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No.

116
2017
Tp ch Khoa hc v Cng ngh 116 (2017)

MC LC

1. Xy dng h INS/GPS theo c u truc ghep long s du ng b lo c Kalman trn c s h INS a c 1 16-152
cai thi n chinh xac
Triu Vit Phng1,2, Nguyn Th Lan Hng1*, Tri nh Quang Thng1
1
Trng i hc Bch khoa H Ni
2
Vin o lng Vit Nam

2. Xy dng thut ton iu khin mng nron da theo m hnh mmen tnh ton cho robot almega 16 6 15-107
V Thu H - Trng i hc Kinh t K thut Cng nghip

3. S dng cc tiu ha tng on sai lch u ra trong min thi gian iu khin d bo h bung 12 16-084
sy giy a bin
Trn Kim Quyn1, Bi Quc Khnh2, Nguyn Don Phc2*
1
Trng Cao ng Cng nghip Tuy Ha
2
Trng i hc Bch khoa H Ni

4. iu khin phn hi v tr b kch hot tnh tin ng dng cho vi bm kiu xi lanh 20 16-140
Nguyn Anh Tun, Phm Hng Phc* - Trng i hc Bch khoa H Ni

5. Disk Tool Profiling for Helical Surfaces Generation 26 16-125


Nguyen Thanh Tu1,2, Banh Tien Long1*, Hoang Long1
1
Hanoi University of Science and Technology
2
Thai Nguyen University of Technology

6. Nghin cu nh hng ca v tr xp container n c tnh kh ng on xe ch container 31 16-063


Nguyn Danh 1,2, L Trung Sn3, Ng Vn H1*
1
Trng i hc Bch khoa H Ni
2
Cng ty Sa Vit Nam, VINAMILK
3
Trng i hc Cng Ngh, i hc Quc gia H Ni

7. Nghin cu nh hng ca gc ln ci n qu trnh dp thy tnh phi tm kim loi 37 16-091


L Trung Kin*, Phm Vn Ngh1 - Trng i hc Bch khoa H Ni

8. Cng ngh ch to in cc hn cho dy chuyn hn bn t ng xch neo tu hi qun 42 16-149


Phng Tun Anh - Hc vin K thut Qun s

9. Numerical Investigation of Solidification around a Circular Cylinder with the Presence of the Free 47 16-119
Surface in a Rectangular Cavity
Vu Van Truong*, Truong Viet Anh - Hanoi University of Science and Technology

10. Nghin cu kho st kh nng phn tch ph liu da thuc ca sn xut giy thnh vt liu c cu 52 16-135
trc dng x
on Anh V 1*, Dng Th Hon 1,2
1
Trng i hc Bch khoa H Ni
2
Trng i hc Cng nghip Dt May H Ni

11. Effects of Milling Time on the Properties of In-Situ Binary Niobium-Titanium-Carbide Reinforced 58
Cu Based Composite
Le Minh Hai, Tran Duc Huy - Hanoi University of Science and Technology

12. Cu trc li/v v s pht hunh quang ca dy nan silic 63 16-120


Nguyn Th Thy1,2,*, Nguyn Quang Huy1, Nguyn Khc Tng1,
Vng Tun Dng1, Nguyn Hu Lm1
1
Trng i Trng i hc Bch Khoa H Ni
2
Trng i hc S Phm K Thut Hng Yn
Tp ch Khoa hc v Cng ngh 116 (2017)

13. Tnh cht nhy kh H2S ca cm bin mng mng SnO2/NiO 68 15-138
Nguyn Vn Ton, Nguyn Vn Duy, Nguyn Vn Hiu*
- Trng i hc Bch khoa H Ni

14. Tng hp ng nano ccbon bng phng php CVD nhit: nh hng ca kim loi xc tc 72 16-131
Nguyn Cng T*, Nguyn Hu Lm - Trng i hc Bch khoa H Ni

15. Xc nh hot tnh sinh hc ca hn hp tinh du v qu chanh v cam 77 16-042


Nguyn Vn Li1,*, L Th Phng2
1
Trng i hc Cng nghip H Ni
2
Trng i hc Gio dc, i hc Quc gia H Ni

16. S dng graphene a lp lm cht mang xc tc trong phn ng hydro ha cinnamaldehyde nhm 16-075
thu c hydrocinnamaldehyde vi chn lc cao
Trng Hu Tr - Trng i hc Bch khoa - i hc Nng
Tp ch Khoa hc v Cng ngh 116 (2017) 001-005

Xy d ng h INS/GPS theo c u truc ghep long s du ng b lo c Kalman


trn c s h INS a c cai thin chinh xac
Implementation of a Loosely Coupled Integration INS/GPS System
using kalman filter based on Improved INS System

Triu Vit Phng1,2, Nguyn Th Lan Hng1*, Trinh


Quang Thng1
1
Trng i hc Bch Khoa H Ni S 1 i C Vit, Hai B Trng, H Ni
2
Vin o lng Vit Nam S 8 Hong Quc Vit, Cu Giy, H Ni
n Ta son: 27-7-2016; chp nhn ng: 24-11-2016

Tm tt
Kt hp INS/GPS l gii php hiu qu trong bi ton dn ng kt hp a cm bin. Bi v GPS v INS
c th b sung cho nhau t kt qu ti u da trn nhng u, nhc im ca chng. Trong bi ton
kt hp thng tin t cc h thng c lp, h kt hp s t chnh xc v tin cy tt hn trn c s thng
tin cung cp bi tng h l ng n. Bi bo ny tp trung trnh by xy dng h kt hp INS/GPS theo
cu trc ghp lng s dng b lc Kalman trn c s h INS c tc gi ci thin qua nng cao
chnh xc IMU v chnh xc xc nh gc nh hng ca vt th. Kt qu th nghim trn i tng
chuyn ng mt t cho thy h ghp lng INS/GPS xut c cht lng, chnh xc v tnh ng dng
cao hn so vi h ghp lng INS/GPS truyn thng.
T kha: H dn ng qun tnh, H thng nh v v tinh ton cu, cu trc ghp lng, b lc Kalman,
khi o lng qun tnh
Abstract
The INS/GPS integration is an effective solution in multi-sensors navigation. This is because, GPS receiver
and INS sensors can complement each other to achieve optimal results based on the advantages and
disadvantages of them. In an information integration system from independent systems, the integration
system achieve accuracy and better reliability based on information provided by each system is correct. This
paper focuses on presentation of a loosely coupled integration INS/GPS using Kalman filter based on INS
system has been improved the accuracy of IMU, objects orientation. Testing results on land vehicle are
shown the quality, accuracy and applicability of the proposed loosely coupled integration INS/GPS higher
than tradition loosely coupled integration INS / GPS.
Keywords: Inertial Navigation System, Global Positioning System, Loosely Coupled, Kalman Filter, Inertial
Measurement Unit

1. Gii thiu* Kalman [1, 4, 5, 6]. H thng GPS c tc cung cp


thng tin chm, tuy nhin thng tin li n nh trong
H dn ng qun tnh (INS) xc nh v tr vt
thi gian di. Kt hp INS vi GPS gip h thng c
th da trn chnh thng tin chuyn ng ni ti ca
th cung cp c thng tin vi tc nhanh, n
vt th, l gia tc chuyn ng. T gia tc chuyn
nh di, chnh xc cao [1, 4, 5, 6].
ng ca vt th, ly tch phn hai ln theo thi gian
s xc nh c v tr ca vt th. H INS c u mt h thng dn ng kt hp thng tin t
im l cung cp thng tin v tr, trng thi vt th nhiu h thng dn ng khc nhau c c
mt cch lin tc v tc thi, c kh nng hot ng chnh xc cao, n nh lu di, i hi tng h phi
c lp trong mi iu kin kh hu, thi tit, a chnh xc, n nh, thut ton s dng kt hp thng
hnh. Tuy nhin do s dng php tnh tch phn nn tin cng phi tin cy. Vi h dn ng kt hp
h INS c th sinh ra sai s tch ly theo thi gian, INS/GPS, cc nghin cu hin nay ch yu tp trung
dn n thng tin cung cp bi h ch chnh xc trong vo xy dng, nng cao gii php, thut ton kt hp
khong thi gian ngn [1, 4, 5, 6]. c th xc nh h INS vi h GPS m t ch trng nng cao cht
c chnh xc v tr vt th, cn thit phi p dng lng ca tng h ring r. Trong bi bo ny, cac tc
nhng k thut b tr sai s khc nhau. Hin nay gi tp trung xy dng h ghp lng INS/GPS trn c
phng php b tr sai s ph bin l kt hp INS s h INS c ci thin bng cc phng php
vi h thng nh v ton cu (GPS) s dng b lc c trnh by ti [2, 3]. K t qua thc nghi m trn
i t ng chuy n ng m t t ( t) cho th y h
*
ghp lng INS/GPS xu t hoa t ng n inh,
Corresponding author: Tel.: (+844) 3869 6233
Email: huong.nguyenthilan@hust.edu.vn

1
Tp ch Khoa hc v Cng ngh 116 (2017) 001-005

chinh xac c cai thi n ro r t so vi h ghp lng T nguyn ly hoa t ng cua h INS m ta trn
INS/GPS s du ng h INS truy n th ng. hinh 1, c th thy cht lng ca h INS ph thuc
trc tip vo chnh xc ca khi o lng qun
2. Ci thin chinh xac h INS
tnh (IMU). V vy, vic quan trng cn thc hin
Nguyn l xc nh v tr vt th ca h INS trc khi a IMU vo s dng l hiu chun (xc
kiu strapdown truy n th ng trong h e-frame c nh, loi tr hoc gim thiu nh hng ca cc sai
thc hin theo s Hnh 1. s). Cng vic ny u c cc nh sn xut IMU
thc hin trc khi xut xng, cc gi tr sai s c
Initial Attitude
ghi r trong ti liu k thut. Tuy nhin do mi
trng lm vic thc t khc vi iu kin th

Gyroscope
Gyroscope Attitude
nghim ca cc nh sn xut, cng vi nhiu nguyn
Signal
Initial
Initial Velocity Position
nhn khc, m bo yu cu s dng thc t cn
Project
thit phi thc hin li qu trnh hiu chun ny. Do

Accelerometer Accelerations Correct for Moving
Accelerometer Velocity Position
IMU phi hot ng trong nhiu iu kin mi trng
Signal onto Global Gravity Acceleration
Axes

IMU khc nhau, nn qu trnh hiu chun cn phi c


tin hnh thng xuyn m bm h thng INS
Hnh 1. S nguyn l xc nh v tr vt th ca h lun hot ng chnh xc v n nh. Tuy nhin trong
INS kiu Strapdown [1, 4, 5, 6] h INS s dng cu trc Strapdown, IMU c gn
Cc phng trnh nh v i vi vt th trong c nh vo vt th, cng vi vic cc phng tin
trng hp ny c dng [1, 4, 5, 6]: chuyn ng mt t di chuyn thng xuyn nn r
rng vic tin hnh hiu chun cc cm bin trong
r e v e phng th nghim l rt kh khn v phc tp. iu
e ny i hi phi pht trin cc phng php hiu
v 2ie v ie ie r Cb f g
e e e e e e b e
(1) chun mi cho IMU sao cho c th thc hin mt
e
Cb Cb eb cch nhanh chng, d dng ngay ti hin trng m
e e

vn m bo chnh xc.
Trong :
Do cm bin gia tc s dng trong h INS l
r e : vector v tr vt th xt trong h e-frame cm bin 3 chiu, thng tin o c t cm bin bao
v e : vector vn tc vt th xt trong h e-frame gm gia tc trng trng v gia tc chuyn ng.
Cbe : ma trn chuyn h ta t h b-frame sang Trong trng hp ng yn, thng tin o c ca
cm bin chnh l gi tr gia tc trng trng ti v tr
h e-frame
t. M gi tr gia tc trng trng ti mt v tr c
f b : vector gia tc o c bi cm bin gia tc coi l khng i (thay i v cng nh theo thi
gn trn vt th gian), v vy hon ton c th dng gi tr ny lm
iee : ma trn m t cc thnh phn vn tc gc chun hiu chun cm bin gia tc. Trong [2] tc
gi trnh by phng php mi dng gi tr gia tc
ca h e-frame quay quanh h i-frame
trng trng ti v tr t cm bin lm chun (khng
0 iee 0 cn thm chun, phng tin o tham chiu bn ngoi
m vn m bo chnh xc, tin cy) cho php xc
ie iee
e
0 0 ;iee 7,2921159.105 (rad / s)
0 nh chnh xc sai s h thng (sai s t l v sai s
0 0 bias) ca cm bin gia tc bng vic c lng ln

lt cc sai s s dng phng php bnh phng cc
g e : vector gia tc trng trng xt trong h e-
tiu. Tng t, do t trng Tri t ti mt v tr c
frame thay i rt nh theo thi gian, nn gi tr t trng
eeb : ma trn m t cc thnh vn tc gc ca vt Tri t ti v tr t cm bin cng c s dng lm
th xt trong h b-frame vi e-frame chun hiu chun cm bin t trng trong h INS
theo phng php trnh by trong [2]. Vi cm bin
0 zeb
b
yeb
b
vn tc gc, sai s bias c xc nh bng vic tin
b b hnh thu thp kt qu o trng thi ng yn, sau
eb zeb
b
0 xeb
ly gi tr trung bnh cng loi tr. Bn cnh
yeb
b
xeb
b
0
, t vic c th xc nh chnh xc s nh hng
ca cm bin vn tc gc trong khng gian t kt qu
ebb ibb ieb ibb Cebiee o ca cm bin gia tc v cm bin t trng trng
thi ng yn, hon ton xc nh c gi tr sai s
ibb : vector vn tc gc o bi cm bin vn tc t l ca cm bin vn tc gc da trn so snh gc
gc gn trn vt th quay ca cm bin xc nh t kt qu o ca cm

