1

HA L POLYME
TRUNG TM NGHIN CU VT LIU POLYME
Ging vin: Nguyn Huy Tng
2
Polyme l g?
1820 Thomas Hancock pht hin ra rng khi nghin cao su chy tt hn, d
trn hp vi cht n v d to hnh.
1839 Charles Goodyear nhn thy tnh cht n hi ca cao su t nhin c
th tng ln, v dnh b loi b khi c un nng vi lu hunh - c
cp bng sng ch v lu ho cao su t nhin
1851 Nelson Goodyear (anh trai ca Charles) ng k sng ch khi lu ho
cao su t nhin vi mt lng ln lu hunh to thnh vt liu rt cng
(thng gi l cao su cng) ebonit hay vulcanit
Xenlulo nitrat (nitroxenlulo)
Christian Schonbein pht hin nm 1846, c dng ph bin lm thuc n.
ng dng quan trng hn ca Xenlulonitrat l lm cht do do c tnh cht
n hi, d tan trong dung mi thch hp v to hnh di tc dng ca nhit
v p sut. V d: hn hp ca Xenlulonitrat v long no lm phim chp nh
1892 t nhn to viscoza, mng xellofan
1910 nha Bakelit phenol-formadehyt (tc gi l Leo Baekeland) l polyme
tng hp hon ton c sn xut cng nghip v thng mi ho.
Cao su nhn to u tin c tng hp t 2,3 dimetyl butadien c trong
chin tranh th gii I.
3
Polyme l g?
S pht trin ca ngnh cng ngip polyme b hn ch v s hn ch hiu bit v bn cht ca
polyme. Cc nh khoa hc ch nhn bit c mt s tnh cht bt bnh thng ca polyme v nhn
chung h coi tnh cht ca polyme l tp hp ca nhng phn t nh hn.
Hermann Staudinger (1920) a ra mt s gi thuyt v nhng khi nim quan trng trong ngnh
khoa hc polyme:
Polyme c to bi nhng phn t rt ln l nhng chui nhng n v ho hc n gin lin
kt vi nhau bng lin kt cng ho tr
a ra khi nim i phn t m t polyme.
Cc thc nghim nghin cu v phng php tng hp, tnh cht, cu trc ca polyoxymetylen
v polystyren cho mt cn c vng chc v quan im i phn t.
Cc gi thuyt ca Staudinger c chng minh xa hn na bng nhng nghin cu tinh th
hc ca cc polyme t nhin Herman Mark, Kurt Meyer v cc cng trnh ca Wallace Carothers
v ch to polyamit v polysyren.
u thp k 1930 hu ht cc nh khoa hc u b thuyt phc v cu trc i phn t ca polyme.
Trong vng 20 nm sau, nhng cng trnh v polyme tng nhanh chng, S ra i tp ch Polymer
Science ng nhng cng trnh nghin cu khoa hc ca polyme v nhng khi nim c bn ca
ngnh khoa hc polyme.Nhng l thuyt v thc nghim ca Paul Flory ni bt trong giai on ny,
v ng nhn gii Nolben Ho hc 1974 v nhng ng gp lu di v quan trng ca ng trong
lnh vc khoa hc polyme. Nm 1953 Staudinger nhn gii Nobel v nhng cng trnh nghin cu
tin phong trong lnh vc ny.
Mt lng ln nhng polyme tng hp c thng mi ho nh: polystyren, poly(metyl
metacrylat), nylon 6,6, PE, PVC, .
Mt s lnh vc ng dng tin tin ca polyme:
Polyme chu nhit, chu oxy ha tt ng dng trong tu v tr
Nha k thut thay th cho kim loi
Polyme khng chy, gim ti thiu lng khi hoc hi c
Polyme phn hu sinh hc
Polyme ng dng trong sinh hc v d: ch t tiu, c quan ni tng nhn to
Polyme dn in
4
Polyme l g?
nh ngha
C H
H
H
H
C H
H
C
H
H
H
H
C H
H
C
H
H
C
H
H
H
H
CH
2
H H
n
metan etan propan
polyetylen
Polyme l hp cht cao phn t c cu to t rt nhiu nhm c cu
to ho hc ging nhau lp i lp li v chng ni vi nhau bng lin kt
ng ho tr.

Oligome polyme khi lng phn t thp (hp cht trung gian), cha
mang nhng c trng tnh cht nh polyme. S phn bit gia oligome v
polyme khng r rng, tuy nhin oligome khng c s thay i r rng vi
nhng tnh cht quan trng.

Monome l nhng phn t hu c n gin c cha lin kt kp (i hoc
ba) hoc c t nht hai nhm chc hot ng c kh nng phn ng vi nhau
to thnh polyme tham gia phn ng trng hp.
5
Polyme l g?
Mt xch c bn (repeating unit or monomeric unit): l
nhng phn lp i lp li trong mch polyme.

C CH
2
C
O
N
H
CH
2
O
N
H
4
6
C CH
2
C
O
N
H
CH
2
O
N
H
4
6
n
polystyren
Polyamit 6,6
C H H
2
C
C H H
2
C
C H H
2
C
C H H
2
C
n
6
Polyme l g?
Nhm cui (end groups) l nhm nguyn t c trng nm cui mch
polyme. Nhng oligome hot ng c cha nhm cui c kh nng tham gia
phn ng trng hp thng c dng tng hp copolyme v polyme
khng gian (v d: nha epoxy).

trng hp (P) (degree of polymerizaion) l s mt xch c bn trong
phn t polyme
M = M
o
.P
Trong : M
o
khi lng phn t ca mt xch c bn
M khi lng phn t ca polyme
Nhng phn t polyme ca mt polyme khng c cng chiu di hay khi
lng phn t khi nim: trng hp trung bnh
7
Polyme l g?
+Homopolyme l nhng polyme c to thnh t mt loi monome
Copolyme l polyme c to thnh t hai hay nhiu monome khc
nhau. Rt nhiu polyme tng hp c gi tr thng mi, v du: ABS, cao su
Buna-S,

