VT LIU NANO COMPOSITE GVHD: Th.S.

on Mnh Tun

B CNG THNG
TRNG I HC CNG NGHIP
THNH PH H CH MINH
KHOA CNG NGH HA HC

TIU LUN NHM 21

TNG QUAN V CC VN NGHIN

CU VT LIU NANO COMPOSITE

GVHD: Th.S. on Mnh Tun

Sinh vin: 1. Trn Vn Sng
2. Hunh Th Nh Ho
3. Phan Th Trng Ngha
4. Dng Hunh Thi Bnh

Tp. H Ch Minh 05/04/2017

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

LI CM N

Trong qu trnh nghin cu v hon thnh bi tiu lun ny, Nhm chng
em nhn c rt nhiu s gip qu bu ca cc Thy v C b mn, cc v
bn b.
u tin Nhm chng em xin by t lng bit n su sc n Thy Th.s
on Mnh Tun tn tnh hng dn v to iu kin cho Nhm chng em
hon thnh bi tiu lun ny.
Nhm chng em xin chn thnh cm n Ban lnh o Vin Ha Hc,
Phng Qun l Tng hp, anh ch em phng Cng ngh Vt liu Vin Ha Hc
Trng i Hc Cng Nghip Thnh Ph H Ch Minh, cc hc cng lp gip
v to mi iu kin thun li gip Nhm chng em thc hin tt bi tiu lun
v hon thnh mi th tc cn thit.
Cui cng, Nhm chng em xin by t lng bit n su sc n gia nh,
ngi thn v bn b lun quan tm, ng vin v gip Nhm trong sut
qu trnh hc tp v hon thnh bi tiu lun.

Tp HCM, ngy 05 thng 04 nm 2016

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

MC LC
LI CM N

ii
DANH MC CC HNH

iv
BNG GII THCH CC CH VIT TT

v
LI M U

1
TNG QUAN V CC VN NGHIN CU VT LIU NANO
COMPOSITE

3
1. GII THIU V VT LIU POLYME NANOCOMPOZIT V CAO SU
NANOCOMPOZIT........................................................................................
2. KHI NIM, PHN LOI V C IM CA VT LIU
NANOCOMPOZITE......................................................................................
2.1. Khi Nim...............................................................................................................
2.2. Phn loi.................................................................................................................
2.3. c im ca vt liu nanocompozit.....................................................................
2.4. u im ca vt liu nanocompozite......................................................................
3. CC PHNG PHP TNG HP VT LIU NANOCOMPOSITE............
3.1. Phng php trn hp.............................................................................................
3.2. Phng php sol gel.............................................................................................
3.3. Trng hp in-situ.....................................................................................................
4. C S HA HA L CA VT LIU NANO COMPOZITE.......................
4.1. Cc ph gia nano.....................................................................................................
4.3. Cao su thin nhin v cao su nitril butadien.........................................................16

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

5. TNH HNH NGHIN CU VT LIU POLYME NANOCOMPOZIT............

KT LUN

26
TI LIU THAM KHO

27

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

DANH MC CC HNH

Hnh 1.1: M hnh cu trc vt liu nanocomposite

5
Hnh 1.2: Nguyn l chung ch to vt liu polyme nanocompozit

8
Hnh 1.3: C ch cun ng hnh thnh CNT t graphen

8
Hnh 1.4: Hnh m phng ca ng nano carbon n tng (a) v a tng (b)

9
Hnh 1.5: Cc nng dng ca ng carbon nano

11
Hnh 1.6: S bin i dng tinh th ca silic dioxit

12
Hnh 1.7: Cng thc cu to ca cao su thin nhin

18

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

BNG GII THCH CC CH VIT TT

CNT ng nano carbon

CSTN Cao su thin nhin
DMF Dimetylfomamid
FESEM Knh hin vi in t qut trng pht x
FTIR Ph hng ngoi bin i Fourier
IR Ph hng ngoi
MWCNT ng nano carbon a tng
NBR Cao su nitril butadien
SVR Cao su nh chun Vit Nam
SWCNT ng nano carbon n tng
TESPT (hay Si69) Bis-3-(trietoxysilylpropyl)tetrasulphit
TEM Knh hin vi in t truyn qua
TGA Phn tch nhit trng lng
TCVN Tiu chun Vit Nam
UV-vis Ph t ngoi kh kin

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

LI M U
Khoa hc v cng ngh nano l mt lnh vc ang ni ln trong vic nghin
cu v pht trin vt liu mi. y l mt lnh vc rng v kh mi m i vi th
gii ni chung v Vit Nam ni ring. Vi nhiu tnh cht u vit, vt liu polyme
nanocompozit thu ht s quan tm ca nhiu nh khoa hc. Vt liu polyme
nanocompozit kt hp c c u im ca vt liu v c (nh tnh cht cng,
bn nhit) v u im ca polyme hu c (nh tnh linh ng, mm do, l cht
in mi v kh nng d gia cng). Hn na chng cng c nhng tnh cht c
bit ca cht n nano iu ny dn ti s ci thin tnh cht c l ca vt liu.
Mt c tnh ring bit ca vt liu polyme nanocompozit l kch thc nh
ca cht n dn ti s gia tng mnh m din tch b mt chung so vi cc
compozit truyn thng.
Vt liu cao su nanocompozit gm c pha nn l cao su hay cao su blend v
cc cht n gia cng. Cao su thin nhin (CSTN) c tnh cht c hc tt nhng
kh nng bn du km. Trong khi , cao su nitril butadien (NBR) c bit n
vi c tnh vt tri l kh nng bn du m rt tt. Do vy, vt liu cao su blend
CSTN/NBR va c tnh cht c hc tt ca CSTN va c kh nng bn du m
ca cao su NBR [6]. tng kh nng ng dng cho vt liu cao su cng nh cao
su blend, cc vt liu ny thng c gia cng bng mt s cht n gia cng
nh than en, silica, clay,... [39]. Kh nng gia cng ca cht n cho cao su ph
thuc vo kch thc ht, hnh dng, s phn tn v kh nng tng tc vi cao su
[24,30]. Cc cht n nano c kch thc t 1-100 nm, c th ci thin ng k
tnh cht c hc ca cc sn phm cao su. Vi din tch b mt ln, cc ht nano
s tng tc tt vi cc i phn t cao su, dn n nng cao hiu qu gia cng.
Do vy, cc ht nano rt quan trng gia cng cho vt liu cao su [34].
Nanosilica c tc dng gia cng tt hn so vi silica thng thng do chng c
kh nng phn tn tt hn trong nn cao su. Tuy nhin, chng li c xu hng kt
t do nng lng b mt cao v hnh thnh lin kt hydro lin phn t thng qua
cc nhm hydroxyl (silanol) trn b mt [3]. iu ny dn n s tng tc mnh
gia cht n vi cht n m khng thun li cho hiu qu gia cng. Vn

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

ny c th c khc phc thng qua bin tnh b mt cc ht silica. Tc nhn

ghp ni silan l tc nhn c s dng thng dng nht bin tnh b mt
nanosilica [3,41]. Bn cnh , cc ng nano carbon (carbon nanotube-CNT) cng
l loi cht gia cng rt tt cho polyme do CNT c tnh linh hot cao, t trng
thp v b mt ring ln [27], iu ny gp phn to nn vt liu cao su
nanocompozit c nhng u im vt tri. T nhng c s trn, chng ti chn
ti: Nghin cu ch to v tnh cht vt liu nano compozit trn c s
blend ca cao su thin nhin vi cao su nitril butadien v mt s ph gia nano
lm ch cho lun vn thc s ca mnh.
Mc tiu nghin cu ca lun vn l xc nh c nhng iu kin thch hp
ch to ra cc loi vt liu cao su nanocompozit trn c s blend ca
CSTN/NBR gia cng nanosilica v gia cng CNT.

