B GIO DC V O TO VIN HN LM KHOA HC V CNG NGH VIT NAM

VIN HO HC

LNG NH HI

NGHIN CU NG DNG TRO BAY LM CHT N

GIA CNG CHO VT LIU CAO SU V CAO SU BLEND

LUN N TIN S HA HC

H Ni - 2015

1
B GIO DC V O TO VIN HN LM KHOA HC V CNG NGH VIT NAM
VIN HO HC

LNG NH HI

NGHIN CU NG DNG TRO BAY LM CHT N

GIA CNG CHO VT LIU CAO SU V CAO SU BLEND

Chuyn ngnh: Ha Hu c
M s: 62.44.27.01

LUN N TIN S HA HC

NGI HNG DN KHOA HC:

1. PGS. TS. Quang Khng
2. PGS. TS. Ng K Th

H Ni - 2015

2
 M U
Tro bay (fly ash - FA) l nhng ht tro rt nh b cun theo kh t ng
khi ca cc nh my nhit in do t nhin liu than. Loi ph thi ny nu
khng c thu gom, tn dng s khng ch l mt s lng ph ln m cn l
mt him ha i vi mi trng-nht l trong thi k pht trin mnh m
ca cc ngnh cng nghip hin nay. Chnh v vy, vic nghin cu, x l, tn
dng tro bay trong cc lnh vc kinh t, k thut v ang c cc nh
khoa hc, cng ngh trong v ngoi nc quan tm c bit.
Tro bay c th c ng dng trong nhiu lnh vc ca i sng k
thut, cc ng dng ca tro bay c chia thnh ba nhm: ng dng cng
ngh thp, ng dng cng ngh trung bnh v ng dng cng ngh cao. Cc
ng dng cng ngh thp nh s dng tro bay trong san lp, lm k, va h
v nn ng, n nh lp mng, ci to t,... Cc ng dng cng ngh trung
bnh nh s dng tro bay trong xi mng, ct liu nh, cc loi b tng c
sn/b tng m ln, gch, p lt, Cc ng dng cng ngh cao lin
quan n vic s dng tro bay lm nguyn liu thu hi kim loi, cht n
cho compozit nn kim loi, compozit nn polyme v lm cht n cho mt s
ng dng khc.
Tro bay c thnh phn ha hc chnh l SiO2 cng vi nhng u im
nh t trng thp, tnh cht c hc cao, bn nhit, chng co ngt kch thc,...
tro bay c th l cht n gia cng c hiu qu cho cc vt liu cao su v
cht do. Tro bay c th thay th cc cht n gia cng truyn thng nh
canxi cacbonat, oxit silic, hoc phi hp vi than en trong hp phn cao
su. Vic s dng tro bay lm cht cht n gia cng cho cao su gp phn
gim gi thnh sn phm (v tro bay c gi rt thp) m vn m bo c
tnh cht ca vt liu. Tuy nhin tng kh nng tng tc ca tro bay vi
cao su, ngi ta thng phi x l, bin tnh b mt tro bay. Trong trng
hp ny, i vi tng polyme hay cao su c gia cng cn phi la chn
hp cht silan cho ph hp thc hin qu trnh bin tnh b mt tro bay.

3
 nc ta nhng cng trnh nghin cu no s dng tro bay trong lnh
vc cao su hu nh cha c quan tm. Trong khi , Vit Nam l mt
trong nhng nc sn xut ch bin cao su thin nhin (CSTN) ln trn th
gii. Chnh v vy, ti Nghin cu ng dng tro bay lm cht n gia
cng cho vt liu cao su v cao su blend c chn lm ch cho lun n
tin s ca mnh.
Mc tiu nghin cu ca lun n l nh gi c kh nng gia cng
ca tro bay Ph Li ti tnh cht ca vt liu cao su thin nhin (CSTN) v
blend ca chng t nh hng cho vic ng dng tro bay trong ngnh
cng nghip gia cng cao su. thc hin mc tiu trn, lun n thc
hin cc ni dung nghin cu ch yu sau:

- Nghin cu x l b mt tro bay bng cc hp cht silan khc nhau,

- Nghin cu kh nng gia cng ca tro bay (khng v bin tnh)
cho cao su thin nhin,
- Nghin cu kh nng gia cng ca tro bay (khng v bin tnh)
cho mt s cao su blend trn c s CSTN,
- Nghin cu ng dng vt liu cao su gia cng tro bay ch to sn
phm ng dng trong thc t.

4
 Chng 1: TNG QUAN
1.1. Khi nim v phn loi tro bay
Trong cc nh my nhit in, sau qu trnh t chy nhin liu than
phn ph thi rn tn ti di hai dng: phn x thu c t y l v phn tro
gm cc ht rt mn bay theo cc kh ng khi c thu hi bng cc h thng
thu gom ca cc nh my nhit in.
Trc y chu u cng nh Vng quc Anh phn tro ny thng
c cho l tro ca nhin liu t c nghin mn [1]. Nhng M, loi
tro ny c gi l tro bay bi v n thot ra cng vi kh ng khi v bay
vo trong khng kh. V thut ng tro bay (fly ash) c dng ph bin trn
th gii hin nay ch phn thi rn thot ra cng cc kh ng khi cc nh
my nhit in.
mt s nc, ty vo mc ch s dng m ngi ta phn loi tro bay
theo cc loi khc nhau. Theo tiu chun DBJ08-230-98 ca thnh ph Thng
Hi, Trung Quc, tro bay c phn lm hai loi [2] l tro bay c hm lng
canxi thp v tro bay c hm lng canxi cao. Tro bay c cha hm lng
canxi 8% hoc cao hn (hoc CaO t do trn 1%) l loi tro bay c hm lng
canxi cao. Do , CaO trong tro bay hoc CaO t do c s dng phn bit
tro bay c hm lng canxi cao vi tro bay hm lng canxi thp. Theo cch
phn bit ny th tro bay c hm lng canxi cao c mu hi vng trong khi
tro bay c hm lng canxi thp c mu hi xm.

Theo cch phn loi ca Canada, tro bay c chia lm ba loi [3]:
Loi F: Hm lng CaO t hn 8%
Loi CI: Hm lng CaO ln hn 8% nhng t hn 20%
Loi C: Hm lng CaO ln hn 20%
Trn th gii hin nay, thng phn loi tro bay theo tiu chun ASTM
C618. Theo cch phn loi ny th ph thuc vo thnh phn cc hp cht m
tro bay c phn lm hai loi l loi C v loi F [4].

5
 Bng 1.1: Tiu chun tro bay theo ASTM C618
Cc yu cu theo tiu chun n Ln nht Nhm Nhm
ASTM C618 v /nh nht F C
Yu cu ha hc
SiO2 + Al2O3 + Fe2O3 % nh nht 70 50
SO3 % ln nht 5 5
Hm lng m % ln nht 3 3
Hm lng mt khi nung % ln nht 5 5
Yu cu ha hc khng bt buc
Cht kim % 1,5 1,5
Yu cu vt l
mn (+325) % ln nht 34 34
Hot tnh pozzolanic so vi xi mng (7 % nh nht 75 75
ngy)
Hot tnh pozzolanic so vi xi mng % nh nht 75 75
(28 ngy)
Lng nc yu cu % ln nht 105 105
n trong ni hp % ln nht 0,8 0,8
Yu cu ng u v t trng % ln nht 5 5
Yu cu ng u v mn % ln nht 5 5
Phn loi theo tiu chun ASTM:
Tro bay l loi F nu tng hm lng (SiO2 + Al2O3 + Fe2O3) ln hn 70%.
Tro bay l loi C nu tng hm lng (SiO2 + Al2O3 + Fe2O3) nh hn 70%.
1.2. Cc c trng ca tro bay
1.2.1. Thnh phn ha hc trong tro bay
Tro ca cc nh my nhit in gm ch yu cc sn phm to thnh t
qu trnh phn hy v bin i ca cc cht khong c trong than [5].
Thng thng, tro y l chim khong 25% v tro bay chim khong 75%
tng lng tro thi ra. Hu ht cc loi tro bay u l cc hp cht silicat bao
gm cc oxit kim loi nh SiO2, Al2O3, Fe2O3, TiO2, MgO, CaO, vi hm
lng than cha chy ch chim mt phn nh so vi tng hm lng tro,
ngoi ra cn c mt s kim loi nng nh Cd, Ba, Pb, Cu, Zn,... Thnh phn
ha hc ca tro bay ph thuc vo ngun nguyn liu than s dng t

6
v iu kin t chy trong cc nh my nhit in.
Bng 1.2: Thnh phn ha hc ca tro bay theo vng min [6]

Thnh Khong (% khi lng)

phn Chu u M Trung Quc n Australia
SiO2 28,5-59,7 37,8-58,5 35,6-57,2 50,2-59,7 48,8-66,0
Al2O3 12,5-35,6 19,1-28,6 18,8-55,0 14,0-32,4 17,0-27,8
Fe2O3 2,6-21,2 6,8-25,5 2,3-19,3 2,7-14,4 1,1-13,9
CaO 0,5-28,9 1,4-22,4 1,1-7,0 0,6-2,6 2,9-5,3
MgO 0,6-3,8 0,7-4,8 0,7-4,8 0,1-2,1 0,3-2,0
Na2O 0,1-1,9 0,3-1,8 0,6-1,3 0,5-1,2 0,2-1,3
K2O 0,4-4,0 0,9-2,6 0,8-0,9 0,8-4,7 1,1-2,9
P2O5 0,1-1,7 0,1-0,3 1,1-1,5 0,1-0,6 0,2-3,9
TiO2 0,5-2,6 1,1-1,6 0,2-0,7 1,0-2,7 1,3-3,7
MnO 0,03-0,2 - - 0,5-1,4 -
SO3 0,112,7 0,12,1 1,02,9 - 0,10,6
MKN 0,832,8 0,211,0 - 0,5-5,0 -

Ty thuc vo loi nhin liu m thnh phn ha hc trong tro bay thu c
khc nhau. Cc nh khoa hc Ba Lan tin hnh nghin cu thnh phn ha hc
ca tro bay vi hai ngun nguyn liu s dng trong cc nh my nhit in ca
nc ny l than nu v than en [7]:

Bng 1.3: Thnh phn ha hc tro bay Ba Lan

t cc ngun nguyn liu khc nhau
Loi tro Thnh phn (%)
bay SiO2 Al2O3 Fe2O3 TiO2 MgO CaO
Than en
ZS-14 54,1 28,5 5,5 1,1 1,9 1,8
ZS-17 41,3 24,1 7,1 1,0 2,0 2,7
Than nu
ZS-13 27,4 6,6 3,8 1,0 8,2 34,5
ZS-16 47,3 31,4 7,7 1,6 1,9 1,7

Kt qu trn cho thy, thnh phn ca cc loi tro bay c c sau qu

7
trnh t chy than en (ZS-14 v ZS-17) v mu tro bay c c sau qu
trnh t chy than nu (ZS-16) l cc nhm silicat. Cn mu tro bay c c
sau qu trnh t chy than nu (ZS-13) l loi canxi silicat.

Cc th nghim kho st thnh phn ha hc trong cc mu tro bay cc

nc khc cng c tin hnh v thu c cc kt qu tng t. a s
cc mu tro bay Trung Quc c thnh phn ch yu l SiO 2 v Al2O3, hm
lng ca chng vo khong 650 g/kg n 850 g/kg. Cc thnh phn khc bao
gm lng than cha chy, Fe2O3, MgO v CaO. Tro bay Trung Quc cha
hm lng than cha chy cao l do h thng l t cc nh my nhit in
Trung Quc. Theo tiu chun phn loi ASTM C 618 th tro bay Trung
Quc thuc loi C hay tro bay c cht lng thp. iu ny nh hng ln
n cc ng dng ca tro bay Trung Quc [8].
* Cc nguyn t vi lng trong tro bay
Qu trnh t chy than l mt trong nhng nguyn nhn chnh lm
nhim khng kh v pht tn cc kim loi cc nguyn t vi lng c hi.
Hiu c s thay i ca cc nguyn t vi lng trong qu trnh t than
cng nh hm lng ca n c trong tro bay to thnh l iu rt quan trng
trong vn nh gi tc ng mi trng ca cc nh my nhit in cng
nh cc ng dng tro bay. Hm lng cc nguyn t vi lng trong tro bay
ph thuc ch yu vo hm lng ca chng c trong nguyn liu ban u.
Da trn kt qu nghin cu cc mu tro bay thu c t 7 nh my
nhit in khc nhau Canada [5], cc nh nghin cu nc ny cho bit
hm lng ca cc kim loi nng nh As, Cd, Hg, Mo, Ni hay Pb trong tro
bay c lin quan vi hm lng lu hunh c trong nguyn liu than ban
u. Thng thng, cc loi than c hm lng lu hunh cao s c hm
lng cc nguyn t ny cao. Tro bay Canada c thu hi bng phng
php kt lng tnh in hoc phng php lc ti. Kt qu cho thy hm
lng cc nguyn t trn trong cc loi tro bay thu c t phng php lc
ti cao hn so vi cc mu tro bay thu c bng phng php kt lng tnh
in trong cng mt nh my.
8
1.2.2. Cu trc hnh thi ca tro bay
Hu ht cc ht tro bay u c dng hnh cu vi cc kch thc ht khc
nhau, cc ht c kch thc ln thng dng bc v c hnh dng rt khc
nhau [9]. Cc ht tro bay c chia ra lm hai dng: dng c v dng rng.
Thng thng, cc ht tro bay hnh cu, rn c gi l cc ht c v cc ht
tro bay hnh cu m bn trong rng c t trng thp hn 1,0 g/cm3 c gi l
cc ht rng. Mt trong cc dng thng thy tro bay thng c to nn
bi cc hp cht c dng tinh th nh thch anh, mulit v hematit, cc hp
cht c dng thy tinh nh thy tinh oxit silic v cc oxit khc.

Hnh 1.1: S tng phn v kch thc Hnh 1.2: Biu din c trng dng
gia cc ht tro bay hnh cu ln v cu ca cc ht trong khong kch
cc ht nh thc thng thy nhiu hn

Cc ht tro bay c c khi lng ring trong khong 2,0 - 2,5 g/cm3 c
th ci thin cc tnh cht khc nhau ca vt liu nn nh cng v bn x.
Cc ht tro bay rng c th c s dng trong tng hp vt liu compozit siu
nh do khi lng ring rt nh ca chng, ch khong 0,4-0,7 g/cm3, trong khi
cc cht nn kim loi khc c khi lng ring trong khong t 1,6-11,0 g/cm3.
C hai loi ht ny thng thy c lp v khng hon chnh (b r).

* Cu trc bn trong:
Cc ht bn trong c th c thy bi cc quan st n gin. Cu trc
ny b che lp bi lp v thy tinh, v th n c th c quan st khi c x
l vi dung dch HF, dung dch ny c th ha tan nhanh chng phn thy
tinh v l ra lp v bn trong.

9
 Hnh 1.3 biu din hai ht tro bay cnh nhau sau khi tip xc ngn (1/2
gi) vi dung dch axit hydrofloric 1%, hai cu trc bn trong rt khc nhau
c l ra. Cc ht bn tri l cc ht c t tnh giu st, v vt liu c cu
trc tinh th bn c dng hnh cy c nghin cu bi nhm Biggs v
Brunsnel. Tt c chng u c hnh lp phng v c hy vng hon ton
khng c cc phn ng ha hc trong b tng.

Hnh 1.3: Cu trc ht tro bay sau khi Hnh 1.4: Cu trc tro bay tip xc vi
tip xc ngn vi dung dch HF dung dch HF trong thi gian di

Cc ht bn phi hnh 1.3 cha mt cu trc c trng ca cc ht

mullit c dng thanh mng hay dng hnh kim, Al 2O3.2SiO2 tm thy trong
hu ht cc ht khng c t tnh ca cc ht tro bay c hm lng canxi thp
in hnh.

S v cng hn tp ca cc ht tro bay v cu trc c nhn thy, bao

gm cc ht khc nhau trong cng loi tro bay c th hin trong hnh 1.4.
Mu tro bay ny c tip xc nh trong thi gian lu hn vi qu trnh x l
bng axit hydrofloric trong thi gian 1 gi. Phn thy tinh trong cc ht vng
gia v trong ca mt s ht khc c phn b xung quanh phn b ha tan
mc ln.

1.2.3. Phn b kch thc ht trong tro bay

Kch thc ht tro bay l mt yu t quan trng quyt nh n kh nng

ng dng ca n. Mi loi tro bay ty thuc vo ngun nguyn liu, iu kin
t v phng php thu hi m c s phn b kch thc ht trong tro bay
10
khc nhau. Tro bay c kch thc ht nm trong khong 10-350 m, phn
on c ng knh ht nh hn 45 m chim t trng ln.

Bng 1.4: Phn b kch thc ht cc phn on tro bay Israel [10]
Ngun nguyn liu
Phn on Kch thc
(mesh) (m) Nam Phi Colombia
(%) (%)
< 100 > 150 1,9 4,5
100200 15075 8,2 10,0
200325 7545 10,6 9,2
> 325 < 45 79,2 76,3

Ty thuc vo mc ch v nhu cu s dng m c th tch cc phn

on kch thc khc nhau. Hai loi tro bay thng phm ca Cng ty Boud
Minerals & Polymers (Anh Quc) s dng lm cht gia cng cho cht do
c kch thc ht th hin trn bng 1.5.

Bng 1.5: Kch thc ht tro bay thng phm

Thng s n v Plasfill 5 Plasfill 15
D50 m 3,8 11,5
D99 m 19,5 110
D90 m 8,5 52
T trng g/cm3 2,15 2,25
Mu sc Ghi sng Ghi sng

1.3. Sn lng tro bay v tnh hnh s dng tro bay trn th gii
1.3.1. Sn lng tro bay trong v ngoi nc
Nhu cu tiu th in nng trn th gii khng ngng tng ln theo tc
pht trin ca nn kinh t x hi. Cc ngun cung cp in nng mi hin
nay ang pht trin nhanh chng phi k n nh nng lng mt tri, nng
lng gi, nng lng thy triu, Tuy c nhiu u im v c khuyn
khch s dng nhng cc ngun cung cp in nng ny hin nay mi ch p
ng c mt lng rt nh nhu cu in nng ton cu v ch tp trung
mt vi nc pht trin. Ngun cung cp in nng ch yu vn da trn cc

11
ngun truyn thng v khng ngng pht trin hng nm. Trong cc nh
my nhit in s dng nhin liu ha thch chim mt t trng ln.

Hnh 1.5: Biu sn lng tro bay v

phn trm s dng tro bay M t 1966-2012
M l mt trong cc quc gia tiu th in nng hng u th gii v
cng l nc c sn lng cc sn phm t qu trnh t chy than trong
cc nh my nhit in ln ca th gii [11]. Nm 2007, M to ra hn
125 triu tn cc sn phm t than bao gm tro bay, tro y l, x l,
Phn trm s dng tro bay M gim trong nhng nm 2007 - 2010,
nhng sau t l s dng tro bay li tng.
Trung Quc l nc ng u v sn xut in nng t than , do vy
lng tro bay to ra t vic t than cng rt ln. Nm 2009, cng sut
pht in v in nng ca cc nh my nhit in u tng khong 7-8%.
Mc d, lng tiu th than c gim xung bng cch nng cao hiu qu
ca my pht in, nhng lng tro bay to ra vn duy tr tng [12]. Nm
2010, lng tro bay to ra l 480 triu tn v vi tc tng trng 20 triu
tn mi nm, d kin lng tro bay to ra Trung Quc hin nay t trn 500
triu tn.

12
 Hnh 1.6: Biu lng tro bay to thnh, tro bay s dng v
phn trm s dng tro bay Trung Quc t 2001-2008
n , mt lng ln tro bay to ra trong qu trnh t chy than ca
cc nh my nhit in. Lng tro bay to ra hng nm lin tc tng t khong 1
triu tn vo nm 1947 ln khong 40 triu tn trong nm 1994 v nm 2012 vo
khong 131 triu tn. K t 1996-97 n 2010-11, lng tro bay s dng vo
trong cc lnh vc cng nghip cng tng (nm 1996-1997 l 9,63% n nm
2010-2012 l 56%). Nm 2009-2010 n t c mc s dng tro bay
cao nht 63% [13].
Nh mt iu hin nhin, khi lng than s dng trong cc nh my
nhit in cng nhiu th cc sn phm ph ca qu trnh t chy nhin liu
nh x than hay tro bay sinh ra cng tng theo. Thng k ca cc nh khoa
hc Hy Lp cho thy lng tro bay sinh ra gn nh t l tuyn tnh vi lng
nhin liu than c s dng [14].
Theo c tnh, lng tro bay thi ra trn ton cu vo khong trn 700
triu tn. Sn lng v phn trm s dng tro bay ca mt s nc c trnh
by trong bng 1.6 [11-13,15].

13
 Bng 1.6: Sn lng v phn trm s dng tro bay mt s nc
Nc sn Sn lng tro bay hng Tro bay s dng
TT
xut nm (triu tn) (%)
Trung Quc
1 480 67
(2010)
2 n (2012) 131 54
3 M (2010) 70 45
4 c 40 85
5 Anh 15 50
6 Australia 10 85
7 Canada 6 75
8 Php 3 85
9 an Mch 2 100
10 2 100
11 H Lan 2 100

Vit Nam, phn ln cc nh my nhit in t than ch yu tp trung

pha Bc, do gn ngun than. Tng cng sut cc nh my nhit in ang
vn hnh tnh thi im 2010 l 4.250 MW [16] v d kin vo nm 2020
s l 7.240 MW.

Bng 1.7: Tro bay t cc nh my nhit in trong giai on 2010-2030

TT Nm Cng sut, Tiu th than, Lng tro bay,
MW triu tn/nm triu tn/nm
1 2010 4.250 12,75 3,82-4,46
2 2015 6.240 18,72 5,61-6,55
3 2020 7.240 21,72 6,51-7,60
Ngun cung cp than nhin liu trong nc cho cc nh my in
thng l loi than cht lng thp, c tro ln hn 3132%, thm ch n
4345%. Do , cc nh my nhit in thi ra lng tro bay kh ln, c th
chim ti 20-30% lng than s dng. Vi sut tiu hao than trung bnh
khong 500 g/kWh, tng lng than s dng cho nhit in v lng tro bay
to thnh c trnh by trong bng 1.7.

14
1.3.2. Tnh hnh s dng tro bay
Tro bay c s dng rt thnh cng trong ngnh cng nghip b
tng trn th gii hn 50 nm qua. M c hn 6 triu tn v chu u l
hn 9 triu tn c s dng trong xi mng v b tng [17]. C nhiu d
n ln trong thi gian gn y s dng b tng tro bay, bao gm cc p ngn
nc, cc nh my in, cc cng trnh ngoi bin, cc ng hm di bin,
ng cao tc, sn bay, cc ta nh thng mi hay dn c, cu, cc ng
ng dn,...
n nm 2008, tng lng cc sn phm t t than ca nh my
nhit in Chu u l 58 triu tn, trong tro bay chim gn 68% tng
ng khong 39 triu tn. Khong 18 triu tn tro bay c s dng trong
cng nghip xy dng v san lp hm m. Phn ln tro bay lm ph gia b
tng, kt cu ng v lm vt liu sn xut clinke xi mng. Tro bay cng
c s dng trong xi mng trn, b trong khi v lm cht in lp [18].
Cng nh nhiu quc gia trn th gii, hng trm nh my nhit in
trn khp lnh th Trung Quc thi ra hng trm triu tn tro bay mi nm
[8]. Do vy, chnh ph Trung Quc rt khuyn khch pht trin cc cng ngh
lin quan n vic s dng tro bay. Mt vi thnh ph s dng rt tt tro
bay trong nhng nm gn y nh thnh ph Nam Ninh. Nm 2005, lng tro
bay c s dng thnh ph ny vt qua c lng tro bay c to ra.
Tuy nhin, Nam Ninh ch l mt trng hp ngoi l. Tro bay Trung Quc
c s dng trong cc lnh vc ch yu sau: Cc sn phm b tng (ph gia
cho xi mng, va, b tng, gch,...); Xy dng ng giao thng; Xy dng
cng; Ci to t trng; X l nhim nc; S dng lp cc m hay cc
vng t ln hn dc theo b bin. Ngoi ra, tro bay cn c s dng cho
mt vi ng dng khc nh tng hp zeolit, cht gia cng cho cao su.
Ti n , Chnh ph nc ny c nhiu quy nh nng cao nhn
thc v li ch ca vic s dng tro bay cho cc sn phm khc nhau [19-21].
Tro bay l mt nguyn liu tim nng tuyt vi cho sn xut vt liu xy dng
nh xi mng pha trn , gch tro bay , gch p lat v cac khi rng trong xy

15
dng. Chng c ng dng m t l ng l n rai ng, xy dng k, v san
lp hm mo. Sn phm tro bay c nhiu li th hn so vi cc sn phm thng
thng. Lng xi mng s dng trong sn xut sn phm xy dng c th
gim bng cch thay th bng tro bay v lng tro bay thay th c th ln n
50%. Nhng sn phm cha tro bay c bn cao, hiu qu hn v tit kim
ng k nguyn liu. Vic s dng tro bay n to ra cng n vic
lm cho khong 3.000 lao ng [22].
1.3.3. ng dng tro bay trong mt s lnh vc cng nghip trn th gii
1.3.3.1. Tro bay s dng trong lnh vc xy dng
* Tro bay dng lm vt liu in lp: Tro bay c th dng phc hi v
ci to cc vng t yu bi cc hot ng khc. Tro bay c s dng cho pht
trin cc cng trnh cng cng nh cng vin, bi u xe, sn chi,... Tro bay c
bn m nn tng ng hoc ln hn t nn thng c s dng trong
cc lnh vc bi p t [23].