2
Tp ch Khoa hc v Cng ngh 116 (2017) 001-005

bin vn tc gc vi gc quay xc nh c t cm s gc nh hng ( ), vn tc ( v e ), v tr ( r e )


bin gia tc v cm bin t trng (sau khi cc cm ca h INS, vi tn hiu quan st l sai lch gia v
bin gia tc v t trng c hiu chun, s dng e e
tr, vn tc thu c t GPS ( rGPS , vGPS ) v v tr, vn
cc gi tr o c t cc cm bin ny lm chun).
e e
tc xc nh c t INS ( rINS , vINS ). Ly kt qu gc
Mt khc, theo nguyn ly hoa t ng cua h INS
m ta trn hinh 1, vic xc nh chnh xc cc gc nh hng ( INS ), vn tc, v tr xc nh c t h
nh hng ca vt th trong khng gian c tnh INS tr i cc gi tr sai s ny s thu c gc nh
quyt nh, nh hng trc tip n chnh xc ca hng, vn tc, v tr chnh xc ca vt th. Kt qu
h INS. AHRS l h thng xy dng trn c s cc c on sai s gc nh hng, vn tc, v tr, cng
cm bin qun tnh, cung cp thng tin v cc gc c phn hi iu chnh li h INS. u im ca
nh hng (gc hng, gc nghing, gc ngng) ca m hnh ny l n gin, kh nng m rng v tnh
vt th trong khng gian. AHRS l mt phn ca h k tha cao [1,4,5,6].
dn ng qun tnh v c ng dng nhiu trong
cc h thng dn ng cho t, my bay, tn la,
trong cc h thng iu khin robot, hoc cc h cn
bng [1]. Khi vt th ng yn, gi tr gc nghing v
ngng c xc nh t kt qu o ca cm bin gia
tc, gi tr gc hng c xc nh t kt qu o ca
cm bin t trng. Sau khi xc nh c gi tr cc
gc nh hng trng thi ng yn, khi v t th
chuyn ng, bng vic ly tch phn kt qu o t
cm bin vn tc gc s xc nh c cc gc nh
hng mi ca vt th. Tuy nhin, d c hiu
chun, kt qu o ca cc cm bin vn tn ti sai s, Hnh 2. M hnh kt hp INS-GPS theo cu trc
cc sai s ny tch ly theo thi gian lm gim ghp lng s dng b lc Kalman
chnh xc ca h AHRS. V vy, cn thit phi p
dng cc k thut b tr sai s khc nhau. Mt trong M hnh sai s ca h thng INS cung cp thng
cc phng php thng c p dng l kt hp tch tin v ngun gy ra sai s v nh hng ca chng
phn kt qu o t cm bin vn tc gc vi kt qu n sai s xc nh v tr, vn tc ca vt th. M
o t cm bin gia tc xc nh chnh xc gi tr hnh sai s ca h INS c xy dng t h phng
gc nghing v gc ngng, kt hp tch phn kt qu trnh nh v (1) ca h. p dng phng php xy
o t cm bin vn tc gc vi kt qu o t cm dng m hnh sai s cho h INS c trnh by trong
bin t trng xc nh chnh xc gi tr gc [1,4,6], thu c h phng trnh sai s ca h thng
hng. Thut ton ph bin c s dng kt hp INS nh sau:
l b lc Kalman. Vi b lc Kalman, vic xy dng
m hnh h thng cng chnh xc th kt qu thu c v e re
e e e
v S Cb f g 2ie v
e b e e
cng tt. Trong khi , qu trnh hiu chun ch xc (2)
nh v loi tr c cc sai s h thng. Cc sai s iee Cbeibb
ngu nhin vn tn ti trong kt qu o ca cm bin
v l nguyn nhn lm gim cht lng h thng. V M hnh sai s ca h thng INS di dng
vy, trong [3] tc gi trnh by phng php mi m hnh trng thi nh sau [1,4,6]:
cho php xc nh chnh xc gc nh hng ca vt
th bng cch kt hp kt qu o ca cm bin vn x(t ) F (t ) x(t ) u c (t ) (3)
tc gc, cm bin t trng, cm bin gia tc s dng
b lc Kalman kt hp m hnh ha sai s ngu nhin Trong :
ca cm bin vn tc gc bng m hnh t hi quy. T
x(t ) r eT veT T f bT ibb T vector
Cc xut trong [2,3] c tc gi a ra
nhm mc ch nng cao chnh xc ca h INS. trng thi m t sai s ca h
H INS sau khi ci thin c s dng xy dng 033 I 33 033 033 033
h ghp lng INS/GPS. 0
33 2iee S e Cbe 033
3. Xy dng h INS/GPS theo c u truc ghep long F (t ) 033 033 iee 033 Cbe
Trong nghin cu ny, m hnh p dng b lc
033 033 033 033 033
Kalman kt hp h INS v h GPS c m t nh 0
33 033 033 033 033
hnh 2. B lc Kalman l c dng c lng sai

3
Tp ch Khoa hc v Cng ngh 116 (2017) 001-005

T qu o chuyn ng cng c so snh vi qu o


u c (t ) uacc
T
(t ) uTgyro (t ) : vector sai s ngu nhin
chuyn ng ca h ghp lng INS/GPS truyn thng
tc ng ln cm bin gia tc v cm bin vn tc (h xy dng trn c s INS ch s dng kt qu o
gc. ca cm bin vn tc gc xc nh gi tr cc gc
nh hng). H ghp lng xut v h ghp lng
4. Thc nghim v kt qu
truyn thng u tnh ton trn cng mt b s liu
th nghim v nh gi phng php thu thp. m bo chnh xc v tin cy trong
xut, trong nghin cu ny, khi IMU c s dng so snh, qu o chuyn ng c la chn ti khu
l 3DM-GX3-35 ca hng MicroStrain (hnh 3). IMU vc t b che chn tn hiu GPS thu c l tt
3DM-GX3-35 bao gm cc cm bin MEMS ba nht, tn s cp nht ca b thu GPS c chn l 4
chiu: cm bin gia tc, cm bin vn tc gc, cm Hz, thng tin v tr thu c t b thu GPS sau
bin t trng. Ngoi ra, khi 3DM-GX3-35 cng c tuyn tnh ha c tn s cp nht l 100 Hz,
bao gm mt b thu GPS. B thu GPS ny c s ging vi tn s cp nht ca h ghp lng INS/GPS.
dng xy dng h ghp lng INS/GPS. Mt vi Thi gian cp nht GPS ca h ghp lng INS/GPS
c tnh k thut c bn ca khi IMU 3DM-GX3-35 xut v truyn thng cng c thay i nhm
c th hin trong bng 1. kho st tnh ng dng. Cc phn mm phn tch kt
qu o, x l d liu c tc gi xy dng da trn
mi trng Matlab.
Mt s c tnh k thut c ban ca b thu
CW46 c th hin trong bng 3.
Bng 3. c tnh k thut ca b thu GPS CW46
Thng s k thut
Hnh 3. Khi IMU 3DM-GX3-35
chnh xc vn tc 0,05 m/s
Bng 1. c tnh k thut c bn ca khi IMU
3DM-GX3-35 chnh xc v tr <5 m rms
Thng Cm bin Cm bin Cm bin t Qu o chuyn ng xc nh t h ghp lng
s gia tc vn tc gc trng INS/GPS xut vi chu k cp nht GPS 1 s v h
Di o 5 g 300 /sec 2,5 Gauss GPS c th hin trn hnh 4. th nghi m kha
nng hoa t ng cung nh ng du ng thc t , chu ky
Bias 0,002 g 0,25 /sec 0,003 Gauss c p nh t GPS c thay i ln lt 1 s, 2 s, 5 s, 10 s,
Mt 80 0,03 100 15 s, 20 s.
nhiu g / Hz o
/ sec/ Hz Gauss / Hz
Cac c tnh k thut c ban ca b thu GPS
trong khi 3DM-GX3-35 c th hin trong bng 2.
Bng 2. Mt vi c tnh k thut ca b thu GPS
trong khi 3DM-GX3-35.

Thng s k thut

chnh xc vn tc 0,1 m/s

chnh xc v tr 2,5 m CEP Hnh 4. Qu o xc nh t h ghp lng INS/GPS


xut vi chu k cp nht GPS 1s (ng mu
Mc ch ca th nghim l nhm nh gi t nt) v qu o chun xc nh t h CW46
chnh xc ca h ghp lng INS/GPS xut (h xy (ng mu xanh l)
dng trn c s h INS c ci thin). H ghp
lng INS/GPS xut c gn c nh trn t sau Sai s xc nh v tr ca h ghp lng INS/GPS
cho di chuyn lin tc trn ng trong khong xut vi chu k cp nht GPS 1s c th hin
thi gian 5 pht. chnh xc xc nh v tr ca h trn hnh 5.
ghp lng INS/GPS c xc nh da trn so snh
vi qu o xc nh c t b thu GPS thng mi
cht lng cao CW46 ca hng Navsync. Ngoi ra,

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Tp ch Khoa hc v Cng ngh 116 (2017) 001-005

gian khng c GPS ln hn so vi h ghp lng


INS/GPS truyn thng. Va vi chinh xac nay, co
th ng du ng trong bai toan inh
vi, giam sat phng
ti n vi tin c y cao. Qua o cho th y, tnh ng
dng ca h ghp lng INS/GPS xut l cao hn
h ghp lng INS/GPS truyn thng.
5. Kt lun
Bi bo trnh by xu t xy dng h ghp
lng INS/GPS trn c s h INS c ci thin
Hnh 5. Sai s xc nh v tr ca h ghp lng qua nng cao chnh xc IMU v chnh xc xc
INS/GPS xut vi chu k cp nht GPS 1s. nh gc nh hng ca vt th. Nghin cu cng
tin hnh kho st chnh xc ca h ghp lng
T cc kt qu th hin trong hnh 4 v hnh 5,
INS/GPS xut vi cc chu k cp nht GPS khc
c th nhn thy qu o xc nh c t h ghp
nhau. Cc kt qu trong bi bo cho thy h ghp
lng INS/GPS xut vi chu k cp nht GPS 1 s
lng INS/GPS xut c chnh xc cao hn so vi
bm st vi qu o di chuyn thc t. Sai s v tr
h ghp lng INS/GPS truyn thng va hoan toan co
nh hn 6 m .
th ng du ng c trong bai toan inh vi, giam sat
Sai s v tr trung bnh ca h ghp lng phng ti n vi tin c y cao. iu ny mt ln na
INS/GPS xut v h ghp lng INS/GPS truyn khng nh tnh ng n ca cc xut nhm ci
thng vi cc chu k cp nht GPS khc nhau c thin h INS c tc gi trnh by trong [2,3].
th hin trong bng 4. nng cao hn na chnh xc trong vic xc nh v
tr vt th cc nghin cu tip theo s tp trung xy
Bng 4. Sai s v tr trung bnh ca h ghp lng
dng h ghp cht INS/GPS s dng b lc Kalman
INS/GPS xut v h ghp lng INS/GPS truyn
trn c s h INS ci thin.
thng vi cc chu k cp nht GPS khc nhau
References
Sai s v tr ca
Sai s v tr ca [1]. David H.Titterton and John L.Weston, Strapdow
h ghp lng
Chu k cp h ghp lng Inertial Navigation Technology, 2nd Edition, 2004,
INS/GPS
nht GPS (s) INS/GPS The Institution of Electrical Engineers, Michael
truyn thng
xut (m) Faraday House, Peter Peregrimus Ltd.
(m)
1 2,0951 2,0823 [2]. Trieu Viet Phuong, Nguyen Thi Lan Huong, Trinh
2 4,6462 4,2050 Quang Thong, Implementation Of Self-Calibration
Method For Accelerometer In Inertial Navigation
5 13,8972 7,8987
System, Journal of Science & Technology Technical
10 45,9147 14,5297 Universities 113 (2016), pp 56-61.
15 94,0231 21,8577
[3]. Triu Vit Phng, Nguyn Th Lan Hng, Trnh
20 170,2700 30,1010 Quang Thng, Xy dng h AHRS trn c s cm
bin MEMS s dng b lc Kalman kt hp m hnh
T kt qu th hin trong bng 4 c th thy vi sai s ngu nhin AR, Hi ngh ton quc ln th 3
chu k cp nht l 1 s v 2 s, sai s ca h ghp lng v iu khin v T ng ha VCCA2015, DOI:
INS/GPS xut nh hn sai s ca h ghp lng 10.15625/vap.2015.0124, pp 844-851, Thi Nguyn
INS/GPS truyn thng, tuy nhin sai lch gia hai h 11-2015.
l khng ln. iu ny l do vi chu k cp nht nh, [4]. Isaac Skog, A Low-Cost GPS Aided Inertial
th sai s tch ly trong h INS xut v INS truyn
Navigation System for Vehicular Applications.
thng l nho, cha to nn s khc bit r rng.
Master of Science Thesis, Stockholm, Sweden, 2005.
Vi cc chu k cp nht ln hn 5 s, c th thy r
rng s khc bit gia hai h, sai s ca h ghp lng [5]. Jay A. Farrell (2008) Aided Navigation GPS with
INS/GPS xut nh hn nhiu so vi h ghp lng High Rate Sensors. McGraw-Hill Companies, Inc.
INS/GPS truyn thng. Trong thc t , khi cac i
t ng chuy n ng m t t i qua khu vc bi che [6]. Adrian Schumacher (2006) Integration of a GPS aided
ch n, ng h mthng tin GPS m t trong khoang Strapdown Inertial Navigation System for Land
thi gian trn 5 giy la kha thng xuyn. T kt qu Vehicles. Master of Science Thesis Stockholm,
th hin trong bng 4, cng c th thy, cng mt Sweden.
mc sai s cho php th h INS/GPS xut cho php
xc nh chnh xc v tr ca vt th vi khong thi

5
Tp ch Khoa hc v Cng ngh 116 (2017) 006-011

Xy dng thut ton iu khin mng nron


da theo m hnh mmen tnh ton cho Robot Almega 16
A Neural Network Algorithm Based on Computed Torque Method for Robot Almega 16 Control

V Thu H
Trng i hc Kinh t K thut Cng nghip, 456 Minh Khai, Hai B Trng, Ha ni, Vit Nam
n Ta son: 19-8-2015; chp nhn ng: 20-12-2016

Tm tt
Bi bo cp n vn xy dng thut ton iu khin s dng mng nron da theo m hnh mmen
tnh ton cho Robot Almega 16. Khi khng bit chnh xc cc thng s ng lc hc ca Robot Almega 16,
lut s dng mng nron da theo m hnh mmen tnh ton gii quyt vn ny bng vic c lng
cc thng s v b nhiu da theo m hnh mu. Kt qu m phng trn phn mm Matlab-Simulink cho
thy h iu khin chuyn ng Robot Almega 16 p ng c yu cu iu khin: m bo sai s ca
cc khp quay nhanh chng t ti khng v thi gian qu nh.
T kha: Robot Almega 16, iu khin mment tnh ton, iu khin mng nron
Abstract
This paper presents a problem of building up a control algorithm for the Robot Almega 16 using neural
network based on computed torque method. To control the Robot Almega 16, the problems with unknown
kinematic and dynamic parameters is solved by implementing neural network based on computed torque
method to estimate the parameters and compensation the disturbances from the sample model. The
simulation results in the control requirements: steady-state errors of robot joint angles quickly converge to
zero and transient time is short.
Keywords: Robot Almega 16, Computed torque control, Neural network control.