S sp xp ca cc monome trn mch copolyme ph thuc vo
phng php v c ch tng hp. C th chia thnh cc loi sau (cc v
d sau trong trng hp copolyme c cha 2 loi mt xch c bn khc
nhau)
8
Polyme l g?
Copolyme u n
Copolyme khi
Copolyme ngu nhin
Copolyme ghp
9
Polyme l g?
10
Polyme l g?
11
Polyme l g?
12
Polyme l g?
13
Polyme l g?
Hnh dng phn t polyme
(a) mch thng
(b) mch nhnh
(c) mng li
(c) hnh sao
(d) hnh rng lc
(e) hnh thang
(e) hnh cy
(dendrimers and hyperbranched polymer)
14
Polyme l g?
Lin quan n s sp xp ca nguyn t v nhm th trong mch chnh
H
2
C
CH
R
H
2
C CH HC
R
CH
2
R
CH
2
CH
R
HC CH
2
R
n
H
2
C
CH
R
H
2
C CH
R
CH
2
CH
R
H
2
C CH n
R
u ni u
u ni ui
Nu xt v mt nhit ng hc v cu trc khng gian th cu trc u
ni ui chim a s, mc d a s polyme cha mt lng nh cu trc
u ni u.
Nu tng hp c hai dng cu trc u ni u v u ni ui
ring bit thi tnh cht ca 2 polyme khc nhau rt ln
V d: polyisobutylen (Malanga v Vogl 1983)
cu trc u ni u c Tm = 187
0
C
cu trc u ni ui ch kt tinh di p sut v Tm = 50
o
C
15
Polyme l g?
ng phn quang hc: khi c nguyn t cacbon bt i trong mch polyme
H
2
C C
R
n
H
H
2
C C
R
CH
2
C
R
H
2
C C
R
H H H
H
2
C C
R
H
H
2
C C
R
CH
2
C
H
H
2
C CH
R
H R H
CH
2
C
H
R
n
H
2
C C
R
H
H
2
C C
R
CH
2
C
H
H
2
C CH
H
H R R
CH
2
C
R
H
n
izotactic
syndiotatic
atatic
16
Polyme l g?
17
Polyme l g?
Phn loi polyme
a) Phn loi theo phng php tng hp
+ Polyme t nhin
+ Polyme trng hp
+ Polyme trng ngng

b) Phn loi theo cu to ho hc
+ Polyme mch cacbon
+ Polyme d mch: trong mch chnh ngoi nguyn t
cacbon cn c cc nguyn t khc nh O, N, S
H
2
C O
n
O CH
2
O C
O
CH
2
C
O
x y
n
C NH
O
CH
2
NH C O
O
CH
2
O
x y
n
Si O
R
R
n
polyoxymetylen
polyeste
polyuretan
polysiloxan
18
Polyme l g?
c) Phn loi theo tnh cht
polyme
elastome Polyme nhit do Polyme nhit
rn
Tinh th V nh hnh
d) Phn loi theo lnh vc ng dng: cht do, lp ph bo v,
sn, si, cao su, keo dn, polyme compozit,
19
Polyme l g?
Cch gi tn polyme
Cch gi n gin nht tn polyme = poly + tn ca
monome
V d: etylen polyetylen
Vinylclorua polyvinyl clorua

Polyme i t dn xut th 1 ln ca etylen c cha gc
vinyl CH2 = CH - gi l polyme vinylic
CH
2
CH
OH
n
CH
2
CH
F
n
polyvinylalcol
polyvinyl florua
20
Polyme l g?
Polyme i t dn xut nhm th 2 ln ca etylen c cha gc vinyliden
c tn gi: poly + vinyliden + tn nhm th
CH
2
C
n
CH
2
C
CN
n
polyvinyliden clorua
polyvinyliden xianua
CN
Cl
Cl
Polyme d mch: tip u ng poly ri n tn gi hp cht
V d: polyeste, polyamit, polyuretan
21
Polyme l g?
22
Polyme l g?
23
Polyme l g?
24
Polyme l g?

2
0
0
3

B
r
o
o
k
s
/
C
o
l
e
,

a

d
i
v
i
s
i
o
n

o
f

T
h
o
m
s
o
n

L
e
a
r
n
i
n
g
,

I
n
c
.


T
h
o
m
s
o
n

L
e
a
r
n
i
n
g

i
s

a

t
r
a
d
e
m
a
r
k

u
s
e
d

h
e
r
e
i
n

u
n
d
e
r

l
i
c
e
n
s
e
.

25
Polyme l g?
26
Polyme l g?
27
Polyme l g?
28
Polyme l g?
29
Polyme l g?
30
Polyme l g?
31
Polyme l g?
32
Polyme l g?
33
Polyme l g?
34
Polyme l g?
35
Polyme l g?
36
Polyme l g?
37
c im ca tnh cht vt l ca polyme
- Polyme ng thi c tnh cht ca vt th rn v lng.
- nht ca dung dch rt cao
- Kh nng polyme trng ln trong khi ha tan
- Kh nng th hin rt mnh tnh bt ng hng ca tnh cht
mm do ca polyme
38
mm do ca polyme
i + 1
i
|
u

S thay i hnh dng i phn
t polyme mch cacbon khi
quay quanh trc lin kt 2
nguyn t i v i+1. ( - gc ho
tr, u = 180
0
- , |- gc quay
quanh trc lin kt)

39
mm do ca polyme
Cis
Trans
40
mm do ca polyme
E
0

360
G
0
G
0

180
T
T
T
h

n
g

S thay i nng lng ca 1,2-
dicloetan khi mt phn phn t
quay so vi phn kia. Pha di l
cc hnh chiu phn t ng vi
cc gc quay |
Nng lng cn thit phn t
chuyn t mt v tr c th nng
nh nht sang v tr c th nng ln
nht gi l thm th nng quay ni
ti (E
0
).
V tr tng i ca cc nguyn t v
nhm nguyn t trong phn t c th thay
i c m khng c s ph v cc lin
kt ho hc, gi l hnh thi sp xp ca
phn t.
41
mm do ca polyme
Phn t phi
ph v tm thi
lin kt t
quay ri mi
khi phc li khi
quay xong.
V tr tng i ca cc nguyn
t v nhm nguyn t trong
phn t khng th thay i
c nu khng ph v cc
lin kt ho hc, gi l hnh
thi cu to ca phn t.