Hnh 1.7: p Puylaurent Php Hnh 1.8: B tng asphalt

s dng tro bay
* Tro bay trong b tng: Tro bay ci thin bn v kt cu ca b tng
dn n tng tui th ca ng. Thng thng, tro bay c th thay th t 15
n 30% xi mng portland [23]. Hin nay, tro bay c ng dng rng ri
trong xy dng vi cc mc ch khc nhau nh lm ph gia cho b tng xi
mng [24], lm n cho b tng asphalt [25]. Mt s cng trnh xy dng ni
ting trn th gii s dng tro bay trong b tng nh p Puylaurent Php,
cy cu Great Belt East ni Copenhagen (an Mch) vi nhng vng t ca
trung tm chu u,... [26].
16
 * Tro bay lm ng x: Tro bay c th c s dng xy dng
ng v k. Vic s dng ny c nhiu li th hn so vi cc phng
php thng thng nh tit kim t trng trt, trnh to ra cc vng trng,
gim chi ph, lm gim nhu cu t x l / lng ng tro bay.

Hnh 1.9: Gch v tm lp t tro bay [27]

* Gch khng nung t tro bay: Tro bay cng l ph liu thn thin mi
trng [24]. Gch tro bay c to thnh t tro bay, ct v xi mng, trong
tro bay l cht n chnh v ct l cht n th hai. Cn xi mng lm cht kt
dnh tt c cc nguyn liu vi nhau. c, tro bay c ng dng sn
xut gch xy nh. Cc khi gch ny c to ra t hn hp ca tro x, tro
bay, vi v nc c p thnh khun [26].

* Sn phm gch p lt t tro bay: Gch p lat co th c sn xut t

tro bay. Gch p lt gm hai lp: lp m t v lp n n. Lp mt l hn hp gm
nha men, xi mng, b t tro bay v lmit . Lp n n l hn hp gm tro bay
bn kh, xi mng v bi m [23].
* Lm vt liu ct nhe: Nhiu cng ngh c pht trin sn xut
ct liu nhn to t tro bay. Ct li u t sn phm tro bay c th c s dng
cho mt lot cc ng dng trong ngnh cng nghip xy dng, bao gm thnh
phn xy dng, thnh phn b tng c sn, b tng trn sn cho cc ta nh
cao tng, [23].
1.3.3.2. Tro bay dng trong nng nghi p
Mt ng dng trc tip ca tro bay l mt tc nhn ci to t nng
nghip [28,29]. Phn ln cc loi cy trng thch hp vi mi trng pH l 6,5-

17
7 cho s pht trin. Vic b sung tro bay kim cho t chua c th lm tng
pH. Phn ln cc nghin cu chng t kh nng ca tro bay lm tng pH
ca t c mi trng axit bng s dng tro bay loi C, tc l tro bay vi hm
lng CaO cao (> 15%) [30].
Tro bay c th cai ta o t v nng cao kha nng gi m, ph nhiu cho
t. N ci thin s hp thu nc v cht dinh dng ca cy trng, gip s
pht trin ca r cy v k t din h t , d u khong va cacbohydrat d tr s
dng khi cn thit, bo v thc vt cc bnh tt t t gy ra, v gii c t
b nhim. Nng su t cy tr ng cng tng ln, nh cc th nghim trn lc,
hng dng, ht lanh v ht c du khc minh chng.
Nhiu nghin cu bo co v hiu qu ca tro bay ti bn ca t nh
ci thin bn ct v bm dnh ca t. Mt khc, mt s nghin cu cho
thy vic kt hp gia vi v tro bay vo t lm tng s n nh cho t
so vi n nh t ch bng tro bay hoc vi ring r [31,32].
1.3.3.3. Tro bay lm cht hp ph
Trong nhng nm gn y, vic s dng tro bay thu ht rt nhiu
trong cng nghip, vic s dng ny s gim bt gnh nng v mi trng v
nng cao li ch kinh t. Tnh kh thi k thut ca vic s dng tro bay lm
cht hp ph gi r cho cc qu trnh hp ph khc nhau loi b cc cht
nhim trong khng kh v nc c xem xt.
C th dng tro bay thay th than hot tnh thng mi hoc zeolit
cho vic hp ph cc kh NOx, SOx, cc hp cht hu c, thy ngn trong
khng kh, cc cation, anion, thuc nhum v cc cht hu c khc trong
nc. Wang v Wu [33] nghin cu iu tra v cho thy rng thnh phn
cacbon cha chy trong tro bay ng mt vai tr quan trng trong kh nng
hp ph. C nhiu bo co nghin cu s dng tro bay lm vt liu hp ph
loi b cc ion kim loi c hi [34-36], cht gy nhim trong khng kh
[37], cc hp cht hu c v v c [38-44], v hp ph thuc nhum trong
nc thi [45-48].

18
1.3.3.4. Tro bay dng cng nghip gia cng cht do
Tro bay l vt liu ph thi ca qu trnh sn xut in nng t cc nh
my nhit in s dng nhin liu than . Vi thnh phn ch yu l cc
oxit kim loi nh oxit silic, oxit nhm, kch thc ht mn v gi thnh
r, ngoi nhng ng dng ht sc hiu qu trong cc ngnh xy dng, tro
bay bay cn c mt tim nng ln trong lnh vc lm cht n cho polyme.
Trong s cc nha nhit do th PE v PP c s dng ph bin nht.
D.C.D. Nath v cng s ch to vt liu compozit trn c s PP gia cng
bi mt hm lng ln tro bay (60%) c kch thc ht 5-60m bng phng
c phun 210oC. Theo cc tc gi, trong iu kin kh quyn, nhm OH hoc
ion trn b mt kim loi hoc oxit kim loi nh tro bay c vai tr quan trng
trong hnh thnh cc lin kt vt l gia b mt tro bay vi nn polyme [49].

Hnh 1.10: Cc chi tit dy in trong thn t ch to t vt liu

LDPE/FA ca hng General Motor [50]

Hnh 1.11: ng dng compozit tro bay lm vch ngn, ni tht

19
 Vt liu compozit LDPE/10% tro bay c bn ko t, modul n hi
cao hn LDPE v vt liu compozit LDPE/10% CaCO3. Tro bay ci thin tnh
cht c hc ca LDPE cao hn so vi CaCO3 v tro bay c kh nng lin kt
vi polyme nn tt hn CaCO3. Vt liu compozit LDPE/tro bay c cc
hng ch to t General Motor dng ch to mt s chi tit nh kp nh
v, mc dy in bn trong thn t (hnh 1.10).

Vt liu polyme compozit s dng tro bay lm cht n v vi ay lm

ch t gia cng. Sau khi x ly , vi ay c chuy n vo ch t n n cn thnh
tm. Cc t m c s y kh nhit v p sut c th. S lng t m c s
dng theo dy yu cu. Vt liu polyme/tro bay compozit s dng vi ay
gia cng thay th vt liu g trong nhiu sn phm nh ca chp, vch
ngn, gch lt nn, tm tng, trn, [51].
Tro bay cng vi cc ph gia khc nh bt kim loi v vi cht do a
vo cao su ti sinh ch to tm lt ng ngang xe la [52]. M. Hossain v
cc cng s nghin cu ca trng i hc Kansas cng b kt qu s
dng cao su ti ch t lp t lm lp asphalt tri ng c s dng ph
gia tro bay [53]. y l cng trnh rt c gi tr v khoa hc mi trng, khi
cng trnh ny c p dng th mt lng ln lp t ph thi c s dng
thay th nha ng v nh vy s lm gim gi thnh xy dng.
Nhiu nghin cu nh gi kh nng gia cng ca tro bay ti tnh cht
vt liu cao su nh CSTN, SBR, BR,[54-58] v cao su blend nh
CSTN/NBR, CSTN/SBR, CSTN/CR [59-61]. i vi tro bay khng bin tnh
kh nng gia cng cho vt liu cao su l khng ng k. Khi tro bay c
bin tnh bng cc cc hp cht silan, kh nng gia cng ca tro bay c ci
thin ng k. Hm lng tro bay ti u dng gia cng cho vt liu polyme
ni chung v vt liu cao su ni ring vo khong 10 n 30 pkl. Tro bay c th
thay th cc cht n truyn thng nh clay, canxi cacbonat hoc s dng kt
hp vi than en. Mt khc, tro bay c gi thnh rt thp nn tro bay lm gim
gi thnh ca sn phm. Nhiu sn phm cao su s dng tro bay lm cht
n gia cng hoc lm cht n thay th cht thng thng c ch to.
20
1.4. Cc phng php x l, bin tnh tro bay
1.4.1. X l b mt tro bay bng hp cht mui hu c
Shashwat S. Banerjee v cng s nghin cu x l tro bay (FA) bng
hp cht hexadecyltrimetyl amoni (HDTMA) dng lm cht hp thu du.
Kt qu nghin cu cho thy, HDTMA-FA c th lm cht hp thu x l s
c trn du. Cc c tnh hp thu ca tro bay c tng cng rt nhiu khi
bin i bng cht hu c HDTMA. Sn phm HDTMA-FA cng c hiu qu
trong vic loi b cacbon hu c ha tan c trong nc bin nhim du. iu
ny chng t HDTMA-FA l ng c vin tt hn so vi hp th thng thng
[62]. K. Karakasi v cng s cng nghin cu v c tnh hp thu du ca
tro bay hm lng canxi cao (HCFA) cho thy s cn thit phi ci thin
kh nng ni ca chng. t iu ny, vic x l tro bay vi mt tc nhn
hot ng b mt c p dng, cht hot ng b mt l natri oleat (SO)
c la chn, do chi ph thp v c kh nng phn hy sinh hc cao. Vic x
l thy nhit HCFA vi SO cho kt qu tng khng ng k kh nng hp thu
du, k c vic tng xp l khng . Hm lng CaO dng nh li ng
vai tr ng k, t c tnh hp thu du ca HCFA vi lng vi cao c ci
thin t l HCFA:SO thp, trong khi vi lng vi t i hi t l cao hn
nhiu [63].
Nath v cng s thc hin ph b mt tro bay bng cht hot ng b
mt natri lauryl sulfat vi tc nhn lin kt ngang l andehit glutaric (GLA).
Tro bay x l b mt c s dng lm cht n cho mng poly(vinyl alcol)
compozit phn hy sinh hc. bn ko ca mng compozit c tng ln
khi thm cht n tro bay x l, bn t cao nht khi hm lng tro bay l
20% v bn ko tng 75% so vi PVA tinh khit. hm lng 20% tro
bay, modul ca cc vt liu compozit tng ln 218%, nhng dn di khi
t ca vt liu li gim [64].

1.4.2. X l b mt tro bay bng hp cht axit, baz

Nhm tc gi Z. Sarbak v M. Kramer-Wachowiak [65] x l b mt

ca tro bay bng cc dung dch NaOH, NaOH/NH4HCO3, EDTA v HCl vi
21
mc ch l xc nh s thay i din tch b mt v cu trc xp ca tro bay
cng vi s bin i ha hc ca chng. Bng di y th hin cc c trng
v xp v din tch b mt ca tro bay c x l.
Bng 1.8: Cc c trng tro bay sau cc qu trnh x l b mt khc nhau

Din tch b Bn knh l xp

Dung dch x l xp (cm3/g)
mt BET (m2/g) trung bnh ()
Khng x l 3 34 0,01
NaOH 59 48 0,14
NaOH/NH4HCO3 60 43 0,13
EDTA 60 50 0,18
HCl 105 17 0,10
Trong tt c cc trng hp, din tch b mt ca tro bay c x l
b mt u ln hn so vi mu tro bay ban u. Din tch b mt tro bay tng
nhiu nht trong trng hp tro bay c x l bng dung dch HCl. Trong
trng hp ny kt qu cho thy bn knh l xp gim xung khong 2 ln so
vi tro bay ban u. Qu trnh x l vi cc dung dch khc dn n s tng
mt lng nh bn knh l xp. nh hng ng k t qu trnh bin i ha
hc l xp, cc mu u c xp tng hn 10 ln so vi mu tro bay
cha x l. xp tng ln nht vi mu tro bay c x l trong dung dch
EDTA. Trong trng hp ny, bn knh l xp cng tng nhiu nht. Khi tro
bay x l vi dung dch HCl cho kt qu din tch b mt l ln nht c c
trng bi bn knh l xp trung bnh nh nht v xp nh nht so vi tt c
cc mu c bin i ha hc.
Vic chc ha b mt tro bay t c bng hn hp axit H2SO4:
HNO3 vi thnh phn khc nhau v hiu qu ca qu trnh oxy ha khng kh
ti nhm COOH c kim tra v cho thy thnh phn ti u ca
H2SO4:HNO3 l 85:15 v th tch. Kt qu FTIR cho thy vic bm khng kh
trong qu trnh bin tnh nng cao kh nng chc ha ca tro bay. Ngoi ra,
vic gn nhm cacboxylic trn b mt tro bay tng ln vi s gia tng nng
HNO3 vo hn hp axit ln n 15%. Sau , s st gim cc nhm chc axit
22
v gn mt s nhm khng bo ha c pht hin. Phn tch nhiu x tia X
cho thy s gia tng trong cu trc cacbon tinh th trn b mt tro bay bin i.
Din tch b mt tro bay bin i tng t 7,36 m2/g n 157,76 m2/g trong s c
mt ca khng kh v vi nng HNO3 trong hn hp l 15% [66].
Phng php x l b mt trn lm tng din tch b mt cng nh
xp ca tro bay. Tuy nhin, vic loi b nc thi cha kim hay axit lm
tng thm kh khn. Ngoi ra, cc phng php ny khng th ci thin mu
sc ca tro bay do lm hn ch ng dng rng ri tro bay lm cht n.
p ng cc yu cu cho ngnh cng nghip nha ni ring hay polyme
ni chung, vic pht trin cc cng ngh x l b mt ci thin tnh cht
ca tro bay vi gi tr trng cao v din tch b mt ln l mt hng
nghin cu quan trng ng vai tr ch cht. Theo hng ny, Yang Yu-Fen
v cc ng nghip x l b mt tro bay trong t hp Ca(OH)2-H2O-CO2
[67]. Qu trnh c thc hin trong h m vi mt my khuy p sut
thng, nhit khng i trong khong 85-90C, thi gian x l t 0,5-7
gi. Qu trnh phn ng kt thc, dung dch c lm lnh v kh CO 2 c
thi qua trung ha phn Ca(OH)2 cn d. Phn ng trung ha ny hon
thnh khi pH ca dung dch t ti 7, sau cht rn c lc ra v sy kh.
T cc kt qu phn tch cho thy, mu tro bay sch ban u vi kch thc
ht nh hn 45 m, din tch b mt 2,86 m2/g v trng 36,68, sau khi
c x l b mt tro bay c din tch trong khong t 8,69 n 10,01 m2/g
v tng trng ln trong khong 63,37 n 73,13. Th nghim kh nng gia
cng ca tro bay c x l b mt cho thy, b mt th rp ca tro bay
nh hng n kh nng tip xc v ci thin kh nng tng tc pha gia
polypropylen (PP) v tro bay. Kt qu cho thy vi tro bay x l b mt u
cho cc ch s nh bn ko t, bn nn, modul n hi v bn un
ca vt liu cao hn so vi tro bay khng x l b mt.
1.4.3. Bin tnh b mt tro bay bng cc hp cht silan
Ngoi nhng kh khn lin quan n phi trn, silica ni chung v tro
bay ni ring l mt cht c tnh axit do nhm silanol axit trn b mt, chng

23
s v hiu ha lu hunh cho qu trnh lu ha cao su. iu ny lm chm
qu trnh lu ha, kh nng trn s kh khn hn v tnh cht phn tn ca
silica a nc thng c iu chnh vi mt tc nhn lin kt silan [68].
Phng php bin tnh cc cht n ni chung bng cc hp cht silan
ngy cng tr nn ph bin do c nhiu u im, c bit l kh nng tng
cng tnh cht ca vt liu. Cc tc nhn lin kt silan l cc hp cht ha
hc trn c s silic c cha hai nhm hot ng chnh l nhm v c v
hu c trn cng mt phn t. Hu ht cc tc nhn lin kt silan c s
dng rng ri gm c mt thnh phn hu c v ba thnh phn v c c
kh nng thy phn vi cu trc in hnh ca n l [69]:
(RO)3SiCH2CH2CH-X
Trong RO l nhm c kh nng thy phn nh: metoxy, etoxy hay
axetoxy v X l nhm hu c cha cc nhm chc nh amin, metacryloxy,
epoxy, Ty tng loi polyme hay cao su c gia cng m cn phi la
chn hp cht silan cho ph hp thc hin qu trnh bin tnh tro bay.
Thnh phn ch yu trong tro bay l cc oxit kim loi, v vy trn b mt ca
chng c cha cc nhm hidroxyl (-OH). Trong phn ng silan ha b mt
ca tro bay, theo nhiu ti liu cp [69,70], qu trnh ny thng din ra
nh sau:
u tin l s thy phn 3 nhm alkoxy to ra cc thnh phn cha
silanol (Si-OH).
Tip l qu trnh ngng t ca cc silanol to ra oligome.
Cc oligome sau to lin kt hydro vi cc nhm OH trn b mt
ca cht nn.

Cui cng l qu trnh lm kh, mt lin kt cng ha tr c hnh

thnh i km vi s tch nc.

24
 Hnh 1.12: Cc giai on xy ra trong qu trnh bin tnh b mt
cht n bng hp cht silan

Phng php thng dng nh tnh hp cht silan gn trn b mt cht

n nh silica hay tro bay l phng php ph hng ngoi thng qua xc nh
cc nhm chc c trng c trong hp cht silan xut hin trn ph. Tc gi
Thi Hong v cng s [70] nghin cu bin tnh tro bay bng hp cht 3-
glycidoxy propyl trimetoxy silan (GPTMS), kt qu cho thy trn ph hng
ngoi ca tro bay bin tnh silan (hnh 3.13) xut hin thm cc pic cc
vng 2850-2983 cm-1 ng vi lin kt C-H trong -CH2, -CH3 v cc pic
1245 v 910 cm-1 ng vi lin kt n C-O ca hp cht silan. iu chng
t, sau khi bin tnh tro bay bng GPTMS xut hin lin kt gia tro bay
vi silan hu c, tro bay bin tnh tr nn a hu c hn, c th trn ln v
bm dnh vi nn poolyme hu c tt hn.

25
 Hnh 1.13: Ph hng ngoi ca tro bay ban u v tro bay bin tnh
bng 3-glycidoxy propyl trimetoxy silan (GPTMS)

Tc nhn lin kt silan bis-(3-trietoxysilylpropyl) tetrasulphit (TESPT

hoc Si69) c p dng trong ch to lp sch "Green tyre". Cu trc chung
ca silan h sulphit c a ra nh sau [72]:

Vi R l metyl, etyl hoc propyl, n=1-3 v x=1-4

S nh hng ca nhm thy phn ti hot ng ca tc nhn lin kt

silan c xc nh bng vic so snh cc metoxy, etoxy propoxy v cc dn
xut. Tc ca phn ng silan ha ra ph thuc vo nhm alkoxy trong
silan v gim theo th t nh sau:
CH3O- > C2H5O- > C3H7O- > C4H9O-
Vi nhm propoxy, tc phn ng ni chung l qu chm. Mc d
nhm metoxy phn ng rt nhanh, tuy nhin do c tnh nn t c s dng
(do to thnh metanol). Nhm etoxy cho phn ng nhanh v v hi nu c
bin php phng nga nn c u tin s dng.

Tc nhn lin kt silan s hot ng b mt phn cch pha gia hp

cht v c (nh si thy tinh, cht n hay kim loi) v hp cht hu c
(nh polyme hu c, cao su hay nha) lin kt hay ghp ni hai loi vt

26
liu t tng thch ny [68,73].

Nh cp trn, l do chnh tro bay cha c s dng rng ri

lm cht n cho cc hp cht polyme l do kh nng tng tc yu ca b mt
tro bay vi cht nn. V vy cng nh nhiu cht n v c khc, bin tnh ca
tro bay l cn thit trong nhiu trng hp lm gim hn ch ny ca tro
bay. Sau khi bin tnh bng cc hp cht silan, b mt ca tro bay c hot
ho nh cc nhm chc hu c nh amino, epoxy hay vinyl. Khi gia cng
cho cc vt liu polyme hay cao su, tro bay c th to lin kt ho hc hay vt
l vi cc pha nn c m t trong 2 trng hp di y:
- Tham gia phn ng lu ho cao su

- To lin kt vt l vi polyme:

Trong qu trnh gia cng tro bay cho vt liu trn c s epoxy, T.
Chaowasakoo v cng s s dng tc nhn lin kt silan l N-(2-aminoetyl)-3-
aminopropyl trimetoxysilan bin tnh ca tro bay [74]. Trong nghin cu ny,

27
hp cht silan c s dng cc nng ln lt l 0,5%, 1,0% v 1,5%.

Hnh 1.14: C ch tng tc gia tro bay v

cht nn epoxy qua tc nhn lin kt silan

Kt qu thu c cho thy vi hm lng silan 0,5% th cc tnh cht c

l ca vt liu c gi tr cao nht nh modul ko, modul un, bn ko
t, bn un v bn nn. Vt liu vi hm lng silan ti u 0,5% cho
thy s hnh thnh lin kt gia tro bay v epoxy, kt hp vi cc lin kt
ngang c to ra bi phn ng ha hc gia tc nhn lin kt silan vi cc ht
tro bay, v lin kt ngang N-C gia cc nhm amino trong tc nhn lin kt
silan vi nha epoxy, s c ch ca phn ng c m t trong hnh 1.14.

Vic gim tnh cht dn di hm lng silan cao (trn 0,5%) c cho
l do phn ng bn ngng t ca cc tc nhn lin kt ni silan thy phn
hoc thy phn mt phn, kt qu l hnh thnh cc phn t polysilanol linh
ng trn b mt tro bay. Cc phn t polysilanol linh ng ny s lm gim
kh nng phn ng gia nha epoxy v tc nhn lin kt, v do dn n
lm gim kh nng xm nhp ca nha epoxy vo mng li polysiloxan.
Kishore v cng s da vo kh nng bm dnh ca vt liu nghin
cu nh hng ca tro bay bin tnh ti tnh cht ca polyme compozit [75].
Vic bin tnh tro bay bng hn hp silan-axeton lm gim bm dnh v
tng ch s do. Sombatsompop v cng s nghin nh hng ca vic
x l b mt tro bay ti tnh cht ca cao su thin nhin/tro bay compozit [76].