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

TNG QUAN V CC VN NGHIN CU

VT LIU NANO COMPOSITE

1. GII THIU V VT LIU POLYME NANOCOMPOZIT V CAO SU

NANOCOMPOZIT
Cng ging nh vt liu polyme compozit, vt liu polyme nanocompozit
cng l loi vt liu gm pha nn (polyme) v pha gia cng cc dng khc
nhau. Tuy nhin, iu khc bit y l pha gia cng c kch thc c nanomet
(di 100 nm). Nh vy c th hiu, vt liu polyme nanocompozit l vt liu c
nn l polyme, copolyme hoc polyme blend v ct l cc ht hay si khong
thin nhin hoc tng hp c t nht mt trong 3 chiu c kch thc trong khong
1-100 nm (kch c nanomet). Do vy, vt liu cao su nanocompozit l mt trng
hp ca polyme nanocompozit c nn l cao su hoc cao su blend. V vy, cao su
nanocompozit c tt c cc c tnh chung ca polyme nanocompozit.
Vt liu polyme nanocompozit kt hp c c u im ca vt liu v c
(nh tnh cht cng, bn nhit) v u im ca polyme hu c (nh tnh linh
ng, mm do, l cht in mi v kh nng d gia cng). Hn na chng
cng c nhng tnh cht c bit ca cht n nano iu ny dn ti s ci thin
tnh cht c l ca vt liu. Mt c tnh ring bit ca vt liu polyme
nanocompozit l kch thc nh ca cht n dn ti s gia tng mnh m din
tch b mt chung so vi cc compozit truyn thng (xem bng 1) [10]. Vt liu
nn s dng trong ch to polyme nanocompozit rt a dng, phong ph bao gm
c nha nhit do v nha nhit rn, thng l: nha polyetylen (PE), nha
polypropylen (PP), nha polyeste, cc loi cao su,...

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

Bng 1.1: Mi quan h gia kch thc ht v b mt ring

ng knh ht B mt ring [cm2/g]
1 cm 3
1 mm 3.10
100 m 3.102
10 m 3.103
1 m 3.104
100 nm 3.105
10 nm 3.106
1 nm 3.107

Khong thin nhin: ch yu l t st vn l cc ht silica c cu to dng

lp nh montmorillonit, vermicullit, bentonit kim tnh cng nh cc ht graphit,

Cc cht gia cng nhn to: cc tinh th nh silica, CdS, PbS, CaCO 3, hay
ng carbon nano, si carbon nano,.

2. KHI NIM, PHN LOI V C IM CA VT LIU

NANOCOMPOZITE
2.1. Khi Nim
Vt liu nanocomposite (hay vt liu cu trc nano) l vt liu tng hp t
hai hay nhiu vt liu khc nhau to nn vt liu mi c tnh nng hn hn cc vt
liu ring r ban u. ng thi ch c mt phn ca vt liu c kch thc nm
hoc trong thnh phn vt liu tn ti cu trc nano khng chiu, mt chiu, hai
chiu an xen ln nhau. Trong kch thc & cu trc nano c hiu khi qut
l kch thc ht vt liu chim trong vng khng gian khong mt vi nm n
nh hn 100 nm.

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

Hnh 1.1: M hnh cu trc vt liu nanocomposite

2.2. Phn loi

Polyme nanocompozit ni chung hay cao su nanocompozit ni ring c
phn loi da vo s chiu c kch thc nanomet ca vt liu gia cng :
- Loi 1: L loi ht c c ba chiu c kch thc nanomet, chng l cc ht
nano (SiO2, CaCO3,).
- Loi 2: L loi ht c hai chiu c kch thc nanomet, chiu th ba c kch
thc ln hn, thng l ng nano hoc si nano (thng l ng, si nano carbon)
v c dng lm ph gia nano to cho polyme nanocompozit c cc tnh cht c
bit.
- Loi 3: L loi ch c mt chiu c kch thc c nanomet. N dng phin,
bn vi chiu dy c kch thc c nanomet cn chiu di v chiu rng c kch
thc t hng trm n hng ngn nanomet. Vt liu dng ny thng c ngun
gc l cc loi khong st, graphen,

2.3. c im ca vt liu nanocompozit

- Vi pha phn tn l cc loi bt c kch thc nano rt nh nn chng phn
tn rt tt vo trong polyme, to ra cc lin kt mc phn t gia cc pha vi
nhau cho nn c ch khc hn vi compozit thng thng. Cc phn t nh phn
tn tt vo cc pha nn, di tc dng ca lc bn ngoi tc ng vo nn s chu
ton b ti trng, cc phn t nh mn phn tn ng vai tr hm lch, lm tng
bn ca vt liu ng thi lm cho vt liu cng n nh nhit cao.
- Do kch thc nh mc phn t nn khi kt hp vi cc pha nn c th
to ra cc lin kt vt l nhng c bn tng ng vi lin kt ha hc, v th
cho php to ra cc vt liu c nhiu tnh cht mi, v d nh to cc polyme dn
c rt nhiu ng dng trong thc t.
- Vt liu gia cng c kch thc rt nh nn c th phn tn trong pha nn
to ra cu trc rt c, do c kh nng dng lm vt liu bo v theo c ch che
chn (barie) rt tt.

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

2.4. u im ca vt liu nanocompozite

So vi vt liu polyme compozit truyn thng, vt liu polyme nanocompozit
c nhng u im chnh nh sau:
- Vt liu nano gia cng hiu qu hn bi v kch c ca n nh hn dn ti
s ci thin ng k tnh cht ca nn (ch vi mt lng nh vt liu gia cng)
iu ny lm cho vt liu polyme nanocompozit nh hn, d gia cng hn.
- S chuyn ng sut t nn sang cht n hiu qu hn l do din tch b mt
ln v kh nng tng tc tt gia cc pha.

3. CC PHNG PHP TNG HP VT LIU NANOCOMPOSITE

Polyme nanocompozit hay cao su nanocompozit c th c ch to theo mt
s phng php ty theo cch thc kt hp gia hai pha v c v hu c. Cho ti
nay, ngi ta a ra 3 phng php chnh ch to polyme nanocompozit, tu
theo nguyn liu ban u v k thut gia cng: phng php trn hp (nng chy hoc
dung dch,), phng php sol-gel v phng php trng hp in-situ.

3.1. Phng php trn hp

Phng php ny ch n gin l phi trn cc vt liu gia cng nano vo
trong nn polyme. Qu trnh phi trn c th thc hin trong dung dch hoc trng
thi nng chy. Kh khn ln nht trong qu trnh trn hp l phn tn cc phn t
nano vo trong nn polyme sao cho hiu qu.