1. t vn Khu th nht: Gc chuyn ng: 1350. Tm


trc tnh t nh n chn : 28cm. ng tm ca
Robot* Almega 16 c biu din nh hnh 1,
trc I n tm ca tr: 35cm. Khu th hai: Gc
[2]. y l loi Robot hn ng c c tnh di chuyn
nhanh, nhp nhng, chnh xc, gm 6 trc quay, mi chuyn ng: 1350. Chiu di gia hai tm trc I v
trc khp c trang b mt ng c Servo ng b II l 65cm. Khu th ba: Gc chuyn ng: +900 v -
nam chm vnh cu, iu khin theo vng kn. Trong 450. Chiu di gia hai tm trc I v II l 47cm.
bi bo ch s dng 3 trc khp y lm i tng Tng th tch ca Robot Almega16:
nghin cu, c th cc thng s k thut chnh ca 3
trc khp c iu khin nh sau : V = 0,12035m3
Tng khi lng ca Robot: 250kg
Khi lng ca cc khu nh sau: m0 = 100 kg,
m1 = 67 kg, m2 = 52 kg, m3 = 16 kg, m4 = 10 kg,
m5 = 4 kg, m6 = 1 kg.
Trong bi bo [1], vic xy dng thut ton iu
khin thch nghi Li Slotine cho thy u im ca
phng php ny l khi khng bit chnh xc cc
thng s ng lc hc ca Robot, lut iu khin
thch nghi theo Li Slotine gii quyt vn ny
bng vic c lng cc thng s , lm khi lng
tnh ton gim nhiu so vi cc phng php iu
khin khc [2] m vn m bo Robot vn hnh linh
hot ng thi kh c cc thnh phn sai lch gc
Hnh 1. Robot Almega 16
khp v v tr ca khu tc ng cui lm cho h
chuyn ng Robot n nh, chnh xc vi thi gian
qu nh. Nhng nhc im ln nht ca phng
*
a ch lin h: Tel: (+84) 913024989
php iu khin ny l yu cu khi lng tnh ton
Email: vtha@uneti.edu.vn
6
Tp ch Khoa hc v Cng ngh 116 (2017) 006-011

on-line ln, v khng bn vng khi c tc ng nhiu D (q) qd K D qd - q K P qd - q h(q, q )


ngoi. Trong khi phng php iu khin mng (4)
nron da theo m hnh mmen tnh ton [3], [5] l =D (q) qd K D E K P E h(q, q )
phng php b nhiu da theo m hnh mu, m
hnh mu y l m hnh m men tnh ton, vi mt Trong : E l sai lch gc khp
s tnh cht tnh ton tt rt ph hp s dng vi
mng n ron. u im ca phng php ny n E qd - q ; E qd - q
gin v mt ton hc, gim khi lng tnh ton on- Thay biu thc (4) vo biu thc (2) xc nh c
line m vn m bo tnh thch nghi cao, kh nhiu
phng trnh ng lc hc kn:
ngoi, p ng s hi t ca sai lch v tr cc khp
v khng. E K E K E D 1 D(q)q h(q, q)
D P
(5)
2. Xy dng h thng iu khin robot almega 16
Trong :
s dng mng nron theo m hnh mmen tnh
ton D(q) - sai s gia cc gi tr c lng ma trn
Khi khng bit chnh xc cc thng s ng lc qun tnh D (q) vi cc gi tr thc D(q),
hc ca Robot [1], [2], lut iu khin s dng mng
nron da theo m hnh mmen tnh ton gii h(q.q) - sai s gia cc gi tr c lng vect
quyt vn ny bng vic c lng cc thng s
v b nhiu da theo m hnh mu. Thng thng tng h v ly tm h(q.q) vi cc gi tr thc h(q.q) ,
ngi ta hay s dng mng nhiu lp truyn thng Trong trng hp l tng phng trnh (5) tr thnh
lm m hnh mu, lm cc b iu khin cho i
tuyn tnh trong khng gian khp nu D 0, h 0
tng l phi tuyn. Khi h thng c nhn dng
vi chnh xc nht nh, qu trnh iu khin c th :
bt u cho u ra ca h thng bm theo u ra
vEK EK E 0 (6)
ca m hnh n nh. D P

i tng nghin cu l Robot Almega 16 c 3 S cu trc h iu khin theo m hnh mmen


khp quay [2]. Phng trnh ng lc hc c xy tnh ton nh hnh 2:
dng, m t bi, [4]:
D q .q h(q, q) (1)

Trong : moment t ln khp i khi thc hin


chuyn ng quay, D - ma trn qun tnh (mxn), h -
vect tng h v ly tm (1xn), q - bin khp, q -
o hm bc nht ca bin khp theo thi gian.
Da theo b iu khin mmen tnh ton [3],[4],
trong khng gian khp:

D (q)u h(q, q) (2)


Hnh 2. S cu trc h thng iu khin theo m
hnh m men tnh ton
Trong : D (q) - gi tr c lng ca ma trn qun
tnh D ; T hnh 2 cho thy, xc nh c h thc sai
lch (6) l iu rt kh khn hoc khng xc nh
h(q, q) - gi tr c lng ca vect tng h v ly c trong phng php iu khin mmen tnh ton
v cn phi bit y v chnh xc cc thng s
tm v vect trng trng h(q, q) , cng nh c tnh ng lc hc ca robot. Tuy nhin
u(t) - tn hiu iu khin. cc thng s ng hc ca robot thay i trong qu
trnh lm vic, nn kh cc thnh phn phi tuyn
Tn hiu iu khin u c xc nh [4] nh sau: cng nh phn ly c tnh ng lc hc ca cc thanh
ni robot th cn phi c lng chnh xc cc thng
u qd KD qd - q KP qd - q (3) s ca robot trong qu trnh lm vic. Hn na kh
nng chng nhiu ca phng php ny cn hn ch.
Trong : KP , KD - h s iu chnh ca b iu
Tuy nhin n li cung cp cho mt kh nng ton hc
khin; qd - bin khp t.
s dng mng nron da theo m hnh ny to
Th (3) vo (2):

7
Tp ch Khoa hc v Cng ngh 116 (2017) 006-011

ra mt m hnh mi vi nhng c tnh iu khin Bi bo la chn cu hnh mng nron truyn


vt tri, y l ni dung chnh ca bi bo. thng c hai lp l lp u vo v lp u ra, hnh 4.
2.1. Xy dng h thng iu khin s dng mng Trong : q: vecto u vo; a: vecto u ra ; W: ma
nron cho Robot Almega16 trn rng s;
B iu khin dng mng nron da trn m w1,1 w1,2 .... w1,R
hnh mmen tnh ton l phng php iu khin trc
w w2,2 w2,R
tip cc khp t tn hiu ra ca mng nron, b iu W 2,1

khin ny s hun luyn cho tn hiu sai lch v (5) v
khng, khi cc khp ca Robot s bm chnh xc wS,1 wS,2 wS,R
theo qu o t.
b: ma trn ngng; f: hm truyn.
T m hnh m men tnh ton hnh 2, [3] tc gi
bi bo la chn c cu trc ca h thng iu b1
khin s dng mng nron phn hi kiu b nhiu b
da theo m hnh nh hnh 3, [5,6]: b 2
....

b2
Trin khai c th cho Robot Almega 16 vi 03 khp
u l mng nron c 9 u vo cho l cc gi tr ri
rc ha ca v tr cc khp.

q1 (t ); q1 (t 1); q1 (t 2); q2 (t ); q2 (t 1); q2 (t 2)


X
; q3 (t ); q3 (t 1); q3 (t 2)

Lp th nht c ma trn trng lng l ij1 l ma trn


c kch c 9x6, ma trn ngng bij1 c kch c 1x6,
Hnh 3. S cu trc h thng iu khin b nhiu u ra l ma trn Y c kch c 1x6. Vy hm lp u
s dng mng nron da theo m hnh m men tnh vo mng n ron c chn l hm Sigmoidal, [4]:
ton
1
T hnh 3 cho thy u vo l cc tn hiu v tr, f ( x) (10)
u ra l gi tr b vo u ra ca b iu khin b , 1 e x
tn hiu sai lch hun luyn mng n ron y l Lp th hai c ma trn trng lng l l ma trn
v . Vy b iu khin s dng mng nron da trn
m hnh m men tnh ton xc nh, [4],[5]: c kch c 6 x 3, ma trn ngng b c kch c 1 x 3, -2

u ra l ma trn k c kch c 1 x 3. Vy hm lp ra
D (q)(U b ) h(q, q) (7) l hm tuyn tnh, [4]:
f ( x) x (11)
T (5) v (7), xc nh c:
T thit lp c cng thc tnh u ra k theo
E K E K E D 1 D(q)q h(q, q) b
D P
(8) u vo v cc ma trn thnh phn theo :
tha mn (6), b cn xc nh: n
H 2 1
wik bk
2 (12)

b D 1 (D(q)q h(q, q))


k n
(9)
j 1
i I1 X1 wij1 b1j

1 e

Trong :
nH - n s mng n ron lp n;
nI - s u vo mng n ron;
- phn t thuc ct th k ca ma trn k ;
k
wij1 - phn t thuc hng i ct j ca ma trn w1 ;
Hnh 4. Cu trc mng nron hai lp
wik2 - phn t thuc hng i ct k ca ma trn w 2 ;
2.2. Thit k mng nron Robot Almega16 X i - phn t thuc ct th i ca ma trn X;

8
Tp ch Khoa hc v Cng ngh 116 (2017) 006-011

b1j - phn t thuc ct th j ca ma trn b1 ; J T


b v (18)
2
bk - phn t thuc ct th k ca ma trn b 2 . w w
Nu n l tng u vo mng nron th tng trng Theo thut ton lan truyn ngc s dng cp
lng: nhp cc gi tr trng lng mi, lut hc c ci
tin bng cch b sung thm mt thnh lut gi l
(n 1)n (n 1)n
T I H H
(14) hng s ng lng,[4]:
Tng nI u vo mng n ron xc nh: w(t)= w(t-1)+w(t) (19)
n = nI - nH
Tb
Trong mng n ron nh chn, xc nh c: w(t ) v w(t 1) (20)
w
nH = 6; nI = 9; n = 3 Trong :
Suy ra: T =81 . - tc hc tp, ta chn 0.9 thch hp vi
Cu hnh mng nron la chn c th nh hnh 5. kiu b nhiu;
- h s ng lng, c chn 0, 01 .

T (20) vi cc phn t ca cc ma trn 1 , 2 , b1 , b2


c cng thc cp nhp tng trng s ca cc ma trn
ca tng lp v tng ngng ca mng nron, nh
sau:

ij1 (t ) y j (1 y j ) X i vk 2jk ij1 (t 1)


n
(21)
k 1

ij2 (t ) vk y j ij2 (t 1) (22)

b1j (t ) y j (1 y j ) vk 2jk b1j (t 1)


n
(23)
k 1

bk2 (t ) vk bk2 (t 1) (24)


Hnh 5. S cu trc Neural Network
Thut ton hun luyn mng c bi bo la Cng thc tnh u ra sau lp vo ca mng nron :
chn l theo lut ton lan truyn ngc cp nht 1
y n
(25)
cc trng s theo hng gim dc sao cho gim j
X i w1ij b1j

thiu sai s ca m hnh ,(8). Sai s c o bng 1 e i 1

phng php trung bnh bnh phng sai lch. Hm Cng thc tnh u ra sau lp ra ca mng nron:
thng s ca mng c xc nh theo biu thc n
H
(15),[4-6]: y y j 2 b2 (26)
k j 1 jk k
1
J T (15)
Trong : y , y
2
j k l phn t ct j,k ca vc t u ra
Thc hin tnh o hm ca J theo cc trng s ca
mng xc nh c, [4],[5]: ca lp u.
3. ng dng iu khin s dng mng nrron da
J vT
. . (16) theo m hnh mmen tnh ton cho 3 khp u
w w robot Almega16
v
T (8) cho thy mi quan h gia v nh M hnh ng hc ca Robot Almega 16
w w
c tnh ton theo [2]. Chng trnh m phng
sau : mng nron ti ph lc [7]. M phng Robot Almge
v 16 vi cc thng s sau: Khi lng khp 1 : m1 =
b (17)
w w 67 kg ; Khi lng khp 2 : m2 = 52 kg ; Khi lng
khp 3 : m3 = 16 kg .
T (16) v (17) thit lp c mi quan h gia o
hm ca J theo cc trng lng vi o hm ca u Tham s b iu khin v cc gi tr t, bng 3.1.
ra b vi cc trng lng :

9
Tp ch Khoa hc v Cng ngh 116 (2017) 006-011

Bng 3.1 Tham s ca b iu khin gi nguyn nh bng 3.1, cc thng s ng lc hc


thay i nh sau :
K Tn
Gi tr tham s cc trc khp 2 52.005, m
1 = 67.005; m
m 16.005
hiu tham s 3

K P =3000
1 q d1 q d2

KP
H s K P =3000
q1
q2
t l 2

K P = 3000
3

K D =250
1

KD
H s K D =250
vi phn 2

q d3
K D = 250
3 q3

Trng hp khng bit r cc thng s ng lc


hc ca h thng v c nhiu tc ng ng dng b
iu khin momen tnh ton
Kt qu m phng: Hnh 7. Biu din p ng gia cc gc khp t
(qd) v gc khp thc (qthc)

K D1 20 K D 2 20 2.5

K P1 100 K P 2 100 2
Truc z (m)

1.5

0.5

K D 3 20 0
1.5

K P 3 100 1
2.5
2
0.5
1.5
0 1
Truc y (m) Truc x (m)

Hnh 6. Biu din p ng gia cc gc khp t Hnh 8. Biu din chuyn ng t gc khp t (qd)
(qd) v gc khp thc (qthc) n gc khp thc (qthc) trong khng gian 3 chiu
Nhn xt: Vi nhiu tc ng th h thng b Nhn xt: Cc gc khp thc (qt) ca ba khp
dao ng, khng n nh. T kt qu m phng trn u bm gc khp t (qd) vi sai lch gia cc gc
ta c th thy kh nng chng nhiu ca b iu khp t (qd) v gc khp thc (qt) nhanh chng tin
khin m hnh mmen tnh ton l cha tt. Tuy ti 0, h khng c dao ng. B iu khin mng
nhin m hnh iu khin da theo mng n ron c nrron da trn m hnh mmen tnh ton loi b
th khc phc c iu ny. c hon ton nhiu tc ng vo h thng.
Trng hp khng bit r cc thng s ng lc 4. Kt lun
hc ca h thng v c nhiu tc ng ng dng b
iu khin mng nrron da theo m hnh momen Qua l thuyt v kt qu m phng cho thy, h
tnh ton. thng iu khin Robot Almega 16 s dng mng
Nron da theo m hnh mment tnh ton khc
Vic xc nh c chnh xc thng s ng lc phc c hu ht cc nhc im ca cc b iu
hc ca h thng Robot ALmega16 l rt kh khn khin truyn thng, c kh nng thch nghi cao,
dn n cc thng s ng lc hc a vo b iu chng nhiu tt, n nh bn vng, c kh nng iu
khin l khng chnh xc. kim chng thut ton khin cc i tng c cng m hnh vi tham s
iu khin bi bo gi thit Robot ALmega16 c khc nhau, thm ch l bin thin. c kim chng
khi lng v chiu di cc thanh ni khng xc nh trn m hnh m phng ca h thng iu khin bng
c chnh xc cc thng s ny nn cc thng s Matlab-Simulink, kim nghim thnh cng cc vn
ng lc hc a vo b iu khin l cc gi tr c l thuyt. nh hng m rng l thit k m hnh
lng : m1 , m
2,m
3 , gi s cc thng s iu khin vn

10
Tp ch Khoa hc v Cng ngh 116 (2017) 006-011

thc ca h thng. Nng cao tc x l ca h thut H Ni, (2004).


thng. [4]. Li Khc Li, Nguyn Nh Hin: H m v nron,
TI LIU THAM KH O NXB khoa hc v k thut H Ni, (2007).