28
Cc tc gi s dng bis-(3-trietoxysilylpropyl) tetrasulphit (Si69) vi cc
nng khc nhau bin tnh tro bay. Cc tnh cht c hc ca vt liu
compozit tng ln khi nng Si69 l 4%, trong khi tro bay x l bng NaOH
khng ci thin tnh cht ca vt liu. Vic s dng cc hp cht silan bin
tnh ca tro bay lm tng thi gian lu ha v thi gian lu ha sm ca vt
liu. Jun Xie v cng s nghin cu x l b mt tro bay bng tc nhn lin
kt silan 3-(trietoxysilyl)-propylamin. Tro bay bin tnh bng hp cht silan
lm tng bn, kh nng chu ti, bn ro v gim ht m ca b tng
nha [77].
1.5. Nhng kt qu nghin cu ng dng tro bay trong lnh vc polyme
Ngay t nhng ngy u tin, cc cht n dng ht ng vai tr
sng cn i vi cc ng dng thng mi ca vt liu polyme. u tin,
chng c xem nh cc cht pha long gim gi thnh, do c tn l
cht n. Mui than l cht n gia cng c s dng rng ri nht
trong cng nghip gia cng cao su, nh cc c trng l-ha cng nh kh
nng ng dng m n mang li cho cao su lu ha [78]. Nm 1950, oxit
silic bt u c s dng lm cht n gia cng cho cc sn phm cao
su. Nm 1976, Wagner nghin cu k vic s dng oxit silic v silicat
trong cao su v nhn thy rng, vi s c mt ca cc thnh phn ny mt
s tnh cht c trng ca vt liu c ci thin nh s khng rch,
tnh mm mi, khng mi mn, cch nhit, tng cng, modul, tch nhit
thp, tnh n hi cao, song mu sc khng r rt. Tuy nhin, vic s dng
oxit silic lm tng gi thnh sn phm, trong nhiu trng hp, gi
thnh ca sn phm tng ln ng k, do ngi ta phi kt hp s dng
cc cht n khong khc nh clay, vi (CaCO 3). iu ny li lm gim
cc tnh nng k thut ca sn phm.
Tro bay l vt liu ph thi ca qu trnh sn xut in nng t cc nh
my nhit in s dng nhin liu than . Vi thnh phn ch yu l cc
oxit kim loi nh oxit silic, oxit nhm, kch thc ht mn v gi thnh
r, ngoi nhng ng dng ht sc hiu qu trong cc ngnh xy dng, tro

29
bay bay cn c mt tim nng ln trong lnh vc lm cht n cho polyme.
1.5.1. ng dng tro bay trong cng ngh nha nhit do
Ngnh nha l mt trong nhng ngnh tng trng n nh trn th gii,
vi tc tng trng trung bnh l 9% trong vng 50 nm qua. Hin ti,
Trung Quc, Trung ng v Nga sn xut v xut khu nguyn liu nha
nhiu nht th gii. Th trng Trung Quc c sc tng trng mnh nht, 6
thng u nm 2010, Trung Quc sn xut 21 triu tn ht nha, tng 23%
so vi cng k nm ngoi. Trong khi , Trung ng l khu vc sn xut
polyetylen (PE) ln nht. Xut khu PE Trung ng theo c tnh tng t
4,3 triu tn ln 11,7 triu tn trong nm 2013, vt chu v Ty u [79].
Cc loi nha nhit do ngy cng c quan tm nghin cu v s dng
lm pha nn trong sn xut vt liu compozit. Z. Yunsheng v cng s ch
to vt liu compozit t si ngn polyvinyl alcol (PVA) gia cng bi tro bay
bng phng php n trng thi nng chy. Vt liu compozit PVA vi
hm lng nh tro bay c bn va p v cng rt ln [80]. Y. Li v
cng s nghin cu vt liu xy dng trn c s nha polyetylen
terephtalat (PET) ph thi v tro bay (hm lng ti 50%). Tro bay lm hn
ch qu trnh phn hy nhit ca PET, gim co ngt trong qu trnh gia
cng sn phm, lm tng bn nn ca PET t 31 n 53% [81]. Sn phm
ny p ng c cc tiu chun ca vt liu xy dng. Khi nghin cu
kh nng dp la ca vt liu compozit polycacbonat/tro bay, M. Soyama v
cng s nhn thy rng, tro bay kch thc ht tng i nh (< 10m) tng
kh nng dp la cho polycacbonat nh vo cc lin kt hydro gia
polycacbonat v cc nhm -OH trn b mt tro bay. Khi s dng hm lng
tro bay ti 25%, polycacbonat vn gi nguyn cc tnh cht quan trng nh
tnh cht c hc, kh nng c khun v kh nng dp la tng t
polycacbonat gia cng bng si thy tinh [82]. X.F. Ma v cng s ch
to vt liu compozit t tinh bt ha do bi ure-formamit v tinh bt ha do
bi glyxerin v tro bay. Kt qu cho thy, tro bay lm tng bn ko t t
4,55 ln 12,86 MPa, modul n hi tng t 76,4 ln 545 MPa cho vt liu

30
compozit [83]. Vt liu compozit PVC/tro bay cng c nghin cu, tnh
cht lu bin ca vt liu compozit PVC khng ha do/tro bay c ci
thin, trong khi thi gian ha do v momen xon cc i ca vt liu
compozit nn PVC gim [84]. So snh mi mn ca vt liu compozit
PVC/tro bay, F. Yang v cng s cho thy khi hm lng tro bay ln hn
10%, mi mn ca vt liu mi gim [85].
Trong s cc nha nhit do th PE v PP c s dng rt ph bin nht.
D.C.D. Nath v cng s ch to vt liu compozit trn c s PP gia cng
bi mt hm lng ln tro bay (60%) c kch thc ht 5-60 m bng phng
c phun 210 oC. Kt qu thu c cho thy mt s tnh cht ko dn ca
compozit PP/tro bay cc hm lng khc nhau, modul n hi ca tt c cc
mu nhit th khc nhau u ln hn t 10 n 60% so vi mu PP ban
u. 25 oC, s suy gim bn ko t ca cc mu vt liu compozit
PP/tro bay gim mnh (ti 47%), trong khi 50 oC v 70 oC, s suy gim ca
bn ko t gim nh hn (15%). Kh nng bn ko dn ca cc mu
compozit PP/tro bay 25oC nh hn so vi cc mu c cng thnh phn th
nghim 50 oC v 70 oC [49].
J.Y.Hwang nghin cu ch to vt liu compozit t PP, LDPE v
HDPE vi tro bay kch thc ht 30 m c ch to bng cch trn nng
chy trn thit b Brabender vi tc 50 vng/pht trong 30 pht, nhit
trn tng ng ln lt l 250, 190 v 200oC. Trc khi s dng, tro bay
c bin tnh bng hp cht silan c k hiu Z-6032 tng tip xc b mt
vi polyme. Kt qu trn nh SEM ca vt liu PP/tro bay cho thy cc ht tro
bay trn ln v bm dnh kh tt vi nn PP. Tc gi cng tin hnh p
phun LDPE/tro bay trn my p phun vi nhit cc vng l 210, 220,
230oC. So vi qu trnh gia cng vt liu compozit PP/CaCO3 trn cng mt
my p phun, th qu trnh gia cng vt liu compozit/tro bay d dng hn.
Trong khi LDPE cha 80% CaCO3 khng th p phun 250 oC di p lc
2200 psi th LDPE cng cha 80% tro bay c th p phun iu kin gia
cng nh nhng hn (nhit 230 oC v p lc phun 900 psi) [50]. Vt liu

31
compozit LDPE/10% tro bay c bn ko t, modul n hi cao hn
LDPE v vt liu compozit LDPE/10% CaCO3. Tro bay ci thin tnh cht c
hc ca LDPE cao hn so vi CaCO3 v tro bay c kh nng lin kt vi
polyme nn tt hn CaCO3. Vt liu compozit LDPE/tro bay c cc
hng ch to t Chrysler v General Motor dng ch to mt s chi tit
nh kp nh v, mc dy in bn trong thn t .
Khi ch to vt liu compozit HDPE/tro bay vi t l 70:30 v 80:20 (v
khi lng), HDPE v tro bay c trn ln vo nhau v ko thnh si
nhit khong 200-230 oC. Sau khi ngui v ng rn, si c ct thnh
cc ht c kch thc ng u (sng 6 mm). nh SEM ca vt liu compozit
HDPE/tro bay t l 80:20 cho thy, cc ht c ng nht v kch thc gn
nh nhau [86].
Tro bay x l nh hng r rt ti cc tnh cht v hnh thi cu trc ca
vt liu compozit nn PE v PP. C.Alkan v cng s nghin cu bn
ko t v bn ha cht ca vt liu compozit HDPE/tro bay. Khi hm
lng tro bay trong vt liu compozit nh, bn ko t ca vt liu kh
cao. Khi ngm trong cc mi trng NaOH 5%, CH3COOH 5%, C2H5OH
95%, H2SO4 5% v nc, khi lng ca vt liu compozit HDPE/tro bay hu
nh khng i [87]. U. Aikler v cng s ch to vt liu compozit
HDPE/tro bay trong my trn kn Haake. Trc , tro bay c bin tnh
bng 3-aminopropyl trietoxy silan, tro bay c bin tnh tr nn a hu c
v ci thin ng k tnh cht c ca vt liu compozit HDPE/tro bay [88].
Khi nghin cu vt liu compozit PP/tro bay, B.M. Sole v cng s nhn thy
tro bay c tc dng gia cng cho PP, tuy nhin lm gim bn mi mn
ca vt liu ny [89]. Tro bay dng vi cu c kch thc ht t 25 m lm
bn va p, bn un v cc tnh cht ko dn ca vt liu compozit PP/tro
bay tng ng k khi hm lng tro bay t 0 n 30% [90]. c tnh bn un
ca compozit PP/tro bay c nghin cu v cho thy tro bay l cht n
tt cho vt liu polypropylen compozit. Vi vic b sung tro bay vo
polypropylen ci thin bn un v modul un, nhng gim ng k

32
dn di khi t. Ht tro bay mn nht cho bn un tt nht tt c cc hm
lng. Cc tnh cht c hc ca compozit ph thuc vo kch thc ht,
phn tn, s tng tc b mt gia cht n v nn polyme. Cht n dng
hnh cu nh tro bay ci thin ng k cng do din tch b mt ln
[91]. Cc c tnh bin dng v nt gy ca vt liu compozit PP/tro bay c
v khng c anhydrit maleic chc ha PP (MAPP) lm tc nhn lin kt
c kho st. Kt qu cho thy, bn ko v dn di khi t ca compozit
khng c MAPP u gim khi hm lng tro bay tng, trong khi cc c tnh
ny li khng ph thuc vo hm lng tro bay vi compozit c thm MAPP.
S c mt ca MAPP dn n s phn tn tt hn ca cc ht tro bay trong
cht nn, lm tng bm dnh b mt. iu ny c gii thch do MAPP
cn tr c ch t ng rn do cc ht tro bay gy ra [92].
Ngoi ra tro bay cng c nghin cu ng dng trong mt s polyme
khc nh nylon-6, polypyrrol, EVA, Suryasarathi Bose v P.A.Mahanwar
nghin cu nh hng ca tro bay ti tnh cht c hc, nhit, in v cu
trc hnh thi ca vt liu nylon-6. Kt qu cho thy, tro bay c kch thc ht
ln hn ci thin tnh cht c hc vi s tng hm lng tro bay so vi
kch thc ht nh hn. Tuy nhin tro bay kch thc ht nh hn li ci thin
tnh cht in mi tt hn so vi tro bay kch thc ht ln hn. Cht n v
c nh tro bay thm vo polyme ci thin cng, kh nng chu nhit v
n nh kch thc [93]. Murugendrappa v cng s tng hp vt liu
compozit polypyrrol/tro bay (Ppy/FA) vi hm lng tro bay l 10, 20, 30, 40
v 50% khi lng). Kt qu ca c hai dn a.c. v d.c u ph thuc
mnh vo phn trm khi lng ca tro bay trong polypyrrol. Kch thc ca
tro bay trong polyme c nh hng ln ti dn ca vt liu [94]. B. Wulf
nghin cu vt liu bn la c ch to t EVA, nhm hidroxit v mt s
bt khong, trong c tro bay. Vt liu bn la dng tm dy 5 mm c
thnh phn l EVA/Al(OH)3/tro bay vi t l 100/170/170 v khi lng [95].
R. Satheesh Raja v cng s nghin cu cc c tnh c hc ca vt liu
compozit epoxy gia cng bng si thy tinh E v tro bay. Kt qu nghin

33
cu cho thy rng vic b sung cht n tro bay nng cao cc tnh cht c
hc ca vt liu nh bn ko, bn nn, cng v bn va p. c
bit l hm lng 10% cht n tro bay trong vt liu compozit (70% khi
lng nha v 20% khi lng si) cho kt qu tt nht [96].
1.5.2. ng dng tro bay trong cng ngh cao su
Nm 1999 din ra Hi ngh quc t v ng dng tro bay (International
Ash Utilization Symposium) ti Vng quc Anh [71]. Nhiu cng trnh
cng b cc kt qu nghin cu ng dng rt a dng tro bay vo cng
nghip, ch yu lm ph gia cho cc vt liu xi mng, cao su v nha tng
hp. Nhm nghin cu ca Nam Phi s dng 2 loi tro bay thng phm
plasfill 5 v plasfill 15 nghin cu gia cng cho cao su thin nhin [22].
Qua kho st tnh cht lu bin (momen quay cc i v cc tiu, thi gian
lu ho,...) thy rng nht ca cao su gim xung v nh vy, tro bay
gip cho qu trnh gia cng tn t thi gian hn. nh hng ca tro bay n
tnh cht c l ca vt liu khng khc nhiu so vi cht n khc nh CaCO3
cc hm lng 50, 100 v 150%. Vi cc tnh cht c l ni tri, ch yu l
bn ko t v modul n hi ca vt liu c bt cao lanh gia cng, s
gia tng dn di khi t ca vt liu c s dng plasfill, chng t tnh u
vit ca tro bay cng nh cao lanh trong cng nghip gia cng cao su.
Tro bay cng vi cc ph gia khc nh bt oxit kim loi v vi cht do
a vo cao su ti sinh ch to tm lt ng ngang xe la [52]. M.
Hossain v cc cng s nghin cu ca trng ai hc Kansas cng b kt
qu s dng cao su ti ch t lp t lm lp asphal tri ng c s dng
ph gia tro bay [53]. y l cng trnh rt c gi tr v khoa hc mi trng,
khi cng trnh ny c p dng th mt lng ln lp t ph thi c s
dng thay th nha ng v nh vy lm gim gi thnh xy dng.
Tro bay cng vi cao su lp ph thi v xi mng porland cn c s dng
ch to vt liu xy dng. Vt liu m nhm tc gi Arin Yilmaz ch to c
c bn nn gim khi tng hm lng cao su trong tt c cc thi gian lu
ha th nghim (14, 28 v 56 ngy), tuy nhin, bn ca vt liu tng ln

34
khi tng hm lng tro bay [97]. O. Figovsky v cc cng s ch to b
tng polyme t cao su butadien, ct thch anh v tro bay. Loi b tng ny c
bn axit v c bn kim rt cao, dai v bm dnh tt vi cc bt oxit kim
loi. Mt khc, vt liu ny cn c bn nn ln v hp th nc nh. Sn
phm c s dng trong xy dng cc kt cu cng nghip i hi bn ho
cht, tip xc thng xuyn vi axit sulfuric, dung dch hydroxit kali m c
[98]. Erdal Cokca v Zeka Yilmaz nghin cu nh gi kh nng ng dng
tro bay ch to mt loi vt liu c h s thm thu thp t tro bay, cao su
ti ch v bentonit, trong tro bay chim mt lng ln (90%). Kt qu cho
thy vt liu c tim nng ch to vt liu lt [100]. bn thy lc tng
ln khi tng hm lng cao su v gim hm lng bentonit, tuy nhin bn
nn v modul n hi ca vt liu gim xung khi hm lng cao su tng.
Tro bay c hiu qu r rt khi lm cht n gia cng cho cc vt liu t
cao su thin nhin (CSTN), cao su clopren, cao su butadien v cao su nitril.
Tro bay c nghin cu gia cng cho cao su clopren [101]. Tc gi
thy rng tro bay khng x l v x l u c tc dng lm tng bn
ko t v modul n hi ca vt liu. Khi s dng 10-100% tro bay c x
l b mt bi 1% neopentyl (diallyl) oxy, trineodecanonyl titanat, sn phm
cao su clopren c bn ko t v modul n hi tng nhiu ln so vi mu
s dng tro bay khng x l. D.G. Hundiwale cng nghin cu tc dng
ca tro bay trong cao su butadien. Kt qu cho thy, khi c mt ca CaCO 3 v
bt talk, tro bay c tc dng gia cng tt hn cho cao su butadien. T hp
vt liu ny c bn ko t ln nht hm lng tro bay 35% v dn
di khi t ln nht hm lng tro bay 38% [99]. Khi tro bay c bin tnh
bng cc hp cht silan, cc tnh cht c l ca vt liu tng ln ng k.
Trong mt nghin cu khc, Nabil A. N. Aldakasi cng cc cng s nghin
cu nh hng ca bis-(3-trietoxysilylpropyl) tetrasulphit n tnh cht c l
ca cao su butadien styren (SBR) n tro bay. Tnh cht ca vt liu c s
dng tro bay bin tnh c tng ln ng k. bn ko tng ln 20% trong
khi modul 100% tng ln 30%. Tng t, modul n hi ca vt liu cng

35
tng ln 22% [102]. Vt liu nanocompozit trn c s cao su styren butadien
(SBR) vi tro bay cu trc nano (NFA) c ch to trong phng th
nghim bng phng php trn nng chy trong my trn kn. Cht lu ha
c trn thm vo bng my cn trn 2 trc. Vt liu compozit SBR-NFA
th hin trng thi lu ha v cc thuc tnh bn cao hn so vi vt liu
compozit SBR n tro bay v than en cng hm lng. bn x v chu
mi mn ca vt liu compozit SBR-NFA vt tri so vi SBR-FA v SBR-
silica, nhng li km hn so vi SBR-than en. Vt liu compozit SBR-NFA
cho cng thp hn so vi c hai compozit cha n than en v silica
[103]. Vt liu compozit l s kt hp ca hai hay nhiu vt liu, c tnh cht
vt tri so vi bt k vt liu ring bit khc. Mt nghin cu v compozit
ca tro bay (FA) - cao su butadien styren (SBR) vi nha epoxy l vt liu
gc c kho st. Kt qu cho thy vi s gia tng ca hm lng tro
bay, t trng ca vt liu tng ln nhng n mt hm lng nht nh th tnh
cht ny li gim. bn ko ca vt liu compozit li gim vi s gia tng
ca hm lng tro bay. Tuy nhin, vi vic b sung tro bay, tc mi mn
ca compozit ban u gim xung nhng nu tip tc tng hm lng tro bay
th tc mi mn li tng [104]. Compozit polyme trn c s cao su styren
butadien clor ha (CSBR) cha hm lng FA khc nhau c ch to
bng phng php trn nng chy vi dicumyl peroxide lm cht lu ha. S
nh hng ca hm lng FA ti cc c tnh lu ha, tnh cht c hc, kh
nng n nh nhit, bn chy v chu du c kho st. S gia tng hm
lng FA trong cao su CSBR y nhanh qu trnh lu ha tng 37% so vi
mu khng c cht n. S phn b ng u ca FA trong CSBR c
nh gi bng knh hin vi in t qut, qua gii thch cc tnh cht c hc,
bn chy v du ca vt liu c ci thin. Tc khuch tn ca cc dung
mi hydrocarbon thm thng qua mng compozit l thp nht i vi
compozit cha 30 pkl cht n v tc ny tng ln vi s tip tc gia tng
ca hm lng cht n. Tnh cht c hc nh bn ko, modul v cng
ca cc mu gim sau khi ngm trong du ASTM v xu hng gim thp nht

36
 mu cha 30 pkl cht n FA [105].
Alkadasi, Hundiwale v Kapadi s dng tro bay lm cht n cho cao
su butadien v nghin cu nh hng ca tc nhn lin kt silan (Si69) n
tnh cht c l ca vt liu [54]. Trong trng hp khng bin tnh, tro bay
khng c nh hng r rng n tnh nng c l ca vt liu trong khi tro
bay c bin tnh c kh nng gia cng tt hn nhiu. So snh vi trng
hp tro bay khng bin tnh, kt qu nghin cu vi tro bay bin tnh cho
thy, bn ko cng tng 193%, modul 400% tng 700% v modul n
hi cng tng ln 170%.
Tro bay (FA) c s dng lm cht n gia cng cho compozit bt
cao su ti sinh (RR) c s dng tc nhn lin kt. Hm lng FA c thay
i t 10 n 35 pkl. Nghin cu v kh nng tng hp v lin kt ngang
bng nh SEM v ph hng ngoi cho thy compozit FA/RR c cc c tnh
c hc v nhit tt hn khi cht xc tin (M) v axit stearic (SA) c cho
vo u tin, sau trn vi lu hunh v dicumyl peroxit (DCP), v cui
cng l 3-Aminopropyltrietoxysilan (KH-550). T l khi lng ca
compozit FA/RR l 25/100 v iu kin lu ha l 145C trong 40 pht vi
p sut 9 MPa. Kt qu cho thy, FA l mt cht n tuyt vi v c th c
s dng thay th cho oxit silic gia cng cho compozit bt cao su ti sinh
[106]. Sukanya Satapathy v cng s nghin cu ch to v tnh cht ca
cao su nhit do t polyetylen ph thi (WPE) v cao su ti sinh (RR). Kt
qu cho thy, bn va p ca tt c cc compozit u c ci thin ng
k vi s gia tng ca hm lng RR. Compozit WR15 cho thy s cn bng
tt nht v tnh cht c hc. bn ko v bn un ca blend tng n 21,8
v 19 MPa t 18,2 v 14 MPa vi s kt hp ca 50% tro bay. Khi tro bay
c x l vi Si69, bn ko v bn un tng thm tng ng l 24,8 v
23,9 MPa. Kh nng n nh nhit ca compozit WR15-FA c ci thin
ng so vi cc compozit khc [107].
Cao su thin nhin (CSTN) cng l i tng nghin cu ca nhiu cng
trnh ng dng cht gia cng l tro bay. R. Menon v cng s ch to

37
vt liu trn c s CSTN cha tro bay c mt ca nha cardanol photphorylat
ho v cht ng rn l hexametylen tetramin. Nha cardanol photphorylat
ho ng vai tr cht lin kt gia 2 pha CSTN v tro bay [55]. Vi s c mt
ca cardanol photphorylat ho, qu trnh cn luyn v ch to vt liu tn t
nng lng hn, thi gian lu ho ngn hn v vt liu c bn ko t,
bn x v bn nhit ln hn. Nhm nghin cu ca S. Thongsang s
dng tc nhn lin kt silan l bis-(3-trietoxysilylpropyl) tetrasulphit bin
tnh tro bay. Tro bay bin tnh c gia cng cho cao su thin nhin. Vi
nng 2-4% hp cht silan, modul n hi v bn x ca vt liu
CSTN/tro bay tng ln ng k [108,109]. Tro bay cng vi oxit silic thng
mi c s dng gia cng cho cao su thin nhin v nghin cu tnh
cht n hi ng hc ca vt liu. Kt qu cho thy, cao su lu ha khng s
dng cht n th hin kh nng n hi tt hn so vi vt liu cao su lu ha
c s dng cht n oxit silic thng mi v tro bay. So vi oxit silic, cao su
lu ha c gia cng cc ht tro bay c kh nng n hi tt hn, kh nng
n hi gim xung khi tng hm lng oxit silic nhng cng ng hc li
tng ln [57]. Tnh cht c hc ng v ma st ca compozit trn c s cao su
thin nhin vi hn hp n gm silica t tro bay (FASi) v silica kt ta
(PSi) c nghin cu bng cch thay i hm lng silica trong hn hp
FASi/PSi. Kt qu cho thy tng tc cao su - cht n v gia cng cho cao
su l r rng nht khi tng hm lng silica l 40 pkl. Phn silica (PSi) trong
hn hp FASi/PSi nh hng ti vic ci thin tnh cht c hc ca vt
liu. S gia cng ca hn hp n cho CSTN l do s tng tc cao su
cht n c minh chng bng s gim tan max. Vt liu compozit cao su
cht n vi cc ht FASi nh (< 25 mm) c tnh cht c hc tt hn so vi
vt liu compozit c ht ln (45-74 mm) vi thnh phn PSi khng i. Vt
liu CSTN/FASi/PSi c hm lng 75% PSi trong hn hp n cho tnh cht
c hc v chu mi mn l tt nht [58].
C. Kantala v cng s [59] nghin cu nh hng ca silica kt ta
(PSi) v silica t tro bay (FASi) n tnh cht lu ha v cc tnh cht c l

38
trc v sau khi gia nhit v s lo ha du ca blend cao su thin nhin
(CSTN) v cao su acrylonitril-butadien (NBR) c v khng c cao su
cloropren (CR) hoc cao su thin nhin epoxy ha (ENR) lm cht tng hp.
Kt qu cho thy, thi gian lu ha sm v thi gian lu ha gim i khi
thm silica v nht ca hp cht tng ln khi tng hm lng silica. Cc
tnh cht c l ca vt liu CSTN/NBR n silica kt ta cao hn so vi khi
s dng silica t tro bay. PSi c th c s dng gia cng cho qu trnh lu
ha NR/NBR trong khi FASi c ch ti nh l cht n kt hp. S c
mt ca CR hoc ENR nh hng n tnh cht c l ca blend CSTN/NBR
trong ENR c nh hng nhiu hn v cng tng hp tt hn vi blend
ny. Tc gi N. Sombatsompop s dng silica t bay tro (FA) lm cht n
gia cng cho cao su blend cao su thin nhin/cao su styren-butadien
(CSTN/SBR). Vi cng mt hm lng silica, t l CSTN:SBR l 1: 1 (hay
50: 50 pkl) cho cc tnh cht c hc ti u nht. Khi tro bay khng x l, thi
gian lu ha v cc tnh cht c hc ca blend CSTN/SBR gim vi s tng
hm lng tro bay. Cc tnh cht c hc ca vt liu c ci thin bng cch
b sung Si69 vi hm lng l 2,0% khi lng so vi silica. bn ko ti
u ca CSTN/SBR t c hm lng silica l 10-20 pkl. Vic b sung tro
bay trong CSTN/SBR cho thy ci thin tnh cht n hi nh bn nn
v kh nng hi phc tt hn so vi silica kt ta thng mi [60].
Hiu ng ca hm lng silica kt ta (PSi) v silica t tro bay (FASi)
ti tnh cht c hc ca blend cao su thin nhin/cao su cloropren (CSTN/CR)
theo lo ha nhit v nhit-du c nghin cu vi s thay i ca hm
lng CSTN trong blend CSTN/CR. Kt qu thu c, c so snh vi
blend ca cao su thin nhin/cao su nitril (CSTN/NBR). Thi gian lu ha
ca cao su CR gim vi s gia tng hm lng CSTN, nhng tng vi cht
n silica. nht Mooney ca cao su CR gim vi s gia tng hm lng
CSTN. Vic b sung CSTN khng c tc dng ti modul bn ko v bn
ko ca blend CSTN/CR n FASi, nhng xu hng ngc li vi blend
CSTN/CR n PSi. Hiu qu sau lu ha c ngha hn vi blend CSTN/CR

39
n PSi so vi blend CSTN/CR n FASi. bn ko ca blend CSTN/CR
gim nh sau khi lo ha nhit c bit l hm lng CSTN cao, s gim
mnh hn khi lo ha nhit du. dn di khi t ca blend CSTN/CR vi
c hai cht n silica dao ng trong khong 400-900%. Vic b sung PSi
trong blend CSTN/CR lm tng ng k bn x, nhng hiu qu khng r
rt i vi n FASi. Tnh cht co gin ca blend CSTN/CR c xu hng
gim vi s gia tng hm lng silica. S bin dng d khi nn gim khi hm
lng CSTN tng. Cht n PSi ci thin s bin dng d khi nn cao hn
n FASi. Nhng nh hng ca silica v lo ha ti tnh cht c hc ca
blend CSTN/CR cng ging nh blend CSTN/NBR [61].

