)
A number of factors are affecting the value of Tg.
( 1) Branching and cross linking
(2) Plasticizers
(3) Molecular weight & molecular Structure
(4) Melting point
(5) Entropy and Enthalpy
(6) Polar groups
(7) Presence of Double bond in backbone
(8) Functionality
(I) Branching and Cross linking: The effect of branching and cross linking on
Tg can be explained in terms of free volume. Increase in alkyl chain length
results in high Tg values Exp. Increase in Tg has been observed with addition
of number of methylene units in side group chaiil cf phosphazene polymer.
~ lass , ransmition Temperature & Crystallinity of Polymers 81

(2) Plasticizers: On addttion of plasticizer to polymers plasticizer gets in between

the polyn'ler_chains a~d spaces them apart from each other increasing the free
vol~me. This results 1n poly1ner chains more easily. As a result the polymer
chains can more ar~u~d at _lower temperatures resulting in decrease of Tg of a
polymer. Exp: Plasttcizers includes, mtrobenzene, carbon disulphide, glycerine
etc.
(3) M olecular Weight and Molecular Structure: In case of straight chain
polymers. increase in molecular weight leads to decrease in chain end
concentration. This results in decreased free volume at end group region and
increase in Tg.
lnseration of bulky, inflexible side groups increases Tg of material due to
decrease in mobility. Exp: Poly-N-vinyl carbazole shows increased Tg due to
substitution of bulkies group.
(4) M elting point: Increase in melting point of polymer affect glass transition
temperature by following equations

Tg = .!.rm (for symmetrical polymers)

2
2
Tg = Tm (for unsymmetrical polymers)
3
(5) Entropy and E ntha lpy: The value of entropy for amorphous m aterial i s
h igh er a nd low for crystalline material. If the value of entropy is h i gh, then
value of Tg is also high.
(6) Polar groups: Presence of polar groups increases intermolecular for ces, inter
c h ain a ttraction and cohesion leading to decrease in free volu me r esu lting in
increase in Tg.
(7) Presence of Double bond in backbone : Presence of Double b ond in backb one
o f mol ecule decrease bond rotation leading to increase in free volume and
ultimately d ecrease in Tg.
(8) Functionality: M ono-functional aliphatic monomers due to high flexib ility
exhibit l ow Tg.

6.3 GLASS TRANSITION TEMPERATURE & MOLECULAR WEIGHT

T h e g lass tra n sitio n temperature of a polymer is influenced by its molecular weight,
at least upto aro und a valu e of 20,000.
6 .3.1 Mathematical Relation of Tg and Molecular Weight {M)
Two m a thematical rel ationship have been established between the two:

Tg - oo K
Tg ---
Mn
l l A
00
Tg Tg Mn
w h e re Tg 00
= Glass transition temperature at infinite molecular weight
K & A = Arbitrary constants.
 82 Fundamental of Polymer Science & Ti
echno1 GfSf
Og~ I
I

real

Molecular weight
around 20,000

Molecular weight -

Fig. 6.2: Plot showing effect of Molecular weight on Tg of polymers

The polymer chains made of thousands of monomeric units comprise .
. . Th b 1· several
segments each made of a few tens of monomenc umts. e mo a 1ty of chain se
' gm~~
influences the Tg.

Chain E
end Chain Chain
segment end
Fig. 6.3: Schmatic representation of a polymer chain showing chain ends and
segments
The segments that are away from the chain ends, have less restriction for motio
n.
For a given molecular weight of a polymer, a low molecular weight sample will
have more chain end segments than a high molecular weight sample. The presenceof
larger the number of chain segments, responsible for longer effective segmental motion
Therefore, the Tg value is lower for low molecular weight polymers. ·

6.4 GLASS TRANSITION TEMPERATURE AND MELTING POINT

On Basic considerations, that factors affecting Tg will also effect Tm (Melting point).
So based on experimental observation, Tg and Tm (in degrees Kelvin), have been
shown to be as follows
(a) For Symmetrical polymers
I
Tg == -Tm ...(1)
2
(b) For unsymmetrical polymers

Tg ==
2
-Tm ...(2)
I
3
However, both the above equations are not universal relations. In the case of man)
polymers it shows deviations. A combined equation with the help ofabove two equations
(I) & (2) irrespective of molecular symmetry is

I Tg 2
< -<- ...Ol
2 Tm 3
 01855 Transmition Temperature & Crysta//inity of Polymers 83

This relation gives a range for Tg/Tm (rather than a sharp value) it may more
realistically reflect the thermal behaviour of polymers.