[1]. Bi Quc Khnh, Nguyn Phm Thc Anh, V Thu [5]. Seul Jung; Neural network controllers for robot
H, Xy dng thut ton iu khin thch nghi Li- manipulators University of California (1991)
Slotine cho Robot IRB 2400, tp ch khoa hc cng [6]. Howard Demuth , Mark Beale, Martin Hagan; Neural
ngh cc trng i hc k thut, s 69, (2009). Network Toolbox 6 - The MathWorks, Inc (2008).
[ 2] . V Thu H, Lun n tin s: Trng H BKHN, [7]. Phm Tun Anh, n tt nghip: Trng H
2012 BKHN, 2009.
[3]. o Vn Hip: K thut Robot, NXB khoa hc v k

11
Tp ch Khoa hc v Cng ngh 116 (2017) 012-019

S dng cc tiu ha tng on sai lch u ra trong min thi gian iu


khin d bo h bung sy giy a bin
Using Receding Horizon Minimization of Output Errors In Time Domain for Model Predictive
Control of Multivariable Paper Drying Systems

Trn Kim Quyn1, Bi Quc Khnh2, Nguyn Don Phc2*


1
Trng Cao ng Cng nghip Tuy Ha, Nguyn Tt Thnh, TP. Tuy Ha, Ph Yn
2
Trng i hc Bch khoa H Ni, s 1, i C Vit, Hai B Trng, H Ni
n Ta son: 22-4-2016; chp nhn ng: 20-12-2016

Tm tt
Bi bo xut mt phng php iu khin d bo cho h MIMO vi m hnh d bo l h phng trnh
sai phn trong min thi gian. Phng php iu khin d bo xut ny lm vic theo nguyn tc cc
tiu ha tng on sai lch u ra ca h trong min thi gian. B iu khin ny c cu trc tng t nh
ca GPC truyn thng, ch thay i khu d bo tn hiu ra v khu ti u ha tnh hm iu khin trc
tip trn min thi gian thay v trong min tn s, nh khng cn phi tm nghim phng trnh
Diophaltine m vn m bo c cht lng iu khin bm gi tr t trc. Hn th na, b iu khin
xut ny cn c tnh tch knh v khng nhiu cao hn b iu khin GPC truyn thng. minh chng
cho kt lun ny, bi bo cng trnh by mt ng dng ca b iu khin xut vo iu khin a bin
bung sy giy, sau so snh cht lng iu khin thu c vi cht lng ca h khi c iu khin
bng iu khin phn hi u ra kt hp vi b iu khin truyn thng tch knh, cng nh cht lng
ca h khi c iu khin vi b iu khin GPC truyn thng.
T kha: m, Ti u ha tng on, Bung sy, MPC, Min thi gian
Abstract
The paper proposes a model predictive control method for MIMO system, in which the difference system
equations are used for output prediction. The proposed control method is based on piecewise minimizing of
output tracking errors in time domain. The structure of proposed controller is similar to that of conventional
GPC, except that its system output prediction and minimization of tracking error will be carried out directly in
time domain instead of frequency domain. Hence the solution of Diophaltine equation can be avoided but
the tracking control performance to a desired value is still guaranteed. Moreover, the decoupling and
disturbance attenuation behavior of proposed controller is much better than conventional GPC. To
demonstrate these assertions, the paper presents also an application of proposed method to control the
multivariable paper drying system and then compares the resulted system control performance with which
obtained by using the output feedback control system in combination with the feedforward controller for
system decoupling, and also with which obtained by using conventional GPC.
Keywords: Moisture, Piecewise optimization, Drying section, MPC, Time domain

1. Gii thiu chung vn hnh 4.75kg s . Lu lng nh mc l


*
Bung sy giy l khu cui trong dy chuyn 9.5kg s . Nhit kh thi 75 C . m t l l
xeo giy. Giy t p keo c m tng i 0.15kg kg . Nhit im sng c t l 60 C .
0.2 kg kg c a qua bung sy t m u
ra mong mun l 0.05kg kg . Hnh 1 trnh by s t c cc thng s k thut trn, h iu
khin hin ti trong nh my giy Bi Bng c bn
nguyn l iu khin bung sy giy.
nhim v c th nh sau:
Bung sy c 10 l sy vn hnh n nh ti tc
iu khin gia nhit cho gi cp vo bung
xeo V 600 m min vi nh lng 50 g m 2 . Gi sy. Gi ly t ngoi tri lu lng Wal c gia
nng vo Wa1 c lu lng vn hnh l 3.25 kg s . nhit mt phn t khng kh thi qua b HRU (b thu
Lu lng nh mc l 6.5kg s vi nhit 110 C . hi nhit), sau gi m c a sang thit b trao
i nhit v c gia nhit thm bng hi bo ha.
m t l 0.001kg kg . Gi thi ra c lu lng Nhit gi sy c iu chnh nh van iu khin
lu lng hi. Mch vng iu khin gia nhit gi
*
a ch lin h: Tel: (+84) 976791415 hot ng tng i c lp.
Email: phuoc.nguyendoan@hust.edu.vn
12
Tp ch Khoa hc v Cng ngh 116 (2017) 012-019

Ws 700kg / h
Ps 3.5Bar Air

TC TC

Ngng t Air Ngng


t

LC
Td ,
TT
Wa1 23447kg / h
1100 C Wa 2 33445kg / h
Ttb 750 C
kt 0.15kg / kg

T 1100 C
u 0 . 001 kg / kg

LT

26 28 30 32 34 600 m/pht
Tp , nh lng 50 g / m 2

m giy 0.2 kg/kg 25 27 29 31 33


m giy ra 0.05 kg/kg

Hnh 1. S P & ID ca bung sy


Gi nng c nhit 110 C , m t l khin thng qua iu chnh lu lng gi ra Wa 2 nh
0.001kg kg c thi vo hai mt giy bng vi qut ht [4].
phun, kt hp vi sy p sut hi cp cho l sy to Trong thc t sn xut, cc h iu khin qu
nn mch vng iu khin sy giy. ng hc qu trnh cng ngh phn ln l h iu khin a bin,
trnh sy trong bung sy c trnh by chi tit gii php thit k v ci t l iu khin phn hi kt
trong ti liu [4]. hp vi iu khin tch knh Feedforward.
iu khin cn bng gi vo-ra, vi mc Tuy nhin mt s gii php thit k cn cha
tiu m bo gi nng chim gi khong khng gia p ng c yu cu cng ngh nh i vi h cn
hai l (vng sy) truyn nhit cho mt giy phc bm lng t v khng nhiu. C th l:
v qu trnh bay hi, nn cn iu khin cn bng gi
nng thi vo Wa1 kt hp vi lng hi nc bay ra Thut ton iu khin theo m hnh, vit tt
l MAC c xy dng da trn m hnh p ng
t giy Wbh , phi cn bng vi gi ht kh thi ra
xung cho h tuyn tnh SISO. Thut ton ny ch p
khi bung sy Wa 2 , sao cho khng c khng kh dng c cho cc qu trnh SISO n nh. Hn na,
lnh t ngoi ht vo vng sy. iu khin cn bng y
do khng s dng tn hiu u ra t i tng
thng qua im p sut khng nn ngi ta gi l h ngc v hiu chnh li m hnh d bo cng nh
iu khin ZL. i lng iu khin l lu lng gi trong khu ti u ha, nn MAC l phng php iu
thi vo Wa1 , c cu chp hnh l qut thi c khin vng h. Cc ti liu [3], [8] cn khuyn co
nghin cu trong [5]. thm l ch nn p dng khi i tng iu khin l:
Ch c nhiu hng tc ng u ra, c tnh ng hc
iu khin mi trng sy thng qua nhit chm.
im sng. Khi sy giy nc bay hi vo khng
kh, lm cho m khng kh tng dn n tng nhit Phng php ma trn ng hc iu khin,
im sng. Khi nhi t im sng tng cao thi vit tt l DMC c xy dng da trn m hnh p
kh nng bay hi nc t giy cng gim, nu nhit ng bc nhy cho h tuyn tnh SISO. Theo [8], [9]
im sng gn vi nhit mi trng th nc th DMC mang tnh bn vng cao, d ci t, song li
c xu th ngng t. hn ch l cn phi c tham s M , N ln, cng
Nhit im sng trong bung sy c gi nh khi c thm iu kin rng buc l tn hiu iu
n nh thp hn nhit mi trng sy trong khin b chn v n cng ch l b iu khin vng
h.
khong 15 25 C . Nhit im sng c iu
Khc vi MAC v DMC, phng php iu
khin d bo GPC ca Clarke a ra nm 1987 li s

13
Tp ch Khoa hc v Cng ngh 116 (2017) 012-019

dng m hnh hm truyn khng lin tc ca qu Xt h hai vo, hai ra, c tr vi m hnh tng
trnh (i tng iu khin). Phng php GPC p qut trong min thi gian:
dng c cho nhng i tng, qu trnh khng n
nh [8]. Hn th na n cng cn c th p dng y1[k ] a11 y1[k 1] a1n1 y1[ k n1 ]
c cho c nhng qu trnh c tnh pha khng cc b10u1[k m11 ] b11u1[k m11 1]
tiu [8], v cho ti nay n c bit l phng php
iu khin d bo ph thng v p dng nhiu nht b1q11 u1[ k m11 q11 ]
trong thc t, c th pht trin m rng cho h MIMO c10 u2 [k m12 ] c11u2 [k m12 1]
[8].
Do phng php GPC c xy dng trn nn
c1q12 u2 [ k m12 q12 ]
(1)
m hnh hm truyn khng lin tc, c cc tham s y2 [k ] a21 y2 [k 1] a2 n2 y2 [ k n2 ]
rt d c xc nh bng nhng thut ton nhn
dng, nn GPC hon ton c th c pht trin
b20u1[k m21 ] b21u1[k m21 1]
thnh b iu khin vng kn mang tnh thch nghi b2 q21 u1[ k m21 q21 ]
nu nh ta b sung thm khu nhn dng trc tuyn
cc tham s hai a thc ny. c20 u2 [k m22 ] c21u2 [k m22 1]

Ngoi ra, cng v s dng hm truyn lm m c2 q22 u2 [ k m22 q22 ]


hnh d bo nn vic ti u ha trong n bt buc
phi c thc hin trong khng gian phc thng qua trong
bc trung gian l tm nghim phng trnh m11 l tr u vo th nht ng vi u ra th
Diophaltine. iu ny hn ch kh nng khng
nhiu cng nh cht lng tch knh ca h thng nht v m12 l tr u vo th hai ng vi u
trong min thi gian. ra th nht,
T kt qu phn tch u nhc im ca tng m21 l tr u vo th nht ng vi u ra th
phng php iu khin d bo ni trn, chng ti hai v m22 l tr u vo th hai ng vi u ra
i n mt phng php iu khin d bo mi cho
th hai.
h MIMO, trong m hnh d bo l h phng
trnh sai phn trong min thi gian, thay v s dng Nhim v iu khin t ra y l xc nh b iu
ma trn hm truyn. Phng php iu khin d bo khin, tc l tm (u1[k ], u2 [k ]) c cht lng bm:
xut ny, v cu trc n hon ton tng t nh
GPC truyn thng, ngoi vic thay i khu ti u ( y1[k ], y2 [k ]) ( w1[k ], w2 [k ])
ha tnh hm iu khin v thc hin tm nghim
bi ton ti u trc tip trn min thi gian. iu ny vi w1[k ], w2 [k ], k 0,1, l dy gi tr mu t
gip ta trnh c vic phi tm nghim phng trnh trc cho tng knh.
Diophaltine v c th kt hp thm cc iu kin rng
Khng mt tnh tng qut ta lun vit c li
buc v tn hiu iu khin trong li gii.
m hnh (1) thnh:
Ni dung bi bo trnh by gm ba phn. Phn
mt trnh by phng php thit k iu khin d y1[k ] a11 y1[k 1] a1n y1[k n]
bo ti u ha tng on cho h MIMO a bin, tc b10u1[k m1 ] b11u1[k m1 1]
l v nguyn tc lm vic ca b iu khin c
b1q u1[ k m1 q]
xut. Phn hai l ng dng ca n vo iu khin
bung sy giy v cc kt qu m phng, so snh vi c10u2 [k m2 ] c11u2 [k m2 1]
cht lng ca h khi s dng b iu khin GPC
truyn thng. Cui cng trong phn ba l nhng nh c1q u2 [ k m2 q]
(2)
gi u nhc im ca b iu khin c xut. y2 [k ] a21 y2 [k 1] a2 n y2 [k n]
2. Ni dung b20u1[k m1 ] b21u1[k m1 1]
2.1. Thut ton iu khin d bo h MIMO c tr b2 q u1[ k m1 q]
trong min thi gian bng phn hi u ra
c20u2 [k m2 ] c21u2 [k m2 1]
Phng php iu khin d bo xut ny s
c nhm tc gi gi l b iu khin d bo ti u c2 q u2 [ k m2 q]
ha tng on. V cu trc iu khin tng t nh
MPC truyn thng, ch thay i khu ti u ha tc l:
tnh hm iu khin v thc hin trn min thi gian