1.6. Tnh hnh nghin cu x l v ng dng tro bay Vit Nam

Nc ta hin ang trong qu trnh pht trin xy dng cu cng, cc
cng trnh thu in, cc k. Theo kho st th cc cng ty b tng cung
cp cho th trng khong 15% l b tng c sn, 85% cn li l do cc nh
my xi mng bn thng cho ch u t xy dng. Tro bay c dng lm ph
gia b tng khi ln cho cc cng trnh p thu in p dng cng ngh
b tng m ln nh nh my thu in Sn La, Bn V, Sng Tranh 2, v
mt s cng trnh khc nh p Bi Thng (Thanh Ho), p Tn Giang
(Ninh Thun), p Lng Sng (Bnh Thun), [16]. Tc gi Nguyn Cng
Thng v cng s nghin cu ch to b tng cht lng siu cao
(BTCLSC) s dng hn hp ph gia khong silica v tro bay, cho thy c th
s dng tro bay Vit Nam thay th mt phn xi mng ch to BTCLSC.
Vic s dng tro bay thay th mt phn xi mng s ci thin tnh cht ca hn
hp BTCLSC [110].
Tro bay c hm lng mt khi nung nh hn 11% c th dng trn
vo xi mng vi t l trung bnh 1020%. Hin ti, tro bay Ph Li (SCL-
FLY ASH) c s dng lm nguyn liu sn xut ti Nh my xi mng
Hong Thch vi t l trn 14%, ti nh my xi mng Sng Gianh vi t l
trn 18% [111].

40
 S dng gch xy khng nung t tro bay cho nh cao tng c hiu qu
kinh t kh cao. Hn hp vt liu lm gch gm tro bay, xi mng, vi, thch
cao v bt nhm, trong tro bay l thnh phn chnh, chim n 70% khi
lng. V vy nhu cu tro bay cung ng cho th trng sn xut gch
khng nung, gch b tng nh v b tng l rt ln [16].
B mn ng b, Trng i hc Giao thng Vn ti tin hnh
nghin cu s dng tro bay lm cht lin kt gia c vt liu ct, lm mt
ng. Kt qu cho thy, hn hp 80% tro bay v 20% vi dng lm cht lin
kt gia c ng s t c bn c hc kh cao. Khi lm mt ng
c th s dng cc hn hp sau: +vi+tro bay m; tro bay m+xi mng
hoc tro bay m+vi +thch cao. Hin c d n th nghim xy dng
ng giao thng nng thn huyn Kim ng, Hng Yn. Loi t gia c
bng tro bay s c cng kh cao, loi vt liu ny hon ton c th snh
vi gia c bng vi v mt s ho cht cht khc. Vi loi t gia c ny c
th dng lm mng ng hoc gia c l, mi dc ta luy s cho hiu qu cao.
nc ta, tro bay c ng dng ch yu trong lnh vc xy dng, vn
s dng tro bay lm vt liu x l mi trng v ci to t cha c quan
tm nhiu. L Thanh Sn v Trn Kng Tu chuyn ha tro bay thnh zeolit
c th dng ci to t [112]. Tc gi T Ngc n v cng s nghin
cu x l tro bay thnh zeolit P1 v c s dng lm cht x l nhim mi
trng [113]. Tro bay c x l bng dung dch NaOH 3,5M c kh nng s
dng lm cht hp ph trong phn tch mi trng. Sn phm to thnh l mt
hn hp cc ht rt nh, hnh cu v tng i ng u; v trong c cha
ch yu l cc ht Quartz, Mullite v Zeolit P1 (Na). Tro bay sau khi x l
c s dng nh gi kh nng hp ph v tch cht i vi hai hn hp
M1 v M2. Hiu sut thu hi cht i vi M1 l 83,3 n 89,5%, i vi M2 l
51,28 n 93,75% [114]. Do kh nng hp ph kim loi nng khng cao, nhiu
cng trnh nghin cu bin tnh tro bay, ch yu l chuyn ha thnh zeolit
bng cch trn vi xt rn v nung nhit cao khong 500-600oC. Nguyn
Th Thu v cng s nghin cu chuyn ha tro bay Ph Li thnh dng

41
zeolit dng lm vt liu hp ph ci to t [115].
Vn nghin cu x l, bin tnh tro bay ng dng trong lnh vc cao
su v cht do cng c mt s tc gi quan tm. Tc gi Thi Hong v
cc cng s nghin cu bin tnh b mt tro bay bng 2 tc nhn lin kt
silan l vinyl trimetoxy silan (VTMS) v 3-glycido propyl trimetoxy silan
(GPTMS). Kt qu thu c cho thy, trn b mt tro bay hnh thnh mt lp
mng silan hu c rt mng [116].
Tro bay bin tnh to ra c s dng trong nghin cu ch to v tnh
cht compozit trn c s nha PE, PP v EVA. Trn c s cc kt nghin cu
tnh cht c l, kh nng chng chy, bn oxy ha nhit v cu trc hnh
thi ca vt liu compozit nhit do (PE, PP, EVA) vi tro bay khng bin
tnh (FA) v tro bay bin tnh (MFA) cho thy: - Thnh phn thch hp ca
vt liu compozit trn c s PE l 15% hn hp OFA/MFA(V) vi t l 70/30
v khi lng. Vt liu thu c c bn ko t ln hn 20 MPa, dn
di khi t ln hn 200%. - Thnh phn thch hp ca vt liu compozit trn
c s PP l 15-20% hn hp FA/MFA(G hoc V) (vi t l 70/30 hoc 80/20
v khi lng. Vt liu thu c c bn ko t ln hn 20 MPa, dn
di khi t ln hn 200%. - Thnh phn thch hp ca vt liu compozit trn
c s EVA l 10% hn hp FA/MFA (G) vi t l 70/30 hoc 80/20 v khi
lng. Vt liu thu c c bn ko t ln hn 15 MPa, dn di khi
t ln hn 160% [116].
Cng cc tc gi trn nghin cu ch to compozit HDPE/FA v
HDPE/MFA (polyetylen t trng cao/tro bay v tro bay bin tnh) vi hm
lng cht n FA v MFA khc nhau c ch to bng phng php nng
chy. nht tng i ca compozit HDPE/FA v HDPE/MFA tng ln vi
s gia tng ca hm lng FA v MFA. Cc tnh cht c hc ca compozit
HDPE/FA v HDPE/MFA thp hn so vi HDPE v gim khi hm lng FA
v MFA tng. Vt liu compozit HDPE/MFA c tnh cht c hc cao hn so
vi vt liu compozit HDPE/FA vi cng hm lng cht n. C hai cht
n FA v MFA u gim tnh cch in HDPE [117].

42
 T nhng ni dung trn y cho thy, kh nng ng dng ca tro bay rt
a dng, c bit trong lnh vc lm vt liu xy dng. Vic nghin cu cc
bin php x l, bin tnh tro bay ng dng vo cc lnh vc kinh t, k
thut l vn khng ch c ngha khoa hc, kinh t r rt m cn c gi tr
c bit l tn dng mt cch hiu qu mt loi vt liu ph thi, gp phn s
dng hp l ti nguyn v bo v mi trng.
Ring trong lnh vc cng ngh vt liu cao su, cht do, vic ng dng
ca tro bay mi ch l bt u v vn ang cn rt tim nng. Bi v ng
dng mt cch c hiu qu, i vi tng loi cao su, cht do i hi nhng
x l b mt tro bay ph hp v c hiu qu v mt khoa hc, cng ngh v
kinh t. i vi cao su thin nhin v cc loi cao su blend trn c s CSTN
cng c mt s kt qu nghin cu c cng b, song vic ng dng vo
thc t cha thy nhiu, c bit Vit Nam nhng nghin cu v hng ny
hu nh cha thy. Chnh v vy, gp phn m rng vic ng dng tro bay
trong cng ngh gia cng cao su, vic hon thin cc nghin cu bin tnh v
ng dng tro bay gia cng cho CSTN v blend trn c s CSTN l v
cng cn thit, n khng ch c ngha khoa hc, kinh t, x hi m cn c
gi tr thc tin cao.

43
 Chng 2: THC NGHIM
2.1. Vt liu nghin cu
2.1.1. Tro bay
Tro bay c cung cp t cng ty c phn Sng 12-Cao Cng. y
l sn phm c tuyn tch, tinh ch t tro bay thu c ca nh my nhit
in Ph li. Cc tnh cht ca tro bay c th hin trong bng 2.1 do cng
ty cung cp.

Bng 2.1: Cc ch tiu k thut ca tro bay

TT Tn ch tiu n Hm Phng php th
v lng
1 SiO2 % 57,85 ASTM C311
2 Fe2O3 % 6,07 ASTM C311
3 Al2O3 % 25,01 ASTM C311
4 SO3 % 0 ASTM C311
5 Hm lng mt khi nung % 3,51 ASTM C311

Vi hm lng SiO2 + Fe2O3 + Al2O3 = 88,93% (>70%), theo tiu chun

ASTM C618, tro bay s dng trong nghin cu thuc loi F. Tro bay c s
dng c kch thc ht trung bnh 7,374 m tp trung ch yu 5,503 m
c phn tch ti Vin nghin cu Snh s Thy tinh Cng nghip.

2.1.2. Cc hp cht silan

Nm hp cht silan c s dng ca hng DowCorning M:
Bis-(3-trietoxysilylpropyl) tetrasulphit (Si69) l cht lng trong sut
mu vng sng, c nht thp, tan trong dung mi bo v dung mi
thm nh ru, ete, xeton. Nhit si: 25oC, t trng: 1,08 g/ml.
OC 2H5
S S OC 2H5
H5C2O Si (CH 2)3
(CH 2)3 Si OC 2H5
OC 2H5 S S
OC 2H5

-metacryloxypropyl trimetoxysilan (MPTMS) l cht lng c nht

thp, trong sut khng mu. Mi tng t nh ca mercaptan. Tan
trong cc dung mi bo v dung mi thm nh ru, ete v xeton. N
44
 cng c th ho tan trong nc, tuy nhin, xy ra qu trnh thy phn.
Nhit si: 213oC, t trng: 1,057 g/ml.
CH2=CH(CH3)COO(CH2)3Si(OCH3)3
(3-Mercaptopropyl) trimetoxysilan (A-189) l cht lng trong sut mu
vng nht, nht thp, mi trng thi, tan trong dung mi bo v
dung mi thm nh ru, ete, xeton. Tan trong nc, tuy nhin xy ra
qu trnh thy phn. Nhit si: 190oC, t trng: 1,045 g/ml.
HS(CH2)3Si(OCH3)3
N-(2-Aminoetyl)-3-aminopropyl silantriol (AEAPS) l cht lng mu
vng. N c th tan trong ru v nc. 25% trong nc, ch yu l
dng oligome. Nhit si: 100oC, t trng: 1,0 g/ml.
H2N(CH2)2NH(CH2)3Si(OH)3
-Aminopropyl trimetoxysilan (APTMS) l cht lng trong sut khng
mu n hi vng, c nht thp, mi ging nh amin. Tan trong
ru v cc hydrocacbon bo hoc thm. C th ha tan trong nc,
nhng thy phn xy ra. Nhit si: 194oC, t trng: 1,1 g/ml.
H2N(CH2)3Si(OCH3)3
2.1.3. Cao su v cc ph gia cao su
- Cao su thin nhin (CSTN) l loi SVR - 3L ca Cng ty cao su Vit
Trung, Qung Bnh.
- Cao su nitril (NBR) l loi KOSYN KNB35 ca Hn Quc.
- Cao su styren butadien (SBR) l loi 1502 ca hng Nipon (Nht Bn).
- Cc cht ph gia gm:
Lu hunh ca hng Sae Kwang Chemical IND. Co. Ltd (Hn Quc)
Oxit km Zincollied ca n
Axit stearic ca PT. Orindo Fine Chemical (Indonesia)
Xc tin DM (Trung Quc)
Xc tin D (Trung Quc)
Phng lo A (Trung Quc)
Phng lo D (Trung Quc)

45
2.1.4. Cc ha cht khc
- Dung dch axit HCl, NaOH, Ca(OH)2
- Dung dch etanol 96%, axit axetic.
2.2. Phng php nghin cu
2.2.1. Tinh ch tro bay
Tro bay th ca Nh my Nhit in Ph Li c Cng ty c phn
Sng 12-Cao Cng tuyn tch, tinh ch thu sn phm tro bay tinh ch 1.
Tro bay ny tip tc c lm sch bng dung dch axit HCl long, dung dch
c khuy trn trong thi gian 4 gi. Sau , lc v ra sch tro bay bng
nc ct cho sch vt axit v sy kh, thu c tro bay tinh ch 2.
2.2.2. X l b mt tro bay bng axit, baz
a- X l bng axit
Tro bay c x l bng dung dch axit HCl nng 2,5 M 90 oC
trong thi gian 8 gi. Qu trnh x l kt thc, sn phm c lc v ra
nhiu ln bng nc ct cho n khi pH = 7, sau c sy 100 oC trong
thi gian 2 gi [65].
b- X l bng kim
Tro bay c x l trong dung dch NaOH 3,5 M c gia nhit n 95 oC
trong thi gian 8 gi. Khi phn ng kt thc, ra sn phm nhiu ln bng
nc ct cho n khi pH = 7. Sn phm c lc, sy kh 100 oC trong thi
gian 2 gi [65].
c- X l bng Ca(OH)2
Phn ng thc hin trong bnh cu, c cnh khuy v sinh hn hi lu.
Lng Ca(OH)2 cn thit l 1/5 so vi tro bay. Phn ng thc hin trong mi
trng nc vi t l cht lng/cht rn = 20/1.
Qu trnh c thc hin trong h m vi mt my khuy p sut
thng. Phn ng thc hin trong 7 gi nhit 95 C. Qu trnh phn ng
kt thc, dung dch c lm lnh v thi kh CO2 trung ha phn Ca(OH)2
cn d. Phn ng trung ha ny hon thnh khi pH ca dung dch t ti 7,
sau sn phm c lc ra v sy kh [67].

46
2.2.3. Bin tnh tro bay bng hp cht silan
Kho st qu trnh bin tnh tro bay bng -metacryloxypropyl
trimetoxysilan c thc hin trong dung dch etanol 96%. Cc phn ng tin
hnh trong dung dch c iu chnh pH = 4 5 cha 0,5 2% silan theo
khi lng. Thi gian phn ng ln lt l 0,5; 1,0; 1,5 gi. Nhit ca
phn ng c kho st ln lt 30 C, 50 C v 70 C. Dung dch c
khuy trn u v khng i trong sut qu trnh tin hnh cc phn ng. Hn
hp thu c sau phn ng c lc v lm kh trong 4 gi nhit 60 C
trong t sy vi p sut kh quyn.
Kho st qu trnh bin tnh tro bay bng bis-(3-trietoxysilylpropyl)
tetrasulphit c thc hin trong dung dch etanol 96%. Cc phn ng tin
hnh trong dung dch c iu chnh pH = 4 5 cha 2 8% silan theo khi
lng nhit 30 oC. Dung dch c khuy trn u v khng i trong
sut qu trnh tin hnh cc phn ng. Hn hp thu c sau phn ng c
lc v lm kh trong 4 gi nhit 60C trong t sy vi p sut kh quyn.
Qu trnh silan ha c kho st cc iu kin phn ng khc nhau
xc nh c ch v iu kin phn ng ti u :
- Nng silan trong dung dch.
- Thi gian phn ng.
- Nhit phn ng.
2.2.4. Phng php ch to mu
a. Mu CSTN
Trn c s n phi trn t CSTN v cc ph gia c nh, nh hng ca
hm lng tro bay ti tnh cht ca vt liu c kho st. Thnh phn tro
bay v CSTN trong cc mu kho st c trnh by trong bng sau:

47
 Bng 2.2: Thnh phn tro bay v ph gia trong mu CSTN
Mu M0 M1 M2 M3 M4 M5
Thnh phn
CSTN 100 100 100 100 100 100
Km oxit 5 5 5 5 5 5
Phng lo D 2 2 2 2 2 2
Axit stearic 1 1 1 1 1 1
Xc tin D 0,6 0,6 0,6 0,6 0,6 0,6
Xc tin DM 0,3 0,3 0,3 0,3 0,3 0,3
Lu hunh 2,5 2,5 2,5 2,5 2,5 2,5
Tro bay 0 10 20 30 40 50

b. Mu cao su blend trn c s CSTN

Trn c s n phi trn t cao su blend CSTN/NBR v CSTN/SBR u

c t l l 80/20 vi cc ph gia c nh, nh hng ca hm lng tro bay ti
tnh cht ca vt liu c kho st. Thnh phn tro bay trong cc mu c
trnh by trong bng sau:

Bng 2.3: Thnh phn tro bay v ph gia trong mu cao su blend
Mu B-0FA B-10FA B-20FA B-30FA B-40FA B-50FA B-60FA
Thnh phn *

CSTN 80 80 80 80 80 80 80
NBR hoc SBR 20 20 20 20 20 20 20
Km oxit 5 5 5 5 5 5 5
Phng lo D 2 2 2 2 2 2 2
Axit stearic 1 1 1 1 1 1 1
Xc tin D 0,6 0,6 0,6 0,6 0,6 0,6 0,6
Xc tin DM 0,3 0,3 0,3 0,3 0,3 0,3 0,3
Lu hunh 2,5 2,5 2,5 2,5 2,5 2,5 2,5
Tro bay 0 10 20 30 40 50 60
* i vi mu vt liu CSTN/SBR
c. Cn trn
Mu nghin cu c ch to bng phng php cn trn trn my cn hai
trc th nghim ca hng TOYOSEIKI (Nht Bn). Cc thng s ca my cn:

48
 - ng knh trc: 7,5 cm,
- Chiu di trc: 16 cm,
- Tc trc chm: 7,5 vng/pht
- T tc: 1:1,2.
Mu nghin cu c ch to bng phng php cn trn trn my cn
hai trc th nghim ca hng TOYOSEIKI (Nht Bn). Cc bc to mu vt
liu c thc hin nh sau:
- u tin CSTN vi NBR hoc SBR c cn ct mch s b tng
kh nng phi trn.
- Sau hai cao su ny c cn trn vi nhau to ra ng u nht nh.
- Tip theo cn trn t hp CSTN/NBR hoc CSTN/SBR vi tro bay v cc
ph gia khc nhit phng. Lu hunh c u vo cn trn cui cng.
- Kt thc qu trnh cn trn, mu c xut tm chun b cho cng
on lu ha.
d. Lu ha
Mu c p lu ha trong khun c kch thc 200 x 200 mm v c
chiu dy 2 mm. Cc thng s ca qu trnh p lu ha nh sau:
- p sut p: 6 kg/cm2
- Thi gian lu ha: 20 - 25 pht
- Nhit lu ha: 145 oC
Qu trnh p lu ha c thc hin trn my p thy lc th nghim
TOYOSEIKI (Nht Bn).
2.2.5. Phng php v thit b kho st qu trnh x l b mt tro bay
a. Kho st tnh cht ca tro bay
- Thnh phn ha hc v tnh cht ca tro bay c xc nh ti Vin
Vt liu Xy dng theo phng php th ASTM C311 v phn loi tro bay
theo tiu chun ASTM C618
- Kch thc v phn b ht tro bay c xc nh qua tn x laser
trn thit b Horiba LA-300 (M) ti Vin nghin cu Snh s Thy tinh
Cng nghip.

49
 - Din tch b mt ca cc mu tro bay c o bng phng php hp
ph vt l vi cht hp ph nit lng trn my o Mircomeritics ASAP 2010
ti Phng Ha du, trng i hc Bch khoa H Ni.
b. Kho st qu trnh x l b mt tro bay
- Qu trnh x l b mt tro bay c kho st bng knh hin vi in t
qut (SEM) trn thit b JSM-6490 (JEOL-Nht Bn) ti Trung tm nh gi
h hng vt liu, Vin Khoa hc Vt liu.
- Sn phm ca qu trnh silan ha tro bay c kho st bng ph hng
ngoi bin i fourier FT-IR v phng php phn tch nhit trng lng (TGA).
+ Ph hng ngoi FT-IR c o bng phng php o phn x trn
mu bt KBr c tinh khit cao ti Khoa Ha hc, trng i hc Khoa hc
t nhin v trn my ph hng ngoi Nexus ca M ti Vin K thut Nhit
i, Vin Hn lm Khoa hc v Cng ngh Vit Nam.
+ Phn tch nhit TGA c thc hin trn cc my Shimadzu TGA-50H
ca Vin Ha hc, Labsys TG ca hng Setaram (Php) ca trng i hc
Khoa hc T nhin. Tc gia nhit l 10C/pht, khong nhit nghin
cu t 25-900 C, trong mi trng kh Argon.
2.2.6. Cc phng php xc nh cu trc v tnh cht ca vt liu
a. Tnh cht c hc
Tnh cht c hc ca vt liu c xc nh theo tiu chun hin hnh
ca Vit Nam.
- bn ko t: Ct mu thnh hnh mi cho v o trn my o ko t
ca i Loan theo tiu chun TCVN 4509:2006 ( o bn ko t, dn
di khi t).

F
bn ko t c tnh theo cng thc: S =
B.h

50
 Trong : S : bn ko t (MPa) hay N/mm2
F : lc ko t mu (N)
B : b rng mu trc khi ko (mm)
h : chiu dy mu trc khi ko (mm)
- dn di khi t: dn di khi t c tnh theo cng thc:
l1 l 0
= . 100%
l0

Trong :
l0 : l di gia 2 im c nh du ln mu trc khi ko (mm)
l1 : l chiu di gia 2 im nh du trn mu ngay khi t (mm)
- cng: cng ca vt liu xc nh theo tiu chun TCVN 1595-1:2007.
cng ca vt liu c o bng my TECLOCK k hiu Jisk 6301A (Nht
Bn). Cch o: Lau sch b mt mu, t mu ln mt phng nm ngang.
Dng ngn tay n mnh ng h o xung mu. c v ghi gi tr hin trn
ng h hin th sau 3 giy. Mi mu vt liu o 5 v tr khc nhau v ly
gi tr trung bnh.
- mi mn: mi mn ca vt liu c xc nh bng phng php
AKRON, theo tiu chun TCVN 1594-87 bin son li nm 2008.
Mu o hnh tr c kch thc ng knh vng ngoi 680,1mm,
ng knh l trong 12,70,1 mm, chiu dy 12,70,5 mm. Gc mi mn 15o.
Lc t trn mi l 27,2 N. mi c ng knh 150 mm, dy 25 mm, c
k hiu A36-P5. Vn tc mu quay 76 80 vng/pht, vn tc mi 3335
vng/pht. mi mn c tnh theo cng thc:

m1 m2
V (cm3/1,61 km)
d

Trong : m1: l khi lng ca mu trc khi o, g

m2: l khi lng ca mu sau khi o, g
d: l khi lng ring ca mu, g/cm3
b. Xc nh kh nng lu ha ca vt liu
Qu trnh lu ha ca vt liu c kho st trn thit b lu ha ca hng
51
EKTRON (i Loan) ti Trung tm cht lng, Cng ty C phn Cao su Sao
Vng H Ni. Cc thng s ca my o:
- Khi lng mu: 8,5 g
- Thi gian lu ha: 25 - 30 pht
- Nhit lu ha: 140oC.

c. Phng php xc nh cu trc hnh thi ca vt liu

Cu trc hnh thi c xc nh bng phng php hin vi in t qut
(SEM) thc hin trn my JMS 6490 ca hng Jeol (Nht Bn) ti trung tm
nh gi h hng vt liu, Vin Khoa hc Vt liu.
Phng php c tin hnh nh sau: Mu vt liu c b gy trong
mi trng nit lng vi kch thc thch hp. Sau mu c gn trn gi
, b mt gy ca mu c em ph mt lp Pt mng bng phng php
bc bay trong chn khng di in p tng tng phn. Mu c cho
vo bung o ca knh hin vi in t qut SEM chp nh b mt gy.

d. nh gi kh nng bn nhit ca vt liu

Kh nng bn nhit ca cc mu vt liu cao su v cao su blend c

nh gi bng phng php nhit trng lng (TGA) c thc hin trn
thit b Labsys TG ca hng Setaram (Php) ca trng i hc Khoa hc T
nhin. Tc gia nhit l 10C/pht, khong nhit nghin cu t 25-
800C, trong mi trng khng kh.

e. anh gia b n mi trng

- bn mi trng c nh gi theo h s gi ha (xc nh theo
tiu chun TCVN 2229 : 2007) trong t sy Memmert (c) 70 oC trong
thi gian 72 gi. Sau thi gian quy nh mu c ly ra yn t nht 4 gi
nhit phng v khng qu 96 gi ri tin hnh o cc tnh cht ca mu
sau khi thc hin php th gi ha. H s gi ha (K) ca vt liu c tnh
theo bn ko t trc v sau khi gi ha theo cng thc:

K 2
1

52
 Trong o:
1: l bn khi ko t trc khi gi ha;
2: l bn khi ko t sau khi gi ha.
- Kh nng bn du m c nh gi thng qua trng ca vt liu
c ngm trong du diezen. trng ca vt liu cao su blend trong du
diezen c thc hin theo tiu chun TCVN 2752 : 2008. Nguyn tc ca
phng php l xc nh s thay i v khi lng, th tch ca mu cao su
blend trc v sau khi ngm mu th trong du diezen. Phn trm thay i
khi lng m (%) ca cao su blend c tnh theo cng thc:
(m m )
m 1 0
x100
m 0

Trong :
m0: l khi lng mu trc khi ngm (g);
m1: l khi lng mu sau khi ngm (g).