6_5 GLASS TRANSITION TEMPERATURE

The glass transition temperature is very important parameter of polymers.
1. 1t is helpful to measure the mechanical stress in polymer molecule.
2. Tg value decodes the behaviour of polymer.
J . It is also measure the flexibility in polymer molecule.
4. It gives an idea of the thermal expansion, heat capacity of polymer.
5. lt is important to note that polymers above their glass transition temperature
(Tg) will be soft and flexible and exhibit a delayed elastic response (visco
elasticity) whereas below their Tg it will be hard and brittle.
6. It is also helpful in choosing the right processing temperature.

6.6 HEAT DISTORTION TEMPERATURE

It is closely associated with glass transition temperature. Glass transition temperature
provides a temperature range over which a hard polymeric substance tends to become
soft under static conditions whereas the heat distortion temperature indicates the
temperature range over which the polymeric substance starts softening and gets
deformed due to influence of load.
In polymeric industries heat distortion temperature is more often used than glass
transition temperature as an empirical method of comparing the transition behaviour
of different polymers from the hard solid state to the soft viscous state. The heat
distortion temperature can be expressed as the narrow range of temperature over which
a standard test specimen at a standard rate of heating gets distorted to a fixed extent
under a given load. lt will be close to glass transition temperature for amorphous
polymers and Tm is close for crystalline polymers.

6. 7 DEGREE OF CRYSTALLINITY
Crystallization adds a lot of important properties in a material which are not present in
the amorphous polymers. Thus it is important to have crystalline polymers for different
Applications. The fraction of crystalline material in the polymer is called degree of
crystallinity.
However, since the boundary between "Crystalline" and amorphous is not well
defined, the degree of crystallinity is also a somewhat uncertain quantity. The degree
of crystallinity also depends on the method of measurement and it can be expressed as
a weight fraction Kw or a volume fraction Ky. Each of the two quantities can be
calculated from the other by a relation using the density of the total polymers, and the
density of the ideal crystalline state of the polymer pK Kw = Kw - pK/p.
Most calculations involving the degree of crystallinity of semicrystallinc
thermoplastics are based 011 a two phase model consisting of perfectly crystalline and
perfectly amorphous regions. This is a simplifying assumption because the various
lattice and other defects and the amorphous crystaline transition areas must account for
several percent of total volume.
ij4 ru11uc,l11 v ttL- · - · . ., .
• • •• - I v-.;11no1
Ogy
Because the dependence on structure and crystal fr>rn1, scn1i crystalline thermo , . .
· degree o t· crysta II 12,1
ex \[Link] t1·1ff'crcnt but typical . · t.1011. PIcl.\tic

by

Fig. 6.4: Schematic representation of a polymer matrix showing crystalline re .

(Fringed micelle model) 9ton
 , cRYSTALLISABILITY
6,8, all imi hi JI ty 1·, de fit 11;d 1,11 "Hi11 thema;,; imum i;1y .wllinity that a pr,I ymcr c~n 111,hii:ve
( I 1/~
1, 1 ·c,•l'tr tt;u1r11;r111Uu:. ·1✓hn1 1 ;'!';r the ot,rcr
L j' '
cono1t111n~of u;-,•,a,.,1a•1111r1.
' '
at i1 p,1 11 •, ,
,8,1 Effect of crystallinlty and Proporttos of Polymers
,6he pmpcrt ic:.,,f pol ymi;n, wlll b1; afleeted h; ,,, y ,t.1 llirut; ·, 1ch a I hardnc ,.,, pcrrm:ability,
1

1 ci1p:11,1ty, d1;r11,rly m11dul1m, etc. 'Jhe 1,1 J•,tallinity ~l·.c, depend upon th!: phy ical
hciit
,talc ,c, wlwthi:r 11 ~mnplc 1·, u ; •,t:11lim: t1111tc 1,1 i11norptr1,u·, [Link] will '--xhibit different
1
propcrticH even fr1,tlr tire 1,1:t1c ,,J <.ot11p1,und having wmc chemical compot,ition, Such
"' ilc11H1ly of' 111norplroll', 11:gi,,rr 1·, J,,11cr than cry1itallinc region. If we plot the graph
between natur:d ruhbcr of' d1f for1;nt c1y1,tllllinily valucn againbl Your1g', modulu•. The
gr1tph ir1 itiull y •,IJI rw J,, w v~ Iw; {rl uc u, :Im1,rph1,ubn»tw c of fl' ,JymcrJ itccply incrca<,e~
due to incrca•c of' lhc :rmou11t ,,t ,,ry•,t11llrm: evmp•,ncnt in the rubr,cr .ample.