42
on l mt phn ca phn t polyme m v tr ca n trong khng gian
khng ph thuc vo v tr cc mt xch ln cn
Cc yu t xc nh mm do ca i phn t:
- Thm th nng quay: gi tr ca n ph thuc vo tng tc ni
phn t v gia cc phn t, ngha l vo thnh phn ha hc v
cu to mch.
+ Khi trong mch c cc nhm phn cc th mt s v tr
trong khng gian s khng c li v nng lng. Nh vy vic
chuyn sang cc v tr y s kh khn v phi vt qua cc hng
ro th nng ln.
+ Khi cc nhm phn cc i xng nhau qua mch chnh
th mc phn cc ca nhm b trit tiu v mch phn t s
mm do.
p o l y v i n y l i d e n c l o r u a p o l y v i n y l i d e n x i a n u a
C H
2
C
C N
n
C N
C H
2
C
n
C l
C l
43
Cc yu t xc nh mm do ca i phn t:
- Khi lng phn t: v l thuyt th khi lng phn t (hay di
phn t) khng nh hng n mm do ca mch v gi tr thm
th nng khng ph thuc vo di mch m do cu trc quyt
nh. Nhng khi mch di hn th s lng hnh thi sp xp tng
ln do cch mch phn t cng vn cun li c m khng
dng thng.
- Mt mng khng gian: s tng tc mnh gia cc phn t s
lm gim linh ng ca cc on nh ta thy trng hp cc
lin kt hydro trong polyamit. Cc lin kt ha hc bn vng gia cc
i phn t cn nh hng mnh hn n linh ng ca cc
on.
- Kch thc nhm th: cc nhm th c kch thc v trng lng
ln mch nhnh ca phn t polyme lm cn tr s quay ca mt
xch
- Nhit : c tc dng lm tng linh ng ng hc ca cc on
trong mch polyme
44
Hin tng hi phc ca polyme
Cc hin tng da trn s chuyn t trng thi khng cn bng sang trng
thi cn bng do kt qu s chuyn ng nhit ca cc phn t ng hc
c gi l cc hin tng hi phc.
n hi sau tc dng (s chy do)
t
1

Thi
gian
a
a
1
2
b
c
ktn
b
B
i

n

d

n
g

ng cong n hi sau tc dng.
1. Polyme mch thng
2. Polyme mch khng gian
c
ktn
bin dng d khng thun nghch

o=constant
o=constant
c
45
Hin tng hi phc ca polyme
Do mm do ca cc mch phn t, chuyn ng nhit trong cc mch
c thc hin bng cch thay i lin tc cc hnh thi sp xp. Lc ko bn
ngoi lm cc phn t cun trn b dui ra, v cng vi chng cc cu trc ngoi vi
phn t cng b thay i. Kt qu l bin dng mm cao xy ra. Nhng bin dng
mm cao cng c gii hn, n khng th pht trin n v cng, trong khi s dn
di ca mu trong mt s trng hp ko di hng thng, thm ch hng nm.
Khi thi gian tc dng lc ln, c tnh ca ng cong n hi sau tc
dng c thay i - n dn dn tin ti ng thng. iu ny ch ra s thit lp mt
qu trnh n nh. Qu trnh ny ch c th l chy, ngha l s pht trin ca bin
dng do khng thun nghch. Nu vo thi im t1 ngng tc dng lc ko, mu
s co li dn dn, tuy nhin n khng th tr li kch thc ban u; sau mt thi
gian no mu s khng co li na v vn cn di hn kch thc khi cha b
ko dn. Nh vy ta thy r bin dng chy khng thun nghch pht trin ng
thi vi bin dng mm cao thun nghch. Nguyn nhn pht trin bin dng khng
thun nghch nh sau: trong mu polyme v nh hnh mch thng b ko dn, sau
mt khong thi gian no s thit lp mt cn bng gia lc c hc c tc dng
ko dui cc cun i phn t v lm chng dch chuyn tng i vi nhau, vi
chuyn ng nhit c xu hng lm i phn t cun li. Kt qu l cc i phn
t dui ra mt phn bt u chuyn ng chm chp m khng thay i mc
cun trung bnh ca chng na - bt u qu trnh chy nht trong mu chu ng
sut.

46
Hin tng hi phc ca polyme
o=constant
o=constant
o=constant
47
Hin tng hi phc ca polyme
2
1
Thi gian

n
g

s
u

t
,

o
0

Hi phc ng sut
c =constant
0
o
c =constant
ng cong hi phc ng sut
1. Polyme mch thng
2. Polyme mch khng gian
Nu ko nhanh mt mu polyme v nh hnh mch thng n mt di no
th ng sut c hc cn thit gi cho di ny khng i s gim dn
theo thi gian.
48
Hin tng hi phc ca polyme
Hin tng ng sut trong mu gim l do nguyn nhn sau: khi mu b
ko nhanh, cu trc ca n khng kp thay i v cc i phn t khng th
ngay lp tc dui thng ra, cng khng th chuyn ng tng i vi
nhau.
V vy s ko dn xy ra khng nhng do cc i phn t hoc cc b dui
ra, m cn do bin dng cc gc ho tr hoc thay i khong cch gia cc
nguyn t trong phn t, ngha l theo kiu bin dng ca cc vt rn thp
phn t. S thay i ny i hi lc tc dng rt ln, ln hn nhiu so vi
lc cn thit ko dui i phn t ra.
Polyme b ko cng nhanh th cc on i phn t cng khng kp dui
thng hoc sp xp li, v ng sut trong mu cng mt dn di s
cng cao. Ta bit rng moun n hi , do tc bin dng cng
ln th mun n hi cng ln. Ni cch khc, khi tc ko mu tng ln
th mu c v nh cng hn.

c
o
d
d
M =
49
Hin tng hi phc ca polyme
trng thi ko cng, di tc dng ca chuyn ng nhit, trong mu dn
dn xy ra s sp xp li cc on. y l qu trnh t pht trin a mu
n mt trng thi cn bng mi ph hp vi iu kin bn ngoi. S sp
xp li cc on trc ht dn dn khi phc li cc khong cch nguyn
t v cc i lng gc ho tr ban u. iu ny xy ra c l do s
chuyn t t qua v s hnh thi sp xp, t cun cht n dui dn ra, ca
cc i phn t v cc b phn t. S bin dng cc lin kt (yu t nng
lng) c thay th dn bi s sp xp li ca cc n v ng hc, mt
hnh dng mi ca i phn t (yu t entropi). Qu trnh ny lm gim
mnh lc gi mu dn di cho trc. Khi thi gian tc dng ca ng
sut ln, do s cn tr ca lc ko ngy cng gim, chuyn ng nhit
(yu t entropi) bt u dn dn cun cc phn t dui thng li. Qu trnh
cun phn t li km theo s trt ca chng vi nhau, ngha l cc phn
t bt u dch chuyn khng thun nghch. y chnh l bin dng chy.
Kt qu l ng sut cn thit duy tr dn di ban u tip tc gim
xung. Hu qu ca tt c s sp xp li cu trc polyme k trn l hnh
dng mu thay i (khng thun nghch) ph hp vi dn di cho.