14
Tp ch Khoa hc v Cng ngh 116 (2017) 012-019

a 0 a 0 y[k 1] B0,0 u[k 1] B1,0 A1,0 B0,0 u[k ]


y[k ] 11 y[k 1] 1n y[k n]
0 a21 0 a2 n Bq ,0 A1,0 Bq 1,0 u[k q 1] A1,0 Bq ,0 u[k q ]
b c b1q c1q
10 10 u[k ] u[k q ] A2,0 A1,0 A1,0 y[k 1] A3,0 A1,0 A2,0 y[k 2]
b20 c20 b2 q c2 q
trong : An,0 A1,0 An 1,0 y[k n 1] A1,0 An,0 y[k n]
q max(q11 m11 , q12 m12 , q21 m21 , q22 m22 ), B0,1 u[k 1] Bq 1,1 u[k q ]
n max(n1 , n2 ),

A1,1 y[k 1] A2,1 y[k 2] An ,1 y[k n]
m1 min(m11 , m12 ), m2 min(m21 , m22 )
vi cc h s ca n ln c c xc nh theo
y [k ] y [ k 1] cng thc truy hi sau:
y[k ] 1 , y[k 1] 1 ,
y2 [ k ] y2 [k 1] B0,1 B0,0
y [ k n]
y[k n] 1 B1,1 B1,0 A1,0 B0,0
y2 [ k n ]
u [k m1 ] u1[k m1 1] Bq ,1 Bq ,0 A1,0 Bq 1,0
u[k ] 1 , u[k 1] ,
u2 [k m2 ] u2 [k m2 1] Bq 1,1 A1,0 Bq ,0
u [k m1 q ] (6)
u[k q ] 1 A1,1 A2,0 A1,0 A1,0
u2 [k m2 q ]
A2,1 A3,0 A1,0 A2,0
K hiu tip:

a 0 a 0 An 1,1 An ,0 A1,0 An 1,0


A1,0 11 , , An,0 1n ,
0 a21 0 a2 n An ,1 A1,0 An,0
(3)
b c b1q c1q
B0,0 10 10 , , Bq ,0 Tng t nh vy, khi i 2 th:
b20 c20 b2 q c2 q
y[ k 2] B0,2 u[ k 2] Bq 2,2 u[ k q ]
th m hnh ban u (1) ca h s tr thnh:
y[k ] A1,0 y[k 1] An,0 y[k n]
A1,2 y[ k 1] A2,2 y[ k 2] An ,2 y[ k n]
(4)
B0,0 u[k ] Bq ,0 u[k q] trong :

T y ta c cc u ra d bo ca h l B0,2 B0,1
y[k i], i 0,1, , N 1 , vi N max(n, q) , nh B1,2 B1,1
sau: B2,2 B2,1 A1,1 B0,0
Khi i 0 th:

y[k ] B0,0 u[k ] B9,0 u[k 9] Bq 1,2 Bq 1,1 A1,1 Bq 1,0


A1,0 y[k 1] A2,0 y[k 2] (5) Bq 2,2 A1,1 Bq ,0 (7)
A1,1 A2,0 A1,0 A1,0
Khi i 1 th:
A2,1 A3,0 A1,0 A2,0
y[k 1] B0,0 u[k 1] Bq ,0 u[k q 1]


A1,0 y[k ] A2,0 y[k 1]
An,0 y[k n 1] An 1,1 An ,0 A1,0 An 1,0
B0,0 u[k 1] Bq ,0 u[k q 1] An ,1 A1,0 An ,0


A1,0 B0,0 u[k ] Bq ,0 u[k q ] Tng qut cho tt c cc ch s i 3, 4, , N 1
cn li, ta c:

A1,0 y[k 1] A2,0 y[k 2] An ,0 y[k n]
y[k i ] B u[k i ]
0,i Bq i ,i u[k q ]
A2,0 y[k 1] An,0 y[k n 1] (8)
hay:

A1,i y[k 1] A2,i y[k 2] An,i y[k n]
15
Tp ch Khoa hc v Cng ngh 116 (2017) 012-019

v: v

y[k i 1] B0,i 1 u[k i 1] B1,0 B2,0 Bq ,0



Bq i 1,i 1 u[k q ]
B2,1 B3,1 Bq 1,1
B2 ,


A1,i 1 y[k 1] A2,i 1 y[k 2]
BN 1, N BN 2, N

Bq N , N
An,i 1 y[k n] A1,0 A2,0 An ,0

A1,1 A2,1 An ,1
trong A (13)

B0,i 1 B0,i
A1, N 1 A2, N 1 An, N 1
B1,i 1 B1,i
u[k 1] y[k 1]

u[k 2] / y[k 2]
Bi ,i 1 Bi ,i u
/
, y

Bi 1,i 1 Bi 1,i A1,i B0,0
u[k q ] y[k n]

Bq i ,i 1 Bq i ,i A1,1 Bq 1,0 (9) Nh vy, cng thc (11) th u cho bi (10) l
Bq i 1,i 1 A1,i Bq ,0 vector cc tn hiu iu khin tng lai cn xc nh,
y l vector cc tn hiu u ra tng ng c d
A1,i 1 A2,i A1,i A1,0
bo trong tng lai v chng l nhng gi tr cha
A2,i 1 A3,i A1,i A2,0 / /
bit. Cn li cc vector u , y trong (12) nh ngha
bi (13) u l nhng gi tr qu kh nn l bit
An 1,i 1 An ,i A1,0 An 1,0 thi im k hin ti, hay g cng l hng s bit.
An ,i 1 A1,i An ,0
Tip tc, t c mc ch y[k ] w[k ] , ta
Tip theo, xy dng hm mc tiu phc v s xy dng hm mc tiu tng ng vi nhim v
mc tiu iu khin bm y[k ] w[k ] ca bi ton, y w , hay e y w 0 , trong
ta s vit li ton b N 1 gi tr u ra d bo
y[k i], i 0,1, , N nu trn chung li thnh w col w[k ], w[k 1], , w[k N ] (14)
mt phng trnh nh cc k hiu nh sau: l vector cc gi tr t, nn cng l bit. Hm mc
tiu ny c dng nh sau
y[k ] u[k N ]
J e Qk e u Rk u min
T T

u[k N 1] ,
y[ k 1] (15)
y , u
trong Qk , Rk l hai ma trn trng s i xng xc

y[k N ] u[k ] nh dng ty chn.
(10)
B0,0 Thay e y w v (11) vo (15) s c:

B0,1 B1,1
B1 J (y w ) Qk (y w ) u Rk u
T T


BN 1, N BN , N (B1 u g w ) Qk (B1 u g w ) u Rk u
T T

B0, N
v l k hiu ca ma trn c tt c cc phn t u u
T
B Q B
T
1 k 1
Rk u 2(w g )T Qk B1 u
bng 0. Vi cc k hiu ny, cc phng trnh (5)-(8) (g w ) Qk (g w )
T

cho tt c cc ch s i 0,1, , N s c vit


chung li thnh: nn nhim v (15) l tng ng vi:
y B1 u g B Q B R u 2 w g
T
(11) Qk B1u min
T
u T
1 k 1 k

trong : C th thy ngay y l bi ton ti u ton


phng nn trong trng hp khng b rng buc th
g B2 u Ay
/ /
(12)

16
Tp ch Khoa hc v Cng ngh 116 (2017) 012-019

khi p dng phng php Newton-Raphson, ta c 7. Xc nh vector g theo (12) v w theo (14).
nghim ti u ca n nh sau:
8. Tnh u theo (16) v u[k ] theo (17) ri a vo
u B1T Qk B1 Rk B1T Qk w g
1
(16) iu khin i tng.
Nu vit ra mt cch chi tit nghim ti u u 9. o tn hiu ra y y1 , y2 ca h ri sp xp li
T

tm c trn thnh: / /
hai mng d liu u , y nh sau:
u col u[k N ], u[k N 1], , u[k ]
ui/ : ui/ 2 , i 2q, 2q 1, ,3
ta s thy lun ly ra c t tn hiu iu khin
hin ti: u1/ : u1[k p ] v u2/ : u2 [k q ]

u1[k m1 ] y /j : y /j 2 , j 2n, 2n 1,
u[k ] , , , I 2 u ,3 v
(17)
u2 [k m2 ]
y1/ : y1 , y2/ : y2 .
iu khin i tng, trong I 2 l ma trn n
v kiu 2 2 . Tt nhin ta lun ly ra c c nhng 10. Gn k : k 1 v quay v 6.
gi tr tn hiu vt trc: 2.2. p dng vo iu khin bung sy giy
u1[k p ] M hnh bung sy giy c xy dng theo ti
vi m1 p N , m2 q N
u2 [ k q ] liu [4] cho nh my giy Bi bng c cu trc ma
trn hm truyn nh m t hnh 2 gm bn hm
t u theo cng thc: truyn nh sau:

u1[k p ] 0.000815 14 s
G11 e ,
C(2 N 1 2 m1 2 p ),(2 N 2 2 m2 2 q ) u P *
48s 1
u2 [ k q ]
0.0007945 28 s
G12 e
trong C( i ),( j ) l ma trn 2 hng, 2( N 1) ct c hai Wa 2 *
68s 1
phn t (1, i ) v (2, j ) bng 1, cc phn t cn li Td 0.334 50 s
G21 e
ng nht bng 0. P* 210 s 1
Tng kt li th b iu khin ti u ha tng Td 0.2671 45 s
G22 e
on iu khin bm gi tr t trc cho h a Wa 2 *
202 s 1
bin s lm vic theo cc bc sau:
1
1. Chn rng N max(n, q) cho ca s d bo `

v xy dng cc ma trn: S P P *
GD1

`
Gc1 ` G11 `

A1,0 , , An ,0 , B0,0 , , Bq ,0

t cc tham s m hnh hm truyn theo (3). G21


2. Xy dng cc ma trn Ai , j , Bi , j theo cc cng
thc (6),(7) v (9).
G12
3. Xc nh cc ma trn B1 , B2 , A theo (10),(13).
S P T Wa 2 * Td
/ / d
4. Khai bo mng d liu mt chiu u , y , trong ` Gc2 `
G22 `

/ /
u c 2q phn t v y c 2n phn t nh
ngha theo (13) vi th t nh sau:
Hnh 2. M hnh bung sy giy
u u1/ , u2/ , , u2/ q , y y1/ , y2/ , , y2/ n
/ /
Chn chu k trch mu T 5s v khi k hiu li
cc u vo ra:
5. Gn u 0, y 0 v k 0 .
/ /

y1 , y2 Td , u1 P* , u2 Wa 2*
6. Chn Qk , Rk i xng xc nh dng .

17
Tp ch Khoa hc v Cng ngh 116 (2017) 012-019

th h phng trnh sai phn ca n dng (4) s c cc nhit u vo tng ln, tc l chnh p P tng, lu
tham s ln lt l n 2, q 9 v: lng hi vo nhiu hn tng nhit sy, ko m
giy u ra bm theo gi tr t. Mch vng nhit
a11 1,8302, a12 0,8372 im sng tc ng tc l Wa 2 tng, lm gim nhit
a21 1,9521, a22 0,9527 im sng. Kt qu m phng ny cho thy h
b10 1, 68.105 , b11 1,561.105 , hot ng n nh p ng tt vi nhiu m u
vo, m cht lng giy u ra.
b12 0,382.105 , b13 3,549.106 ,
2.3. So snh kt qu khi iu khin vi b iu
b14 b15 b16 b17 b18 b19 0,
khin GPC truyn thng
b20 b21 b22 b23 b24 b25 b26 b27 0,
Kt qu m phng bung sy giy dng b iu
b28 0, 007858, b29 7, 666 khin MPC trong Toolbox Matlab Simulink, c tn
gi l b iu khin GPC cho hnh 5 v hnh 6.
c10 2,303.105 , c11 3,33.105 ,
T kt qu m phng ny v khi so snh vi cc
c12 2, 07.105 , c13 3.105 ,
hnh 3 v hnh 4 ta thy nu tc ng nhiu u vo
c14 c15 c16 c17 c18 c19 0 gama1, m ca giy tng ln ng thi gy nh
c20 c21 c22 c23 c24 c25 c26 c29 0, hng n mch vng nhit im sng. Di tc
ng ca b iu khin MPC trong toolbox Matlab
c27 0, 00653, c28 6,3765.103 Simulink iu khin m ca giy v gi tr t
p dng thut ton iu khin ti u tng on nhng thi gian iu chnh ln (ln n 104 s ), iu
trnh by trn iu khin h bung sy giy, ny chng t b iu khin mc nh hot ng cha
ta thu c kt qu nh m t hnh 3 v hnh 4. tt nh hng n cht lng sn phm giy.