% Gryt;talhn1/ -

Fig. 6.5: Plot chowln9 dopendence of loung's modulus on

Cry';tallinity in a sample of natural Rubber
crystall' . . · , c1f mcc·}1anrca
/\ comparison • of tw11 p1,lycthylcnc samples of different
· l propcrtrc~
inity is given below in Lab](.;~ I.
Mechanical properties · of two polyethylene samples of different crystaHinity n
 I \111\'1011''""'_, - · '
., ..

Sum,,h- \ S111111•h• n
lI ''" ('1 ~ ,tnllhw\ llllithl~ t ••~·111n111111.I
\)')\ I \)I)\' t) 1)\ l (l llM
\ \•nsit~·
l\a\\\n1.·:-,, ,h,,.11\' n ,I I ,o hh /\
I
l\·n,ik ,l\\'ll~lh \ w' p.1) ~\ \ I•I l I
\ I II
Fk•,m,1\ ~ h,,h,lus \ I0(\ l'11) IOOO l~SI

.... 11I1.• n is, 11\\ll\' 1.'I •\'Slt1ll11w

In th1.· u\\,,w sumpl 1.'s. .~11111 • Ill lllll\ll'l' 1h1111 '-,lltllph· I ,~ u
h,,th t\w ,.11npk, slhm d, ll1.'t\'l\t phys11.•t1I pn ip,·1lll.'S
t\h,h,\·ulm \h'l~~ht hns n gi1.·nt 1.'11~'1.'l llll :1 p11ly11wr's phys11.·nl prnpt 1l1l•s A IICI
\.'l1\'\'{ I.I.' \'Ill\\ lllt\l..'\I \,1•1·h... 1,,t'1.•,,..,t•llh1111v
,.. · ' · 11111I 111nk1.·11l111 ,wight 1111 phy~11.·11I propci1i1:,
is sl\ln, n hd,," m Ft~. 2.
I I
I
'I 'I
I
I 1lnrd tmlllu 'I Ihull, f:lr01111 81111
I
'I
'
I
I 'I
I

Non polymulc
'I
1--~
'
I

I
II
'
I
I Solt wuxy Ilrml, l>rllllu OI
I
I
lh11p, lloxlhlt,
I
I
I
'I
I

I
Nono I

, 1000 100 10,000 > 10,000

Fig. 6.6: Dopondonco of Physical Proportlos of Polyrnor on lholr C1yt,l,1llinlly ,111~
Moloculor wolghl
So1111.: of pm1wrt11.•s also nff1.·ct1.·d by nystall11111y surh as 1wn11l'llh1l1ty. II 1s 1kl'11ll'd
as th1.: Rah: Ill' pl'lldnllill11 nnd llw L'Xll.'nt ()r lk1u1d m vnpou, tlloli:l.'llks lh1 nugh lhl·
polymcnr 111:1tl.'n11I. Th1.· poly1111.·r rrystn II i11i I y dl'rrcasL'S, I hL· prrn IL'nhi Ii l y i11r1 L't1s1.·s Sn
th1.· Amorphous polym1.·rs a1\· 11101\· pl.'rnttabll.' th:1111.·1 ystnll111c p11ly11wrs.