53
 Chng 3
KT QU V THO LUN

3.1. Nghin cu x l v bin tnh tro bay

3.1.1. Nghin cu x l b mt tro bay bng axit, baz
3.1.1.1. Nghin cu cu trc b mt tro bay
Tro bay t nh my Nhit in Ph Li c Cng ty C phn Sng
12-Cao Cng thu hi v tuyn tch trong vi nm gn y phc v cho
cc cng trnh xy dng, ch yu l cng trnh Thy in Sn La. Cu trc
hnh thi ca tro bay c kho st bng knh hin vi in t qut (SEM)
nh cc hnh di y.

Hnh 3.1: nh SEM mu FA th Hnh 3.2: nh SEM cu trc ht FA

ban u

Hnh 3.3. Cu trc

hnh thi ca FA
c tinh ch

Hnh 3.1 phn nh hnh dng cc ht tro bay th ban u. Cc ht hnh

cu c kch thc rt khc nhau, t mt vi m n hng trm m. Mt khc

54
tp cht cn li kh nhiu, ch yu l cc phn than cn li cha chy ht. Sn
phm ny ch cht lng s dng cho cc cng trnh xy dng v thc
t c cung cp ch yu cho cng trnh thy in.
Cu trc bn trong ca cc ht tro bay c nhn thy r t cc ht cu b
v phn v bc bn ngoi, n l tp hp ca cc ht vi cu (hnh 3.2). Cc ht
vi cu bn trong c kch thc nh hn nhiu.
c th s dng lm ph gia cho cc vt liu polyme v cao su, tro
bay cn phi c tuyn tch tinh mt ln na. Sau qu trnh ny, kch thc
ca cc ht u n hn v phn th c loi b (hnh 3.3). Kt qu
c kim tra bng cch xc nh kch thc ht v phn b ca chng.

(a) (b)
Hnh 3.4: Cu trc hnh thi cc ht tro bay Trung Quc (a)
v Vit Nam (b)

Sn phm ny ca nh my Nhit in Ph Li c kch thc ht ng

u hn so vi cc loi tro bay ca mt s nc cng b, ht cu c kch
thc nh hn, c b mt trn nhn v bn vng hn (hnh 3.4).

3.1.1.2. Kho st phn b kch thc ht tro bay

Kch thc v phn b ht tro bay ca Cng ty C phn Sng 12-

Cao Cng c nh gi bng phng php tn x Laser. Kt qu cho thy,
phn b kch thc ht ca tro bay c tinh ch hp i ng k (hnh 3.6, 3.7)
so vi tro bay ban u (hnh 3.5). Kch thc trung bnh ca tro bay gim i,
t 28 m xung cn 7,1 7,4 m vi phn b c thu hp (bng 3.1).

55
 Hnh 3.5: phn b kch thc ht tro bay th

Hnh 3.6: phn b kch thc ht tro bay tinh ch 1

56
 Hnh 3.7: phn b kch thc ht tro bay tinh ch 2

Bng 3.1: Kt qu phn tch c ht v phn b ca tro bay

trc v sau khi tinh ch

n Tro bay Sng 12-Cao Cng

TT Tn ch tiu
v Th Tinh ch 1 Tinh ch 2
1 Kch thc trung bnh m 28,1228 7,3742 7,1160
(Mean)
1 Kch thc gia m 21,0208 5,8975 5,7527
(Median)
3 Kch thc tri m 24,3642 5,5032 5,4970
(Mode)
4 phn b
D40 m 16,8495 5,0202 4,8758
D70 m 32,6786 8,2066 8,0591
D90 m 58,9768 13,4779 13,1710
D95 m 77,1697 17,6411 17,0165

3.1.1.3. Xc nh phng php x l b mt tro bay

* X l bng axit
Cc ht tro bay hnh cu vi b mt trn nhn nh thy tinh s bm dnh

57
km vi cc polyme nn trong cc vt liu polyme compozit. tng kh
nng tng tc pha, b mt tro bay cn phi c x l bng cch to cc
nhm hot tnh hoc tng nhm v din tch b mt ring. Vi mc ch
ny, tro bay c x l trc ht bng axit HCl.
Trn hnh 3.8b thy rng, sau 8 gi x l bng HCl, b mt tro bay hu
nh khng b thay i. Trong khi tro bay ca mu so snh (Ba Lan) c
b mt bin i kh nhiu (hnh 3.8a). Tc gi Z. Sarbak [65] thng bo rng,
dung dch HCl lm tng din tch b mt ca tro bay nhiu nht so vi cc
tc nhn dng x l l NaOH, hn hp NaOH/NH4HCO3 v EDTA, song
bn knh l xp v xp li nh nht. iu ny c ngha l c mt lng
ln cc vi l xp xut hin.

(a) ( b)
Hnh 3.8: nh SEM tro bay sau khi x l bng HCl
a: Mu so snh; b: Mu th nghim

Mu tro bay t nh my Nhit in Ph Li (Vit Nam), khng b

bin tnh trong qu trnh x l bng dung dch HCl. iu ny c th c gii
thch rng, b mt ca tro bay rt bn vng, trn nhn v thnh phn cng c
khc vi tro bay ca Ba Lan. Thc t cho thy, hm lng thnh phn khng
bn vi axit nh CaO, MgO trong tro bay ca Vit Nam l rt thp.
Nh vy, tro bay tinh ch t tro bay ca nh my nhit in Ph Li c
kch thc nh, u v bn vi mi trng axit, rt c gi tr lm cht n
gia cng cho cc vt liu polyme.

58
* X l bng kim
Tro bay x l bng kim c thc hin 95 oC trong thi gian 8 gi.
Cu trc hnh thi b mt ca cc ht tro bay x l bng kim c th hin
trn hnh 3.9. Kt qu cho thy, dung dch NaOH n mn ng k b mt
ca tro bay, lm ph v cu trc ca ht. Hu nh tt c cc ht hnh cu b
bin dng, lm cho b mt ca n x x hn v chc chn din tch b mt
c tng ln. iu ny rt c gi tr trong n lc lm tng kh nng tip xc
v lin kt pha vi cc vt liu polyme.

Hnh 3.9: Cu trc ht ca tro bay b ph v

khi x l bng dung dch NaOH 3,5 M

Bng 3.2: Din tch b mt ca tro bay trc v sau khi x l bng NaOH

Mu tro bay Din tch b mt Bn knh l xp Th tch l xp

BET (m2/g) trung bnh () (cm3/g)
Cha x l 1,2906 127,277 0,001958
X l bng NaOH 3,5 M 37,4354 273,129 0,077444

Dung dch NaOH n mn, lm ph v lp v bc ngoi ca cc ht

tro bay, gii phng tp hp cc ht vi cu bn trong. Bng 3.2 cho thy, din
tch b mt tro bay sau khi x l bng kim tng ln ng k (gp khong
30 ln), th tch l xp tng ln gn 40 ln.
* X l bng Ca(OH)2
Nh trn trnh by, tro bay c x l bng dung dch Ca(OH)2 trong 7
gi nhit 95 oC. Kt qu ca php x l l rt kh quan, hu nh trn tt c
b mt cc ht tro bay u c kh nhiu nhng ht nh kt dnh. Cc ht c

59
bao ph trn b mt ca ht tro bay c kch thc nh hn 1m (hnh 3.10).

Hnh 3.10: Cu trc ca tro bay c x l

bng dung dch Ca(OH)2

Bn thn tro bay cha x b mt c hot tnh thp [118]. Lp b mt thy

tinh ca ht tro bay l rn chc v bn ha cht. Lp b mt ny bo v cc
thnh phn bn trong, xp v v nh hnh vi hot tnh cao hn. Chui thu
tinh silica-alumina ca lp b mt c thnh phn Si, Al cao nn bn vng.
Chui ny cn phi b phn hy tng cng hot tnh ho hc cho tro bay.

Hnh 3.11: B mt ht tro bay x l bng Ca(OH)2 th rp v trng hn

60
 Dung dch hot ha Ca(OH)2 c tnh baz cao nn lp bn ngoi ca tro
bay d b n mn v cc ht vi cu bn trong c l ra [119]. Nu nh nng
nhm -OH ln nh trng hp NaOH trn, chui thu tinh silica-
alumina s nhanh chng b ph v v s sinh ra mt lng ln cc nhm hot
tnh. Cng vi s n mn lp b mt thu tinh bn ngoi, cc phn hot tnh
bn trong cng b ph hu. V tro bay c hot ho ho hc, cc silica v
alumina phn ng vi dung dch Ca(OH)2 to thnh nhng sn phm silicat
v aluminat khc nhau, lng ng to mm v pht trin trn b mt ht tro
bay. Nhng cht phn ng ny ph ln b mt ht tro bay khng nhng lm
thay i hnh thi b mt m cn lm tng trng ca tro bay (hnh 3.11).
Nhn xt 1:
Tro bay cng nh cc khong cht v c khc c b mt trn nhn v
km tng tc vi cc cht nn polyme khi chng c s dng lm cht n
gia cng. X l b mt tro bay l cn thit tng kh nng ng dng ca
chng trong vic ch to cc vt liu polyme compozit cha tro bay. Tro bay
c x l c b mt th rp hn vi din tch b mt ln hn hoc trn b
mt c gn tc nhn lin kt nh cc hp cht silan nhm tng kh nng tng
tc vi cht polyme nn.
- Tro bay Ph Li c Cng ty C phn Sng 12-Cao Cng tinh
ch c cht lng cao, b mt nhn bng v bn vng, khng b ph hy bng
dung dch HCl. Tro bay sau khi c tinh ch c kch thc ht v phn
b hp, rt ph hp lm cht n gia cng cho cc vt liu polyme.
- Dung dch NaOH lm ph hy b mt cc ht tro bay, gii phng tp
hp cc ht vi cu bn trong lm cho b mt cc ht tro bay th nhm hn v
kch thc trung bnh gim i. Din tch b mt ca tro bay x l tng ln
gn 30 ln, th tch l xp ca n tng ln gn 40 ln.
- Tro bay c x l bng dung dch Ca(OH)2 c b mt th rp hn
v c bao ph bng cc ht nh c di 1m c thnh phn l canxi
aluminat v silicat. y l phng php n gin, thn thin mi trng v
cn c tc dng ci thin trng ca tro bay.

61
3.1.2. Nghin cu bin tnh b mt tro bay bng cc hp cht silan
Tro bay x l bng NaOH v Ca(OH)2 lm cho b mt ca n th rp
hn, din tch b mt tng ln. Do vy, tng tc vt l gia tro bay vi
polyme c ci thin. ci thin hn na kh nng lin kt b mt tro bay
vi cao su nn, trong phn ny, lun n nghin cu bin tnh tro bay bng
cc hp cht silan vi mc ch gia tng s tng tc ca tro bay vi polyme
bng cc lin kt ha hc.

Hnh 3.12: Biu tc thy phn v ngng t ca phn t silan

ph thuc vo pH ca dung dch
Mi trng ca dung dch phn ng bin tnh tro bay bng cc hp cht
silan c iu chnh c pH trong khong 4 5. iu ny khng ch lm
tng kh nng ha tan ca cc phn t silan trong dung dch m theo nhiu ti
liu cng b [120], n cn tng tc thy phn ca cc nhm metoxy v
lm gim tc ngng t ca cc nhm silanol to thnh (hnh 3.12). iu ny
gip cho hiu sut ca phn ng bin tnh tng ln.
Lun n tin hnh nghin cu bin tnh tro bay bng hai hp cht silan
l: -metacryloxypropyl trimetoxysilan (MPTMS) v bis-(3-
trietoxysilylpropyl) tetrasulphit (Si69). y l 2 hp cht silan c cc nhm
chc c trng to thun li cho qu trnh kho st phn ng bin tnh. T
rt ra c quy trnh ph hp bin tnh b mt tro bay bng cc hp cht
silan khc nhau.

62
3.1.2.1. Bin tnh b mt tro bay bng -metacryloxypropyl trimetoxysilan
Ph hng ngoi ca -metacryloxypropyl trimetoxysilan (MPTMS) c
biu th trn hnh 3.13. Nh bit, cc pic hp th 2947 cm-1 v 2842 cm-1
c trng cho dao ng ha tr ca lin kt C-H. Pic hp th nhn v mnh
1719 cm-1 c trng cho dao ng ha tr ca nhm C=O. Dao ng ha tr
ca nhm vinyl C=C c nh hp th 1637 cm-1.

Hnh 3.13: Ph FT-IR ca -metacryloxypropyl trimetoxysilan

Do nh hng ca hiu ng truyn in t lin hp trong phn t silan

gia nhm vinyl v cacbonyl C=C-C=O lm cho tn s hp th c trng ca
cc nhm ny chuyn dch v pha tn s hp th thp hn so vi cc hp cht
ring bit. Ngoi ra, cc tn s c trng ny s thay i khi cc hp cht
silan c polyme ha v tn ti trng thi rn, cc nhm c s tng tc
in vi nhau mnh m hn gy ra s thay i tn s hp th.

63
 Hnh 3.14: Ph FT-IR ca tro bay ban u

Hnh 3.14 biu din ph hng ngoi ca tro bay ban u. Vch ph
3658 cm-1 c trng cho dao ng ha tr ca cc nhm hydroxyl khng to
lin kt hydro. Pic hp th mnh v rng 1073 cm-1 c trng cho dao ng
ha tr ca cc lin kt Si-O ca tro bay.

* nh hng ca hm lng silan n phn ng bin tnh

Cc hnh 3.15 (a, b,) biu din ph hng ngoi ca cc mu tro bay
c bin tnh vi hp cht silan MPTMS vi cc nng 0,5%; 1,0%; 1,5%
v 2%. Bng phng php phn tch nhit trng lng (TGA) mc 3.1.2.3,
i vi mu tro bay bin tnh bng 1% MPTMS xc nh ng silan gn
trn b mt tro bay l 0,093%.

64
 Hnh 3.15: Ph FT-IR ca tro bay bin tnh bng silan MPTMS
vi nng khc nhau (a) FA ban u; (b) 0,5% MPTMS;
(c) 1% MPTMS; (d) 1,5% MPTMS v (e) 2% MPTMS
Trn ph hng ngoi ca cc mu tro bay bin tnh bng cc hp cht
silan c th nhn thy, s xut hin pic hp th mi 1620 cm-1 c trng
cho dao ng ha tr ca nhm vinyl (C=C) trong phn t silan trn b mt
ca tro bay. Tuy nhin, cc pic hp th ca nhm C=O (cacbonyl) v C-H ca
hp cht silan li khng th r, iu ny c th gii thch l do hm lng
silan kho st thp. V vy cn c vo cng pic ca nhm vinyl nh
gi mc phn ng gia tc nhn silan MPTMS vi tro bay
C th thy rng, hm lng silan 0,5% trn ph xut hin vai pic
vng 1600 cm-1 cha r nh (ng b), khi hm lng silan tng n 1%,
cng ca vch ph tng v xut hin 1 pic r nt 1620 cm-1 (ng c).
Khi vt qu nng ny, cng vch ph tng khng ng k (ng d
v e). iu ny c th c gii thch rng khi tng hm lng hp cht silan,
mt cc phn t silan c cha cc nhm silanol to lin kt hydro vi cc
nhm hydroxyl trn b mt tro bay tng ln dn n kt qu hm lng silan
trn b mt tro bay cng tng ln. Tuy nhin khi tip tc tng nng hp
65
cht silan, mt cc phn t silan trong dung dch tng ln lm tng kh
nng ngng t ca hp cht silan ng thi lm gim kh nng lin kt ca
hp cht silan vi b mt ca tro bay, dn n lm gim hiu sut ca phn
ng bin tnh. Theo ti liu [121] v tc nhn lin kt silan ca hng Shin-
Etsu Silicone vi hp cht silan h vinyl, nng dung dch silan dng
bin tnh cht n l t 0,5 n 2%. Do vy, nng dung dch silan MPTMS
l 1% c chn tip tc nghin cu.

* nh hng ca thi gian phn ng n qu trnh silan ha b mt tro bay

Cc hnh 3.16 biu din ph hng ngoi ca tro bay bin tnh cc thi
gian khc nhau 0,5; 1,0; 1,5 v 2,0 gi.

Hnh 3.16: Ph FT-IR ca tro bay bin tnh bng 1% silan MPTMS vi thi
gian khc nhau (a) FA ban u; (b) 0,5 gi;
(c) 1,0 gi; (d) 1,5 gi; (e) 2,0 gi
Vi thi gian bin tnh l 0,5 gi, trn ph hng ngoi ca tro bay bin
tnh gn nh khng thay i so vi ph hng ngoi ca tro bay cha bin tnh.
Khi thi gian bin tnh tng ln 1 gi, trn ph xut hin vch ph c
trng ca lin kt C=C khong 1620 cm-1 (ng c). Khi tip tc tng thi

66
gian bin tnh ln 1,5 gi v 2 gi th cng pic ca nhm vinyl th hin r
nt hn. Cng pic ca nhm vinyl trong tro bay bin tnh 2 gi thay i
khng ng k so vi tro bay bin tnh 1,5 gi .
S thay i hm lng silan trn b mt tro bay theo thi gian ch c th
c gii thch da vo thi gian thy phn ca cc nhm metoxy cng nh
tc ngng t ca cc thnh phn silanol to thnh. Chnh v vy, thi gian
bin tnh b mt tro bay 1,5 gi c chn tip tc nghin cu.

* nh hng ca nhit phn ng n qu trnh silan ha b mt tro bay

Cc hnh 3.17 biu din ph hng ngoi ca cc mu tro bay bin tnh
bng dung dch 1% silan, trong 1,5 gi v cc nhit khc nhau l 30 C,
50 C v 70 C.

Hnh 3.17: Ph FT-IR tro bay bin tnh bng 1% silan MPTMS trong 1,5 gi
nhit khc nhau (a) FA ban u; (b) 30 C; (c) 50 C; (d) 70 C
Da vo vch ph c trng ca nhm vinyl ca hp cht silan trn ph
1620 cm-1, c th nhn thy rng, nhit bin tnh l 30 C cng
pic cng nh nt th hin pic c trng ca nhm C=C. Khi nhit bin
tnh tng ln 50 C, cng ca pic ny gim v khng c r nt. Nu

67
tip tc tng nhit bin tnh ln 70 C, cng ca pic c trng cho hp
cht silan rt yu. Nh vy khi tng nhit bin tnh tro bay bng tc nhn
lin kt silan MPTMS, hm lng hp cht silan gn trn b mt tro bay
gim. iu ny c th gii thch, khi tng nhit ca phn ng ln 70 C,
tc ngng t km theo s tch nc ca cc nhm silanol trong dung dch
phn ng tng nn lm gim hiu sut ca phn ng gia hp cht silan
vi b mt tro bay mt cch r rt.
Nh vy nhit phn ng bin tnh tro bay trong dung dch silan 1%
thi gian 1,5 gi l 30 C l ph hp.

3.1.2.2. Bin tnh b mt tro bay bng bis-(3-trietoxysilylpropyl) tetrasulphit

* nh hng ca nng silan n phn ng silan ha b mt tro bay
Hp cht silan bis-(3-trietoxysilylpropyl) tetrasulphit (c gi l Si69
theo tn thng mi) c thnh phn S4 gip cho n d b phn tch nhit
lu ha cao su, ng vai tr nh l cht lu ha.

Hnh 3.18: Ph FT-IR ca tro bay bin tnh bng Si69 cc nng khc
nhau (a)- FA ban u; (b)- 2% Si69;
(c)- 4% Si69; (d)- 6% Si69 v (e)- 8% Si69

Hnh 3.18 biu din ph hng ngoi ca cc mu tro bay c bin tnh

68
bng hp cht silan nng 2, 4, 6 v 8 % trong dung dch etanol. Phn
ng c thc hin nhit 30 oC trong thi gian 1,5 gi. Ph hng ngoi
ca tro bay ban u (ng a) th hin pic c trng cho cc nhm OH trn
b mt hp th 3409 cm-1, vch ph c trng cho dao ng ha tr ca cc
lin kt Si-O-Si chim thnh phn ch yu trong tro bay vng 1052 cm-1.
Vi cc mu tro bay c bin tnh bng hp cht silan, trn ph hng
ngoi thy xut hin cc pic dao ng mi c trng cho phn t silan trn b
mt ca tro bay. Cc pic ny c th d dng nhn thy 2972 cm-1, 2925 cm-1
v 2886 cm-1 c trng cho dao ng ha tr ca cc lin kt C-H c trong
phn t silan. Cng ca cc pic dao ng ny tng mnh t khong nng
t 2% n 6%. nng cao, cng cc pic ny khng thay i nhiu.
iu ny c th c gii thch l do trong dung dch ca hp cht silan, cc
nhm -OH trn b mt ca tro bay to cc lin kt hydro vi cc nhm silanol
ca cc phn t silan thy phn. Cng ca cc pic ny tng ln khi tng
nng ca hp cht silan, tuy nhin n mt nng nht nh hm lng
cc phn t silan sau khi thy phn to lin kt hydro vi b mt ca tro bay
t ti trng thi bo ha. nng cao kh nng ngng t ca cc phn t
silan thy phn tng ln, lm gim hiu qu ca qu trnh polyme ha. Mt
khc, theo nhiu cng b, lp silan trn b mt cht x l cng mng s cng
bn vng, hm lng hp cht silan cao cc lp ngoi cng s km bn
vng hn [69,120].

* nh hng ca qu trnh polyme ha silan n bn ca lp b mt silan

Qu trnh polyme ha lp ph silan ng vai tr quyt nh n bn

ca lp ph trn b mt ca cht n. Trong dung dch x l, cc phn t
silan sau khi thy phn ch yu lin kt vi b mt cc ht tro bay bng cc
lin kt hydro cng nh bng cc tng tc tnh in khc. Cc ht tro bay
sau khi thc hin phn ng trong dung dch c em sy kh thc hin
qu trnh polyme ha. Trong qu trnh ny, cc phn t nc tch ra bng
phn ng ngng t ca cc nhm -OH trn b mt tro bay v ca silanol

69
to thnh cc lin kt ha tr bn vng. C ch phn ng c chng minh
khi thc hin qu trnh ra mu sn phm tro bay trc v sau khi sy.

truyn qua (a.u)

Hnh 3.19: Ph FT-IR ca tro bay bin tnh bng Si69 cc iu kin khc
nhau (a)- FA ban u; (b)- Ra trc khi sy;
(c)- Ra sau khi sy; (d)- Khng ra

Trn hnh 3.19 biu din ph hng ngoi cc mu tro bay c bin tnh
bng dung dch cha 8% hp cht silan v cc mu tro bay c ra trc v
sau khi sy nhit 60 C trong thi gian 4 gi. nng 8% hp cht
silan, lp b mt bin tnh kh dy nn nh hng ca qu trnh polyme ha
c th hin r hn. T ph hng ngoi c th nhn thy d dng cc pic
c trng cho cc phn t silan ca mu tro bay c ra sau khi sy ch b
suy gim mt phn (ng c) trong khi mu c ra ngay sau khi phn ng
hu nh khng cn cc pic c trng cho phn t silan (ng b). iu ny
chng minh cho c ch phn ng bin tnh b mt tro bay bng hp cht
silan c din ra nh di y:

70
 Hnh 3.20: C ch phn ng v phn ng ha hc
gia tro bay vi tc nhn lin kt silan Si69

Trn b mt tro bay c cha nhm sulphit trong phn t nn khi s dng
tro bay lm cht gia cng cho cao su, nhm sulphit ny cng tham gia vo
qu trnh lu ha cao su.
3.1.2.3. Xc nh mc silan ha bng phn tch nhit
Phn tch nhit trng lng l k thut c s dng phn tch nh
lng silan gn trn b mt tro bay trn c s xc nh suy gim khi
lng ca mu o trong qu trnh gia nhit.