50
Hin tng hi phc ca polyme
Ni cch khc, do s sp xp li dn dn cc n v cu trc (cc on), cc
i phn t s cn chuyn dch chng no trong mu cn ng sut. Chng s
sp xp sao cho trong hnh dng mi do ngoi lc gy ra, mu s khng phi
chu ng sut, tc l trng thi cn bng mi. c trng sp xp phn t v
s phn b cc hnh thi sp xp ca chng trong mu ban u v mu
hi phc hon ton l ging ht nhau. Do c th khng nh rng do kt
qu ca qu trnh hi phc ng sut vt th polyme dng nh b "c chy"
t dng ny sang dng khc.
Nu mu polyme mch thng c tho ti trc khi hi phc hon ton, n
s co li mt phn, nhng khng hon ton. S khi phc hnh dng ban u
s hon ton hn nu nh trong thi gian tc dng lc cc qu trnh chy
nht t kp pht trin hn. Cng nh n hi sau tc dng, qu trnh hi phc
ng sut s pht trin cng nhanh nu nhit cng cao v tng tc gia
cc phn t cng yu.
51
Hin tng hi phc ca polyme
52
Xc nh trng thi vt l ca polyme
1
2
3
4
5
6
Cn Carghin-Sokolova
1. Cn; 2. i trng; 3. Thanh
hnh tr; 4. Mu polyme; 5.
n nh nhit; 6. H thng
quang hc o bin dng

T
g
T
m

III
II
I
c
T
I: Trng thi thy tinh
II: Trng thi mm cao
III: Trng thi chy nht
T
g
: Nhit ha thy tinh
T
m
: Nhit chy nht
53
Xc nh trng thi vt l ca polyme
Phng php c nhit xc nh trng thi vt l ca polyme do Carghin
v Sokolova xut, da trn dng c c t tn l cn Carghin-
Sokolova. trng thi ban u cc qu cn 2 cn bng vi trng lng ca
thanh hnh tr 3, do mu polyme 4 khng chu ti trng (nn). Khi ly bt
mt qu cn, ti trng nn ln mu polyme s tng tng ng. Ti trng
ny c duy tr trong mt thi gian c nh cho c th nghim. Khi mu
bin dng, cnh tay n ca cn s dch chuyn v s dch chuyn ny
c ghi li nh h thng quang hc 6. Sau khi ghi li bin dng thi
im kt thc khong thi gian chn, qu cn c t tr li v mu
polyme tr v trng thi khng ti. Tip tc a nhit ln vi vn tc gia
nhit khng i, php o bin dng nh trn c lp li nhit cao
hn. Kt qu cc php o cho ta ng cong ph thuc ca bin dng vo
nhit . ng cong ny c gi l ng cong c nhit.
54
Trng thi mm cao
T nm 1805 Gough v sau l Kelvin (1857) v Joule (1859) khi
nghin cu s bin dng ca cc mu cao su pht hin ra bn cht
entropy ca cc bin dng ny. iu ny th hin ch: a) Mu cao su ko
cng bi mt lc c nh s copolyme li khi b sy nng v b) mu cao su
to nhit khi b ko cng ra. Nhng quan st ny ph hp vi quan im cho
rng entropy ca cao su gim i khi b ko cng. Bin dng xy ra do thay i
cc hnh thi sp xp dn n phn t b ko di ra v tr nn km bn vng
hn. trng thi ny linh ng ca cc segment kh ln, do d bin dng
xy ra gn nh tc thi khi mu chu tc dng lc.

Bn cht nhit ng ca bin dng mm cao

Hy xt qu trnh bin dng n hi ni chung theo quan im cc nh
lut nhit ng hc. Theo nh lut th nht ca nhit ng hc, cng do h
thng sinh ra (-dA) bng s tng ni nng (dU) v nhit to ra (-dQ) - Du tr
ch hng ca i lng c xt l t h thng i ra.

55
Trng thi mm cao
-dA = dU - dQ

Trong cc qu trnh nhit ng hc thun nghch (bin dng n hi l mt
qu trnh nh vy), theo nh lut th hai ca nhit ng hc ta c:
dQ = TdS
dS - s thay i entropi

Nh vy -dA = dU - TdS

Cng c hc thc hin khi ko (hoc nn) vt th l
-dA =Fdl
trong : F - lc tc dng
dl - dn di ca vt th di tc dng ca lc F
Do : Fdl = dU TdS

Hay


T T
l
S
T
l
U
F
|
.
|

\
|
c
c

|
.
|

\
|
c
c
=
56
Trng thi mm cao
ng thc quan trng ny cho thy nguyn nhn chng li lc gy bin
dng n hi l s thay i ni nng v entropi ca vt th bin dng. T
rt ra kh nng c hai loi n hi - mt loi ch lin quan n s thay i ni
nng khi bin dng, loi khc ch lin quan vi s thay i entropi.
V d ca loi th nht l s n hi ca tinh th l tng, khi



Trong trng hp ny ton b cng ca lc ngoi c tiu th thay
i ni nng ca vt bin dng bng cch thay i nng lng tng tc
gia cc phn t v nguyn t (thay i gc ho tr v khong cch gia cc
nguyn t).
V d ca loi th hai l n hi ca cc kh l tng. Ta bit rng ni
nng ca cht kh l tng khng ph thuc vo th tch ca n, tc l