SUMMARY
An 1mpmt:1111 rnnh:rinl propi.:rty olkn dis1..·11ssl.'d in s1.·111irn11llm·t111 p11l'k11gi11g l'llrks
1s th1.· glass trans1tw11 klllpl.'rntu1'l.', or simply Tg. lklmv 111\' somc k1.·y po111ls aho111
Tg:
• Thi.! [Link] transition lcmpcrah,rl.! (Tg) ol' 11 11011 l.!tystnllim· 111all'rial is thl' l'rtlll'al
11.'mpcraturl.! 111 whil'h thl.' material d11111gL'S 1ts hd111v1111 frm11 hl'in1i 'gl11ssy' 111
hl.'ing 'ruhlK•ty'. '( ilassy' in this l'nntcxt 11wnns hard a11d lmllk (n11d ll1rn•l'otc
n.:lallwly easy to brcnk), while 'ruhhl.'ry' 1111.•ans 1.·lastir 1111d lkx1hk.
• Note that llw c[Link]pt of Tl!, only appli1.·s tu nystnllme solids, whtrh 11n·
11011
st
mu ly cithl'r glasses nr ruhlK·rs. A 1,tlass is ddi1wd 11s a 11111tl'ri11I thnl lrns llll
Ion~~ 1'11IIHC utn111i_c or mok·rnlar onb· and ts hclow th1.· k111pn11tlll'l' al whtrh ti
1carn111gl'111L'llt ol tis atoms or mnkrulL•s L'llll llLTllr. ( ln llw otlwr hnnd, 11 111\ihl'I
is a non crystalline solid whusc 1110111s. or 111ok·l.·uk 11 rnt1 Ol'CIII. <)l1 till' olhl'1
hand, n 111hhL·r rs II non l'1yst11ll1111.• sulid whosl.' alonis 111• IIHlil'l'llll•s l'IIII 111k1 ~ll
rc11rrn11gcmcnt. 11
 1211·-----------~------------------------
i ansrnition Ternperature & Crystallinity of Polymers 87
Glass r
Non-crystalline solid are also known as 'amorphous materials'. Amorphous
' terials are materials that do not have their atoms or molecules arranged on
::attice that repeats periodically in space.
At room temperature, hammering a piece of glass will break it, while hammering
• a piece of rubber ~on 't. The r~bber would s_imply absor~ the energy b_y
omentarily deformmg or stretchmg. However, 1f the same piece of rubber 1s
:bmerged in liquid nitrogen (LN2), it will behave like brittle glass-easy to
:hatter with a hammer. This is because LN2-cooled rubber is below its Tg.
For all amorphous solids, whether glasses, organic polymers, or even metals,
• Tg is the critical temperature that separates their glassy and rubbery behaviors.
If a material is at a temperature below its Tg, large-scale molecular motion is
• not possible because the material is essentially frozen. If it is at a temperature
above its Tg, molecular motion on the scale of its repeat unit (such as a single
mer in a polymer) takes place, allowing it to be 'soft' or 'rubbery'.
, Since the definition of Tg involves atomic or molecular motion, time does have
an effect on its value, i.e., the mechanical behavior of an amorphous material
depends on how fast a load is applied to it. Simply put, the faster a load is
applied to a material at its Tg, the more glass-like its behavior would be because
its atoms or molecules are not given enough time to 'move.' Thus, even if an
amorphous material is at its Tg, it can break in a 'glass-like' fash:~n if the
loading rate applied to it is too high.
, In the semiconductor industry, knowledge of the Tg's of the various materials
used in packaging not only in optimizing manufacturing processes, but in
understanding the reliability implications of exposure of the products to thermo-
mechanical stresses as well.

CONCEPTUAL QUESTION
Q.1 What is the importance of melting and glass transmittion temperature for
polymers?
Ans. These parameters are important relative to the temperature range over which
a particular polymer may be utilized and proceed. The magnitude of Tm &
Tg increase with increasing chain stiffness; stiffness is enhanced by the
presence of chain double bonds and side groups that are either bulky or
polar. Molecular weight & degree of [Link] also affect Tm and Tg.
Q.2 When the crystallinity exist in a polymer.
Ans. When the parking of molecular chains is such as to produce an ordered
atomic arrangement, the condition of crystallinity is said to exist. In addition
to being entirely amorphuses, polymers may also exhibit varying degree of
crystallinity; i.e. crystalline regions are inter dispered with in amorphous
areas. Crystallinity is faciliated for polymers that are chemically simple &
that_have regular and symmetrical chain structures. The crystallinity of long
cham polymers is influenced by a number of factors e.g. chain length,
branching, presence of large random side groups and plasticizers.
 rs effecting T
g
✓
Molecular weight As the molecular weight increases, bulkiness increases and heocc T
increases. . t

2. Molecular structure
(a) Insertion of bulky inflexible side group increases T, because of decrease jn mobilitr,
(b) Increase in the length of the side chain, presence of double bond in the backbone of
polymeric chain decreases T g.
· · (c) Increase in cross-linking decreases mobility and increases Tg.
vPiastic~r Addition of plasticizer to the p~lymer help_s the polymeric chains to slicx: past
t ·_
·. ~ch other even at low temperature resulting m decrease m T,..
·: 4:· Water or moisture content Increase in moisture leads to increase in the formation of
·hydrogen bond with polymeric chain. This increases the distance between the palymeric
rf chains. The increase in free volume between polymeric chains results in the deer= in :r.-
i· 5. Cooling rate If the cooling rate of molten solid is higher, the T, is higher. Moreover, if the
rate of cooling is slower, then T g obtained is low.
6. Flexibility of polymer chain Polymers in which the polymeric chains are flexible hare low
T g, whereas those in which the chains do not move have high T g.
7. Branching Increased branching results in decreased mobility of the polymer chain and
increased chain rigidity results in high T.g

\Jmportance ofTg ~✓
.9 The Tg value gives information whether the polymer could be used as rubber or plastic. The
materials having low T are usually sticky in nature. Hence if the T of the material is increased by
~ddition of substance h;ving high Tg values then the'product wouIJ not be sticky. It becomes hard
~ and easy to process for industrial use. In glassy state, the substance is tough ar.d has good suength.
Glass transition temperature can be ~ed to modify physical properties of solids. By altering T
of the polymer or drug they can be maintained in an amorphous solid form at ambient or bod)~
temperature. Improvement in handling characteristics, solubility and reprod~cibility in dissolution
of solids can be achieved by increasing the T g of solids. •
 .. .l -- - - ·