71
 Hnh 3.21: Gin TGA cc mu tro bay
a) khng bin tnh; b) bin tnh bng 1% MPTMS;
c) bin tnh bng 2% Si69

Hnh 3.21 biu din gin TGA ca cc mu tro bay khng bin tnh,
mu tro bay bin tnh bng 1% MPTMS v mu tro bay bin tnh bng 2%
Si69. C th nhn thy s thay i khng ng k trn gin phn tch nhit
ca cc mu tro bay bin tnh vi tro bay ban u. Khc bit ch th hin s
thay i khi lng trong vng nhit 450 C. S thay i khi lng ny
tng ng cho qu trnh phn hy ca hp cht silan trn b mt tro bay.
Trong trng hp tro bay bin tnh bng MPTMS, khi lng suy gim thm

72
so vi tro bay ban u l 0,093%, cn vi Si69 l 0,812%. Ngoi ra trn cc
gin phn tch nhit cn nhn thy qu trnh suy gim khi lng trong
khong 600-800 C tng ng vi qu trnh kt tinh li cng nh tch b cc
nhm hydroxyl c trong tinh th ca mt s thnh phn khong c trong tro
bay. Vic to ra lp ph silan mng vi hm lng nh l cn thit lp ph
ny c bn vng.
3.1.3. Quy trnh bin tnh b mt tro bay bng hp cht silan
Trn c s cc kt qu nghin cu, tro bay sau khi tinh ch tip tc c
bin tnh bng cc hp cht silan.

Thit b
Etanol 96%
Phn ng
iu chnh pH
bng axit CH3COOH

Hn hp
Phn ng 1

Hp cht silan

Hn hp
Phn ng 2

Tro bay

Hn hp
Phn ng 3

Lc

Cht rn 1
Lm kh t
nhin
Cht rn 2
Sy kh
60C

Tro bay
bin tnh

Hnh 3.22: Quy trnh bin tnh tro bay bng hp cht silan

73
 Quy trnh bin tnh tro bay bng hp cht silan gm cc bc sau:
Bnh phn ng cha etanol 96% lm dung mi cho hp cht silan
Dung mi c iu chnh pH = 4 5 bng dung dch axit axetic,
hn hp c khuy trn u bng khuy t vi tc 500
vng/pht (tc khng i trong qu trnh phn ng).
Hp cht silan c cho t t vo dung dch. Hn hp tip tc c
khuy trn trong 30 pht.
Tro bay theo t l cho trc c cho vo phn ng. Qu trnh din ra
nhit 30 C, p sut kh quyn. Thi gian cn thit cho qu trnh ny
l 1,5 gi.
Sau khi kt thc phn ng trong dung dch, hn hp c lc. Cht
rn thu c c lm kh t nhin trong 12 gi.
Cui cng, cht rn c sy 60 C trong 4 gi.

Nhn xt 2:
Qu trnh silan ha b mt tro bay c nghin cu bng cc phng
php ph hng ngoi (IR) v phn tch nhit TGA. Cc kt qu nghin cu
cho thy, lng hp cht silan gn trn b mt tro bay ph thuc ch yu vo
cc yu t: nng dung dch silan, thi gian v nhit phn ng.
C ch ca qu trnh silan ha din ra trn b mt ca tro bay l phn
ng ngng t km theo s tch nc gia cc nhm silanol ca phn t silan
vi cc nhm hydroxyl c trn b mt ca tro bay.
Tro bay bin tnh bng dung dch cha 1% MPTMS vi thi gian 1,5 gi
nhit 30 C s to ra lp ph silan mng trn b mt tro bay vi hm
lng 0,093%. Vi mu tro bay bin tnh bng dung dch cha 2% Si69 vi
thi gian 1,5 gi 30 C, lp ph silan c to ra trn b mt ca tro bay l
0,812%.

3.2. Nghin cu kh nng gia cng ca tro bay cho cao su thin nhin
3.2.1. nh hng ca cc hp cht silan khc nhau ti tnh cht c hc
Bn hp cht silan khc nhau c la chn lm tc nhn lin kt l:

74
 1: N-(2-Aminoetyl)-3-aminopropyl silantriol (AEAPT)
2: (3-Mertaptopropyl) trimetoxysilan (A-189)
3: -Aminopropyl trimetoxysilan (APTMS)
4: Bis-(3-trietoxysilylpropyl) tetrasulphit (Si69)
28
bn ko t (MPa)

25

22 Cc mu CSTN/FA:

19 1- Tro bay khng bin tnh

2- Tro bay bin tnh bng AEAPT
16 3- Tro bay bin tnh bng A-189
4- Tro bay bin tnh bng APTMS
13 5- Tro bay bin tnh bng Si69

10
1 2 3 4 5
Mu CSTN/FA

Hnh 3.23: bn ko t ca mu CSTN cha

30 pkl tro bay bin tnh bng cc hp cht silan

Trong hai hp cht silan l AEAPT v APTMS c nhm hot tnh amin,
hai hp cht A-189 v Si69 c nhm hot tnh mercapto v sulphit. Cc nhm
chc ny c nh hng nh l cht xc tin hoc tham gia vo qu trnh lu ha
CSTN. Phn ng bin tnh tro bay c tin hnh trong dung dch etanol 96%
vi nng silan 2%, thi gian phn ng 1,5 gi 30 C. Dung dch c
khuy trn u v khng i trong sut qu trnh tin hnh cc phn ng. Hn
hp thu c sau phn ng em lc v sy kh trong 4 gi nhit 60 C.
bn ko t ca cc mu cao su cha 30 pkl (phn khi lng) tro
bay bin tnh bng bn hp cht silan khc nhau c th hin trn hnh 3.23.
C th nhn thy tt c cc mu cao su cha tro bay bin tnh u c bn
ko t ln hn mu cao su cha tro bay khng bin tnh, trong mu cha
tro bay bin tnh bng Si69 c bn ko t ln nht (tng 29,5% so vi
mu cha tro bay khng bin tnh). iu ny cho thy cc tc nhn lin kt
silan c nhng nh hng ng k n kh nng tng tc ca tro bay vi
cht nn cao su, c bit l silan Si69. T kt qu trn chn tro bay bin
75
tnh bng Si69 tip tc nghin cu.

3.2.2. nh hng ca hm lng tro bay ti tnh cht c hc

Cc mu tro bay cha bin tnh v c bin tnh vi 2% hp cht
silan Si69 c gia cng cho CSTN cc hm lng khc nhau t 10 n
50 pkl. bn ko t v dn di tng i ca vt liu c th hin
hnh 3.24.

30 1000

950
25

dn di khi t (%)
bn ko t (MPa)

900
20
850

15 800

750
10
Tro bay bin tnh 700
5 Tro bay khng bin tnh
650

0 600
0 10 20 30 40 50
Hm lng tro bay (pkl)

Hnh 3.24: nh hng ca hm lng tro bay ti bn ko t

v dn di khi t ca vt liu CSTN

Kt qu trn cho thy, khi hm lng tro bay cha bin tnh tng t 0
n khong 30 pkl th cc tnh cht c hc ca vt liu tng ( bn ko t
tng khong 20%, dn di khi t cng tng). Khi hm lng tro bay trong
khong 30 pkl n 50 pkl th bn ko t v dn di khi t ca vt liu
li gim.
Vi tro bay bin tnh bng 2% hp cht silan cng thy cc tnh cht c
hc ca vt liu c xu hng tng t nhng c gi tr cao hn, c bit
bn ko t ca vt liu tng ng k khi c gia cng hm lng 30 pkl
( bn ko t tng gn 30%). Khi hm lng tro bay ln hn 30 pkl, bn
ko t ca vt liu li gim nhanh.

76
3.2.3. nh hng ca nng tc nhn lin kt silan ti tnh cht c hc
Hm lng ti u tro bay bin tnh l 30 pkl c la chn tip tc
nghin cu nh hng ca nng silan ti tnh cht c hc ca vt liu. Cc
mu tro bay c bin tnh bng dung dch Si69 c nng ln lt 0,5%,
1%, 2%, 4%, 6% v 8%. Cc gi tr bn c hc ca vt liu c th hin
trn hnh 3.25.

30 1000

25 950
bn ko t (MPa)

dn di khi t (%)
20 900

15 850

10 800

5 bn ko t 750
dn di khi t

0 700
0.5 1 2 4 6 8
Nng dung dch silan (% )

Hnh 3.25: nh hng ca nng dung dch silan ti bn ko t

v dn di khi t ca vt liu CSTN
T kt qu trn cho thy, khong nng thp, khi tng nng hp
cht silan bn ko t ca vt liu tng ln v t gi tr ln nht 2%.
Khi nng silan ln hn 2%, bn ko t ca vt liu gim ng k.
iu ny c th c gii thch l nng cao hp cht silan c nh
hng nhiu hn n qu trnh lu ha ca vt liu do cc phn t cng knh
ca hp cht silan gy ra hiu ng n ng khng gian. Mt khc, lp silan gn
trn b mt tro bay s km bn vng v b dy ca chng tng.

3.2.4. nh hng ca cc hp cht silan khc nhau ti qu trnh lu ha

Trong cng trnh ny, tin hnh nghin cu kh nng lu ha ca cc
mu vt liu CSTN c cha tro bay bin tnh bng cc tc nhn lin kt khc
nhau. Theo kt qu nghin cu trong mt cng b khc [108], nng hp

77
cht silan 2% cho cc tnh cht lu ha ca vt liu tt hn so vi nng
hp cht silan cao do hiu ng n ng khng gian. Do trong nghin cu
ny la chn bin tnh b mt tro bay vi cc hp cht silan khc nhau
nng 2%. Kho st qu trnh lu ho ca t hp cao su c thc hin trn
thit b Rheometer 140C, trong 30 pht.

Hnh 3.26: Gin lu ha ca cc mu CSTN vi tro bay khng bin tnh (FA)
v tro bay bin tnh bng silan A-189 (FA2Mc), AEAPT (FA2A) v Si69 (FA2S)

Hnh 3.26 trnh by gin lu ha ca vt liu CSTN vi tro bay khng

bin tnh v bin tnh bng 3 loi hp cht silan A-189, AEAPT v Si69. Trn
gin lu ha xut hin momen xon cc tiu v cc i (M min v Mmax).

Bng 3.3: Kh nng lu ha ca CSTN cha tro bay bin tnh

bng cc hp cht silan khc nhau
Hp cht Nng dung Mmin Mmax TC90
K hiu mu
silan dch silan (%) (kgf.cm) (kgf.cm) (pht-giy)
CSTN/50FA2Mc A-189 2 8,78 17,22 8-58
CSTN/50FA2A AEAPT 2 9,12 18,08 10-12
CSTN/50FA2S Si69 2 7,45 17,59 12-05
CSTN/50FA 0 0 9,55 18,33 10-55

78
 Cc gi tr momen xon cc tiu (Mmin) th hin tnh do hay linh
ng ca hn hp cao su trng thi chy mm ban u. Cc gi tr momen
xon cc i (Mmax) th hin bn, cng ca cao su sau qu trnh lu ho.
nh hng ca cc hp cht silan khc nhau ti qu trnh lu ha CSTN
c th hin bng 3.3.
Kt qu cho thy, momen xon cc tiu ca mu vt liu cha tro bay
bin tnh bng Si69 l thp nht, chng t rng loi hp cht silan ny cho
kh nng linh ng ca vt liu tt nht, kh nng tng hp ca tro bay bin
tnh bng hp cht silan ny vi cht nn cao su tt hn. Trong khi ,
momen xon cc i ca c ba mu vt liu li khng khc nhau nhiu, iu
ny cho thy nh hng ca 3 hp cht silan n bn ca vt liu nng
ny l gn nh khng thay i so vi mu tro bay khng bin tnh.
Thi gian lu ha ca mu cao su cha tro bay bin tnh bng A-189 l
thp nht so vi hai loi hp cht silan cn li. iu ny c gii thch l do
A-189 c cha nhm SH, nhm chc ny rt d tham gia vo qu trnh lu
ha ca vt liu nn hay gy ra hin tng lu ha sm. Cn mu cao su cha
tro bay bin tnh bng AEAPT cng c thi gian lu ha ngn l do trong hp
cht silan AEAPT c nhm NH2, nhm ny ng vai tr xc tin qu trnh
lu ha cao su.

Hnh 3.27: Phn ng lu ha gia hp cht silan Si69 trn b mt tro bay vi CSTN

i vi mu cao su cha tro bay bin tnh bng Si69, hp cht silan ny
tham gia vo qu trnh lu ha nhng kh khn hn do phi tri qua qu trnh
ct chui mch lu hunh trong phn t Si69 v hiu ng cn tr khng gian
79
cng knh ca n nn thi gian lu ha ln nht. Phn ng lu ha gia hp
cht silan Si69 trn b mt tro bay vi cao su thin nhin trong hnh 3.27.

3.2.5. Cu trc hnh thi ca vt liu CSTN/FA

Cu trc hnh thi ca vt liu cao su gia cng bng tro bay c kho
st bng knh hin vi in t qut (SEM). Cc mu vt liu CSTN c gia
cng vi hm lng tro bay 30 pkl khng bin tnh v bin tnh bng tc
nhn lin kt silan Si69 c th hin trn cc hnh 3.28 v 3.29 tng ng.

Hnh 3.28: nh SEM mu vt liu CSTN/30FA

Hnh 3.29: nh SEM mu vt liu CSTN/30FA2S

80
 Kt qu nh SEM cho thy, trn b mt vt liu xut hin cc vt lm
hnh trn v c s phn tch pha gia pha nn v cht n tro bay. iu
chng t kh nng tng tc gia tro bay khng bin tnh vi cao su khng
tt. Khi tro bay c bin tnh b mt bng tc nhn lin kt Si69, kh nng
tng tc pha ca tro bay vi cht nn cao su c ci thin r rt, khng
c hin tng phn pha, cc ht tro bay bm dnh tt vi nn cao su. iu ny
c th gii thch, tc nhn lin kt khng ch lm gim sc cng b mt gia
hai pha, cn lm tng kh nng phn tn ca cht n vo trong pha nn.
Ngoi ra, lp silan Si69 trn b mt tro bay cn tham gia vo qu trnh lu
ha vi CSTN nn kh nng lin kt gia cht n vi cht nn c ci
thin, t nng cao tnh cht ca vt liu.

3.2.6. Nghin cu bn nhit ca vt liu CSTN/FA

bn nhit ca vt liu CSTN/FA c nh gi bng phng php
phn tch nhit trng lng (TGA). Trn hnh 3.30 l gin TGA ca vt
liu trn c s CSTN. T gin thu c c th thy, trong qu trnh nng
nhit, vt liu xut hin 2 vng phn hu mnh nht c trng ca cao su
thin nhin trong nhng vng nhit l 379,63 oC v 534,29 oC. vng
nhit 379,63oC cao su b phn hy cc mch hydrocacbon vi tn tht
khi lng ln ti 84,12 %.

81
 Hnh 3.30: Gin TGA ca mu CSTN

vng nhit u khi lng vt liu suy gim phn ln, n c

trng cho bn nhit ca vt liu. Khi cao su c gia cng bng tro bay
cc vng nhit ny thay i. Di y trnh by cc nh hng c th
ca tro bay n bn nhit ca vt liu cao su thin nhin.

3.2.6.1. nh hng ca hm lng tro bay ti bn nhit ca vt liu

Trn bng 3.4 trnh by bn nhit ca cc mu CSTN cha tro bay

bin tnh bng 2% Si69 cc hm lng khc nhau.

Bng 3.4: bn nhit ca cc mu CSTN cha tro bay bin tnh bng Si69
vi hm lng khc nhau
Hm lng tro bay
0 10 20 30 40
(pkl)
Nhit phn hy
379,63 384,39 389,43 387,78 386,21
mnh nht (C)
Tn hao khi lng
84,12 76,96 73,75 66,41 66,46
n 460 oC (%)

Ging nh hu ht cc cht n, tro bay cng lm tng nhit phn hy

ca vt liu cao su thin nhin. hm lng thp, khi tng hm lng tro bay

82
th nhit phn hy c xu hng tng ln, nhit phn hy t gi tr ln
nht hm lng 20 pkl tro bay. Trn hm lng ny, nhit phn hy ca
mu vt liu cao su li c chiu hng gim xung.
Nhit phn hy ca mu vt liu CSTN t gi tr ln nht 20-30
pkl tro bay c th c gii thch l hm lng ny tro bay phn b ng
u trong vt liu, va lin kt cht ch vi cht nn to thnh mt cu
trc bn vng nn nhit phn hy ca vt liu cha 20-30 pkl tro bay cao
hn so vi cc mu vt liu cha tro bay hm lng khc. hm lng 30
pkl tro bay, vt liu c nhit phn hy thp hn mt cht, song tn hao
khi lng l thp nht (66,41%). iu ny hon ton ph hp vi cc kt
qu thu c khi o tnh cht c hc ca cc mu vt liu CSTN/tro bay,
bn ko t ca mu vt liu cao su thin nhin cha tro bay t gi tr ln
nht trong khong hm lng 20-30 pkl.
3.2.6.2. nh hng ca loi hp cht silan bin tnh b mt tro bay ti
bn nhit ca vt liu
kho st bn nhit ca cc mu vt liu cao su thin nhin c cha
30 pkl tro bay c bin tnh b mt bng 4 loi hp cht silan khc nhau:
bis-(3-trietoxysilylpropyl) tetrasulphit (CSTN/FA2S); (3-Mercaptopropyl)
trimetoxysilan (CSTN/FA2Mc); N-(2-Aminoetyl)-3-aminopropyl silantriol
(CSTN/FA2A) v -Aminopropyl trimetoxysilan (CSTN/FA2Am). Nhng
kt qu thu c, c th hin trong bng 3.5.

Bng 3.5: bn nhit ca cc mu CSTN cha tro bay bin tnh

bng cc hp cht silan khc nhau
Loi tro bay FA FA2S FA2Mc FA2A FA2Am

Nhit phn hy 385,16 387,78 383,24 382,47 386,18

mnh nht (C)
Khi lng suy gim
69,09 66,41 66,27 67,38 68,05
n 460 oC (%)

Cc hp cht silan bin tnh b mt tro bay u l cc hp cht hu c,

v vy nhit phn hy ca chng kh thp. Khi c s dng lm cht bin

83
tnh b mt, chng lm tng kh nng lin kt gia cht n vi cht nn hu
c, t lm tng nhit phn hy ca vt liu. Tuy nhin bn thn cc hp
cht silan cng phn hy, v vy m ty tng loi khc nhau c th lm tng
hoc gim nhit phn hy ca vt liu. T kt qu phn tch nhit cc mu
cao su cha tro bay bin tnh bng 4 loi hp cht silan khc nhau cho thy,
ch c hai mu cao su c cha tro bay bin tnh bng Si69 v APTMS l bn
nhit hn, trong mu cao su cha FA2S c nhit phn hy ln nht. Tro
bay bin tnh bng Si69 gia tng bn nhit cho vt liu CSTN, loi hp
cht silan ny to ra mng li bn vng trn b mt tro bay v c kh nng
lin kt ha hc vi CSTN bng phn ng lu ha.
3.2.6.3. nh hng ca nng silan bin tnh b mt tro bay ti bn
nhit ca vt liu
Trong phn nghin cu tip theo, nh hng ca nng cht bin tnh b
mt bng Si69 ti bn nhit ca vt liu c kho st. Cc mu CSTN
u cha 30 pkl tro bay bin tnh bng hp cht silan vi nng khc nhau.
Kt qu phn tch TGA c trnh by trong bng 3.6 di y.

Bng 3.6: bn nhit ca cc mu CSTN cha tro bay bin tnh

bng hp cht silan vi nng khc nhau

Nng silan (%) 0 2 4 6 8

Nhit phn hy 385,16 387,78 384,45 383,88 385,22

mnh nht (C)
Khi lng suy gim 69,09 66,41 67,87 65,35 67,57
n 460 oC (%)

Kt qu phn tch nhit cho thy nng hp cht silan 2% th bn

nhit ca mu vt liu t gi tr ln nht, cc nng hp cht silan cao,
bn nhit gim xung. Nh vy tro bay c bin tnh bng 2% hp cht silan l
ph hp to ra lp ph bn vng trn b mt. trn nng ny, kh nng
polyme ha xy ra kh khn hn, lm gim bn lin kt ca tro bay vi cht
nn, t lm gim tnh cht c hc cng nh bn nhit ca vt liu.

84
3.2.7. bn mi trng ca vt liu CSTN/FA
T cc kt qu nghin cu, la chn mu CSTN cha 30 pkl tro
bay bin tnh bng 2% bis-(3-trietoxysilylpropyl) tetrasulphit nh gi kh
nng bn mi trng ca vt liu. Trong bng 3.7 trnh by nhng kt qu th
nghim thu c theo tiu chun TCVN 2229 : 2007 (nhit th 70 oC, thi
gian th 72 gi trong mi trng khng kh v nc mui 10%).

Bng 3.7: nh hng ca qu trnh bin tnh

ti h s gi ho ca vt liu
H s gi ha Trong nc
Trong khng kh
Mu mui
CSTN 0,83 0,86
CSTN/30FA 0,89 0,84
CSTN/30FA2S 0,94 0,92

Kt qu trn cho thy, mu CSTN v cc ph gia c bn mi trng

thp nht, khi c thm 30 pkl tro bay khng bin tnh th kh nng n nh
trong khng kh tng ln nhng trong nc mui khng tng m cn c phn
gim. Khi mu cao su cha tro bay bin tnh b mt bng Si69 th h s gi
ho trong khng kh v nc mui u tng ln ng k. iu ny c th gii
thch, khi tro bay c bin tnh, kh nng phn tn ca chng trong nn
CSTN tt hn, cu trc ca vt liu tr nn ng u, cht ch v bn vng
hn do hnh thnh cc lin kt gia cht n vi cht nn cao su thng qua
hp cht silan. iu ny lm cho kh nng bn vi cc tc ng ca nhit ,
xy khng kh v nc mui ca vt liu tng ln.
Nhn xt 3:
Nghin cu s dng tro bay ch to vt liu compozit CSTN/FA cho
thy, tro bay c tc dng gia cng cho vt liu cao su. Tnh cht c hc ca
vt liu thay i theo hm lng tro bay v t gi tr cc i 30 pkl tro bay
khng bin tnh v bin tnh b mt bng hp cht silan Si69. Hp cht
silan ny c tc dng gia tng bn ko cho vt liu hn c so vi cc hp

85
cht silan khc c gc amin v mercapto. bn ko t ca vt liu c cha
30 pkl tro bay bin tnh bng 2% Si69 cho gi tr ln nht.
Qu trnh lu ha ca CSTN cha tro bay bin tnh b mt bng A-189
din ra nhanh hn so vi cc loi silan khc c kho st, song Si69 li gip
cho vt liu cao su linh ng hn, tng tc tt hn. Hm lng tro bay c
bin tnh b mt bng loi silan ny (Si69) tng ko di thi gian lu ha
v lm tng cc momen xon cc i v cc tiu.
Vt liu trn c s cao su thin nhin s dng tro bay lm cht n c
bn nhit cao hn so vi so vi mu vt liu khng cha tro bay. bn nhit
ca vt liu t gi tr ln nht khi s dng 20-30 pkl tro bay bin tnh lm
cht n (nhit phn hy mnh nht tng gn 10 C).
Tro bay cho vo hp phn CSTN khng ch lm gia tng bn nhit
m cn lm tng bn mi trng ca vt liu c bit l vi mu tro bay
c bin tnh b mt bng hp cht silan.

3.3. Nghin cu kh nng gia cng ca tro bay cho blend CSTN/NBR
3.3.1. nh hng ca tc nhn lin kt silan ti qu trnh lu ha blend
CSTN/NBR
Cn c vo cc kt qu nghin cu trc y v ch to h blend
CSTN/NBR ca tc gi Ng K Th v cng s [122], t l CSTN/NBR l
80/20 c la chn nghin cu kh nng gia cng ca tro bay.
tin hnh nghin cu kh nng lu ha ca cc mu vt liu c cha 50 pkl
(phn khi lng) tro bay bin tnh b mt bng ba loi hp cht silan khc
nhau. Cc tc nhn lin kt silan c la chn c cha lu hunh nhm tng
kh nng lu ha ca vt liu hoc c cha nhm chc amin thc y qu
trnh lu ha. Cc tc nhn lin kt silan khc nhau ln lt c kho st l:
(3-Mercaptopropyl) trimetoxysilan (A-189), N-(2-Aminoetyl)-3-aminopropyl
silantriol (AEAPT) v bis-(3-trietoxysilylpropyl) tetrasulphit (Si69). Cc gi
tr momen xon cc i, cc tiu v thi gian lu ha t 90% (TC90) c
trnh by trn bng 3.8.