Hnh 3. p ng ca b iu khin MPC ti u tng Hnh 5. p ng ca b iu khin MPC khi thay i


on cho bung sy giy, khi thay i nhit m nhiu m giy u vo (S dng Toolbox MPC
u vo 25% ca Matlab)

Hnh 4. p ng ca b iu khin MPC ti u tng


on cho bung sy giy, khi thay i nhit
im sng 10%
Kt qu m phng cho thy khi tng nhiu
m giy u vo lm m giy u ra tng, mch Hnh 6. p ng ca b iu khin MPC khi thay i
vng iu khin m tc ng lm cho cng sut nhit im sng

18
Tp ch Khoa hc v Cng ngh 116 (2017) 012-019

3. Kt lun [4] Trn Kim Quyn, Bi Quc Khnh, L Khc Trng,


ng hc qu trnh sy giy i lu,tp ch T ng
T vic phn tch thit k b iu khin MPC ha ngy nay, chuyn san iu khin v T ng ha
tch hp sn trong toolbox Matlab Simulink, so snh s 11, thng 12 nm 2014, pp 58-63.
vi b iu khin MPC ti u ha tng on ta thy
[5] Trn Kim Quyn, L Khc Trng, Phm Vn
b iu khin MPC ti u tng on p ng tt vi Tuynh: ng hc qu trnh cn bng gi -Zerolevel
nhiu tc ng hay ni cch khc l h c kh nng trong bung sy giy. Tp ch T ng ho ngy nay,
khng nhiu khi thay i thng s m u vo, c chuyn san iu khin v T ng ho s 12, thng
bit m bo tch knh gia iu khin m v 4/2015, pp36-41.
nhit im sng, h bm c lng t khi vn
[6] Trn Kim Quyn, on Quang Vinh, and L Khc
hnh thay i m v nhit im sng. Kt qu
Trng: iu khin a bin tch knh cho bung sy
nghin cu l ng n v c th trin khai ng dng giy. 2015, Hi ngh t ng ha Ton quc, VCCA
trong thc t sn xut. 2015.
Ti liu tham kho [7] Camacho, E. and Bordons, C. (1999): Model
predictive control. Springer.
[1] Ti liu thit k v k thut vn hnh giy Bi bng
(nng cp ln 2), 2014. [8] Holkar, K.K. and Waghmare, L.M.(2010): An
overview of model predictive control. Int. Journal of
[2] Bi Quc Khnh, et al. (2014): iu khin qu trnh.
Control and Automation, Vol. 3, No. 4, December
NXB khoa hc k thut H Ni.
2010, pp. 47-64.
[3] Th T Anh, Nguyn Don Phc (2013): Gii
[9] Maciejowski, M.J. (2011): Predictive control with
thiu v iu khin d bo h tuyn tnh. Hi ngh
constrains. Prentice Hall.
khoa hc khoa in t i hc Cng nghip Thi
Nguyn.

19
Tp ch Khoa hc v Cng ngh 116 (2017) 020-025

iu khin phn hi v tr b kch hot tnh tin


ng dng cho vi bm kiu xi lanh
Position Feedback Control for Linear Actuator for Microsyringe Pump Application

Nguyn Anh Tun, Phm Hng Phc*


Trng i hc Bch khoa H Ni, S 1, i C Vit, Hai B Trng, H Ni .
n Ta son: 24-8-2016; chp nhn ng: 20-12-2016

Tm tt
Trong nghin cu ny, chng ti kho st, nh gi ng dng ca b kch hot tnh tin ECLIA cho vi bm
kiu xi lanh vi phng php iu khin phn hi v tr c v khng s dng tham s iu khin Kp. Thanh
trt vi bc dch chuyn nano mt tc ng vo pt tng c th y ra lng cht lng vi th tch rt nh
(pL). Kt qu cho thy, th tch cht lng c y ra u xi lanh t l thun vi dch chuyn ca thanh
trt/pt tng. Trong trng hp iu khin c tham s Kp th mc tuyn tnh ca th tch cht lng y
ra tt hn do khng c s dao ng v vt qu im ch xc lp ca pt tng. Kt qu ny hng ti cc
ng dng hiu qu ca ECLIA nh mt b kch hot trong cc h vi c in t (MEMS).
T kha: ECLIA, b kch hot tnh tin, iu khin phn hi v tr, vi c in t.
Abstract
In this study, we investigate a microsyringe pump application of a linear actuator using a position feedback
control with and without a tuning gain KP. The slider pushes the microsyringe directly in step motion with
nanometer resolution that repels a very small volume of liquid (pL). Experimental results show that the liquid
volume was direct propotion to the sliders stroke. The repeled liquid volume was better linear when using
the feedback control with the the tuning gain K P compared to that without KP; it was due to no overshoot and
no ossilation of the slider/piston. These results intent to a significant implementation in MEMS of the linear
actuator.
Keywords: ECLIA, linear actuator, position feedback control, MEMS

1. Gii thiu tnh in v lc y ca PZT, ECLIA c th ng vai


tr nh mt ng c tuyn tnh c lc y ln dn
Trong cc vi h thng phn tch v nh gi
*
ng cho cc thit b ngoi vi trong nhng ng dng
tng th/ton din (TAS) vic thu nh kch thc
nh vi bm kiu mng [11]. nng cao hiu qu
ca thit b ng thi vi kim sot th tch dung
ca lc ht tnh in nhm tng lc y, chng ti
dch c pico lt (pL) rt quan trng. nh lng chnh
a ra thanh trt gm nhiu lp polymer v cu trc
xc cc dung dch mu th tham gia trong qu trnh
kiu xng c [12]. H thng iu khin phn hi
phn ng ha hc s lm tng tin cy ca kt qu
cng c p dng hng ti vic kim sot v tr
th nghim. H thng iu khin vi lng cht lng
chnh xc ca thanh trt. Trong nghin cu ny
l s tch hp ca vi bm v cc van. kch hot
chng ti kho st, nh gi hiu qu ca vic ci
thit b vi bm c th dng kh nn [1, 2] hoc cc b
tin kt cu thanh trt v iu khin phn hi v tr
kch hot c thit k vi ng dng ca hiu ng
khi ng dng ECLIA cho vi bm kiu xi lanh.
tnh in [3, 4]; hiu ng p in [5, 6], hiu ng t
[7, 8],...B kch hot tnh tin ECLIA kt hp hiu 2. Nguyn l lm vic ca b kch hot tnh tin
ng tnh in v p in to nn chuyn v bc nh ECLIA
(nm), hnh trnh di (mm) v lc y ln (mN) ca
Trong nghin cu ny chng ti gii thiu mt
cc thanh trt c lp nhau [9]. Cu to ca ECLIA
ng dng ca ECLIA dng iu khin phn hi v tr
gm phn t kch hot PZT, in cc dn ng, in
cho vi bm kiu xi lanh. V vy trong phn ny cu
cc gi v cc thanh trt song song; tt c c t
to v nguyn l hot ng ca ECLIA s c trnh
trn mt gi (Hnh 1(a)). Vi kh nng chuyn
by. B kch hot gm cc thanh trt t song song
ng vi bc ca cc thanh trt cho php lm suy
trn in cc dn ng v in cc gi; ngun dn
gim mt ph nhm lm u nng lng ca cc
ng PZT gn vi in cc dn ng bng keo
bc sng, ECLIA c ng dng trong truyn dn
epoxy; tt c c t trn thn gi (Hnh 1(a)).
quang nhiu knh [10]. Nh s kt hp ca lc ht
S tn hiu in p cung cp cho PZT, in cc di
ng, in cc gi v thanh trt c m t nh
*
a ch lin h: Tel: (+84) 987751970 hnh v 1(c). Xung in hnh thang t vo PZT lm
Email: phuc.phamhong@hust.edu.vn
20
Tp ch Khoa hc v Cng ngh 116 (2017) 020-025

cho n gin ra sn ln v co li sn xung. Khi (3) in p ca thanh trt i chiu lm cho c cu


cp in p gia thanh trt v in cc gi /di ng kp tnh in vi in cc dn ng tch ra, ng
tri du s sinh ra lc ht tnh in, v do vy to nn thi hnh thnh s kp ny vi in cc gi.
mt c cu kp dng lc ht tnh in, t nay s gi
(4) sn xung ca tn hiu, PZT co li, mang theo
tt l c cu kp tnh in. Cn khi cp in p ny
in cc dn ng tr v v tr ban u trong khi
cng du th khng cn lc ht tnh in, c cu kp
thanh trt vn c gi yn bi lc kp tnh in
tnh in c gii phng, thanh trt c th trt
vi in cc gi.
trn b mt ca in cc. S phi hp in p nh
trong hnh 1(c) s cho php thanh trt di chuyn Tn hiu iu khin c lp li theo chu k T
mt bc sau mi chu k. Hnh 1(b) m t bn giai gm bn giai on nh m t trn cho php
on to nn mt bc di chuyn ca thanh trt thanh trt di chuyn c hnh trnh di nh mong
mun (Hnh 1(d)). Trong phn tip theo chng ti
1) C cu kp tnh in c hnh thnh gia thanh
gii thiu tm lc kt qu iu khin phn hi v tr
trt v in cc dn ng nh cp in p tri du
ca b kch hot tnh tin ECLIA.
t ln chng. Trong khi in p cng du to nn
lc y gia thanh trt v in cc gi. Bng 1. Kch thc ca vi chit p
(2) PZT gin ra sn ln ca xung in, n y
in cc dn ng cng vi thanh trt (nh c cu L(mm) W H (m) l (m) we ws h (m)
kp tnh in) di chuyn mt bc trn b mt in (mm) (m) (m)
cc gi. 25 5 5 3500 600 500 40

Hnh 1. ECLIA: (a) s cu to, (b) tit din ngang A-A, (c) tn hiu in p iu khin, v (d) th m t
chuyn ng ca PZT v thanh trt

21
Tp ch Khoa hc v Cng ngh 116 (2017) 020-025

3. iu khin phn hi v tr ca ECLIA ch to vi cc kch thc th hin Bng 1.


nhy ca cm bin l 62 m1 tng ng vi 0.77
3.1. Cm bin v tr
mV m1, v phn gii l 6 m.
Trong iu khin phn hi th thnh phn cm
bin xc nh v tr ca thanh trt l mt trong
nhng b phn quan trng nht. Cm bin khng
nhng c yu cu cao v phn gii m cn phi t
gy tr ngi nht c th n chuyn ng ca thanh
trt. Cm bin o khong cch laser (Micro-epsilon
ILD 2200-2LL) c th o c s chuyn ng ca
i tng vi chnh xc ln ti nano mt v khng
gy cn tr c hc n vt th chuyn ng. Tuy
nhin n yu cu phi c b mt phn x theo hng
di chuyn (mt u ca thanh trt) v khng gian
ln thit t h thng. iu ny rt kh trong vic
p dng vo b kch hot ECLIA vi nhiu thanh
trt c chiu dy nh c vi micro mt. Thm na,
trong ng dng cho vi bm, u thanh trt s tc
ng y pt tng. V vy khng th p dng loi cm Hnh 2. Vi chit p vi tip im mm: (a) s
bin quang hc trong trng hp ny. Chng ti pht cu to v (b) m hnh ha
trin mt loi vi chit p dng dung dch dn in
lm in tr nh v tr ca vt th chuyn ng.
Cu to ca vi chit p gm hai mi nhn kim loi
nhng vo hai vng (-pool) dung dch dn in
(1-ethyl-3-methyl, conductivity: 10 mS cm1) c kt
cu c m t nh trn Hnh 2(a). Vng th nht
c gi l cc cm bin c lin kt in vi
vng th hai c y l mt lp mng kim loi Au
(120 nm) v tr vch ngn. Nh vy vng th hai
ng vai tr l cc tip im. S nhng ca u
nhn kim loi vo vng dung dch ny to nn mt
lin kt mm. Vi c im tip in mm ny,
vi chit p loi tr c cn tr c hc ca lin kt
cng trong chit p c truyn thng. Chng ti s
dng vi chit p ny cho vic xc nh v tr ca
thanh trt trong bi ton iu khin phn hi b
kch hot ECLIA.

Cm bin vi chit p t trn thanh trt (Hnh


2(a)); v tr tng i ca thanh trt c xc nh
bi in tr ca cc cm bin o gia hai u nhn
kim loi c nh. Vi chit p c m hnh ha bi
mt bin tr nh Hnh 2(b). Nu thanh trt chuyn
ng tin hoc li th in tr Z o gia hai u cc
kim loi s thay i t l tng ng vi khong dch
chuyn. Do vy vi chit p s xc nh c v tr ca
thanh trt vi s cn tr ti thiu ti chuyn ng
ca n (ch c s cn tr ca dung dch u mi Hnh 3. Quy trnh ch to thanh trt tch hp cm
kim). cung cp in p iu khin cho thanh trt bin vi chit p
chng ti cng thit k mt tip im mm nh
trn. Hnh 3 m t quy trnh ch to thanh trt c 3.2. p ng ca h thng
tch hp cm bin vi chit p. Thanh trt c ch
to t cc lp vt liu polymer (PEDOT-parylene)
vi chiu dy vi micro mt kt hp cu trc xng
c tng hiu qu lc ht tnh in cng nh
cng dc trc [12]. iu ny cho php nng cao lc
y ca thanh trt ln pt tng trong ng dng cho
c cu vi bm ca nghin cu ny. Thanh trt c Hnh 4. S khi ca h thng iu khin phn hi

22
Tp ch Khoa hc v Cng ngh 116 (2017) 020-025

Cc thanh trt ca b kch hot tnh tin thi gian iu khin v cho php chn tham s iu
ECLIA c truyn ng nh c cu kp tnh in. khin nh. Bi ton iu khin phn hi ny c
C cu ny ph thuc vo lc ht tnh in v ma st trnh by trong nghin cu trc y ca chng ti
ca b mt tip xc gia thanh trt v in cc dn [13]. thy c s nh hng tch cc ca tham
ng/gi. N c th gy ra s trt tng i ca s iu khin KP chng ti so snh vi iu khin
thanh trt trong qu trnh truyn ng v kp gi. dng tn s khng i f = 100 Hz. Khi tn s khng
iu ny dn n di cc bc dch chuyn ca i th vn tc ca thanh trt cng khng thay i
thanh trt khng u nhau. Do vy khng th dng khi tip cn ti v tr mong mun. Mt khc vi tn
vic m cc bc tnh chuyn v c. Trong s cao th dn n s dao ng v kh dng chnh
nghin cu ny chng ti s p dng iu khin phn xc ti v tr thit t ca thanh trt. Hnh 5 so snh
hi v tr nhm dn ng thanh trt n v tr chnh p ng ca iu khin phn hi vi tn s in p
xc, ng dng y ng lng dung dch mong mun khng i 100 Hz v c dng cc tham s iu
ca vi bm xi lanh. khin khc nhau, KP = 5 v 10. Kt qu cho thy c
hin tng dao ng v vt qu im thit t ca
Hnh 4 m t s khi ca h thng iu thanh trt khi tn s in p khng i (100 Hz).
khin phn hi. Trong cu hnh ny, khi iu khin Hin tng ny khng cn na vi iu khin c
tnh ton v xut tn hiu iu khin cho ECLIA. tham s KP. iu ny ph hp vi nhng phn tch
Cm bin v tr xc nh v tr thc ca thanh trt Vr. v nhn nh cp trn. Vi kt qu ny chng
Sai s Err l sai khc gia gi tr thc Vr v gi tr ti hng n ng dng ca b kch hot tnh tin
thit t Vd. Gi tr sai s ny c dng tnh ton dng iu khin phn hi c tham s KP cho vi bm
v xut tn hiu iu khin u vo U(t) cho h thng xi lanh trong phn tip theo.
nhm t ti v tr mong mun ca thanh trt.
Phng thc iu khin y l dng tn hiu phn 4. Thit lp th nghim v nh gi kt qu
hi tnh ton in p vi tn s thay i. Nu sai
Vi c im ca b kch hot tnh tin nh
s ln th tn s iu khin cao, thanh trt chuyn
trnh by cc phn trn. Chuyn ng tnh tin ca
ng nhanh tin v v tr thit t. Khi sai s gim,
thanh trt theo tng bc nh nm, hnh trnh ln
tn s in p c pht ra cng gim dn, iu ny
mm cng vi lc y c mN. V vy trong nghin
lm cho thanh trt tip cn v tr thit t mt cch
cu ny chng ti ng dng b kch hot tnh tin vi
n nh v chnh xc. Vi cch thc iu khin ny
iu khin phn hi v tr y pt tng cho vi bm
b kch hot s gim c thi gian iu khin cng
kiu xi lanh. Vi chuyn ng tng bc nh c nm
nh s dao ng v vt qu v tr xc lp ca thanh
ca pt tng cho php y lng dung dch c pL.
trt. Tham s iu khin ph thuc vo bc di
iu ny rt hu ch trong cc ng dng y t hoc
chuyn ca thanh trt v s trt ca c cu kp
cc phn ng ha hc.
tnh in. Bc chuyn ng cng ln th cng gim