-: "tyofpolymers V
~:jdcgree to which the molecules of a polymer are arranged in an ordered pattern with respect to
. .other is a measure of its cry~tallinity. Crystallinity has a vital role in determi!tlng the hardness,
\
1
,ea.l,µity, density, tensile strength, impact resistance, hea.t capacity and solubility of a polymer.
~ ct ,tlQ polymer is 100 percent crystalline. Higher the crystallitiity of the polymer, stronger
-A~ sec~ndary hond4ig and the polymer will be stronger and more brittle. Crystallinity of the

, .er increases as the molecular weight increases. An isotactic polymer has higher crystallinity.
~~u'9lecular bonding (example hydrogen bonding in Nylon and terylene) increases crystallinity.
\- . ;

()f polymer crystallinity on optical properties of the polymers

· .i : ~ orpho~ polymers are generally transparent. They have a constant refractive index throughout
1
•. :!~inaterial. In crystalline polymers, the refractive index arising out of difference in densities of
_ ~:,,;.. _talline regions is different. There will be light s~ttering and the polymer will be translucent.
..., rmetimes crystalline polymers are also transparent. If crystalline structures such as spherulices are
:/ 'aller than the wavelength of light, they will not interfere with the passage of light. As a result,
·. e polymer will appear transparent.
:~ect of pol~er crystallinity on permeability
~ L '
•'J?ftmeability is defined as the rate of penetration of liquid or gases through the polymer matrix. It
'ltepends on polymer crystallinity. Crystalline polymers ha,ve close packing and hence permeability
~ql,lite low. Amorphous polymers above glass transition temperarure have enough free volume
11?8. veen the molecules. Hence, liquids and gases pass through them making them permeable.
/e. beha~ /
-JGlass transition temperature (T ) is defined as the temperature below which an amorphous
;pplymer (sometimes crystalline po!yrner) becomes hard, brirtle and breaks like glass. Above this
,)imperature iLJSsoft, flexible and rubbery. (!::_h~d ahd the brittle state is called the glassy state I
' ~~~dom arrangement of polyrn.~ric chains is similar to the random molecular arrangemeO:t
· found in glass}IT:h_e soft, fle~ble st~te is th_e ~bbery or vis~oelas_tic state: <?n heating ~eyond_Tr; the
-/ -pplymer co~erts 1ntothe highly viscous h~id and starts flowing. This is called as viscoflU1d stat~
~l and the temperature at w}iich this occurs is called the flow temperature T f as explained in Fig. 6.1 S.
. ..:.'"'i

Glassy plastic Rubber state Viscofluid state

Brittle plastic Tough plastic and rubber molten polymer

Tg Tr Temperature

Figur~ 6.15 Thermal behavior of Polymers

Som~ polymers are used to above T g and some below. Hard plastics like polystyrene and poly
methylmethacrylate are used below T , i.e., in their glassy state. Rubbers, elastomers like polyisoprene,
polyisobutylene ure used above thei; T g' i.e., in their rubbery state when they are flexible. Some
polymers like polycarbonate, although amorphous, are considered tough at temperatures well
 3
82 • F11,:111rrri11g r'lm111ury: l·imdammtJth u11J Applirlltiom

. bonds in polycarbonatcs rather than the

below their T. 'l'hh behavior is l.>ec:1~c of the cl1enucaJ
anangemtnl <!f the polymeric chains. ) h of matter solid, Hquid and
•I•he ,bove phenomenon can be exp1ame• d oons,•derm
· g the. t ree
.dbstates they deoomposc before
g~,. I Polymers however cxi,i only in two phases solid and ltqui ccause ents have fr«don,
· I · b · · ·
r<ac ung 1"" o,lmg pomis. In a ong
I chaJ f
n po Y
I °
mer molecuJe, some segm
le is heated first there is [Link]
,
of 'M~en1ent wl,iJe 01hcrs do not. When such a polymer.".'olecu d then the whole molecule sran.,
molnlny of the polymeric segments (called segmental mobility), an d' tand· .
I . (molecular mobility; &cgmcmal mobility can be compared with the au l 1enc:c b·li
mov111g s · th1n
mg
11eor. posn,on
. . or stretching their orms whtle
. watch·mg a movie,. whereas molecu ar mota!1 ty tsbil· c
moving out of the audience during intermission or after the movie). When segmen f mlo .. ?
comes .mto play the solid polymer acquires a soft and rubbery state. With the onset o mo [Link]
[Link] the polymer changes into the liquid state.
Behavior of amoq,hou, polym~ an amorphous polymer, there is absence of long ":".ge
orde1 in the solid stat~. When such a solid [Link] the energy increases. The segmental mobility ,
tncrt-a.~es followed by increase in molecular mobility; hence, it changes into liquid form. During
O transition of an amorphous solid into liquid there is ~o change in the internal order of the
the
'.~ k-cul,r arra,_igemenicl<iiiolccu[c, arc randomly arran~ both in solid and liqwd •tatcsl(
there
"change only m rhe energy of mouo~ If such a I,qutd" cooled the absence oflong-r"."ge order,
which is a characteri.5tic of liquid phase, is retained. However, because of decrease 10 thermal '
energy rite molecule loses its ability to move and becomes immobile whitener or becomes solid
' i physically. I Jenee, [Link],sy sol'd is considered as a super-cooled liquid.0c low temperature, an
amorphous polymer docs not possess segmental or molecular mobility and exists as glassy solid.
On heaning g,..dually, it acquircs segmental mobiliiy and beoomc, rubbeiy. The temperature at
which die amo,phons polymer pmcs from glossy state co rubbeiy state is called the glo,s transition