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 Bng 3.8: Kh nng lu ha ca blend CSTN/NBR cha tro bay bin tnh
bng cc hp cht silan khc nhau
Loi hp Mmin Mmax TC90
K hiu
cht silan (kgf.cm) (kgf.cm) (pht giy)
CSTN/NBR/50FA4Mc A-189 9,25 17,37 9-14
CSTN/NBR/50FA4A AEAPT 9,40 19,89 9-37
CSTN/NBR/50FA4S Si69 11,16 18,91 8-39
Trong :
- 50FA4Mc: tro bay bin tnh bng 4% A-189 vi hm lng 50 pkl
- 50FA4A: tro bay bin tnh bng 4% AEAPT vi hm lng 50 pkl
- 50FA4S: tro bay bin tnh bng 4% Si69 vi hm lng 50 pkl

Gi tr momen cc tiu Mmin th hin tnh do hay linh ng ca cao

su blend trng thi chy mm ban u. Kt qu cho thy, mu blend
CSTN/NBR cha tro bay bin tnh b mt bng Si69 c Mmin cao nht, gi tr
ny cc mu CSTN/NBR/FA4Mc v CSTN/NBR/FA4A thp hn hn. Nh
vy vi vic bin tnh bng tc nhn lin kt silan Si69, kh nng phi trn
ca tro bay vo nn cao su blend km hn so vi tro bay bin tnh bng 2 loi
tc nhn lin kt silan cn li. iu ny l ph hp v Si69 khng c cc
nhm chc phn cc nn kh nng phi trn trong h blend cha cao su c
nhm phn cc b gim i, trong khi A-189 v AEAPT c cc nhm chc
cui mch tng ng l -SH v -NH2 s lm tng kh nng phi trn.
Gi tr momen cc i Mmax ln nht mu blend CSTN/NBR cha tro
bay bin tnh b mt bng AEAPT, sau l cc mu vt liu cha tro bay
bin tnh bng Si69 v A-189. iu ny cho thy, hp cht silan AEAPT l
tc nhn tng tc vi nn cao su tt hn so vi 2 tc nhn silan A-189 v
Si69.
Tuy nhin, thi gian lu ha (TC90) ca mu blend CSTN/NBR cha tro
bay bin tnh bng AEAPT l ln nht. Tro bay bin tnh bng Si69 cho thi
gian lu ha ca vt liu thp nht, t gi tr 8 pht 39 giy. iu ny c th
gii thch, tro bay bin tnh bng AEAPT v A-189 c nhm -SH v -NH2
tng ng, cc nhm ny c th tng tc vi nhm nitril ca cao su NBR

87
nn cc hiu ng lu ha sm hoc xc tin trong qu trnh lu ha b gim.
Gi tr TC90 ngn c gi tr kinh t trong vic gia cng ch to sn
phm. Vi gi tr TC90 thp nht v gi tr Mmax kh cao nn tc nhn lin kt
silan Si69 c la chn tip tc nghin cu.
3.3.2. nh hng ca nng tc nhn lin kt silan ti qu trnh lu ha
blend CSTN/NBR
Tro bay bin tnh b mt bng Si69 c la chn nghin cu nh
hng hm lng ca n ti qu trnh lu ha h blend CSTN/NBR. Lun n
kho st qu trnh lu ha h blend CSTN/NBR vi tro bay c bin tnh
bng Si69 vi cc nng 2; 4 v 8%. Cc gi tr Mmin, Mmax v TC90 c
trnh by trn bng 3.9.

Bng 3.9: nh hng ca nng Si69 ti kh nng lu ha ca blend

CSTN/NBR/FAS
Nng dung Mmin Mmax TC90
K hiu
dch silan (%) (kgf.cm) (kgf.cm) (pht giy)
CSTN/NBR/50FA2S 2 8,91 19,28 9-05
CSTN/NBR/50FA4S 4 11,16 18,91 8-39
CSTN/NBR/50FA8S 8 9,45 19,92 10-02

Trong :
- 50FA2S: tro bay bin tnh bng 2% Si69 vi hm lng 50 pkl
- 50FA4S: tro bay bin tnh bng 4% Si69 vi hm lng 50 pkl
- 50FA8S: tro bay bin tnh bng 8% Si69 vi hm lng 50 pkl

C th nhn thy khi tng nng ca hp cht silan t 2% ln 4% th

thi gian lu ha 90% ca vt liu gim xung. Tuy nhin nu tip tc tng
ln 8% th thi gian lu ha ca vt liu li tng ln. nng silan 4% gi
tr TC90 l thp nht 8 pht 39 giy, ng thi M min t gi tr cao nht. iu
ny chng t nng ny, Si69 c tc dng lm tng tng tc cho cc pha
CSTN v NBR trong t hp vt liu.
Tuy nhin nng cao hn (8%), gi tr Mmin ca vt liu li gim.
iu ny c gii thch, khi nng tc nhn lin kt silan qu cao, cc lp
silan trn b mt tro bay khng cn bn vng, chng rt d tch ra to cc lp
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silan t do. Chnh cc lp silan ny c tc dng nh ph gia qu trnh lm do
ha vt liu. Mt khc bn thn n cng tham gia vo qu trnh lu ha cao su
d hn l khi cn kt ni trn b mt ca tro bay. Vi cu trc phn t cng
knh, do hiu ng khng gian m thi gian lu ha ca blend tng ln.

3.3.3. nh hng ca nng tc nhn lin kt silan ti tnh cht c hc

ca blend CSTN/NBR/FA
Tnh cht c hc ca cao su blend CSTN/NBR cha 50 pkl tro bay bin
tnh bng Si69 vi cc nng 2, 4, 8% c th hin trn bng 3.10.

Bng 3.10: Tnh cht c hc ca vt liu CSTN/NBR

cha tro bay bin tnh bng Si69 vi nng khc nhau
Nng bn ko t dn di
K hiu
dung dch silan (%) (MPa) khi t (%)
CSTN/NBR/50FA 0 10,35 452,78
CSTN/NBR/50FA2S 2 12,85 452,51
CSTN/NBR/50FA4S 4 13,89 491,43
CSTN/NBR/50FA8S 8 9,45 467,76

Tro bay bin tnh b mt c tc dng gia cng cho cao su blend
CSTN/NBR, cc mu CSTN/NBR/50FA2S v CSTN/NBR/50FA4S bn
ko t v dn di khi t tng ng k so vi mu cha tro bay khng
bin tnh b mt. Cc tnh cht c hc ca vt liu t cc i mu c tro
bay c bin tnh b mt nng 4% Si69. Khi nng Si69 tip tc
tng, cc tnh cht ny li gim th hin mu CSTN/NBR/50FA8S c
bn ko t thp hn c mu CSTN/NBR/50FA. Kt qu ny l ph hp vi
cc kt qu khi kho st qu trnh lu ha. Lp silan gn trn b mt tro bay
qu dy, c lin kt yu dn n d b tch ra to lp silan t do.
Nh vy, nng dung dch silan Si69 4% l ph hp cho qu trnh bin
tnh b mt tro bay to sn phm va c tnh c hc cao v va c tnh
kinh t.

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3.3.4. nh hng ca hm lng tro bay ti qu trnh lu ha blend
CSTN/NBR
Kho st nh hng ca hm lng tro bay n qu trnh lu ha blend
CSTN/NBR vi hm lng tro bay bin tnh bng 4% Si69 ln lt l 10, 30
v 50 pkl. Kt qu th hin trn bng 3.11 v cc hnh 3.31 n 3.33.

Hnh 3.31: Gin lu ha ca blend CSTN/NBR/10FA4S

Hnh 3.32: Gin lu ha ca blend CSTN/NBR/30FA4S

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 Hnh 3.33: Gin lu ha ca blend CSTN/NBR/50FA4S
Bng 3.11: nh hng ca hm lng tro bay bin tnh
ti kh nng lu ha ca blend CSTN/NBR
Hm lng Mmin Mmax TC90
K hiu
tro bay (pkl) (kgf.cm) (kgf.cm) (pht giy)
CSTN/NBR/10FA4S 10 9,45 18,82 11-07
CSTN/NBR/30FA4S 30 10,35 18,15 10-33
CSTN/NBR/50FA4S 50 11,16 18,91 8-39

Kt qu trn cho thy, khi tng hm lng tro bay t 10 n 50 pkl thi
gian lu ha 90% (TC90) gim i r rt. Hm lng tro bay c tc dng
gim thi gian lu ha ca cao su blend CSTN/NBR.
Gi tr Mmin tng theo chiu tng ca hm lng tro bay t 10 n 50 pkl.
iu ny cho thy khi hm lng tro bay tng lm gim linh ng cng nh
tnh do ca blend CSTN/NBR. Vi cc gi tr momen xon cc i, c th nhn
thy rng cc gi tr ny thay i khng nhiu khi tng hm lng tro bay. iu
chng t trong khong hm lng t 10 n 50 pkl, bn ca vt liu sau
qu trnh lu ha t b nh hng.
3.3.5. nh hng ca hm lng tro bay ti tnh cht c hc ca blend
CSTN/NBR
Kho st nh hng ca hm lng tro bay bin tnh bng 4% Si69 ti
tnh cht c hc ca vt liu blend CSTN/NBR nhm xc nh hm lng tro
bay ti u c th s dng c. Cc hm lng tro bay 10, 20, 30 v 50 pkl
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 c kho st, kt qu th hin trn bng 3.12.

Bng 3.12: Tnh cht c hc ca vt liu CSTN/NBR/FA

Hm lng bn ko t dn di
K hiu
tro bay (pkl) (MPa) khi t (%)
CSTN/NBR 0 13,12 557,36
CSTN/NBR/10FA4S 10 14,48 564,50
CSTN/NBR/20FA4S 20 16,22 571,48
CSTN/NBR/30FA4S 30 14,39 512,56
CSTN/NBR/50FA4S 50 13,89 491,43
Trong :
- 10FA4S: tro bay bin tnh bng 4% Si69 vi hm lng 10 pkl
- 20FA4S: tro bay bin tnh bng 4% Si69 vi hm lng 20 pkl
- 30FA4S: tro bay bin tnh bng 4% Si69 vi hm lng 30 pkl
- 50FA4S: tro bay bin tnh bng 4% Si69 vi hm lng 50 pkl

Kt qu trn cho thy rng, vi hm lng tro bay t 10 n 20 pkl

lm tng tnh cht c hc ca blend CSTN/NBR. Khi hm lng tro bay ln
hn 20 pkl th bn ko t v dn di khi t ca vt liu li c xu
hng gim. iu ny c th gii thch, khi hm lng tro bay ti u cc
phn t hydrocacbon cao su khng to thnh mt pha lin tc m thnh cu
trc ring bit vi kch thc ln hn nhiu kch thc ht n. Cc cht n
bm bc xung quanh cc cu trc v to thnh cc tp hp cao su-n. Cc
tp hp ny c lin kt vi nhau bng sc cng b mt. Khi hm lng tro
bay vt qu hm lng ti u, cc ht n s phn b vo khong trng gia
cc tp hp v c tc dng nh nhng chic nm tch cc tp hp cao su-n
ra lm gim hiu ng tng cng lc ca cht n dn n lm gim tnh cht
ca vt liu.

3.3.6. Cu trc hnh thi ca ca vt liu CSTN/NBR/FA

Trn hnh 3.33 biu din cu trc hnh thi ca mu vt liu blend
CSTN/NBR c cha 20 pkl tro bay bin tnh b mt.

92
 Hnh 3.34: nh SEM vt liu blend CSTN/NBR/20FA4S
Nhn thy rng, kh nng tng tc pha gia cc ht cht n tro bay vi
pha nn kh tt, th hin khng c khong cch phn pha gia nn cao su v
cc ht tro bay cng nh gia 2 loi cao su. iu ny c th gii thch do tc
nhn lin kt silan khng ch ci thin tng tc pha gia cao su nn v tro
bay m cn ci thin kh nng tng tc pha gia cc hp phn cao su trong
vt liu. Tng tc pha gia CSTN v NBR trong khi vt liu kh tt, s
tng hp ny cn c th hin qua cc kt qu phn tch nhit.

3.3.7. Nghin cu bn nhit ca vt liu CSTN/NBR/FA

Di y l gin TGA ca mu vt liu blend CSTN/NBR c cha 20
pkl tro bay bin tnh b mt bng dung dch 4% Si69.

93
 Hnh 3.35: Gin TGA ca vt liu blend CSTN/NBR/20FA4S
Kt qu trn hnh 3.35 cho thy, vng nhit t 300 n 500 oC, phn
ln khi lng vt liu b suy gim, n c trng cho bn nhit ca vt
liu. Trong vng nhit ny, ch thy xut hin mt nhit phn hy mnh
nht 391,61 oC, iu ny chng t 2 pha CSTN v NBR tng tc kh tt
vo nhau do hai nhit phn hy c trng cho 2 pha thnh phn tin gn
li nhau v chp lm mt (nhit phn hy mnh nht ca CSTN v NBR
ln lt l 379,63 oC v 432,32 oC).
3.3.7.1. nh hng ca hm lng tro bay ti bn nhit ca vt liu
CSTN/NBR/FA
Trong bng 3.13 trnh by nhit phn hy mnh nht ca cc mu
blend CSTN/NBR cha tro bay vi hm lng khc nhau. Cc mu tro bay
c bin tnh bng dung dch Si69 4%.

94
 Bng 3.13: bn nhit ca cc mu CSTN/NBR
cha tro bay vi hm lng khc nhau
Hm lng tro bay (pkl) 0 10 20 30 50

Nhit phn hy mnh 388,95 390,32 391,61 390,85 390,59

nht (C)
Khi lng suy gim 80,83 80,07 72,49 67,84 58,90
n 600 oC (%)

Kt qu trn cng cho thy, khi hm lng tro bay tng th nhit phn
hy c xu hng tng ln v t gi tr ln nht hm lng 20 pkl tro bay.
iu ny c th c gii thch, hm lng ny tro bay phn b ng u
trong vt liu v lin kt cht ch vi cht nn to thnh mt cu trc bn
vng hn. Khi hm lng tro bay ln hn 20 pkl, nhit phn hy ca mu
vt liu cao su li c xu hng gim nh.
3.3.7.2. nh hng nng tc nhn lin kt silan ti bn nhit ca vt
liu CSTN/NBR/FA
Trong phn nghin cu tip theo ny, nh hng ca nng tc nhn lin
kt Si69 ti bn nhit ca vt liu c kho st. Cc mu blend
CSTN/NBR cha 20 pkl tro bay bin tnh bng Si69 cc nng khc nhau.

Bng 3.14: nh hng ca nng tc nhn Si69 ti bn nhit ca blend

CSTN/NBR/FAS
Nng silan (%) 0 2 4 8

Nhit phn hy 385,16 388,85 391,61 389,74

mnh nht (C)
Khi lng suy gim 71,09 72,26 72,49 72,94
n 600 oC (%)

Kt qu phn tch nhit cho thy, nng hp cht silan 4% th bn

nhit ca mu vt liu t gi tr ln nht. Khi nng hp cht silan cao
hn, bn nhit ca vt liu blend gim xung. Nh vy tro bay bin tnh
bng 4% hp cht silan l ph hp to ra lp ph bn vng trn b mt.
Ngoi ra, hp cht silan cn c tc dng nh cht lm tng kh nng tng
tc gia cao su thin nhin v cao su nitril. nng silan cao (8%), kh
95
nng polyme ha xy ra kh khn hn, lm gim bn lin kt ca tro bay
vi cht nn, t lm gim tnh cht cng nh bn nhit ca vt liu.

3.3.8. bn mi trng ca vt liu CSTN/NBR

3.3.8.1. H s gi ha
Trn bng 3.15 trnh by nhng kt qu th nghim cc mu vt liu
blend CSTN/NBR theo tiu chun TCVN 2229 : 2007 (nhit th 70 oC,
thi gian th 96 gi trong mi trng khng kh v nc mui 10%).

Bng 3.15: H s gi ha ca cc mu vt liu blend CSTN/NBR

H s gi ha
Trong khng kh Trong nc mui
Mu
CSTN/NBR 0,80 0,82
CSTN/NBR/20FA 0,86 0,83

CSTN/NBR/20FA4S 0,92 0,91

T kt qu nhn thy rng, mu blend CSTN/NBR v cc ph gia c

bn mi trng thp nht, khi c thm 20 pkl tro bay th kh nng n nh
trong khng kh tng ln nhng trong nc mui ch tng cht t.
Khi mu blend CSTN/NBR c cha 20 pkl tro bay bin tnh b mt bng
Si69 th h s gi ho trong khng kh v nc mui u tng ln ng k.
iu ny c th gii thch, mt mt khi tro bay c bin tnh b mt, kh
nng phn tn ca cht n tt hn. Mt khc, do hnh thnh cc lin kt ca
cht n vi cht nn cao su thng qua hp cht silan, dn n cu trc ca
vt liu tr nn ng u, cht ch v bn vng hn. Do vy lm cho kh
nng bn vi cc tc ng ca nhit , xy khng kh v nc mui ca vt
liu tng ln.
3.3.8.2. trng trong du diezen
Cc mu vt liu cao su blend CSTN/NBR c kho st bn du
bng cch ngm trong du diezen. Trn hnh 3.36 l kt qu kho st nh
hng ca thi gian ngm n trng ca mt s mu vt liu CSTN v

96
blend CSTN/NBR cha tro bay bin tnh v khng bin tnh. Nhn thy rng,
cc mu blend c kh nng bn du tt hn nhiu CSTN, trng trong
du diezen gim ng k nh c cao su nitril vi phn cc cao. Cao su
nitril che chn cho pha cao su thin nhin trong blend, ngn cn s xm
nhp ca du diezen trong qu trnh th nghim.

350

CSTN
300 Blend-0FA
Blend-20FA
Blend-20FA-2S
250
trng (%)

Blend-20FA-4S
Blend-20FA-8S
200

150

100

50

0
0 8 16 24 32 40 48 56
Thi gian (gi)

Hnh 3.36: trng trong du diezen ca vt liu CSTN v

blend CSTN/NBR/20FA

Cng vi , tro bay bin tnh b mt bng cc tc nhn lin kt silan

Si69 cc nng dung dch 2%, 4% v 8% c kho st nh hng n
trng trong du ca vt liu blend CSTN/NBR/FA. Kt qu cho thy,
trng ca vt liu thay i khng nhiu cc nng dung dch tc nhn
lin kt silan khc nhau. Tuy vy, vt liu blend cha tro bay bin tnh bng
4% Si69 c trng trong du l thp nht.

97
 210 Blend-10FA-4S
Blend-20FA-4S
180 Blend-30FA-4S
Blend-50FA-4S
150

trng (%)
120

90

60

30

0
0 8 16 24 32 40 48 56
Thi gian (gi)

Hnh 3.37: trng trong du diezen ca blend CSTN/NBR/FA4S

Vi tro bay bin tnh bng Si69 4%, kho st kh nng bn du ca

vt liu blend khi tng hm lng tro bay t 10-50 pkl. Kt qu nghin cu
c th hin trn hnh 3.37. Nhn thy rng, trng ca vt liu trong du
diezen gim dn khi hm lng tro bay tng. Sau 48 gi ngm mu, trng
ca mu vt liu cha 50 pkl tro bay t gi tr thp nht.
Nhn xt 4:
Trong qu trnh lu ha h blend CSTN/NBR cha tro bay bin tnh b
mt bng cc hp cht silan khc nhau cho thy, kh nng trn hp ca tro bay
bin tnh Si69 vi blend CSTN/NBR km hn so vi tro bay bin tnh bng A-
189 v AEAPT nhng vt liu li c thi gian lu ha TC90 ngn hn, gi tr
ny l thp nht khi nng dung dch Si69 bin tnh b mt tro bay l 4%.
Tnh cht c hc ca vt liu blend CSTN/NBR t gi tr cc i (
bn ko t: 16,22 MPa) ti hm lng 20 pkl tro bay. Khi hm lng tro bay
ln hn 20 pkl, tnh cht c hc ca vt liu li gim chm. Tro bay lm tng
kh nng bn nhit ca blend CSTN/NBR, nhit phn hy mnh nht tng
6,45 C.
Tro bay lm tng bn mi trng ca vt liu c bit l tro bay bin
tnh bng Si69. H s gi ha ca blend CSTN/NBR cha 20 pkl tro bay bin
tnh trong mi trng khng kh v nc mui t kh cao (tng ng l 0,92

98
v 0,91). Mt khc, bn trong du diezen ca vt liu c ci thin khi s
dng tro bay lm cht n gia cng.

3.4. Nghin cu kh nng gia cng ca tro bay cho blend CSTN/SBR
3.4.1. nh hng ca nng tc nhn lin kt silan ti tnh cht ca
blend CSTN/SBR
3.4.1.1. Tnh cht c hc ca blend CSTN/SBR
Trn c s cc kt qu nghin cu ca nhm tc gi thc hin [123], t
l CSTN/SBR c chn l 80/20 nghin cu. Cao su blend CSTN/SBR
cha 30 pkl tro bay bin tnh bng Si69 cc nng 1, 2,... 6 % c
nghin cu. Tnh cht c hc ca vt liu c th hin trong bng di y:

Bng 3.16: nh hng ca nng tc nhn lin kt silan

ti tnh cht c hc ca vt liu blend CSTN/SBR/FA

Tnh cht bn ko dn di cng mi mn

Nng Si69 (%) t (MPa) khi t (%) (Shore A) (cm3/1,61km)

0 11,56 649,2 45,2 1,06

1 12,26 663,5 45,9 1,02
2 13,48 672,4 46,8 0,98
3 15,86 698,9 47,2 0,91
4 13,94 673,2 47,5 0,90
5 12,56 679,7 47,1 0,94
6 11,43 684,5 46,9 1,01

Kt qu trn bng 3.16 cho thy, nng tc nhn lin kt Si69 c nh

hng nhiu ti bn ko t cng nh dn di khi t ca vt liu. Khi
nng Si69 tng t 1 n 3%, cc tnh cht c hc ( bn ko, dn di,
cng, bn mi mn) ca vt liu u tng ng k, nu nng Si69 tip
tc tng th cc tnh cht ny ca vt liu gim. iu ny c th gii thch, khi
nng Si69 thp (1-3%) lm tng kh nng tng tc ca tro bay vi cc
pha cao su trong blend dn n tnh cht c hc ca vt liu tng. Khi nng
Si69 cao, kh nng lin kt ca Si69 vi b mt tro bay khng bn dn n

99
tng tc gia cht n v nn cao su km bn vng, do vy tnh cht c hc
ca vt liu gim.
3.4.1.2. Qu trnh lu ha ca blend CSTN/SBR
Trong nghin cu ny, kh nng lu ha ca cc mu blend CSTN/SBR
cha tro bay bin tnh bng Si69 vi nng khc nhau c nghin cu.
Kho st qu trnh lu ho ca t hp cao su c thc hin trn thit b lu
ha 140C, trong 25 pht. Kt qu o tnh cht lu ha ca cc mu vt liu
c biu din trn gin lu ha.

Hnh 3.38: Gin lu ha ca mu CSTN/SBR/30FA

Hnh 3.39: Gin lu ha ca mu CSTN/SBR/30FA1S

100
 Hnh 3.40: Gin lu ha ca mu CSTN/SBR/30FA3S

Hnh 3.41: Gin lu ha ca mu

CSTN/SBR/30FA5S

Bng 3.17: Kh nng lu ha ca blend CSTN/SBR cha tro bay bin tnh
vi nng dung dch silan khc nhau
Nng dung Mmin Mmax TC90
K hiu mu
dch silan (%) (kgf.cm) (kgf.cm) (pht-giy)
CSTN/SBR/30FA 0 2,92 9,10 15-21
CSTN/SBR/30FA1S 1 3,56 9,77 17-53
CSTN/SBR/30FA3S 3 3,93 10,12 18-46
CSTN/SBR/30FA5S 5 3,71 10,10 19-53
Trong :
- 30FA: tro bay khng bin tnh vi hm lng 30 phn khi lng (pkl)

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 - 30FA1S: tro bay bin tnh bng 1% Si69 vi hm lng 30 pkl
- 30FA3S: tro bay bin tnh bng 3% Si69 vi hm lng 30 pkl
- 30FA5S: tro bay bin tnh bng 5% Si69 vi hm lng 30 pkl

Kt qu trn cho thy, khi tng nng ca hp cht silan t 1% ln 5% th

thi gian lu ha 90% (TC90) ca vt liu tng dn. S gia tng thi gian lu
ha, mt mt l do Si69 c nhm trietoxysilylpropyl cui mch, nhng nhm
ny cng knh c th dn n hiu ng n ng khng gian lm gim kh khu
mch gia cao su v lu hunh. Mt khc, Si69 trn b mt tro bay c th tham
gia phn ng lu ha vi nn cao su hnh thnh lin kt FA-Si69-CS (cao su).
Gi tr momen xon cc tiu ca mu CSTN/SBR/FA l b nht, iu
ny chng t mu blend cha tro bay khng bin tnh c do ban u l tt
nht v cng cho thy tro bay bin tnh t nhiu tng tc vi cc phn t
cao su trong qu trnh cn trn. nng dung dch silan 3%, gi tr M min v
Mmax ca vt liu t gi tr cao nht. iu ny cho thy nng ny, Si69
c kh nng tng tc tt vi cc pha CSTN v SBR trong vt liu.
V vy cn c vo tnh cht c hc v tnh lu bin, chn nng
dung dch silan Si69 l 3% cho qu trnh bin tnh b mt tro bay tip tc
cc nghin cu tip theo.
3.4.2. nh hng ca hm lng tro bay bin tnh ti tnh cht ca blend
CSTN/SBR
3.4.2.1. nh hng ca hm lng tro bay bin tnh ti tnh cht c hc ca
blend CSTN/SBR
kho st nh hng ca hm lng tro bay bin tnh bng Si69 vi nng
3% ti tnh cht c hc ca vt liu blend CSTN/SBR xc nh hm lng
tro bay ti u c th s dng c. Cc hm lng tro bay 10, 20, 30, 40, 50 v
60 pkl c kho st thng qua nh gi tnh cht c hc ca vt liu.