3.2. Phng php sol gel

Phng php sol-gel da trn qu trnh thy phn v trng ngng cc phn t
alcoxide kim loi c cng thc M(OR)4, dn n vic hnh thnh polyme c mng
lin kt M-O-M, v d nh Si-O-Si. Phng php sol-gel cho php a phn t
hu c R c dng Rn M(OR)4-n vo trong mnh v c to ra vt liu hu c-v
c lai to c kch thc nano. C hai loi nanocompozit lai to c ch to bng
phng php sol- gel. S phn chia chng da vo bn cht ca b mt ranh gii
gia thnh phn hu c v v c:
* Nhm 1: Cc thnh phn hu c v v c trong polyme nanocompozit

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

khng c lin kt ng ha tr. loi vt liu ny, tng tc gia cc thnh phn
da trn lc tng tc hydro, lc tnh in v lc Van-der-Waals.
* Nhm 2: Thnh phn hu c v v c trong vt liu c lin kt vi nhau
bng lin kt ha hc.
Phng php solgel c ng dng rng ri ch to vt liu lai v c
hu c. u im chnh ca phng php ny l iu kin phn ng m du: nhit
v p sut tng i thp. Trong trng hp polyme nanocompozit, mc tiu
ca phng php l tin hnh phn ng solgel vi s c mt ca polyme v
polyme cha cc nhm chc nng cao kh nng lin kt vi pha v c.
Qu trnh solgel gm 2 bc:
- Thu phn alkoxide kim loi;
- Qu trnh a t.
im c bit ca phng php ch mng li oxide c to thnh t
alkoxide c kim ngay trong nn hu c. Phng php thng hay s dng vi
cht gia cng l nanosilica.

3.3. Trng hp in-situ

Phng php ny c u im d ch to, nhanh v tnh cht sn phm tt. Qu
trnh trng hp in-situ tri qua ba bc: u tin cc ph gia nano c x l bi
cht bin tnh b mt thch hp v sau c phn tn vo monome ri tin hnh
trng hp trong dung dch hoc trong khi to polyme nanocompozit.

S nguyn l chung ch to vt liu polyme nanocompozit.

Ht nano Trng hp in-situ Monome

Trn thng
thng

Sol - gel

Polyme
nanocompozit

Polyme Tin cht nano

Sol - gel
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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

Hnh 1.2: Nguyn l chung ch to vt liu polyme nanocompozit

4. C S HA HA L CA VT LIU NANO COMPOZITE

4.1. Cc ph gia nano

4.1.1. ng nano carbon
ng nano carbon (carbon nanotube - CNT) l cu trc dng chui cc phn t
nh b ca fulleren. Trong cc nguyn t carbon sp xp vi nhau dng hnh 6
cnh trong cc ng c kch thc rt nh, ng knh ca cc ng nano carbon c
kch thc t vi A0 n trn hng chc nanomet, song c chiu di c vi
micromet. C th n gin ha rng coi CNT c dng hnh tr mt trc gm cc
ng rng c to thnh t cc tm graphen cun quanh trc v c ng li
hai u bng cc bn fulleren.

Bn cht caHnh 1.3:trong

lin kt C ch
ngcun
CNTng hnh
c giithnh
thch CNT t graphen
bi ha hc lng t, c th
l s xen ph obital. Trng thi lai ha ca nguyn t carbon trong CNT l sp2,
mi nguyn t carbon lin kt vi 3 nguyn t ln cn, cu trc lin kt lc gic
ny mnh hn lin kt sp3 trong kim cng to cho CNT cng c bit.
Da vo c tnh n tng hay a tng ca tm graphen ta c th chia CNT
thnh 2 loi:
+ ng nano carbon n tng (Single Wall carbon Nanotube - SWCNT) c
xem nh l tm graphen di c dy mt nguyn t, c cun li thnh mt
hnh tr lin v c gn kn hai u bng hai bn cu fulleren c cng ng
knh.

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

+ ng nano carbon a tng (Multi Wall carbon Nanotube-MWCNT) c th

c xem nh l mt tp hp cc SWCNT ng trc vi ng knh khc nhau.
Chiu di v ng knh ca cc cu trc ny khc nhiu so vi cc SWCNT v
cc tnh cht ca chng cng khc nhau.

Hnh 1.4: Hnh m phng ca ng nano carbon n tng (a) v a tng (b)

- Tnh cht c hc
Modul Young ca CNT vo khong 1 TPa nu ng knh ng l ln, ngoi
ra bn ko khong 11- 63 GPa, khi lng ring khong 2,6 g/cm 3 i vi
MWCNT v 1,4 g/cm3 i vi SWCNT. Trong khi modul Young ca thp ch
c 300 GPa, bn ko ch t 2 GPa.
- Tnh cht nhit
Ni chung, dn nhit ca b CNT n l nhit phng khong 1800
6000 W/mK. Trong khi ng vn c bit n l mt kim loi dn nhit tt th
dn nhit l 385 W/mK. S d t c gi tr cao nh vy, theo gi thit ca cc
nh khoa hc l do photon c qung ng t do trung bnh ln, t b tn x hn.
- Tnh cht in- in t
in tr ca CNT khng ph thuc chiu di ng v qung ng chuyn ng
t do trung bnh ca in t di hn bn thn ng nhiu ln. Cc electron di
chuyn thng qua cc hm cng hng gia cc mc nng lng khng lin tc
ca ng nano v dch chuyn qua chiu di m rng ca ng. dn in ca
CNT c d on rt cao bi v trong cu trc mt chiu, photon rt kh tn
x ngha l in t ch chuyn ng dc theo trc ng. dn in ti a ca

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

SWCNT l 2G0, vi G0 = 2e2/h = (12,9 k)-1 = 7,5S l dn ca mt lng t

n o duy nht.
- Tnh cht ha hc
So vi graphen th CNT hot ng ha hc mnh hn. Tuy nhin mt mc
nh gi ch quan cho thy, CNT tng i bn vng vi cc tc nhn oxy ha
thng thng. C th dng nhng tc nhn oxy ha mnh oxy ha u ng v
ph hy lp v ngoi, do cu trc ng gic ca nguyn t carbon trong CNT
khng bn vng. Vic gn cc nhm chc ln b mt CNT c th thay i kh
nng dn in ca ng nano carbon. Nhiu nghin cu ch ra rng, CNT c
ng knh cng nh th kh nng hot ng ha hc cng mnh. Song do nh
hng ca hiu ng kch thc v hiu ng b mt ca vt liu nano nn CNT rt
d b kt t. S kt t ny lm gim kh nng hot ng ca CNT khin CNT
khng th hin c nhiu tnh cht u vit vn c ca chng. V vy, vn
quan trng l bng cc phng php l ha th no tch b CNT thnh cc ng
ring r.
- Tnh cht pht x in t trng
CNT c th xem nh mt dy dn in c ng knh cc nh, thun li cho
cc ng dng trong in t hay quang in t. Vi hnh dng ng dn n mt
tnh cht c bit quan trng l s truyn in t n o, trong electron
chuyn ng thng theo mt phng hng nht nh, khng b vng mc
v khng c s va chm n cc nguyn t ca vt liu. Khng ch truyn in t
vi tc cao hn, CNT cn c th pht hin nhng thay i v in tch gp
khong 70 ln so vi bng bn dn silicon.
- Cc ng dng ca ng nano carbon
Vi cu trc tinh th c o, tnh dn nhit, dn in tt, tnh pht x in t
mnh,... vt liu CNT v ang m ra nhiu ng dng mi nh trong cng ngh
nng lng, thit b pht x in t trng, u d nano v sensor, ti to chc
nng xc gic, cm bin ng nano carbon dng theo di tnh trng ca bnh nhn
tiu ng, p dng cng ngh nano cho thit b lc nc, x l cc cht hu c

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

c hi, Cc ng dng ca ng nano carbon c c th ha trong hnh di

y.