'4
tcm pcm I nrc \ · On furiher heating, moleculo, mobiliiy sets in and the polymer passes inio liquid
~le and ~tarL5 flowing'. this is the flow poim temperature
Jehavior of [Link] polyme:-J
I
1. (A rrysialline polymer has long range order. All 1he aioms or molecules of the polymer occupy
'fu«d [Link] ion in rl,c crys,aJ. Tloe segments in crystalline polymer ore held by strong intermoleculai
forces; hence they do not J'OSSCSS scgmemal mobility. The energy required to oveioome these
imcrmolccu/ac forces is a/mos, equol 10 the energy required to induce molecular mobiliiy. Hence,
when a crys,alli ne polymer is heated scgmemal mobiliiy alone'cannot set in and hence the polymer
docs no, pass into rnbbe,y Slate and docs no1 possess , glass transi_,ion temperature. le clranges
T,b -
dirmly inio liquid Slate. The tempcrot~rc at which a crysialline polyiner changcs into liquid state
fa/allC'd the fl1clti11g temperature
J!chavior of scmicry~taJline polymer V
/'olym,·r.s ,re mostly patdally crystalli~c and coosiu of '.'?ii, amorphous ,; well 0, crystalline regions.
\nd, polymers hm l,oth glass traos,uon tcmpcraiurc l, a, well a, me/ling <cmperature T . Below
1T rl,c atnorphons >cJ;inn t>im in gli"Y sra1e and the crys1a!Hne region is in crysiallinesta;e. A, T
1,',. aruorpl,uns "ll'"n p,s,cs iruo rubl,cry siote, whereas drc crystalline rc-gion. re,nains crystalline'.
A, T,., c, ysr .rllinc region md" into , liqnid '1arc. Beyond T. rlr camorplrous and crystalline regions
bc.:co11JC• 011(.· :i11d the poly/lier a~ a whole is in liquid ~lalc.

&RJ9J~ Jj"9 k,Ql'\91.v.i~on:

2:... s~ uv-rAoJJ.', t-10 Pb~,~,.t,

 Table 4.3 Dec rva e of T with
lt'['!T',I U4J f-lcx1h1/1/y of S,r/(' Cfl11111••
fpr l'otymoth I ryJ1.1ta Sonas
Gonornllzud Formula H 1 11 (°C)
( II II' fl,\ lo~
I l:th~ I ,, '
( II
"P1"P"I 1,
( (I ,, hut,' ,I
I ,. 1,l \\I
1l
I 1/lllf}' 'fl
I{
" d, d,·l'\ I It

Effect of Symmetry of Tq
Polymer Repent Unit Tu("C)
Pol) prop) knc c II, c II I fl
I
( II l

( II.
I.
t 'II, lli 1()

I
CII,

/ 1J_y(\111_yl dilomlc) -C'll,-C 11- x·

1
(I

/ l'ol) (, 111~ hdcnl' d1lornk) < II

Cl
I

( '

II Relative Effecl5 of cis -lm11s Conftgurat1on on r<J

lrM:,.J
.:,__. _____..~-- Repeat Unit T9(°C)
Polymer
10~
l II

( 11
/

( II Xl ~~
l II < 'II
c~v
~~
, < II .
 Table 4.6 r 1/ocr of l'ut,111ty Oil

Repoat Unit
TI
Oiuloctric
Collf,tant at 1kHz
Tq(°C)
l "---
Polymer
l II < II
., ' ,' \0