102
 Bng 3.18: nh hng ca hm lng tro bay bin tnh ti
tnh cht c hc ca blend CSTN/SBR
Tnh cht bn ko dn di cng mi mn
Hm lng t (MPa) khi t (%) (Shore A) (cm3/1,61km)
FA3S (pkl)
10 12,68 737,2 44,3 0,89
20 13,15 704,7 45,8 0,89
30 15,86 698,9 47,2 0,91
40 13,43 674,2 47,8 0,96
50 12,84 651,8 48,3 1,07
60 11,20 644,1 48,8 1,12

T cc kt qu trn bng 3.18 cho thy, khi hm lng tro bay bin tnh
bng 3% Si69 (FA3S) tng t 10 n 30 pkl, bn ko t ca cao su blend
tng v gim dn nu hm lng FA3S ln hn 30 pkl. C th thy hm
lng 30 pkl tro bay bin tnh l hm lng ti u nn kh nng tng tc
gia cht n v cht nn cao su l tt nht, dn n bn ko t ca vt
liu t cc i. dn di khi t ca cao su blend gim khi hm lng
FA3S tng. Trong khi , mi mn tng khi hm lng tro bay tng. Tuy
nhin, s tng hoc gim tnh cht giai on u (n 30pkl FA3S) cn
chm v sau th nhanh hn. iu ny c th gii thch, i vi vt liu cao
su ni chung v cao su blend ni ring th khi tng hm lng cht n thng
thng th cng, mi mn ca vt liu tng tr cc cht n gia cng.
Song di hm lng ti u th s thay i theo hng tiu cc thng l
chm. Ring cng ca vt liu tng dn u do c im ca cht n v
c thng l cng hn cao su nn.
3.4.2.2. nh hng ca hm lng tro bay bin tnh ti qu trnh lu ha
blend CSTN/SBR
Kho st nh hng ca hm lng tro bay n qu trnh lu ha vi cc
mu c k hiu nh sau: CSTN/SBR/10FA3S, CSTN/SBR/30FA3S v
CSTN/SBR/60FA3S c hm lng tro bay bin tnh bng Si69 ln lt l 10,
30 v 60 pkl. Kt qu nghin cu c th hin trn cc hnh 3.39, 3.41 v
103
3.42 v bng 3.19.

Hnh 3.42: Gin lu ha ca mu

CSTN/SBR/10FA3S

Hnh 3.43: Gin lu ha ca mu

CSTN/SBR/60FA3S
Bng 3.19: Kh nng lu ha ca blend CSTN/SBR/FA3S
vi hm lng tro bay khc nhau
Hm lng tro Mmin Mmax TC90
K hiu mu
bay (pkl) (kgf.cm) (kgf.cm) (pht-giy)
CSTN/SBR10FA3S 10 2,82 8,26 17-46
CSTN/SBR/30FA3S 30 3,93 10,12 18-46
CSTN/SBR/60FA3S 60 3,53 11,81 14-29

104
 Trong :
- 10FA3S: tro bay bin tnh bng 3% Si69 vi hm lng 10 pkl
- 30FA3S: tro bay bin tnh bng 3% Si69 vi hm lng 30 pkl
- 60FA3S: tro bay bin tnh bng 3% Si69 vi hm lng 60 pkl

Kt qu trn cho thy rng, khi tng hm lng tro bay t 10 n 60 pkl,
thi gian lu ha 90% (TC90) tng ln mt cht ( hm lng 30 pkl), sau
gim mnh khi hm lng tro bay l 60 pkl.
hm lng tro bay thp (10 pkl), momen xon cc tiu nh nht, khi hm
lng tro bay tng (30 pkl) th gi tr ny t ln nht. Nu tip tc tng lng
tro bay th momen xon cc tiu li gim mt cht. iu c th gii thch, hm
lng 30 pkl tro bay bin tnh tng tc tt vi cc pha cao su nn lm do
hay linh ng ca vt liu gim.

3.4.3. Nghin cu cu trc hnh thi, kh nng bn nhit ca blend

CSTN/SBR/FA
3.4.3.1. Nghin cu cu trc hnh thi ca blend CSTN/SBR/FA
Phng php knh hin vi in t qut (SEM dng nh gi kh nng
tng tc ca tro bay vi cht nn cao su. Cc kt qu chp b mt gy ca
mt s mu vt liu tiu biu c trnh by di y.

Hnh 3.44: nh SEM b mt mu vt liu CSTN/SBR/30FA

105
 Hnh 3.45: nh SEM b mt mu vt liu CSTN/SBR/30FA3S

Hnh 3.46: nh SEM b mt mu vt liu CSTN/SBR/60FA3S

T cc kt qu cc nh SEM cho thy cng hm lng 30 pkl, i vi

mu blend c tro bay khng bin tnh b mt, cc ht tro bay ni trn nn cao
su, b mt tro bay trn nhn dn n tng tc gia tro bay v nn cao su
khng tt. Khi tro bay bin tnh b mt (FA3S) bng Si69, b mt gianh gii
gia ht tro bay v nn cao su khng c hin tng phn tch pha, iu ny
chng t tro bay bin tnh b mt tng tc tt vi nn cao su. Do vy,
hm lng 30 pkl tro bay bin tnh b mt, blend CSTN/SBR c tnh cht c

106
hc tt nht. Tuy nhin cng l tro bay bin tnh b mt, khi hm lng tro
bay cao (60 pkl), trn b mt gy ca mu vt liu c mt s ht tro bay tng
tc vi nn cao su khng tt. iu ny c th gii thch l do hm lng tro
bay ln hn hm lng ti u nn chng c xu hng kt t vi nhau dn ti
lm gim kh nng tng tc gia cht n vi nn cao su.

3.4.3.2. Nghin cu kh nng bn nhit ca blend CSTN/SBR/FA

Trn c s cc kt qu v tnh lu bin v tnh cht c hc ca cao su
blend CSTN/SBR vi tro bay. Mt s mu tiu biu c chn nh gi
kh nng bn nhit ca vt liu, di y l cc kt qu phn tch TGA ca
cc mu vt liu.

Hnh 3.47: Biu TGA mu blend CSTN/SBR/30FA

107
Hnh 3.48: Biu TGA mu blend CSTN/SBR/30FA3S

Hnh 3.49: Biu TGA mu blend CSTN/SBR/30FA5S

108
 Hnh 3.50: Biu TGA mu blend CSTN/SBR/60FA3S

Bng 3.20: Kh nng bn nhit ca cc mu blend CSTN/SBR/FA

Tnh cht Nhit phn hy Tn hao khi
Mu blend mnh nht (C) lng 480oC (%)

CSTN/SBR/30FA 368,17 67,338

CSTN/SBR/30FA3S 376,04 67,084

CSTN/SBR/30FA5S 370,48 68,692

CSTN/SBR/60FA3S 370,38 57,685

T hnh 3.46 n hnh 3.49 v bng 3.20 cho thy, khi tro bay bin tnh
b mt lm tng bn nhit ca vt liu. Tro bay bin tnh b mt bng
3% Si69, nhit phn hy mnh nht ca vt liu tng ng k (gn 8oC) so
vi vt liu cha tro bay khng bin tnh. Khi nng Si69 tng (5%) th
bn nhit ca vt liu li gim. iu ny c th gii thch do nng Si69
cao, b dy lp silan trn b mt tro tng nn khng bn v d b tch ra dn
n lm gim kh nng tng tc ca tro bay vi nn cao su.
Hm lng tro bay bin tnh b mt cng nh hng ng k ti tnh
cht ca vt liu. Trn hnh 3.47, 3.49 v bng 3.20 cho thy, tro bay bin tnh

109
b mt vi hm lng 30 pkl, vt liu c bn nhit cao nht (376,04 oC),
tuy nhin khi hm lng tro bay l 60 pkl th bn nhit ca vt liu li
gim. iu ny c th gii thch hm lng cao, kh nng tng tc gia tro
bay vi nn cao su b gim.

3.4.4. Kh nng gia cng ca tro bay cho vt liu cao su v cao su blend
Trn c s cc kt qu nghin cu kh nng gia cng ca tro bay cho
cc h vt liu CSTN, blend CSTN/NBR v blend CSTN/SBR, lp bng so
snh mt s tnh cht ca cc h vt liu trn nhm tm mi quan h gia cu
trc v tnh cht.
Bng 3.21: Hm lng tro bay v nng silan Si69 ti u
ti tnh cht ca vt liu CSTN v blend trn c s CSTN
Vt liu
CSTN CSTN/NBR CSTN/SBR
Thng s
Nng dung dch Si69 2% 4% 3%
Hm lng tro bay bin tnh 30 pkl 20 pkl 30 pkl
S gia tng bn ko t, 6,12 MPa 3,76 MPa 4,30 MPa
k=kb-k0
S gia tng nhit phn
2,62 oC 6,45 oC 7,88 oC
hy mnh nht,
tm = tmb - tm0
Trong :
- kb: bn ko t ca vt liu cha tro bay bin tnh
- k0: bn ko t ca vt liu cha tro bay khng bin tnh
- tmb: nhit phn hy mnh nht ca vt liu cha tro bay bin tnh
- tm0: nhit phn hy mnh nht ca vt liu cha tro bay khng bin tnh

T nhng kt qu nghin cu kh nng ng dng ca tro bay cho vt liu

CSTN v cao su blend trn c s CSTN cho thy, hm lng tro bay ti u
dng gia cng cho vt liu cao su l 20-30 pkl. Nng dung dch Si69
ti u dng bin tnh tro bay l 2-4% ty tng h vt liu cao su. Tro bay
bin tnh bng Si69 lm tng ng k bn ko t v bn nhit ca
vt liu.

110
Nhn xt 5:
- i vi cao su blend CSTN/SBR (80/20), nng Si69 dng bin
tnh b mt tro bay l 3%, nng ny cht n tro bay tng tc tt vi nn
cao su dn n tnh cht c hc ca vt liu tt nht. Vi cng hm lng tro
bay l 30 pkl, bn ko t ca blend CSTN/SBR/FA3S tng 37,12% so vi
blend CSTN/SBR/FA. Tro bay bin tnh bng 3% Si69 c th lm cht n gia
cng cho cao su blend CSTN/SBR vi hm lng di hoc bng 30 pkl.
- Tro bay bin tnh b mt bng Si69 ci thin c kh nng bn
nhit ca vt liu so vi tro bay khng bin tnh b mt. Hm lng tro bin
tnh cng nh hng ln ti kh nng bn nhit ca vt liu. Cao su blend
CSTN/SBR cha 30 pkl FA3S c bn nhit cao nht.
3.5. Nghin cu ng dng tro bay trong ch to sn phm cao su
3.5.1. Nghin cu thnh phn n pha ch
n pha ch ca cc thc nghim c da trn n pha ch ca Cng ty
TNHH Nh nc MTV Giy Thy Khu cho giy chu du. Trong cc bng
th hin thnh phn ca giy nghin cu, y ch lit k cc thnh phn cn
kho st t c cht lng sn phm mong mun. Cc thnh phn khc
khng thay i.
3.5.1.1. Nghin cu thay th CaCO3 bng tro bay
Cht n ch yu ca n pha ch cho giy l SiO2 v CaCO3. y
ch nghin cu thay i thnh phn CaCO3 bng tro bay c bin tnh b
mt bng 4% hp cht silan Si69 v c k hiu l FA4S.

111
 Bng 3.22: Kho st kh nng s dng tro bay thay cho CaCO3
Mu B1 Mu B2
(pkl) (pkl)
Thnh phn
CSTN/ NBR 100 100
Than en 0 0
SiO2 50 50
FA4S 30 0
CaCO3 0 30
Tnh cht c l
bn ko t (MPa) 11,73 10,15
dn di khi t (%) 487 514
Modul n hi (MPa) 0,25 0,19
cng (Shore A) 70 68

Kt qu trn bng 3.22 cho thy, khi s dng 30 pkl tro bay thay cho
CaCO3 bn ko t ca vt liu c ci thin, tng t 10,15 MPa ln
11,73 MPa. Modul n hi v cng ca vt liu cng tng cn dn di
khi t li gim. iu ny chng t tro bay c tc dng gia cng cho
blend CSTN/NBR hn l CaCO3. Tnh cht c hc ca vt liu t yu
cu, tuy nhin trong lun n cng nghin cu cc yu t nh hng khc vi
mong mun ci thin hn na cht lng ca vt liu.
3.5.1.2. nh hng hm lng ca SiO2
Trong phn nghin cu ny, gim hm lng SiO2 t 50 pkl xung 20
pkl (mu B4). Kt qu trn bng 3.23 cho thy, mu B4 c bn ko t v
modul n hi gim i ng k, trong khi dn di khi t li tng ln. Mu
B3 c gia cng thm 10 pkl than en, tnh cht ca vt liu c c ci thin
ng k song vn thp hn mu B1 vi hm lng SiO2 l 50 pkl. iu ny
chng t SiO2 l cht n gia cng cho blend CSTN/NBR vi hm lng cao.

112
 Bng 3.23: nh hng ca SiO2 n tnh cht ca vt liu
Mu B1 Mu B3 Mu B4
(pkl) (pkl) (pkl)
Thnh phn
CSTN/ NBR 100 100 100
Than en 0 10 0
SiO2 50 20 20
FA4S 30 30 30
CaCO3 0 0 0
Tnh cht c l
bn ko t (MPa) 11,73 9,59 7,92
dn di khi t (%) 487 492 514
Modul n hi (MPa) 0,250 0,133 0,106
cng (Shore A) 70 66 65
3.5.1.3. nh hng ca than en
Vi cc kt qu nghin cu trn, mu B1 vn m bo kt qu tt nht,
p ng tiu chun c s ca Cng ty.

Bng 3.24: nh hng ca than en n tnh cht ca vt liu

Mu B1 Mu B2 Mu B5 Mu B6
(pkl) (pkl) (pkl) (pkl)
Thnh phn
CSTN/ NBR 100 100 100 100
Than en 0 0 20 20
SiO2 50 50 30 30
FA4S 30 0 0 30
CaCO3 0 30 30 0
Tnh cht c l
bn ko t (MPa) 11,73 10,15 12,00 14,09
dn di khi t (%) 487 514 421 472
Modul n hi (MPa) 0,250 0,190 0,218 0,212
cng (Shore A) 70 68 67 68

113
 giy chu du khng c tnh cht trang tr nn trong lun n s
dng mt phn than en vi mong mun nng cao cht lng ca vt liu.
Vi cc mu s dng CaCO3 (mu B2 v B5), khi thay th 20 pkl SiO2 bng
than en bn ko t v modul n hi tng song khng nhiu. bn ko
t gia tng ng k, t 11,73 ln 14,09 MPa khi s dng tro bay thay cho
CaCO3 v thay th 20 pkl SiO2 bng than en (cc mu B1 v B6). cc mu
ny dn di, modul n hi v cng li suy gim mt cht, ph hp vi
yu cu cht lng ca giy chu du. Mu B6 c la chn nh l vt
liu c tnh cht ti u.

3.5.2. Kho st kh nng bn du m ca vt liu

Kh nng chu du m ca vt liu giy c kho st bng
trng trong du diezen trong qu trnh ngm mu n 48 gi. Kt qu kho
st thu c, c trnh by trn hnh 3.51 di y.

16

14

12
Mu B1
trng (%)

10 Mu B2
Mu B3
8
Mu B4
6 Mu B5
Mu B6
4

0
0 4 8 12 16 20 24 28 32 36 40 44 48 52
Thi gian (gi)

Hnh 3.51: Kho st trng trong du diezen ca vt liu

Nhn thy rng, cc mu B3 v B4 c trng ln nht, tng ng vi
cc tnh cht c l nh nht c xc nh trn. trng trong du ca
blend CSTN/NBR c lin quan n lu ha ca cao su v hm lng cht

114
n. Cc mu B3 v B4 c hm lng SiO2 gim nn mt lu ha khng
cao dn n trng ca cc mu ny l cao nht. iu ny cng c phn
nh bng s suy gim trng khi thay 20 pkl SiO2 bng than en cc mu
B5 v B6.
Cc mu B1, B2, B5 v B6 c trng thp 10% sau 48 gi ngm,
t yu cu ca giy chu du. Cc mu c gia cng bng tro bay (B1
v B6) c trng thp hn khi s dng CaCO3 (B2 v B5). Tro bay th
hin tnh u vit hn l CaCO3 trong ch to vt liu cao su chu du.

3.5.3. Ch th giy chu du

Trn c s cc kt qu nghin cu trn, ch th giy chu du.
Kt qu o cc ch tiu cht lng ca giy c trnh by trong bng 3.25
di y.

Bng 3.25: Cc ch tiu cht lng giy chu du

Ch tiu cht lng ch Mc cht lng

n v o
yu ca sn phm
TCVN 1677-86 t
- bn ko t MPa 9 14,09
- dn di khi t % 450 472
- cng Shore A - 68
- mi mn cm3/1,61 km 1,5 1,102
- T trng g/cm3 1,4 1,275
- H s gi ho ( 70oC/72
- 0,92
gi)
- bn lin kt:
+ CS blend CS blend N/cm 13 28
+ CS blend vi N/cm 12 16
- bn mi Chu k > 30.000 > 100.000
- trng theo
TCVN 2752 : 2008
% 12 8,82
+ trng
Shore A < + 10 9
+ Tng cng

115
 T nhng kt qu trnh by trong bng 3.25 cho thy, sn phm giy bn
du m c t blend CSTN/NBR gia cng bng tro bay c cc tnh cht
t v vt tt c cc ch tiu cht lng yu cu i vi giy bn du m.

Nhn xt 6:
- xc nh c n phi trn cao su blend ch to cao su chu
du c thnh phn chnh nh sau: CSTN 80 pkl, NBR 20 pkl, than en 20 pkl,
SiO2 30 pkl, tro bay 30 pkl.
- Vi hm lng tro bay 30 pkl trong n phi trn lm giy chu du,
sn phm c tnh cht t yu cu xut khu. Nht l cc yu cu v bn
mi v bm dnh ca giy u ln hn nhiu so vi tiu chun, m bo
cho sn phm bn chc v nng cao thi gian s dng.

116
 KT LUN
T cc kt qu nghin cu thu c cho thy rng:

1. Tro bay Ph Li c Cng ty C phn Sng 12-Cao Cng tinh ch c

cht lng cao, b mt nhn bng v bn vng, khng b ph hy bng dung
dch HCl. Tro bay sau khi c tinh ch c kch thc ht trung bnh 7,116
m vi phn b hp rt ph hp lm cht n gia cng cho vt liu
polyme ni chung v cao su ni ring.
Khi x l bng kim, b mt ca tro bay bin dng, tng kh nng tip
xc vi nn polyme. Dung dch NaOH ph hy b mt cc ht tro bay, din
tch b mt tng ln gn 30 ln, th tch l xp tng ln gn 40 ln. Tro bay
c x l bng dung dch Ca(OH)2 c b mt th rp hn v c bao ph
bng cc ht nh di 1m c thnh phn l canxi aluminat v silicat.
2. Qu trnh silan ha b mt tro bay ph thuc vo nng dung dch silan, thi
gian x l v nhit ca phn ng, nht l qu trnh polyme ha. Silan ha xy
ra trn b mt tro bay l phn ng ngng t km theo s tch nc gia cc
nhm silanol ca phn t silan vi cc nhm hydroxyl trn b mt ca tro bay.
Tro bay bin tnh b mt bng dung dch 1% MPTMS vi thi gian 1,5
gi 30 oC to lp ph silan vi hm lng 0,093%, bng dung dch 2%
Si69 vi thi gian 1,5 gi 30 oC c lp ph silan vi hm lng 0,812%.
3. Tnh cht c hc ca vt liu CSTN t gi tr cc i 30 pkl tro bay
khng bin tnh v bin tnh bng silan Si69. Hp cht silan ny c tc dng
gia tng bn ko cho vt liu hn c so vi cc hp cht silan khc c gc
amin v mercapto v t gi tr cao nht khi tro bay bin tnh bng 2% Si69.
Silan Si69 gip cho qu trnh trn hp thun li hn, tuy nhin qu trnh
lu ha ca vt liu CSTN vi tro bay bin tnh bng loi silan ny din ra
chm hn. Hp cht silan trn b mt tro bay gip cho tng tc pha trong
vt liu CSTN/tro bay c ci thin ng k.
Tro bay lm gia tng bn nhit vt liu trn c s CSTN. Vi hm
lng 20-30 pkl tro bay bin tnh bng dung dch 2% Si69, vt liu c nhit
phn hy cao nht (t 389,43C, tng 10 oC so vi mu CSTN). Tro bay cng
117
 c tc dng lm tng bn mi trng ca vt liu CSTN/tro bay (h s
gi ha trong khng kh v nc mui tng thm ln lt l 13% v 7%).
4. Kh nng trn hp ca tro bay bin tnh Si69 vi blend CSTN/NBR km
hn so vi tro bay bin tnh bng A-189 v AEAPT nhng vt liu li c thi
gian lu ha TC90 ngn hn, gi tr ny l thp nht khi nng dung dch
Si69 bin tnh b mt tro bay l 4%. Tnh cht c l ca blend CSTN/NBR t
gi tr cc i ti hm lng 20 pkl tro bay bin tnh 4% Si69 ( bn ko t:
16,22 MPa; nhit phn hy mnh nht: 391,61 C). Tro bay bin tnh lm
tng bn mi trng v bn du m ca vt liu.
5. i vi cao su blend CSTN/SBR, tro bay c bin tnh bng Si69 ( nng
3%) vi hm lng 30 pkl cho hiu qu tt nht. Ti thnh phn ny, tnh
cht c hc ca vt liu t gi tr cao nht: bn ko t tng 37,12% so
vi blend CSTN/SBR cha tro bay khng bin tnh; nhit phn hy mnh
nht tng 8 oC.
6. Vt liu cao su blend trn c s CSTN/NBR gia cng 30 pkl tro bay bin
tnh p ng yu cu ch to giy bn du m phc v cho tiu dng v xut
khu.

118
 DANH MC CC CNG TRNH KHOA HC LIN QUAN
N LUN N C CNG B

1. Ng K Th, Nguyn Vit Dng, Nguyn Vn Thy, Quang Khng,

Lng Nh Hi, Nguyn Quang Khi, Nghin cu kh nng gia cng ca
tro bay bin tnh cho vt liu cao su thin nhin, Tp ch ha hc, 2010, 48
(4A), 312-318.

2. Lng Nh Hi, Nguyn Vit Dng, Nguyn Vn Thy, Ng K Th,

Quang Khng, Nghin cu bin tnh tro bay bng -metacryloxypropyl
trimetoxysilan, Tp ch Ha hc, 2012, 50 (4B), tr. 109-113.

3. Lng Nh Hi, Nguyn Vit Dng, Nguyn Vn Thy, Ng K Th,

Quang Khng, Nghin cu nh hng ca tro bay x l b mt ti qu
trnh lu ha blend CSTN/NBR, Tp ch Ha hc, 2012, 50 (4B), 105-
108.

4. Luong Nhu Hai, Luu Duc Hung, Ngo Ke The, Do Quang Khang, Effect of
surface treated fly ash on properties and morphology of NR/SBR blends,
Vietnam Journal of Chemistry, 2013, 51 (5A), 100-105.

5. Lng Nh Hi, Nguyn Vit Dng, Ng K Th, Quang Khng,

Nghin cu nh hng ca tro bay x l b mt n tnh cht nhit v mi
trng ca blend CSTN/NBR, Tp ch ha hc, 2013, 51 (6ABC), 249-
253.

6. Lng Nh Hi, Ng K Th, Quang Khng, Tro bay v nhng ng

dng, Thng tin Kinh t & Cng ngh - Cng nghip Ha cht, s 6-2014.

119
 TI LIU THAM KHO

1. Ramesh C. Joshi, Rajinder P. Lohtia, Fly ash in concrete, Gordon and

Breach Science, 1997.
2. Shanghai the standards high calcium fly ash concrete application of
technical regulations DBJ08-230-98(Chinese Edition).
http://thongtinkhcndaklak.vn:81/kqncvn2012/Che_tao_may/Toan_van/8735.pdf
3. Fly ash in Concrete Applications, Lafarge North America Cement Operting
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