Hnh 1.5: Cc nng dng ca ng carbon nano

- Phng php bin tnh b mt CNT

Thc cht, vic bin tnh vt liu CNT l s bin i cc c tnh ca vt liu
sao cho ph hp vi cc yu cu ng dng. V mt l thuyt bin tnh vt liu,
chng ta c th dng cc phng php c, l, ha tc ng ln b mt ca vt liu.
Nhng ch yu l tp trung vo vic x l ha hc b mt ca vt liu CNT
gn cc nhm chc ln b mt ca CNT. Vic x l ha hc c th hiu n gin
l dng cc tc nhn ha hc tc dng ln cc nguyn t carbon trn thnh ng.
Cc nhm chc trn b mt ng lm tng kh nng tng tc ho hc, qua tng
kh nng ha tan v phn tn ca CNT trong cc dung mi v cc vt liu khc.
4.1.2. Nanosilica
4.2.2.1. Cu trc ca silica
Tuy c cng thc phn t l SiO2 nhng silic dioxit (silica) khng tn ti
dng phn t ring r m di dng tinh th. Silic dioxit tinh th c ba dng th

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

hnh chnh l: thch anh, tridimit v cristobalit. Mi dng th hnh ny li c hai

dng: dng bn nhit thp v dng bn nhit cao. Ngoi ba dng

th hnh chnh trn, silic dioxit cn tn ti mt s dng ph khc: dng n tch,

v nh hnh. Di y l s bin i dng tinh th ca silic dioxit:

Hnh 1.6: S bin i dng tinh th ca silic dioxit

Tt c nhng dng tinh th ny u bao gm nhng nhm t din SiO 4 ni vi

nhau qua nhng nguyn t O chung. Trong t din SiO 4, nguyn t Si nm tm
ca hnh t din, lin kt cng ha tr vi bn nguyn t O nm nh ca dnh t
din. Mi nguyn t O li lin kt vi hai nguyn t Si nm hai t din khc
nhau. Gc lin kt O Si O l 109o, di lin kt Si O l 1,61Ao. Tnh trung
bnh trn mt nguyn t Si c hai nguyn t O v cng thc kinh nghim ca silic
dioxit l SiO2.
m t cu trc cc dng SiO 2 tt nht l dng phng php ghp cc t
din SiO4 li vi nhau qua nh O chung. S khc nhau gia cc dng th hnh l
v tr tng i ca hai t din SiO4 hay l s khc nhau ca gc SiO Si.
4.2.2.2. Tnh cht vt l
Silic dioxit tinh th nng chy 1713oC, si 2230oC, khng tan trong nc.
Trong t nhin, silic dioxit tinh th ch yu tn ti di dng khong vt thch
anh, l tinh th ln, khng mu, trong sut. Ct l silic dioxit c nhiu tp cht.
Khi nng chy, SiO2 chuyn thnh cht lng khng mu, lm lnh cht lng
ny ta thu c khi SiO2 v nh hnh trong sut tng t thy tinh.
4.2.2.3.Tnh cht ha hc

12
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

Trong cc loi axit, SiO2 ch tc dng c vi axit HF, ngi ta li dng tnh
cht ny khc ch hay to hnh ln thy tinh.
SiO2 + 4HF SiF4 + 2H2O
SiO2 tan trong kim hoc trong mui carbonat ca kim loi kim nng chy to
thnh silicat:
SiO2 + 2NaOH Na2SiO3 + H2O
SiO2 + Na2CO3 Na2SiO3+ CO2
Na2SiO3 trng b ngoi ging thy tinh v tan c trong nc nn c gi l
thy tinh lng.
Khi nung SiO2 vi than cc theo t l xc nh trong l in khong 2000-
2500oC ta thu c silica cacbua SiC. SiC c cu trc tinh th ging kim cng,
rt cng v bn, chu c nhit cao. N c dng lm cht mi, vt liu chu
la, cht bn dn trong ch to compozit v trong luyn kim.
4.2.2.4. Tnh cht ca ht silica kch thc nano
B mt silica nhn v c din tch ln, do kh nng tip xc vt l vi
polyme nn ln. Silica c th tn ti nhiu dng, mi dng th hin tnh cht vt
l v ha hc khc nhau. Silica khng th ht nc nu b mt ca n c cc
nhm siloxan (-Si-O-Si), kh nng ht nc ca n ch th hin khi b mt c cc
nhm silanol (Si-OH). S c mt ca 2 nhm ny nh hng n tnh cht ca b
mt silica v ng dng ca n.
Silica k nc c th c chuyn thnh silica a nc bng phn ng
hydroxyl ha nhm siloxan thnh silanol. Phn ng ny c th lm ngc li,
silica a nc c th chuyn thnh silica k nc bng phn ng hydroxyl
ha hoc un nng nhit ln hn 300oC.
B mt ca silica trung bnh c 5-6 nhm silanol trn 1 nm 2 nn n c tnh a
nc, cc nhm siloxan cn li khng tham gia phn ng. Cu trc ca nanosilica
l mng 3 chiu. Do c nhm silanol v siloxan trn b mt nn cc ht silica c
kh nng ht nc. B mt silica c c trng bi 3 dng silanol: silanol t do,
silanol lin kt hidro vi nhm bn cnh v silanol ghp i. Cc nhm silica trn
cc phn t k nhau tp hp li vi nhau bng lin kt hidro. Lin kt ny gip

13
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

cho cc phn t silica tp hp li vi nhau ngay c khi b pha trn mnh d cho
khng c phn ng vi polyme nn.
Cc nhm silanol hot ng trn b mt silica c nhim v kt t cc phn t
li vi nhau. Ban u, cc ht silica ghp i vi nhau nh lin kt hidro to
thnh dng kt t bc 1 v sau , chng tip tc kt t vi nhau bn cht hn
to thnh dng kt t bc 2. Khuynh hng kt t ca cc phn t silica c th
c minh ha nh sau:

Dng n ht Dng kt t bc 1 Dng kt t bc 2

Chnh tnh a nc ca nhm silanol trn b mt silica l nhc im lm hn

ch kh nng ng dng ca silica, do cn bin tnh silica. Trong qu trnh bin
tnh, nhm silanol phn ng vi nhm th ca tc nhn bin tnh, lm tng khi
lng ca silica. Do xy ra s phn hy dng kt t v xut hin dng n ca
cc ht silica trong silica bin tnh:

14
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

Dng kt t bc 2 Dng kt t bc 1 Dng n ht

Phn ng ca cc nhm silanol trn b mt silica vi cc hp cht hu c
lm gim hoc lm mt i kh nng ht nc ca silica v lm tng s lng cc
nhm th hu c c i lc ln vi hp cht hu c trn b mt ca silica. Nh c
cc nhm silanol nn b mt ca silica c th phn ng vi hp cht silan, halogen
ca kim loi hoc phi kim, ru, cc cht c hot tnh b mt, Sau khi bin tnh,
mc phn tn ca nanosilica trong pha hu c, s bm dnh gia nanosilica v
cc phn t hu c tng ln, do bn ca cc sn phm polyme (cao su, cht
do,) c tng ln ng k.
4.2.2.5. ng dng ca ht nano silica
SiO2 c nhiu ng dng trong thc t. Ty theo cht lng c th m n c
s dng trong cng nghip v i sng.
ng dng u tin v lu i nht ca bt SiO 2 mn l lm cht gia cng hay
cht tng cng trong cc sn phm do nh giy, cc loi cao su k thut, dy
cp v cc loi lp. a 20-50% khi lng bt mn SiO 2 vo cao su thin nhin
hay cao su tng hp gip ci thin dai, cng, bn x ca sn phm cao
su. Kh nng gia cng ca bt mn SiO 2 cng vt hn hn cc cht n t nhin
v khc vi mui than, n cho php to ra nhng sn phm cao su trng v cao su
mu. Vi cng ngh dy cp, bt ny c s dng ch yu lm v bc c bit
cho cc loi cp dng ngoi tri, bn ma st v bn x ln ca v cp gip
bo v phn li cp khi mi mn v va p.
Trong cc sn phm nha chu nhit, bt mn SiO 2 c s dng nh tc nhn
chng trt trnh hin tng trt phim trong my nh hay ci thin c tnh
ca PVC.