1'11h·p111p\ k11,
I
l II,

~7
\ '\l)
l I\ < II
I'll\\'\\ Ill\ I ,h\11111kl I
l \

\01
( II
5~
Polv \~1y\i,n1tnh. < II
I
l l\

Table 4.7 Effvct of Potnnty on the T

~
of Some AE'.Ylfc pqfy_rners -
'
Polymer - ---
Repeat Value
- -

l II, (II
I
\ Il
I
()

\
I
,,,
\Oh
Polylill.'.rV\1t:: :u.: 11 \) \ \\ -\'l l -
I
\' ()
I
\)

I
\\

l \\ , -('\\- -400
1'0\y(1111c acry\at,•)
\
(

o I "'- () -
/11

- - ----
-"'...--,vv-polvmerization
"\),: ··\ran,1\1,111
l1 .
\<:ll1\1l'rll\llr,:s r ' L T '" .,1,:
·in\ ' . ' 11npor1ant h:chnolo .. I I
""I:".' . m'"'· ,,,1,mble "' "' "''" """'""'' '"'"' 1 '"''. '.'"..,'""''"' ,,r '"'''"'"· h i,
'""""' . ' ""'" """"'""k)'.'[y "'"' h,m I I . • . . . . '" I md,l"od,11 l OI "''h .,,"" Th.
I I m
I"Iy"''.' m,""Ii'"""" -"' "'I"'' yn;, "' """"'"'; ' ,;-'~; ,",."""' '"1'd Ihi, prnb km t" "'"" '";ot ~-,
· ,. ct s u1 sn..:c111..: end ust.:s. · " powcrtul
111
" ' Is Im 1.,' l11rn,, 111, \y"''""'' 1 .. , '' l e0d ,. I h,sc pn«dlltcY Im , bt.:1..L\tll<:
. .l
11
11

i ~ is cor~'Yl'l!l-'llitoJJem
lAj2,,V\ (9 ~
Copyn~h• 2000 by rnn,m 1.1., \ ~ \

U5?~~~~~ ~'(019~
CN\ 1~
 '"'- ''- •v:--· ~---· l . ·. . " . .. , I ' L'\" sta\ltne
th.: · Y·
mdnng pmm~ r'f'l~ff....~- . l Bl
,·,,1"'''l'1c1'l 11~c1\1,,(\
'-' " ' .... l • '
\•)1
'-
[Link]\\lll1''
::, . I •1 ' \ .·I •• 1y 11 •, 11111•·.... ••·l·l111'1t.\llC..,
,... I tn\.'.L' iatllt,
,ndtin\!. poinl 11h \mk .til.1tom..:try. ca\nrnndry. and th_c, Ille\ • n~i .~: "· '"

® .
dkkd- · . nuclca · magnd1c

'1/
.

.
r~:snnanLl'. )· 1 .• ·s r •h:,.,,·it1on· :HH1 l 1 \.Cp.

.
, s l\.S, \.

FACTORS AFFECTING THE CRYSTALLINE MELTING POINT' TM .

. \
L •

' .
lkarin!-!, in mind the peculiar nature ol polyinc1 s. me llllg Ill c · •
- · · l \. · • -·t , \ \ ,
pscudocqu1\ihnurn proo:s:-- thal ma) )Ct \.-.,1..:11 )t.:L )'.) cth· II cc ·
.._
•

Tyst ,llinc rolymu-..

. .
~('11.!.\ equall\lll
-·
..
l,\\l
h•· ..:nnsidcn:d a
'-

T = ~HIT l4 10)
"' ·' S tll
u.._

\n this cas . 6.l\ 111 rcprcsenb the difference in cohesive energies h.:twcen chains in the •'I') ,lallim: a,~J
liquid slat -s, wh1k 6.S 111 rcprescl'\i-; th~ d, tr ~rencc in 1h1.: lkgre(· of orckr between pol) n,:r ,uolc<.:uk" m
the two stmc.,. \Hm is gcnera\\y 11,t.,q)erHknl or 1he mokcular w..:ight. But. a::- would b...: C'<\'h:ct...:d. pola, _
groups on the c1 ain 1 particular\~- 1I dh 1 osed regu\ar1 1 on 1he , hain Sl) as to -:nt:nur· ~~ region..; ol
extensive cooperative br,ndin~ \'. ,lulu enhance 111.: magni1ui.k ol" J\Hm. L\S ,, UC\ l.'nd-. nol only on
molecular wcigh • bu\ abo on structural faclurs like chain st. ffncss. Chains that arc t1 vihl · in the mn\ll.'n
1

state vvou\d be c, pabk l)f assumin~ a rd~. iveh \.11,•..:r number of cunfon11ations than stiff chain.-, and
hence result in,\ \arg.c N::,. \\c no~~ discuss t .:,,.; 1:1cllll'S that affcd T, in grea\1.:r Jct,lil