0 =
|
.
|

\
|
c
c
T
l
S
T
l
U
F
|
.
|

\
|
c
c
=
0 =
|
.
|

\
|
c
c
T
l
U
T
l
S
T F
|
.
|

\
|
c
c
=
57
Trng thi mm cao
Nh vy ton b cng bin dng cht kh bin thnh nhit. T phng trnh
trn nhn thy khi entropi gim xung.
i vi bin dng thun nghch v nhit ng ca cc elastome ngi ta
chng minh c c v l thuyt v thc nghim rng trong phm vi bin
dng ti 100-150% c th xc nh s khng ph thuc ca ni nng vo gi
tr bin dng vi chnh xc cao. V vy bin dng cn bng ng nhit
ca elastome cng tng t bin dng ca cht kh. C ngha l i vi
chng p dng c ng thc:


Khi elastome bin dng, ton b cng ca lc ngoi bin thnh nhit v
entropi ca elastome gim xung.
S gim entropi khi ko dn elastome c th gii thch d dng nu xut
pht t bn cht ca bin dng n hi elastic. Hnh thi sp xp c xc sut
ln nht ca mch phn t mm do l cun li. Khi ko dn elastome, cc
cun phn t b ko dui ra v ri vo hnh thi sp xp c xc sut nh
nht. Nh vy entropi s gim xung v n t l thun vi xc sut nhit
ng W ca h thng:
T
l
S
T F
|
.
|

\
|
c
c
=
58
Trng thi mm cao
S = klnW
(k - hng s Bolzmann)
Khi ngng ko, mu s t ng co li, ngha l tr v hnh thi sp xp vi
xc sut cao nht. Khi entropi s tng ln.

Bin dng mm cao ca cao su thc t:

Bin dng mm cao ca cao su thc t phc tp hn so vi cao su l tng
do cc nguyn nhn sau.

Bin dng ca cao su thc t lun lun c s thay i th tch (V = const).
iu ny c ngha l khong cch gia cc phn t trong h thng (mch,
segment v.v) cng thay i dn n ni nng thay i. c bit khi gi tr
bin dng kh ln, cao su t nhin v mt s cao su tng hp c th kt
tinh, do thay i ni nng cn bao gm c nhit to ra khi kt tinh.
59
Trng thi mm cao
Ngoi ra, khi gi tr bin dng ln, bn cht ca bin dng cng c s
thay i c bn. i vi cao su kt tinh, bin dng xy ra l do s dch
chuyn ca cc nguyn t hoc phn t ra khi v tr cn bng trong mng
tinh th (tng t bin dng mng tinh th thng thng). i vi cao su
khng kt tinh, cc mch phn t b ko dn ra ht c s ng x nh mt
vt th rn. Khi bin dng l do thay i cc d di lin kt v bin dng
gc ho tr (tng t cht rn thng thng). Trong c hai trng hp trn,
bn cht ca bin dng mm cao s chuyn dn sang c trng nng lng
ch khng cn thun tu c trng ng hc (entropy). Trn ng ph
thuc ng sut bin dng, modun n hi s tng mnh v ng cong s
dc hn.
o
c
ng ph thuc ng sut - bin dng ca cao su thc t
60
Trng thi thy tinh
Khi nhit thp s sp xp li cc phn t cht lng s khng xy ra,
trt t gn ca cc ht cht lng cng khng thay i. Khi s xy ra s
ng kt cht lng - s ho thu tinh (tt nhin nu nh khi lm lnh khng xy
ra s kt tinh do xut hin cc trt t sp xp xa). Nu tip tc lm lnh, cc
cu trc ca cht lng ho thu tinh cng khng th thay i theo nhit
c, d tc lm lnh rt nh. S ho thu tinh s d hnh dung hn nu
gi thit l trong qu trnh ny xut hin cc lin kt phn t c nh no
loi tr chuyn ng nhit ca cc phn t (v d s to thnh lin kt hydro
trong cht lng).

Cc c im chuyn ng nhit ca i phn t c nh hng r rt n
quy lut thu tinh ho polyme. i vi cht thp phn t, ch cn c nh mt
im bt k ca phn t l n mt kh nng chuyn ng nhit v
chuyn sang trng thi thu tinh. Nhng i vi cht cao phn t, c nh 1
im khng lm mt linh ng ca phn t. Mun lm mt linh ng
ca i phn t cn phi c nh tt c cc on ca n.
61
Trng thi thy tinh
Nh vy mun polyme chuyn sang trng thi thu tinh cn c mc
khu mch bi cc lin kt phn t ln v khong cch gia cc nt trong
mng khng gian bng hoc nh hn di ca on. di ca on cng
ln th s lng lin kt cn ho thu tinh cng nh. Ngc li, ho thu
tinh mt h thng c i phn t rt mm do cn c s lng lin kt rt ln,
iu ny ch thc hin c nhit thp. S xut hin mng lin kt gia
cc phn t rt c trng cho cc polyme c cc nhm chc phn cc (OH,
Cl, CN v.v...) trong mch phn t hoc mch nhnh. Cc polyme ny ngay
nhit thng cng nm trong trng thi thy tinh.

c im ca polyme trng thi thu tinh

Khi mt h thng i phn t ng c li thnh th thu tinh th trong
khng ch c ton cc phn t polyme kt b cht ch. l v s ho thu
tinh chnh l s c nh cc v tr sp xp tng h ngu nhin ca i phn
t c trng cho trng thi mm cao. Mc d th tch ring ca polyme thu
tinh nh hn ca polyme mm cao, n vn ln hn nhiu so vi gi tr tnh
ton cho cc mch phn t kt b cht ch hoc cho cc thu tinh thp phn
t. Nh vy thu tinh polyme c c trng bi mt " xp" no .
62
Trng thi thy tinh
i vi phn t kh cng, khi ho thu tinh cc on mch rt kh sp xp
li hoc dch chuyn, do phn t c kt b khng cht ch bng trng
hp polyme c mch mm do. xp do s km linh ng ca phn t gy
ra nh vy s th hin cng r khi phn t cng di, tc l khi khi lng phn
t cng ln.
" xp" trong kt b ca polyme thu tinh c nh hng n tnh cht
c hc ca chng. iu ny th hin trc ht l chng khng c gin.
gin - l s ph hoi ca mt vt di tc dng ca ngoi lc m trong
ch pht trin bin dng n hi theo nh lut Hook. Nu s ph hoi xy ra
km theo s thay i khng thun nghch ca cu trc th l ph hoi do
(s chy do). V bin dng Hook (l bin dng xy ra do thay i khong cch
nguyn t v bp mo gc ho tr) thng rt nh (khong 0,01 ~ 0,1%) nn
mt trong nhng du hiu ca ph hoi gin l km theo bin dng rt nh.
S tn ti kt b phn t xp trong polyme thu tinh v mt cht linh
ng, d rt nh, ca cc phn t cu trc lm cho chng c th bin dng rt
ln khi c tc ng ca ngoi lc. V vy, polyme thu tinh khng gin nh cc
ng ng thp phn t ca chng. Khi mm do ca i phn t rt ln,
mt kt b ca chng trong thu tinh khng khc my so vi mt kt b
ca cht thp phn t, c im khng gin ca trng thi thu tinh th hin rt
yu hoc c th khng th hin.
63
Trng thi thy tinh
III
II
I
c
o
b