15
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

Bt mn SiO2 ngy cng c s dng nhiu lm cht lm trng trong kem

nh rng bi kh nng lm sch rt tt m gn nh khng gy xc.
Bt SiO2 c ng dng ph bin trong sn xut sn v vecni. Nh nhp
nh ca b mt mc hin vi nn nh sng khng cn phn x thng na m b
phn tn.
Trong cng nghip giy, bt mn SiO2 c s dng trong cc sn phm giy
c bit (c chm mu ln v tng phn tt khi in). y, ht SiO 2 lp y
vo cc l xp trn giy v to ra b mt nhn.
Ngoi cc ng dng k trn, bt mn SiO2 cn c ng dng lm cht tng
bn kt cu trong nha, trong cht lc v n nh bia, trong phn tch mu,

4.3. Cao su thin nhin v cao su nitril butadien

4.3.1. Cao su thin nhin
4.3.1.1. Lch s pht trin ca cao su thin nhin
Cao su thin nhin (CSTN) l mt polyme thin nhin c tch ra t nha
cy cao su (Hevea Brasiliensis), c thnh phn ha hc l polyisopren. V vy,
trong tiu chun ca M, ngi ta nh ngha Polyisopren c trch ly t cy
Hevea braziliensis c gi l cao su thin nhin . Ngoi cy Hevea Brasiliensis
vt liu ny cn c tm thy trong nha mt s loi cy nh Asclepias spp. v
cy Taraxacum spp.,... Cy Hevea Brasiliensis c ngun gc pht trin trong cc
khu rng nhit i ca Brazil, ngy nay chng pht trin rng ri nhiu nc
vng nhit i c bit l vng ng Nam v mt s nc M Latin v
Chu Phi,...
Cao su thin nhin c mt lch s pht trin lu i, vi nhng kt qu nghin
cu v kho c, ngi ta pht hin ra cc nh cng ngh cao su u tin trong
b tc Aztecs v Mayas ca Nam M, l nhng ngi s dng cao su
lm tt giy, o si v to nhng qu bng khong 2000 nm trc y. T bo
MRPRA (Malaysian Rubber Producers Research Association) cho bit rng vua
Aztec Montezuma c cng np 16.000 qu bng cao su t cc b lc vng
bnh nguyn v cc sn bng c khai qut Snaketown Ty Nam nc M c
nin i t nm 600-900 sau cng nguyn.

16
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

Cho n th k 19, cc sn phm cao su c mt nhc im ln l chng rt

dnh vo nhng ngy nng bc v rt cng vo nhng ngy lnh [32]. Dng nh
s chng c vn g ln cho n khi bn phi ngi trn ci o ma cao su dnh
t ca bn vo ngy nng bc v nhc c gh ln khi bn ng dy. Vn ny
c gii quyt bi mt pht hin ln bi Charles Goodyear Woburn
(Massachusetts, M) vo nm 1839. Goodyear tnh c gh thm xng hng
cao su ca cng ty Roxbury NewYork vo khong nm 1832 v cui cng ng
tr nn m nh vi nhng vn v sn xut cao su. ng trn tr, nghin cu
bin tnh cao su, lm cho chng tin dng hn, ng kt hp lu hunh vi cao
su n . ng ng dng kt qu ny sn xut ti th t cao su c cha lu
hunh v bt mu, song sn phm khng c nh . Sau , tnh c ng gia
nhit hn hp cao su-lu hunh-ch th v pht hin ra rng vt liu to thnh
ging nh da, khng cn b dnh khi nhit cao hn. Nh pht hin quan trng
ny, ng c cp bng sng ch ca M vo nm 1841 nhng ng c hng
rt t t thnh qu . Sau , vo nm 1843, Hancock cng kt hp lu hunh vi
cao su ri gia nhit v to ra vt liu c nhiu tnh nng qu gi. T kt qu ny,
mt ngi bn ngh s ca Hancock t ra thut ng lu ho cho qu trnh ny,
theo tn Vulcan-ng thn la. Pht hin lu ha cao su bng lu hunh mang
li kh nng ng dng rng ln ca cao su bi nhng tnh nng tuyt vi ca n
ch khng ch l vt liu chng dnh. Trong thc t, phn ln cc sn phm ca
cao su ngy nay tn ti l dng c lu ho.
4.3.1.2. Thnh phn ho hc ca cao su thin nhin
Thnh phn ho hc ca cao su thin nhin gm nhiu cc cht khc nhau:
hydrocarbon (thnh phn ch yu), cc cht trch ly bng axeton, m, cc cht
cha nit m ch yu l protein v cc cht khong. Hm lng cc cht ny cng
ging nh latex dao ng rt ln ph thuc vo tui ca cy, cu to th nhng
cng nh kh hu ni cy sinh trng v ma khai thc m. Ngoi ra n cn ph
thuc vo phng php sn xut.
Trong bng di y l thnh phn ha hc ca cao su thin nhin (cao su
sng) c sn xut bng cc phng php khc nhau.

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

Bng 1.2: Thnh phn ho hc ca cao su thin nhin

TT Thnh phn chnh Loi crp
hong khi crp trng bay hi
1 Hydrocarbon 93-95 93-95 85-90
2 Cht trch ly bng axeton 1,5-3,5 2,2-3,45 3,6-5,2
3 Cht cha nit 2,2-3,5 2,4-3,8 4,2-4,8
4 Cht tan trong nc 0,3-0,85 0,2-0,4 5,5-5,72
5 Cht khong 0,15-0,85 0,16-0,85 1,5-1,8
6 m 0,2-0,9 0,2-0,9 1,0-2,5

Hydrocarbon y chnh l CSTN, cn cc cht khc nm trong c th coi

l cc tp cht. CSTN c cng thc cu to l polyisopren m cc i phn t ca
n c to thnh t cc mt xch cu to dng ng phn cis lin kt vi nhau
v tr 1,4 (chim khong 98%). Cng thc cu to ca CSTN c biu th hnh
1.6.
CH 3 H

C C CH 2 CH 2
H 2C CH2
C C

CH 3 H
Hnh 1.7: Cng thc cu to ca cao su thin nhin

Ngoi ra cn c khong 2% cc mt xch lin kt vi nhau to thnh mch i

phn t v tr 1,2 hoc 3,4.
Khi lng phn t trung bnh ca CSTN khong 1,3.10 6. Mc dao ng
khi lng phn t ca CSTN t 105 2.106.
Tnh nng c l, k thut ca CSTN ph thuc nhiu vo cu to ha hc
cng nh khi lng phn t ca n.
4.3.1.3. Tnh cht ca cao su thin nhin
Tnh cht ha hc
Do cu to ha hc ca CSTN l mt hydrocarbon khng no nn n c kh
nng cng hp vi cht khc (tuy nhin, do khi lng phn t ln nn phn ng
ny khng n gin nh cc hp cht thp phn t). Mt khc, trong phn t n