Hnh 5. p ng phn hi ca h thng vi cc tham s KP v ti tn s khng i f = 100Hz

23
Tp ch Khoa hc v Cng ngh 116 (2017) 020-025

Hnh 6. S thit lp th nghim

Thanh trt ca b kch hot c th y vi lc vi Trong ,


mN. Do vy chng ti la chn loi vi bm Hamilton
r: bn knh ca khi cu
10 L vi ci tin phn pt tng nhm tha mn lc
y yu cu ca n nh hn lc y ca thanh trt. h: chiu cao ca m cu
Loi pt tng nguyn bn c hnh dng tr trn nn
a: bn knh ca vng trn chn m cu.
ton b b mt tr ngoi ca n tip xc vi mt tr
trong ca xi lanh. iu ny gy nn s ma st tip Nh vy bng vic o kch thc a v h ca chm
xc v yu cu lc y pt tng ln (25 mN). Chng cu ta tnh c lng dung dch m bm y ra.
ti thay th bng loi pt tng c ng knh nh hn Trong nghin cu ny chng ti dng cht lng l
vi mt ci m silicon u. Bng s ci tin ny H2O. Quy trnh th nghim c thc hin nh sau:
phn tip xc ma st gia pt tng v xi lanh gim i
1- Thit t khong chuyn ng ca thanh trt
ng k v lc y gim i cn 1,5 mN. iu ny
trong chng trnh iu khin. (t v tr xut pht Vr
cho php thanh trt c th d dng y c pt
v ch n Vd)
tng.
2- t vi bm vo v tr u thanh trt tip xc
Hnh 6 m t s thit t th nghim, mt u
vi u pt tng.
thanh trt ca b kch hot tip xc vi u pt tng
ca vi bm, camera t pha trn u xi lanh quan 3- Dng hi-scope camera chp hnh m cu cht lng
st dung dch s c y ra. V lng dung dch u xi lanh ti v tr ban u ny.
c y ra rt nh nn n cha to thnh git
m ch mi hnh thnh nn dng m cu u ra ca 4- Kch hot chng trnh iu khin thanh trt
xi lanh. Phn th tch ca m cu ny c tnh theo y pt tng n v tr thit t.
cng thc: 5- Lp li bc 3: chp hnh m cu cht lng sau
khi pt tng y ra ti v tr cui ny.
h 2
V 3r h (1) 6- Kch thc ca phn m cu c o c v tnh
3
ra th tch cht lng thi im ban u (V1) v cui
a 2 h2 (V2) theo cng thc (1). Dung tch cht lng c
r (2) y ra chnh l hiu ca V2 -V1.
2h

24
Tp ch Khoa hc v Cng ngh 116 (2017) 020-025

Li cm n
Nghin cu ny c ti tr bi Qu Pht trin khoa
hc v cng ngh Quc gia (NAFOSTED) trong
ti m s 107.01-2015.18.

Ti liu tham kho


[1]. M. A. Unger et al (2000), Monolithic Microfabricated
Valves and Pumps by Multilayer Soft Lithography,
Science, Vol. 288, pp. 113116.
[2]. J. W. Munyan et al (2003), Electrically Actuated,
Pressure-driven Microfluidic Pumps, Lab Chip, Vol.
3, pp. 217220.
[3]. L. J. Jin et al (2003), A Microchip-based Proteolytic
Digestion System Driven by Electroosmotic
Pumping, Lab Chip, Vol. 3, pp. 1118.
Hnh 7. th quan h gia th tch cht lng y ra
[4]. A. Brask et al (2006), AC Electroosmotic Pump With
theo khong y ca thanh trt
Bubble-free Palladium Electrodes and Rectifying
Polymer Membrane Valves, Lab Chip, Vol. 6, pp.
Chng ti thc hin th nghim o th tch cht 280288
lng nhiu ln vi cng mt khong chuyn ng
nh trc cng nh ti nhiu gi tr khc nhau ca [5]. M. Koch et al (1996), A Novel Micropump Design
thanh trt/pt tng. Hnh 7 l th biu din mi With Thick-film Piezoelectric Actuation, Meas. Sci.
quan h gia khong dch chuyn ca thanh trt d Technol., Vol. 8, pp. 4957.
v th tch cht lng V c y ra ca vi bm. Kt [6]. S. Kar et al (1998), Piezoelectric mechanical pump
qu cho thy s t l tuyn tnh gia V v d khi p with nanoliter per minute pulse-free flow delivery for
dng iu khin phn hi v tr. Vi iu khin phn pressure pumping in micro-channels, Analyst, Vol.
hi c tham s Kp th tuyn tnh cao hn so vi 123, pp. 14351441.
khi khng dng tham s iu khin. iu ny l do [7]. J. Atencia and D. J. Beebe (2004), Magnetically-
s khng n nh v vt qu im thit t ca driven biomimetic micro pumping using vortices,
thanh trt khi iu khin vi tn s khng i Lab Chip, Vol. 4, pp. 598602.
cp phn 3. ng quan h V-d c th c xem [8]. A. Hatch, et al (2001), A Ferrofluidic Magnetic
nh ng c tnh ca vi bm cho php ta xc nh Micropump, J. Microelectromech. Syst., Vol. 10, pp.
c chnh xc lng cht lng cn bm theo khong 215221.
chuyn ng nh trc ca thanh trt. Tuy nhin
[9]. Konishi S, Ohno K and Munechika M (2002), Parallel
gi tr thc nghim ny nh hn kh nhiu so vi gi
linear actuator system with high accuracy and large
tr tnh ton l thuyt. iu ny c th c gii thch stroke. Sens. Actuators Phys. 9798:6109.
l do s khng kn kht gia pt tng v xi lanh gy
nn s d cht lng qua khe h ny. [10]. Konishi S et al (2005), Batch-fabricated high dense
multi sliders for WDM spectral attenuation, Proc. of
5. Kt lun TRANSDUCERS05 Conference (Seoul, Korea, 5-9
June 2005) Vol. 2 pp. 12425.
Bng vic p dng phn hi v tr cho b kch
[11]. Yokokawa R et al (2006), On-chip syringe pumps for
hot tnh tin chng ti thnh cng trong ng dng
picoliter-scale liquid manipulation, Lab Chip, Vol. 6,
iu khin vi bm kiu xi lanh. Kt qu cng cho pp. 10626.
thy hiu qu ca tham s iu khin Kp trong iu
khin phn hi. S t l tuyn tnh gia V v d cho [12]. T A Nguyen and S Konishi (2014), Characterization
php nh lng c chnh xc th tch cht lng of sliders for efficient force generation of
electrostatically controlled linear actuator, J.
cn bm vi sai s c pL. iu ny rt hu ch trong
Micromechanics Microengineering, Vol. 24, No. 5.
cc ng dng v y t v nng cao hiu sut ca cc
phn ng ha hc. Trong cc nghin cu tip theo [13]. T A Nguyen and S Konishi (2014), Position feedback
chng ti s nng cao s kn kht gia pt tng v xi control for electrostatically controlled linear actuator,
lanh gim d cht lng v hng ti vic tch hp Microsystem Technologies, Vol, 22, Issue 1, pp. 171-
179.
vo trong cc lnh vc c th nh cp.

25
Tp ch Khoa hc v Cng ngh 116 (2017) 026-030

Disk Tool Profiling for Helical Surfaces Generation


Xc nh bin dng dng c dng a gia cng mt xon vt

Nguyen Thanh Tu1,2, Banh Tien Long1*, Hoang Long1


1
Hanoi University of Science and Technology, No. 1, Dai Co Viet, Hai Ba Trung, Hanoi, Viet Nam
2
Thai Nguyen University of Technology, Tich Luong, Thai Nguyen, Viet Nam
Received: June 06, 2016; accepted: December 20, 2016

Abstract
This paper proposed solutions for profiling the disc tool in machining a helical cylindrical surface with
constant pitch. A section method has been developed in AutoCAD environment together with a Boolean
operation. Especially, this work presented a computational problem of determining the any section of a
helical surface, while other documents only refer to the section along axis and cross section. The authors
used a combinative method of analytics, graphics and programming to solve that problem, applying in
designing cutting tool for machining helical cylindrical surfaces. The proposed method has been
implemented and verified through subroutines written in Visual C running in AutoCAD. The testing results
have confirmed that the proposed methods achieve high accuracy for variant profiles of helical surfaces in
short time conputation.
Keywords: Helicoids, Profiling, Disc tool
Tm tt
Bi bo xut nhiu gii php to bin dng c dng a gia cng mt xon vt c bc xon khng i.
Phng php mt ct cng phng php s dng ton t Boolean c trin khai trong mi trng
AutoCAD. c bit, cng trnh trnh by vn tnh ton xc nh tit din bt k ca mt xon vt trong
khi cc ti liu khc ch trnh by tit din dc trc v tit din ngang. Cc tc gi kt hp phng php
gii tch, ho v lp trnh gii quyt vn , ng dng vo thit k dng c gia cng mt xon vt.
Phng php xut c thc hin v kim tra thng qua nhng chng trnh con vit bng Visual C
chy trong AotoCAD. Nhng kt qu kim tra khng nh phng php xut t chnh xc cao cho
cc bin dng khc nhau ca mt xon vt trong thi gian ngn.
T kho: Xon vt, To hnh, Dng c dng a.

1. Introduction* movement decomposition. Complementary analytical


methods have also been developed more recently.
Helical cylindrical surfaces with constant pitch
Examples include the minimum distance method
are encountered in practice as helical slots on the
[5] and the in-plane generating trajectories method
active surfaces of different parts such as helical
[6]. A profiling solution based on the Bezier
screws, worms, helical teeth gears, helical pumps
approximating polynomials for the helical surfaces
components etc. or cutting tools such as helical drills,
generatrix [2] was also proposed recently. This
helical teeth reamers, helical counter bores,
solution allows the determination of the tools cutting
cylindrical mills with helical teeth. Disk tool profiling
edge via a finite number of points along the profile to
for helical surfaces generation involves solving a
be generated with an acceptable precision from an
specific problem: to find the contact conditions and
engineering perspective. These methods allow
the corresponding characteristic curve, at the contact
obtaining solution that is rigorous and suggestive for
between a helical cylindrical surface and the tool
the designer.
primary peripheral surface.
The development of the graphical design
Analytical solutions for profiling tools generated
environment such as AutoCAD or Inventor allows us
by surfaces enveloping are common and have been
to elaborate new methods and dedicated software to
used for a long time. These solutions are based on the
solve the issue of generation of helical surfaces, that
fundamental theorems of the surfaces enveloping
will be presented in this paper.
such as Oliviers first theorem [1] and Gohmans
fundamental theorem [1, 2]. Also, frequently used is 2. Methods for disk tool profiling
Nicolaevs theorem [3, 4], based on the helical
2.1. Fundamental theory in brief

*
The generating process kinematics in the case of
Corresponding author: Tel.: (+84) 903463737 helical surface generation using a tool delimited by a
Email: long.banhtien@hust.edu.vn
26
Tp ch Khoa hc v Cng ngh 116 (2017) 026-030

revolution primary peripheral surface a disc tool 2.2.1. Section method


involves a combination of three motions (see Fig. 1):
Use many cutting planes, that is perpendicular to
the axis of the disk tool. For each cutting plane, the
intersection beetwen the plane and the helical surface
(see Fig. 2: EF) must be tangent to the circle, that is
intersection beetwen the cutting plane and the disk
toll, the contact point can be found. The
characteristic curve (BTCT) is specified by a set of
contact points.

Fig. 2. Two intersections are tangent


a) 3D CAD Methode
Fig. 1. Disc-tool primary peripheral surface and
helical surface to be generated [2] Using 3D CAD software such as Inventor, it is
easy to draw the intersection between any cutting
I rotation motion of the worked piece on which the plane and 3D solid model of the given detail that
helical surface to be generated (cylindrical and hav- contains helical surfaces (see Fig. 3).
ing constant pitch) is placed;
Export Drawing File to AutoCAD, in AutoCAD,
II translation motion along the worked piece specify contact points by using perpendicular osnap
rotation axis, correlated to the rotation motion, having mode (see also Fig. 3).
as purpose to create a helical motion of axis and p
Affter specifying a number of contact points, it is not
parameter identical to the generated surface ones; diffical to specify the axial section of disk tool, then
using Revole command to creeate primary peripheral
III cutting motion tool rotation around its axis, . surface of the disk tool.
The following reference systems have to be consi-
dered:
XYZ, meaning a system attached to the helical
surface to be generated, having the axis coincident
axis of the helical surface.
to
X1Y1Z1 system attached to the disc-tool axis,
Nikolaev theorem applied in order to find the charac-
teristic curve owning to both surfaces, , to be
generated and S tool primary peripheral surface is
[2]: (see also Fig. 1)
, 1) = 0
( , (1)
where: is the vector of the disc-tool surface S
Fig. 3. Specify the contact point P
rotation axis;
b) Computation method (see Fig. 4)

- surface normal, into the XYZ system;


Given:
1 the position vector of the current point from

- The profile BC of cross section N-N of helical


surface, referred to X1Y1Z1 origin, O1. surface.
2.2. Proposed Methods - Position of a cutting plane P-P

27
Tp ch Khoa hc v Cng ngh 116 (2017) 026-030

Specify: The section P-P p d = k (r sin( + d) x0) (8)


The profile BC on section N-N is given by a number The equation (8) can not be solve exactly, but it
of points, as usual, each point of them is given by a can be solve approximately by using computer with
pair r, (polar coordinates), it can be translated into the subroutine in ARX language, running in
Cartesian coordinates as: AutoCAD, its algorithm as follows (see Fig. 5):
x = r sin (2)
y = - r cos (3)

Fig.4 Specify intersection of a helix and cutting plane


The equations of the helical surface are written as:
x = r sin( + d) (4)
Fig.5 The algorithm for solving the equation (8)
y = - r cos ( + d) (5)
Using the above subroutine, after specifying a
z = p d (6) number points on cutting plane P-P, join them by a
Where p is the parameter of the helix, d is spline and find contact point then create axial section
angle that the profile N-N rotates about the axis of the of disk tool by the way shown in the section 2.2.1.a
helical surface. 2.2.2. Boolean operation method
The equation of the cutting plane P-P is written as: In this method, CAD approach is used to
z = k (x-x0) (7) simulate generation machining process. For this
purpose, the cutter and work blank are taken as solid
Where k, x0 are parameters of the given cutting models and simulation is performed using Boolean
plane P-P. operation to remove unwanted material in an
So, the intersection point between cutting plane incremental manner, maintaining the kinematic
P-P and the helix from any point on cross section N- relationship. (see Fig. 6)
N, such as CN, satisfies the equation:

28
Tp ch Khoa hc v Cng ngh 116 (2017) 026-030

The Fig. 7 and Fig. 8 have shown that the disk


tool and the given helical surface seem to satisfy
absolutely the contact conditions.
The accuracy of the disk tool profile have been
also tested by the simulative machining, that has used
the Boolean operation in AutoCAD as shown on Fig.
9, 10.