o
c im th hai ca polyme thu tinh
l chng c kh nng bin dng rt ln
di tc dng ca ng sut rt ln.
Nu cho mt ti trng tng dn tc
dng ln mt mu polyme thu tinh th
giai on u dn di s nh, tng t
bin dng Hook ca vt rn.
Ti mt gi tr ng sut no mu bt u dn di rt nhanh, ti hng
chc, thm ch hng trm phn trm trong khi ng sut khng tng ng k.
Sau qu trnh dn di bc sang giai on III, kt thc bng s ph hu
mu. Trong giai on ny, mu li bin dng tng t vt th rn. S dn di
xy ra trong giai on I v III l thun nghch, chng s bin i khi tho b ti
trng. Nhng s dn di trong giai on II li gn nh khng i khi tho ti,
v vy c coi l khng thun nghch, hay "chy ngui". Tuy nhin s chy
theo ng ngha, tc l s trt tng i vi nhau ca cc i phn t,
trng thi thu tinh t c kh nng. Ngoi ra, bin dng ny thc t vn l
thun nghch: nu mu c sy nng ln n nhit cao hn nhit thu
tinh ho, bin dng s bin mt. iu ny ni ln tnh cht mm cao ca
chng.
64
Trng thi thy tinh
Vic kho st v tr v hnh dng ca cc i phn t trong trng thi
thu tinh cho thy giai on II xy ra s dui thng v nh hng cc phn
t theo hng ko, tc l qu trnh pht trin bin dng mm cao. Nhng khi
polyme cn nm trong trng thi thu tinh, nng lng chuyn ng nhit
khng vt qua nng lng tng tc gia cc phn t v cun chng
li. Do ta mi quan st thy s khng thun nghch biu kin giai on
ny.

Nh vy, v tr c nh ca cc i phn t trong polyme khi cng
chuyn ng nhit ca cc phn t ng hc khng ln ( nhit thp
hn Tg) ch c th b ph v di tc ng ca mt ng sut c hc ln. V
vy bin dng mm cao ca polyme thu tinh c gi l bin dng mm cao
bt buc, cn bn thn hin tng c gi l mm cao bt buc.

Hin tng mm cao bt buc l c trng ring ca polyme. Nh
mm do v di ln ca phn t, s sp xp li cc phn t ring r trong
phn t xy ra m khng ph v s ton vn ca vt th. Cc i phn t, d
kt thnh b hay khng, vn bo ton mi quan h tng tc ngay c khi cc
on ring r chuyn dch kh mnh.
65
Trng thi thy tinh
im cc i trn tng ng
vi s to thnh trn mu
ko dn mt on c thit
din nh i rt rt, thng
gi l "c eo". on bc (gim
ng sut) tng ng vi s
bt u to thnh "c eo",
on cd - s pht trin ca
"c eo" sang cc vng ln
cn dy hn ca mu. Ti
im d qu trnh hnh thnh
"c eo" chm dt, khi
dy ton b mu bng
dy ca "c eo". on de
tng ng vi bin dng ca
mu vi thit din nh (thit
din ca "c eo").
a
b
c
d
e
66
Trng thi thy tinh
Nguyn nhn s gim ng sut thi im hnh thnh "c eo" v bt u bin dng
mm cao bt buc nh sau: polyme thu tinh khng phi h thng cn bng. Trong h
thng ny bt c nhit T no cng tn ti nhng ng sut ni. Cc ng sut ny
khng hi phc c do nht ca h qu ln v linh ng nh ca cc phn t
b "ng bng". Nhng ch cn s dch chuyn di tc dng ca ngoi lc bt u
(khi bin dng mm cao bt buc xut hin), cc ng sut ni s thc y s dch
chuyn ca cc on nhanh hn, gp phn vo vic sp xp li cu trc.
Gi tr ng sut cc i ti xut hin bin dng mm cao bt buc c gi l gii
hn mm cao bt buc, k hiu ob.
o
o
o
b

T
b
T
Khong nhit Tg - Tb ca polyme thu tinh c ngha
thc t to ln v trong khong ny polyme khng th hin
tnh gin. Trn thc t, khong nhit ny dao ng t 0
n 1000C hoc hn na. Cc i phn t mm do khi
ho thu tinh nhit thp s to ra thu tinh cht ch
vi s lng ln cc lin kt gia phn t kh bn vng.
Cc thu tinh nh vy c khong nhit Tg - Tb nh.
Chng hn cc loi cao su b ph hu gin lin sau khi
nhit h xung di Tg. Cc thu tinh kt b xp vi
cc i phn t cng v c kh nng bin dng mm cao
bt buc ln to ra mt nhm ring vi khong Tg - Tb
ln, v d PVC (Tg - Tb =170K), PMMA (Tg - Tb =100K).
67
Trng thi chy nht
S chy, l s pht trin cc bin dng do khng thun nghch, cn khoa
hc nghin cu s chy v cc bin dng trong gi l lu bin hc
(rheology). Mt trong nhng nh lut u tin ca s chy l nh lut Niutn
(Newton, th k 17). Theo nh lut ny, nu tc ng ln cht lng mt ng
sut khng i th cht lng s chy vi mt vn tc khng i, i
lng vn tc chy c xc nh bi hng s gi l nht
t
o
q
dt
d
dz
dv
t
c
q q o = =
dz
dv
gradient vn tc, tng ng vi tc bin dng
dt dc
68
Trng thi chy nht
ng cong chy trong to bnh thng(a) v to logarit (b)
1. Cht lng Niutn; 2. Cht lng nht d thng (vt do biu
kin)
3. H thng dilactan; 4. Vt th do (vt th Bingham).
69
Trng thi chy nht
Theo i lng n c th nh gi mc sai lch tnh cch ca cht lng
trong qu trnh chy so vi cht lng Newton. V vy, gi tr n c gi l ch
s chy. Ch s chy - l c trng vt l ca cht lng.
70
Trng thi chy nht
c im u tin ca polyme nng chy l chng c nht cao. V d
polyizobutylen (khi lng phn t khong 10
6
) 15
0
C c nht
~3.10
11
Pa.s (3.10
12
p); nhit ln hn Tm nht c th gim 1-2 bc,
nhng vn ln n mc polyme vn bo ton hnh dng ca n lu v
thi hn nu khng c lc ngoi tc dng. so snh, ta c nht ca thu
tinh thp phn t l ~10
12
Pa.s. Gi tr nht cao nh vy ca polyme nng
chy l kt qu ca cu trc mch di ca chng; ngc li, cng l mt
bng chng v cu trc nh vy.