18
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

c nhm -metylen c kh nng phn ng cao nn c th thc hin cc phn ng

th, phn ng ng phn ha, vng ha
- Phn ng cng : do c lin kt i trong mch i phn t, trong nhng iu
kin nht nh, CSTN c th cng hp vi hydro to sn phm hydrocarbon no
dng parafin, cng halogen, cng hp vi oxy, nit,
- Phn ng ng phn ha, vng ha: do tc dng ca nhit, in trng, hay mt
s tc nhn ha hc nh H2SO4 , phenol, cao su c th thc hin phn ng to
hp cht vng.
- Phn ng phn hy: Di tc dng ca nhit, tia t ngoi hoc ca oxy, CSTN
c th b t mch, khu mch, to lin kt peroxit, carbonyl,
Tnh cht vt l
nhit thp, CSTN c cu trc tinh th. CSTN kt tinh mnh nht -25 oC.
Di y l cc tnh cht vt l c trng ca CSTN:
- Khi lng ring 913 [kg/m3]
- Nhit thu tinh ha -70 [oC]
- H s dn n th tch 656.10-4 [dm3/oC]
- Nhit dn ring 0,14 [W/mK]
- Nhit dung ring 1,88 [kJ/kgK]
- Na chu k kt tinh -25oC 2-4 [gi]
- H s thm thu in mi tn s 1000 Hz 2,4-2,7
- Tang ca gc tn hao in mi 1,6.10-3
- in tr ring:
Crp trng 5.1012 [.m]
Crp hong khi 3.1012 [.m]
Do c im cu to, CSTN c th phi trn tt vi nhiu loi cao su nh cao
su isopren, cao su butadien, cao su butyl,.. hoc mt s loi nha nhit do khng
phn cc nh polyetylen, polypropylen,... trong my trn kn hay my luyn h
ty loi cao su hay nha. Mt khc, CSTN c kh nng phi trn vi cc loi cht
n cng nh cc ph gia s dng trong cng ngh cao su.
4.3.2. Cao su nitril butadien

19
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

4.3.2.1. Lch s pht trin ca cao su nitril butadien

Cao su nitril butadien cng ngip ra i nm 1937 Cng ha Lin bang c.
Sau chin tranh th gii ln th 2, cao su nitril butadien c t chc sn xut
cng nghip Lin X c. Ngy nay, cao su NBR tr thnh mt trong nhng cao
su c s dng nhiu nht.
4.3.2.2. c im cu to
NBR l sn phm ng trng hp butadien-1,3 v acrylonitril vi s c mt
ca h xc tc oxy ha kh persunfat kali v trietanolamin. Phn ng din ra nh
sau:

n CH 2 =CH CH = CH 2 + mCH 2 =CH CN

( CH 2 =
CH CH CH2 ) a ( CH 2 =CH ) b
CN
Sn phm ny l sn phm chnh, ngoi ra cn c sn phm ph l sn phm
mch vng 4-xiano xiclohecxen to cho NBR mi c trng (mi nha cy u
).

CH2 CH2
HC CH2 HC CH2
+
HC HC CN HC CH CN
CH2 CH2
Hm lng ca monome acrylonitril trong hn hp cng cao th sn phm ph
to ra cng nhiu. NBR c nhiu sn phm ph cng c mu thm hn v c mi
r hn.
Monome butadien-1,3 tham gia vo phn ng hnh thnh mch i phn t ch
yu v tr 1,4 trans ng phn.
V d: Trong cao su CKH-26 c sn sut Lin X c c 77,4% monome
butadien tham gia vo phn ng 1,4 trans v 12,4% monome butadien tham gia
vo phn ng 1,4 - cis v 10,2% monome butadien tham gia vo phn ng v
tr 1,2.

20
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

Khi lng phn t trung bnh ca NBR dao ng trong khong t 200.000
n 300.000.
4.3.2.3 Tnh cht c l v cng ngh
NBR c cu trc khng gian khng iu ha, v th n khng kt tinh trong
qu trnh bin dng. Tnh cht c l, tnh cht cng ngh ca NBR ph thuc vo
hm lng nhm nitril trong n. Kh nng chu mi trng du m, dung mi hu
c tng cng vi hm lng nhm nitril tham gia vo phn ng to mch phn t
cao su. nh hng ca nhm nitril n kh nng chu du m ca NBR c th gii
thch theo hai cch sau:
a. Theo thuyt hp ph
Do lin kt C N trong cao su c phn cc ln (+ nguyn t Carbon
v - nguyn t nit) nn lc tc dng tng h gia cc on mch phn t c
cha nhm CN tng. Nng lng lin kt vt l gia cc on mch cao, nng
lng kt dnh ni cng ln khi hm lng nhm CN cng cao. Nng lng lin
kt ni ngn chn hin tng tch cc phn t polyme ra xa trong qu trnh trng
v ho tan. V th cng vi hm lng nhm nitril tng kh nng chu du m ca
cao su cng tng.
b. Theo thuyt che chn
Do kch thc khng gian cc nhm CN ln v khong cch khng gian gia
nhm ny vi lin kt khng no gn nn n bao trm ln khng gian cc lin
kt khng no, ngn chn s xm nhp ca cc tc nhn tc dng (phn t ca du,
m,) vo khng gian lin kt i v khong khng gian gia cc mch i phn
t. Khi hm lng nhm nitril trong mch cao su cng cao v hiu qu che chn
cng cao hay ni cch khc kh nng chu du m cng cao.
Tuy nhin, nhm CN trong mch i phn t lm tng thm thu nc ca
NBR so vi mt s loi cao su khng phn cc khc [32].
NBR l loi cao su phn cc ln nn n c kh nng trn hp vi hu ht cc
poyme phn cc, vi cc loi nha tng hp phn cc, NBR c cha lin kt
khng no trong mch chnh mch i phn t nn n c kh nng lu ho bng
lu hunh phi hp vi cc xc tin lu ho thng dng.

21
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

Ngoi h thng lu ho thng dng NBR cn c kh nng lu ho bng xc

tin lu ho nhm thiuram, nha phenol formandehit cho tnh cht c l cao v
chu nhit tt.

5. TNH HNH NGHIN CU VT LIU POLYME NANOCOMPOZIT

Do nhng tim nng to ln ca cng ngh nano, cc quc gia trn th gii
khng ngng a ra cc chin lc nhm ch trng u t vo nghin cu v pht
trin cng ngh nano. V mt chin lc, k t nm 1990 cng ngh nano tr
thnh nhim v quc gia cc nc nh M, Nht, Hn Quc v lin minh Chu
u. V mt u t, theo t Lux Reaserch (2004) mt bo co c cng b gn
y ca M, cho bit trong nm 2004 chnh ph ca cc nc trn ton th gii
chi cho cng ngh nano t 4,6 t USD, trong cc nc Bc M chi 1,6 t
USD, cc nc chu chi 1,6 t, cc nc chu u chi 1,3 t v khong 133 triu
USD l ca cc nc khc.
M l quc gia i u trong vic pht trin cng ngh nano. Cng vi vic thng
qua o lut R&D (reaserch and devolop) Cng ngh nano th k 21 v tip theo
l Sng kin Cng ngh nano quc gia, M dnh 3,7 t USD u t cho cng ngh
nano giai on 2005-2008. Ti chu u, mi nc u theo ui nhng chng trnh
pht trin cng ngh nano theo mc tiu ca ring mnh; v c cp EU, vi mt
chng trnh c nn tng rng ri hn. V d, theo chng trnh Khung v Nghin
cu v Pht trin cng ngh ln th 6 (FP 6), EU cam kt ti tr 350 triu euro cho
cng ngh nano nm 2003, chim 1/3 tng chi tiu chu u. Ti chu , theo bo co
ca Chng trnh Thng tin v cng ngh chu (ATIP) th Nht Bn l nc u t
mnh cho cng ngh nano hng u th gii, nm 2004 Nht u t cho lnh vc
ny t 900 triu USD v tng ln 950 triu USD vo cui nm 2005. Chnh ph
Nht coi vic pht trin nhng linh kin mi s dng cng ngh nano l mt
trong 5 d n hng u nhm phc hi kinh t t nc. Ngoi ra cc nc chu
khc nh Trung Quc, n , Hn Quc, i Loan, Thi Lan, cng a ra nhng
k hoch di hn v nhng khon u t ln cho vic nghin cu v pht trin u t
cng ngh nano ng dng cho cc ngnh khc nhau.
Trong s cc vt liu c kch thc nano th nanoclay thu ht c s quan tm