ntermok'cular Rond\ng
eo~e~iv~~ fo;-:-es 111 ~o\yrne~·s i~Yoh c the secondary hondinl! forces ranl!ing fro,~ the weak ~ i,1 J.._ r
,.. dls to_1ccs th. "'ugh d,e much strong~r hvdrogcn hon~\s. \n some cases. these tor.._ . cvc11 mduJc
pnrnary 10111c b~,i~ds. ' 1gure 4.8 shows the ,ariation l)f \ ,., for a homl,'.ogous ,encs of ,[Link] type::- of
polymers. With p,'\vcthyknc as a reference and ncg\..:cting for the m1..1ment possible fine details in tr...:nds.
'NC observe that:
 ./~/
~ \ ~ - Effect of Intermolecular Bonding on T"'
Characteristic Group Melting Temperature (T mH°C)
Po\vmer

61

226
~ly,al)mlact,un tny\011 <~) ~

0 0 l-1 H

✓
.,/'ll'nly(h-.,xamcthykn-., adipam1d-,)
(nylon 6.h)
{~-- tcn 2 i 4 -~-t-tn\~\,-~t 265

0 H

i_~ - (CH~)'}:- ~
1
t - 179

600r-------,-------,-,--------,

500
oPo\ychloro-
t n tluoroethy\ene
400

fbly\ethylene adtpatel
• x
\·tl"l'Nfl isobuty\ ether}
Po\y\e thylene sebacate l
Po\y1sob7ty \ene ~ • Po\ysu\t1de rubber
300 °
Polychloroprene
Natura \ rubber
Diwiettiyl
LOO S1\tmnes•
/ • Symmetrical
o Unsym111etr1ca\
100~---- - - _._____ ___...L_•_C~o~n~d~e~n~s~a~t~•o~n:.:.....J
100 200 300 400
Figure 4.9 Relation between Tm and T 9 for vDrious pof,,mers (From Bayer. R.F., J. Appl. Phys.. 25, 585, 1954
With permiss,on.)

ffect of Structure
ructural dcpendenc' of the crystalline melting temperature i.s es<eentiaHy the same ..s that for the
g I ransition t,'mper-,t~~The only diff..:rence is the effect of structural [Link], which has a profound
influence on cr)'lla',l1a1l~)' of a polymer. T g is virtually unaffected by structural regu\[Link]. from a
close examination of data for scmicrystallinc polymers it itas been established that the ratio T ~/Tm (K)
ranged from 0.5 to 0.75. The ratio is found to be closer to 0.5 m symmdrical polymers (.e.g .. polyethylene
and po\ybutadicne) and closer to 0.75 in unsymmetrical polymers lC.g .. polystyrene and polych\oro-
prenc). This behavior is shown in Figure 4.9.
,/

'-,/4 Chain Flexibility

- ~lymers '>'.1th l'l!!,id churns would be ..:-'-pected to ha'-<: high1..-r melting points than those •,.;th flexible
molecules. ·1 his i•, bccaus~·. l>n melting polymers\, ith ~ackbones have lo\\'cr conformational entropy
--~
l:hu11 ..._,, tlian tlio..,c \\ 11'1 fkx,bh: h 1ckbn11 ..,.\., ~
pn:-.~1ci.: or ).Ul;h ~Houp:..~ U •Ul.U (( (I<)) 111d h\
main chain. l11~cn1on of pol,11 1,!tnup ,111d r"ii1 ,..,
~rr~(:Onfo1111at1011,tl change-. 111 th._ h 1d,h~1111: tr

Table 4.10 Effect or Cham Flox11J11tty to T

Polymer
Repent Unit T C)
../1'111\clh) lcnl{"\' .fl00 \,J~'--' t:J < II < II
Jl'ol)propyl.:nc
< II C 11
I

v;J . .,,""' ' "' "'"' C:

l'11h1p1,•pvh.:11c o:-.1<k1
flM;\,;~I
l H
< 11

< II ll

t II I)
I
< II

u
< II l) ( ll II

() l)

Pol) ( cth) knc tcrcphthalatc 1

- () l•HUt -0 (. r:::
I
u
Pol) (diphcnyl--L-4 <l1cth) icnc
-0 CHCII () (.
carho>..) lall.'J

✓,:",,I) carhonatc _,,-<jj,-e,,-, l I - 0

l 11

-,·11,-@-, 11,-

-, I

p._1Jv( o-mcthylstyrcnc)

\Oil I ,
- l 11,-( II -

'---.../
l'oly(m-mcthy btyrcncl -Cll - Cit -
::: I

<a~
lS~CII