c im th hai ca polyme nng chy l s chy thc lun lun b che
khut bi cc qu trnh bin dng mm cao km theo n. Khi xt cc c tnh
bin dng ca polyme v nh hnh mch thng, nh bit vo bt k thi
im no bin dng ca chng cng c to thnh bi 3 thnh phn:
n hi, mm cao v chy nht. (xem cc hin tng hi phc).
71
Trng thi chy nht
c im th ba l s tng nht ca polyme nng chy trong qu trnh
chy ca n. c im ny gn lin vi c im th hai. S pht trin bin
dng mm cao trong qu trnh chy polyme c nh hng r rt n kh
nng chy ca n. V bin dng mm cao lin quan vi s dui thng mch
phn t nn trong qu trnh chy cc phn t s dui di theo hng chy
cho n khi xc lp c cc gi tr cn bng ca hnh thi sp xp dui
thng. S dui thng ca cc i phn t v s dch chuyn ca chng trong
trng thi ny dng nh tng ng vi s tng nht ca h thng v
iu lm s thay i hnh thi sp xp kh khn hn (h thng cc phn
t dui thng lun lun c nht cao hn cc phn t cun li). S tng
nht ca polyme nng chy trong cc iu kin ng nhit l c trng ring
ch polyme mi c (nu nh trong qu trnh chy khng xy ra qu trnh to
cu trc no). c im ny l c s ca kh nng to mng v to si ca
polyme nng chy trong cc iu kin ng nhit.
72
Trng thi chy nht
c im th t - l c ch chy c bit ca polyme, khc vi cc cht lng
thp phn t. Khi tc ng lc ln mt cht lng thng thng, cc phn t cht lng
vn ang chuyn ng nhit hn lon, bt u chuyn ng ch yu theo hng tc
dng lc. S chuyn ng ny b cn tr bi lc tng tc gia cc phn t, lc ma
st ni, tc l nht ca cht lng. Khi phn t "nhy" t m ny sang m khc,
n buc phi tiu th mt nng lng vt qua s tng tc vi cc phn t ln
cn c. S chuyn ng nh vy ca phn t c th xt nh mt qu trnh bay hi:
phn t chuyn t trng thi ngng t thnh hi v sau li ngng t li. Nu vic
xem xt nh vy l hp l th phi c mi lin h gia nhit ho hi v nng lng
hot ho chy nht.
c im th nm ca s chy polyme l n lun lun km theo cc qu trnh c
ho. di ln hn ca i phn t v nht ca polyme nng chy ( nht c th
cn tng hn na trong qu trnh chy) i hi phi c nhit cao v ng sut ln
gy nn s chy. V vy, ti mt nhit chy cho trc lun lun c th c mt thi
im m nng lng c hc t vo h thng cao ph v lin kt ha hc
trong polyme. Qu trnh ph hu phn t nh vy (cn gi l cracking c - ho) s gy
nn s gim khi lng phn t, d tm thi v cc mnh gy c th li phn ng vi
nhau theo c ch ti hp hoc ghp nu chng l cc gc. Do cc qu trnh c ho,
nht s gim i v s chy c thc y nhanh hn.

73
Ha do polyme
74
Ha do polyme
Polyme ha do l mt dng dung dch polyme m c. Vic a vo
polyme mt lng khng ln (ti 30%) cc cht lng thp phn t c si
cao (gi l cht ho do) l mt trong nhng phng php quan trng nht
bin tnh cu trc vt liu polyme. Trn thc t vic ho do lm tng n
hi ca vt liu, tng chu lnh v lm qu trnh gia cng n d dng hn.
V mt l thuyt, bn cht ca ho do l thay i nht ca h thng, tng
mm do ca i phn t v tng linh ng ca cc cu trc ngoi vi
phn t.
Khi xy ra qu trnh do ho, cc phn t tng i nh ca cht ho do
thm nhp vo polyme, tch cc i phn t polyme ra, ph v cc cu trc
ngoi vi phn t, bao bc cc i phn t bng mt lp n phn t, che chn
cc nhm c cc. Nu cht ho do khng tch cc i phn t ra khi
nhau th cc cu trc ngoi vi phn t c th khng b ph v nhng linh
ng ca chng s tng ln v nh hng n tnh cht polyme. Loi do ho
ny c th xy ra c khi i lc gia polyme v cht ho do rt thp: cc phn
t cht ho do khng th ph v cc cu trc ngoi vi phn t m ch chen
vo gia chng trn mt phng phn cch, dng nh ch thm t v bi
trn chng, tng linh ng ca cc cu trc ny ln. Loi do ho ny c
gi l do ho gia cc cu trc (gia cc b).
75
Ha do polyme
Nu polyme c cc phn t mm
do, vic a cht ho do vo lm
tng linh ng ca cc n v ng
hc dn ti gim nhit ho thu tinh
v nhit chy nht, ng thi lm
cc nhit ny gn li vi nhau.