22
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

ch ca rt nhiu nh khoa hc bi cc c tnh u vit ca chng nh din tch b

mt ring ln c 700800 m2/g, gi thnh r, d iu ch,... Ch vi mt lng nh
c vi phn trm khi lng c a vo polyme ngi ta c th nng cao nhiu
tnh cht c l ca vt liu, nng cao kh nng chng chy, h s chng thm kh ln
rt nhiu ln m khng lm tng ng k trng lng, trong ca vt liu.
Hin nay, s lng cc cng trnh cng b v polyme/silica nanocompozit
ngy cng tng. Nhng pht trin gn y v vic ch to, c im, tnh cht v
ng dng ca loi nanocompozit ny c xem xt. Ch yu c ba phng
php ch to polyme/silica nanocompozit c th c s dng l trn nng
chy, qu trnh sol gel v trng hp in-situ, c ba phng php ny c
nghin cu rng ri. Ngoi cc tnh cht ca cc thnh phn cu t trong
nanocompozit, mc phn tn ca cc ht nano trong polyme v s tng tc b
mt ng vai tr quan trng trong vic gia cng hoc hn ch cc tnh cht chung
ca h. Xu hng cho thy khng c m hnh chung cho cc tnh cht ca vt liu
polyme nanocompozit c th c suy lun tng qut. Tuy nhin cc tnh cht ca
polyme/silica nanocompozit, ni chung l cao hn hn vi nhng polyme tinh
khit v polyme microcompozit.
Polyme/silica nanocompozit ni chung v cao su/silica nanocompozit ni ring
cng c nhiu nh khoa hc quan tm nghin cu, c bit l cao su thin
nhin/silica nanocompozit. Tnh cht ca vt liu cao su thin nhin/nanosilica cho
thy, nanosilica lm tng thi gian lu ha, ng sut ko ca cao su-nanosilica
dn di thp nh hn vi cao su thng. Zheng Peng v cng s [50] nghin cu
cao su thin nhin/silica nanocompozit t ghp, kt qu cho thy nano-SiO 2 phn
tn ng nht trong nn cao su, kch c ht vo khong 60-150nm khi hm lng
SiO2 di 6,5%. hm lng 4% nano-SiO2 nng cao kh nng bn nhit v tnh
cht c hc cho cao su thin nhin trong bn ko t ca vt liu tng mnh
(cao su thin nhin khng n l 15,1 MPa cn cao su thin nhin c 4% nano-SiO 2
l 26,3 MPa). Tc gi Ying Chen nghin cu vt liu nanocompozit t cao su
thin nhin c gia cng bng nanosilica. Kt qu cho thy cc ht nano-SiO 2
phn tn ng nht vo nn cao su thin nhin hnh thnh cc m nano hnh cu

23
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

vi kch thc trung bnh 80 nm khi hm lng nano-SiO 2 l 4 phn khi lng.
Vi s c mt ca nano-SiO2 bn nhit ca cao su thin nhin tng ln ng k,
nng lng hi phc hot ha ca nanocompozit cao hn cao su thin nhin ban
u t 90,1 n 125,8 KJ/mol. Saowaroj Chuayjuljit, v Anyaporn Boonmahitthisud
nghin cu vt liu nanocompozit ca cao su thin nhin v PS c cha nanosilica
c ch to bng phng php kt hp latex. Nanolatex ca PS c cha nanosilica
c tng hp bng phng php trng hp huyn ph micro trc tip. Cc ht
nano lai thu c c hnh thi cu trc nhn-v vi ng knh trung bnh ca cc
ht l 40 nm. Cc ht nanosilica lai c s dng lm cht n cho vt liu cao su
thin nhin nanocompozit. Cc tnh cht ca cao su thin nhin nh bn ko t
v modul ko 300% c ci thin vi s c mt ca PS c cha nanosilica 3 v
3-9 phn khi lng ngoi tr dn di khi t v 9 phn khi lng bn
chy c ci thin ng k. Khi nghin cu tnh cht c ng hc cho thy cc
tnh cht n hi ca CSTN gn nhit ha thy tinh c ci thin cng vi s
gia tng hm lng ca nanosilica c gi thch l do cu trc nano an xen nhau
trong vt liu.
K t khi pht hin ng nano carbon (CNT) ca Iijima vo nm 1991, vt liu
polyme/CNT nanocompozit l ch ca nhiu nghin cu trong Vin hn lm
v trong cng nghip. Vic s dng CNT lm cht n cho polyme ni chung v
cao su ni ring nhm ci thin tnh cht c hc v tnh cht in ca vt liu
[38,44]. CNT c th c phn loi theo s lp tng trong ng l n tng v a
tng, mi lp tng c th tip tc phn thnh cc dng i xng hoc khng i
xng.
Gn y, rt nhiu bi bo nghin cu nh hng ca CNT ti cht cht nn
cao su bng cch n CNT vo trong cao su hm lng thp (thng dng ng
nano carbon a tng hn ng nano carbon n tng). CNT c phn tn trong
cao su bng phng php dung dch, qu trnh ny i hi CNT v cao su tan
trong mt dung mi, sau cho dung mi bay hi th thu c nanocompozit.
Vic ch to nanocompozit trn c cao su vi CNT chc nng ha bng phng
php trn nng chy c bo co.

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

Cc loi cao su c s dng nhiu trong nghin cu CNT nanocompozit l

cao su thin nhin (CSTN) [29] tip theo l cao su styren-butadien (SBR) [18],
cao su silicon [30], cao su nitril hydro ha (HNBR) v cao su etylen-propylen-
dien monome (EPDM). n nm 2010 c ring mt cun sch v vt liu Cao
su nanocompozit c xut bn. Cho ti nay, hng nghin cu ny vn ang
c quan tm vi nhiu cng trnh cng b mi nm.
Ring Vit Nam, hng nghin cu vt liu polyme nanocompozit cng
c nhiu nh khoa hc quan tm. Cc ph gia nano hay c s dng nghin
cu l nanoclay, nanosilica, ng nano carbon, Tc gi ng Vit Hng
nghin cu ch to vt liu nanocompozit trn c s cao su t nhin v cht n
nano-silica bng hai phng php l trn hp nng chy v trn huyn ph. Trong
hai phng php trn th phng php trn huyn ph cho kch thc ht silica
phn tn kch thc 30-100 nm. L Vn Th gn thnh cng dodexylamin
(DDA) v 3- amino propyltrietoxy silan (ATS) ln b mt ng nano carbon a
tng (MWCNT) v ng dng chng trong ch to vt liu nanocompozit vi
carbon/MWCNT/epoxy; hay Nguyn Th Thi thc hin thnh cng qu trnh
hu c ha b mt CNT bng qu trnh oxi ha gn nhm -COOH t nghin
cu cc vt liu nanocompozit trn c s CSTN/PP, CSTN/SBR, CSTN/EPDM,
CSTN/BR. Tip theo , cc tc gi Trn Hi Ninh v cng s cng b kt qu
nghin cu v nh hng ca cao su thin nhin epoxy ha ti tnh cht ca vt
liu cao su thin nhin/silica nanocompozit v gn y, cc tc gi Thi Hong,
Quang Thm, inh Th Mai Thanh tip tc cng b mt s kt qu nghin cu
v cu trc, tnh cht ca vt liu EVA/silica nanocompozit, Tuy nhin nhng
kt qu nghin cu v lnh vc ny cho ti nay cng ch dng li kt qu nghin
cu, cha c trin khai tip tc quy m ln hn vo thc t.
T nhng ni dung trn, cho thy vt liu polyme nanocompozit ni chung v
cao su nanocompozit trn c s cao su gia cng bng nanoclay, nanosilica, ng
nano carbon l mt loi vt liu mi c tim nng ng dng to ln. Tuy nhin, cho
ti nay trn th gii v c bit Vit Nam vn cha c nhiu ng dng ca vt
liu ny trong thc t. V vy vn nghin cu ch to, tnh cht v ng dng ca

25
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

vt liu cao su, cao su blend nanocompozit ang l lnh vc nghin cu cn rng
m v ha hn nhng tng lai tt p cho nhng ng dng cng ngh cao ca
loi vt liu ny.

26
VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

KT LUN
1. Bng phng php trn kn trng thi nng chy to ra c h vt liu
cao su nanocompozit trn c s blend CSTN/NBR vi cc ht nanosilica phn tn
ng u trong nn cao su kch thc a phn di 100 nm. Cng bng phng
php ny phn tn c CNT-g-PVC kh ng u trong nn cao su k trn.
Tuy nhin, nu CNT khng c bin tnh th s phn tn ca chng khng c
ng u. Chnh v vy, cc tnh nng c l, k thut ca h vt liu trn c s
CSTN/NBR gia cng CNT cha tng mt cch thuyt phc nh k vng.

2. T nhng kt qu nghin cu gia cng cho blend CSTN/NBR bng

nanosilica cho thy: Hm lng nanosilica ti u gia cng cho cao su blend
CSTN/NBR l 7%. hm lng ny, tnh cht c hc ca vt liu t gi tr cao
nht ( bn ko t tng khong 25%, nhit bt u phn hy tng 12,5C).
Khi c thm 5% tc nhn ghp ni silan Si69 (so vi nanosilica hay 0,6% so vi
cao su), nanosilica phn tn ng u trong nn cao su vi kch thc ht nh hn
(di 60 nm). Chnh v vy, tnh cht c hc, kh nng bn nhit v bn du m
ca vt liu cao su CSTN/NBR/7nSiO 2 nanocompozit c ci thin ng k (
bn ko khi t tng thm 11%, nhit bt u phn hy tng thm 4C).

3. Trn c s nhng kt qu nghin cu gia cng cho blend CSTN/NBR bng

CNT cho thy, tnh cht c hc ca vt liu CSTN/NBR t gi tr ln nht vi
hm lng CNT l 4%. hm lng ny, bn ko khi t ca vt liu tng
39%, bn mi mn tng y%, nhit bt u phn hy tng 11 oC, Trong khi
h CSTN/NBR/CNT-g-PVC cc gi tr ln nht t c hm lng CNT-g-
PVC l 3%. Ti hm lng ny, bn ko khi t ca vt liu tng 49%, nhit
bt u phn hy tng 14 oC,... Tuy nhin, t kt qu nghin cu cu trc hnh
thi cng ch ra rng, bng phng php trn hp trng thi nng chy, CNT
phn tn cha tht ng u trong nn cao su blend CSTN/NBR v do vy tnh
cht c l k thut ca h vt liu ny cha t c nh k vng.

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

TI LIU THAM KHO

Ting Vit
1. La Vn Bnh (2002), Khoa hc v cng ngh vt liu, NXB i hc Bch
khoa, H Ni.
2. Bi Chng, ng Vit Hng, Phm Thng Giang (2007), S dng silica
bin tnh (3 trietoxysilylpropyl) tetrasunfit (TESPT) lm cht n gia
cng cho hn hp cao su t nhin Butadien, Tp ch ha hc, T.45, N4,
tr.67-71.
3. Nguyn Thy Dng, Nguyn Anh Sn, Trnh Anh Trc, T Th Xun Hng
(2015), ng dng nanosilica bin tnh phenyl trietoxysilan lm cht ph gia
cho lp ph bo v chng n mn, Tp ch ha hc, 53(1), tr.95 100.

4. Nguyn nh Hong (2011), Nghin cu cu trc ca ng nano carbon di

tc ng ca cc loi bc x nng lng cao nh hng ng dng trong
mi trng v tr, Lun vn Thc s trng H Cng ngh - HQGHN.
5. ng Vit Hng (2010), Nghin cu ch to vt liu polyme nanocompozit
trn c s cao su thin nhin v cht n nano, Lun n Tin s k thut,
HBK H Ni
6. Quang Khng (2012), Cao su-Cao su blend v ng dng, Nh xut bn
Khoa hc t nhin v Cng ngh H Ni.
7. Quang Khng (2013), Vt liu polyme - vt liu polyme tnh nng cao,
NXB Khoa hc t nhin v cng ngh H Ni.
8. Quang Khng, Trng Thin, Nguyn Vn Khi (1995), Vt
liu t hp polyme - nhng u im v ng dng, Tp ch hot ng khoa
hc, 10, tr.37 - 41.
9. Phan Ngc Minh (2010), Tng hp, nghin cu tnh cht v ng dng vt
liu ng cc bon nano n tng, a tng, Bo co tng kt nhim v hp
tc quc t v khoa hc v cng ngh Vit nam- Cng ha Php.
10. Nguyn c Ngha (2009), Polyme chc nng v vt liu lai cu trc nano,
NXB Khoa hc t nhin v Cng ngh H Ni, tr. 111- 138.
11. Nguyn Th Thi (2011), Nghin cu nh hng ca cc cht n gia

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VT LIU NANO COMPOSITE GVHD: Th.S. on Mnh Tun

cng carbon (carbon nanotube, carbon black) ln tnh cht v cu trc cc

vt liu polyme hn hp trn c s CSTN, SBR, BR, EPDM v polypropylen,
Lun n Tin s Ha hc, H Ni.
12. Nguyn Th Thi, Nguyn Quang(2010), Nghin cu kho st tnh cht ca
vt liu polyme t hp trn c s cao su thin nhin v polypropylen, cao su
styren butadien gia cng carbon nanotube di tc dng ca iu kin kh
hu nhit i Vit Nam, Tp ch Ha hc, 48 (4A), tr. 429-433.
Ting Anh
13. A. Das,, K.W. Sto ckelhuber, R. Jurk, M. Saphiannikova, J. Fritzsche, H.
Lorenz,M. Kluppel, G. Heinrich (2008), Modified and unmodified
multiwalled carbon nanotubes in high performance solution-styrene-
butadiene and butadiene rubber blends, Polymer, 49, pp. 5276-5283
14. Andrew Ciesielski (1999), An Introduction to Rubber Technology, Rapra
Technology Limited, United Kingdom.
15. d Using BIAT-CBS System, Journal of Polymers, Article ID 798232.
16. Shanmugharaj A.M., Bae J.H., Lee K.Y., Noh W.H., Lee S.H., and Ryu S.H.
(2007), Physical and chemical characteristics of multi-walled carbon
nanotubes functionalized with aminosilane and its influence on the properties
of natural rubber composites Composites Sci.Tech., 67, pp. 18131822.
17. Shaoping Xiao and WenyiHou, Fullerenes (2006), Nanotubes, and
Carbon , Nanostructures,14, pp. 916.
18. T. Jesionowski, J.Zurawska, A.Krysztafkiewicz (2008), Surface properties
and dispersion behaviour of precipitated silicas, Journal of materials
science, Vol. 37, pp. 1621 1633.
19. X. L. Wu, P. Liu (2010), Poly(vinyl chloride)-grafted multi-walled carbon
nanotubes via Friedel-Crafts alkylation, Express Polymer Letters, 4 (11),
pp. 723-728.

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