V vy vng trng thi mm cao
ca polyme chuyn sang vng c nhit
thp hn, ng thi khong nhit
mm cao nh li v moun n hi
gim xung. Khi lng ho do ln,
trng thi mm cao bin mt (ng 4)
tng ng vi s chuyn bin t
polyme do ho sang dung dch
polyme trong cht ho do.
c
76
Ha do polyme
Trong trng hp polyme c i
phn t rt cng, trng thi mm cao
hon ton khng c hoc th hin rt
yu. Khi cht ho do ch c tc
dng lm gim nhit ho thu tinh -
lng ho do cng nhiu th Tg cng
gim mnh.
c
Cng c th do tng tc mnh gia cc phn t cht ho do v cc
nhm nguyn t trong i phn t m mm do ca cc i phn t
polyme tng ln ng k v kch thc ca cc on - n v ng hc ca
i phn t - gim xung. V vy, nhit thu tinh ho s gim mnh (Tg
ph thuc vo kch thc don) trong khi s gim nhit chy vn bnh
thng vi mi s do ho. Do khi a cht ho do vo, c th s xut
hin hoc m rng khong nhit mm cao ca polyme (ng 1,2,3).
Nu vn tip tc tng lng cht ho do khi mm do ca phn t
khng tng c na th s thay i ng cong c nhit li c c tnh
tng t nh i vi polyme c mch mm do (ng 4,5).
77
Ha do polyme
Cn lu rng cn nhiu iu cha r trong c ch ho do. V d khi nghin
cu cc h thng gm polyme v cht ho do u phn cc, ngi ta xc
nh c rng s gim nhit thu tinh ca polyme t l thun vi phn mol
cht ho do c s dng (quy tc phn mol)




Trong : k - hng s; n - phn mol ca cht ho do

Vai tr ca cht ho do l ch khi tng tc vi cc nhm c cc ca polyme
v dng nh che chn chng, cht ho do lm yu tng tc gia cc phn
t v gim Tg. Do mi nhm phn cc trong i phn t ch kt hp c vi
mt phn t cht ho do, s lng cc nhm b che chn trong i phn t
s trng vi s lng phn t cht ho do. Chnh v vy, s gim Tg c xc
nh ch bi s lng cc phn t cht ho do, v - mt cch gn ng - khng
ph thuc vo hnh dng v kch thc ca chng.

n k T
g
. = A
78
Ha do polyme
S ho do ca cc polyme khng phn cc hoc phn cc yu c khi lng
phn t cao li xy ra kiu khc - s gim nhit thu tinh tun theo qui tc
phn th tch bng nhau





Trong : - phn th tch cht ho do


Ngi ta cho rng trong trng hp ny, vai tr chnh khng phi nng lng
tng tc gia cc phn t polyme v cht ho do, m l nhng thay i hnh
thi sp xp ca cc i phn t trong dung dch cht ho do c km theo thay
i entropi. Nu trong h thng th tch do cht ho do chim ch l nh nhau
vi cc loi ho do khc nhau th s lng cc hnh thi sp xp c th c ca
mch polyme cng nh nhau. V vy vi phn th tch nh nhau ca cc cht
ho do khc nhau c th ch i s chuyn dch Tg nh nhau.
. k T
g
= A

79
Polyme blend
Trn hai hoc nhiu polyme vi nhau l mt trong nhng cch bin tnh
chng. V d trn polyme n hi vi mt polyme km n hi s lm tng
cng tnh cht n hi ca polyme sau; b sung mt polyme c bn cao
vo polyme c bn thp hn s tng bn ca sn phm, v.v... Tuy nhin
trong nhiu trng hp cng quan st thy s gim mnh cc tnh cht c - l
ca hn hp polyme. Khi ngi ta cho rng cc polyme khng tng hp vi
nhau. S tng hp ca cc polyme - l s to thnh h thng polyme -
polyme n nh v nhit ng, ngha l to ra dung dch tht ca mt polyme
trong mt polyme khc.
80
Tnh cht c hc ca polyme
ng sut o
F: Lc tc dng, N
S: Tit din ngang
S
F
k
= o
b h
FL
u
2
3
= o
F: Lc tc dng, N
L: Khong cch gia hai gi , mm
b: Chiu rng ca mu, mm
h: Chiu dy ca mu, mm
S
F
n
= o
F: Lc tc dng, N
S: Tit din ngang
ng sut l ti trng t
vo mt n v thit
din mu. Ty vo dng
tc ng m xc nh
ng sut l ko, nn
hoc un c o bng
Pa hay MPa
81
Tnh cht c hc ca polyme
Bin dng tng i
l
t
: di thi im t
l
0
: di thi im ban u
0
0
,
0
0
l
l l
t

= c
Modun n hi
c
o
d
d
E =
Ty vo dng ng sut (ko, trt,..) m c modun n hi ko hoc
modun n hi trt. Thng thng phi ch r E c xc nh gi tr
bin dng no. Nu khng ta hiu l E c xc nh trong vng bin
dng n hi Hook
82
Cu hi n tp
1. Polyme l g? Polyme khc hp cht thp phn t nh th no? Th no
l monome, oligome.
2. Th no l trng hp, nhm cui v mt xch c bn?
3. C my loi copolime? Cho v d minh ha.
4. Hnh thi sp xp khc hnh thi cu to nh th no?
5. C my cch phn loi polyme? Cho v d minh ha.
6. Phn ng trng hp khc g vi phn ng trng ngng? Cho v d minh
ha.

7. c im c trng ca polyme m cc hp cht thp phn t khng c?
8. mm do ca polyme l gi? Cc yu t nh hng n mm do
ca polyme?
9. Hy gii thch ti sao giai on u ca hin tng hi phc ng sut th
cc gc ha tr v di lin kt li b thay i?
83
Cu hi n tp
10. Trong hin tng hi phc ng sut, hy gii thch ti sao cc phn t
polyme trong qu trnh trt ln nhau th chng li cun trn li?
11. Trong trng thi mm cao, ti sao khi tc dng lc ln cc phn t polyme
lm chng dui thng ra th li lm cho entropi gim xung?
12. Hin tng chy ngui trong polyme thy tinh l g?
13. Ti sao khi hiu s T
g
T
b
gim xung th polyme cng mm do?
14. Ch s chy l g? Lm th no xc nh c ch s chy?
15. c im ca polyme chy nht l gi?
16. Trnh by c ch ha do polyme?
17. Ti sao khi cho cht ha do vo th nhit ha thy tinh ca polyme
gim xung?
18. Modun n hi c trng cho tnh cht g ca vt liu?
19. Polyme blend l gi?
20. bn mi tnh (creep) khc vi bn mi ng (fatigue) nh th no?