Fig. 6. Creating the disk tool for helical surfaces in


AutoCAD
3. Testing results, discussion and conclusion
Fig. 9. Simulative machining in AutoCAD
The disk tool created by using the methods
mentioned above and the given helical surface have
been cheeked the tangency condition as follows (see
Fig. 7, 8):

(a) Creating two profiles

Fig. 7. Testing tangency condition on sections

(b) Comparison between two profiles


Fig. 8. Testing tangency condition by using Fig. 10. Testing accuracy of the disk tool by
constrain command in Inventor simulative machining

29
Tp ch Khoa hc v Cng ngh 116 (2017) 026-030

The Fig. 9 and Fig. 10 have shown that the References


helical surface generated after the simulative
[1]. F.L. Litvin, Theory of Gearing, Reference Publication
machining have been compared with the given helical 1212, Nasa, Scientific and Technical Information
surface, the maximum difference between their cross Division, Washington, D.C., 1984.
sections is 0.0182 mm (see also Fig. 10b, in the
AutoCAD text window). [2]. N. Oancea, I. Popa, V. Teodor, V. Oancea, Tool
Profiling for Generation of Discrete Helical Surfaces,
The testing results have confirmed that the Int. J. of Adv. Manuf. Technol., 50 (2010), 3746.
proposed method achieve high accuracy for variant [3]. I. Veliko, N. Gentcho, Profiling of rotation tools for
profiles of helical surfaces in short consumed time forming of helical surfaces, Int. J. Mach. Tools Manuf.,
and have demonstrated the functionality and the 38 (1998) 11251148.
reliability of the proposed methods that confront the
[4]. V.S. Lukshin, Theory of Screw Surfaces in Cutting
complex problem of disk tool profiling for helical
Tool Design, Machinostroyenie, Moscow, 1968.
surfaces generation. The proposed method was
created on implementation point of view while the [5]. V. Teodor, Contribution to the elaboration of a method
most others were conceptual [1,3,4] so the method is for profiling tools Tools which generate by
suitable to create application software running in the enwrapping, Lambert Academie Publishing, 2009.
AutoCAD which is more popular and cheaper than [6]. V.G. Teodor, I. Popa, N. Oancea, The profiling of end
CATIA [2,5,6]. mill and planning tools to generate helical surfaces
known by sampled points, Int. J. Adv. Manuf. Technol,
In near future, we will complete the method in 51 (2010) 439452.
order to design more complex cutting tool based on
upgraded envelope technique.
Acknowledgments
This work was supported by Hanoi University
of Science and Technology in the project T 2016 -
PC-077.

30
Tp ch Khoa hc v Cng ngh 116 (2017) 031-036

Nghin cu nh hng ca v tr xp container n c tnh


kh ng on xe ch container
A Study on Effects of Container Location on Truck Hydrodynamics

Nguyn Danh 1,2, L Trung Sn3, Ng Vn H1*


1
Trng i hc Bch khoa H Ni, S 1, i C Vit, Hai B Trng, H Ni, Vit Nam
2
Cng ty Sa Vit Nam, VINAMILK, Gia Lm, H Ni
3
Trng i hc Cng Ngh, i hc Quc gia H Ni, S 144, Xun Thy, Cu Giy, H Ni, Vit Nam
n Ta son: 28-3-2016; chp nhn ng: 20-12-2016

Abstract
The most economic speed for the truck in transportation is from 60km/h to 150km/h. When the truck
operates at high speed, the air resistances acting on it increase significantly. In case of bad weather
operating conditions as strong wind, the aero dynamic forces acting on the truck cause safe situation. In this
paper, the authors present a study on aero dynamic performances of a 40 feet container truck and the
effects of 20 feet container which locates on truck at several positions to reduce its air resistances by using a
commercial Computation Fluid Dynamic (CFD). By using CFD, the pressure distribution, velocity distribution
around truck and air resistances acting on the truck are investigated. From analysis simulated results of aero
dynamic performances of the truck, the authors give some comments and propose ideas to reduce air
resistances acting on the truck. The study on reduction of resistances acting on truck contributes improving
economy efficiency of the truck transportation.
Keywords: Truck; air resistance; aero dynamic force; CFD; reduce air resistance.
Tm tt
Trong qu trnh vn ti hng ha chuyn tuyn ca on xe ch container, vn tc xe lu thng kh cao,
trong khong t 60 n 150 km/h. Khi on xe lu thng vi vn tc cao, lc cn gi tc ng ln thn v
on xe tng ln ng k. Trong trng hp iu kin thi tit xu, gi mnh, lc kh ng tc ng ln thn
v on xe c th gy mt an ton cho xe. Trong nghin cu ny, tc gi thc hin kho st cc c tnh
kh ng lc hc thn v on xe ch container 40 feet v nghin cu s nh hng ca v tr xp container
20 feet n c tnh kh ng hc on xe ch loi container c kch thc ny. Thng qua vic s dng
cng c m phng s, tnh ton ng lc hc cht lng CFD (Computation Fluid Dynamics), tc gi c th
tnh ton m phng s cc yu t phn b p sut, vn tc dng bao quanh thn v on xe v lc cn kh
ng tc dng ln thn v on xe. T kt qu ca vic phn tch cc yu t kh ng lc hc thn v xe,
tc gi a ra mt s nhn xt v xut gii php nhm gim lc cn gi tc ng ln on xe gp phn
nng cao hiu qu khai thc cho on xe ch container.
T kha: on xe ch container; lc cn gi; lc kh ng; CFD; gim lc cn gi.

1. Gii thiu chung* hoc 2 container 20 feet. Vic chuyn ch 1 container


20 feet v v tr ca n t trn on xe liu c nh
Trong nhng nm gn y, nc ta vi li th
hng g n cc c tnh kh ng hc v lc cn kh
lng hng ha xut nhp khu ngy mt tng,
ng tc ng ln on xe hay khng, y chnh l
thc y pht trin mnh m on xe ch container.
vn t ra cn gii quyt trong nghin cu ny ca
Cng vi s pht trin v s lng, kiu loi, cht
nhm tc gi.
lng xe v cc hng xe khc nhau cng c a
dng ha trong i xe ch container. Trong vn ti c tnh kh ng ca on xe ti gn y
container, thng gp hai loi container c vn c cc nh sn xut v khai thc quan tm n.
chuyn ch yu l container 40 feet v 20 feet. Trong Mt trong nhng c tnh kh ng hc quan trng
thc t vn chuyn hng, ty thuc vo lng hng, cn phi quan tm i vi on xe l lc kh ng,
yu cu vn chuyn v s lng container m on xe bao gm c lc cn v lc nng tc ng ln on xe
c b tr chuyn ch 1 hay 2 container tng ng. trong qu trnh lu thng. Lc cn lin quan n cng
Thng thng on xe c thit k vi iu kin sut tiu hao ca ng c, lin quan n lng tiu
chuyn ch 1 container 40 feet, 1 container 20 feet hao nhin liu ca on xe. Lc nng nh hng n
tnh an ton n nh v bm mt ng ca xe. Trong
nghin cu ny nhm tc gi ch gii hn nghin cu,
*
Corresponding author: Tel.: (+84) 167-9482-746 kho st i vi thnh phn lc cn kh ng tc ng
Email: he.ngovan@hust.edu.vn
31
Tp ch Khoa hc v Cng ngh 116 (2017) 031-036

ln thn v on xe. i vi cc on xe khi khai n 0.69 gim i khong 26% so vi gi tr ca m


thc di vn tc thp, th hnh dng thn v xe t hnh xe ban u [3]. Tng hp kt qu nghin cu ca
nh hng n cc thnh phn lc kh ng tc ng t chc nghin cu vn ti chu u nm 2010 cho
ln xe. Trong trng hp ny, lc cn kh ng tc thy vi mt s nghin cu ci tin phn ui xe ti
dng ln xe ch khong di 10% lc cn tng th. nhm iu khin dng thot sau xe c th gip ci
Tuy nhin, khi on xe khai thc di vn tc cao th thin c c tnh kh ng hc ca xe, nghin cu
s nh hng ca hnh dng thn v xe tng ln ng ny ch ra rng vic ci tin ui xe c th gip
k, thnh phn lc cn kh ng tc dng ln xe c gim c ti 7% tng lng kh thi CO2 ca loi
th tng ln ti 53%, thm ch ln ti 80% tng lc xe ti ny [2].
cn tng th ca xe di vn tc 100km/h [1, 2, 3].
Trong bi bo ny, tc gi thc hin kho st
Trong mt s nghin cu cng b cho thy, vic
c tnh kh ng hc ca m hnh on xe ch
thay i hnh dng hnh hc thn v xe bng cc
container 40 feet vi hnh dng c bn tng ng vi
phng php n gin nh gn thm cc tm kh
mt s mu xe hin ang c khai thc vn ti
ng, thm mui ti nh cabin xe, ci thin hnh dng
chim phn ln Vit Nam, thng qua tnh ton ng
kh ng nc container, ci thin hnh dng gm xe
lc hc cht lng CFD (Computation Fluid
hay thm tm bt chn bnh xe u c th gip gim
Dynamic). Trn c s tc gi thc hin kho st s
lc cn kh ng tc dng ln on xe khi lu thng.
nh hng n cc c tnh kh ng lc hc ca
Vic lm ci thin hnh dng kh ng hc cho on
on xe khi thay i v tr xp container 20 feet trn
xe ny c th lm gim c ti 25% tng lc cn
r mc. T kt qu so snh v phn b vn tc dng
kh ng tc ng ln xe thng qua thc nghim trn
bao quanh thn xe, phn b p sut trn b mt thn
m hnh xe thc v tnh ton m phng s CFD [1, 2,
xe v lc kh ng tc dng ln xe, chng ti a ra
3, 4, 5]. Trong cc bin php ci tin hnh dng kh
cc nhn xt nhm ci thin thn v xe hp l nht
ng cho on xe th vic gn thm mui nc cabin
vi iu kin khai thc s dng on xe ti Vit Nam,
gip ci thin ng k lc cn kh ng tc ng ln
c th gp phn nng cao hiu sut kinh t vn ti
xe, vic ci thin ny n gin v khng lm nh
cho on xe ch container.
hng n tnh nng vn ti ca xe. Bin php che
chn khong trng v thay i khong cch gia 2. M hnh on xe ch container nguyn bn
container v u ko cng mang li hiu qu ng k,
Trong nghin cu ny, on xe ch container 40
tuy nhin vic ci tin ny ch thch hp vi cc on
feet vi u ko c ly theo hnh dng c bn ca
xe lu thng trn cc hnh trnh thng, t quay tr. V
loi u ko thng dng nc ta hin nay nh
vic thay i ny s nh hng n tnh quay tr ca
xe. HD700; HD1000 do tp on Hyundai sm xut c
s dng trong tnh ton m phng s CFD. Bng 1
Nghin cu ca nhm tc gi Ch. Hakansson v th hin mt s kch thc ch yu ca u ko v
M.J. Lenngren (2010) a ra cc nghin cu ci tin container 40 feet c m hnh ha trong cc tnh
hnh dng kh ng hc cho thn xe ti thng qua ng ton m phng. Hnh dng on xe s dng trong
dng CFD tnh ton v phn tch c tnh kh ng nghin cu c th hin trn Hnh 1.
hc. Kt qu nghin cu ch ra nh hng ca hnh
dng kh ng n vic gim lc cn kh ng di Bng 1. Thng s kch thc c bn ca on xe
vn tc 90 km/h vi gc nghing dc ca xe t 0-5 n
. Vic ci thin hnh dng nc cabin v ui xe Th t Tn Tr s
v
gip gim c lc cn kh ng tc ng ln xe mt Chiu di c s 4.35 m
cch r rt t khong 2 n 22% lc cn kh ng Di 6.68 m
tng th tc ng ln xe [4].
Kch thc bao Rng 2.49 m
Nghin cu ca nhm tc gi H. Chowdhury cng Cao 3.13 m
cng s (2013), thng qua phng php thc nghim Trc 2.04 m
m hnh vi t l 1/10 so vi kch thc thc ca xe, Vt bnh xe
Sau 1.85 m
trong ng th kh ng vi mt s bin php ci thin Trc 1.49 m
hnh dng mui xe v che chn thn xe, nhm tc gi Phn nh ca xe
Sau 0.84 m
thc nghim vi 6 m hnh xe khc nhau. Kt qu
Di 12.25 m
thc nghim c thc hin trong di vn tc t Kch thc
40km/h n 145km/h i vi cc m hnh do nhm Rng 2.48 m
mooc xng
nghin cu a ra. Kt qu thc nghim cho thy Cao 1.50 m
vi cc m hnh ci tin h s lc cn kh ng ca Di 12.19 m
Kch thc
xe c th gim c ti 26% so vi ban u, kt qu Rng 2.44 m
container 40 feet
th nghim m hnh cho thy h s lc cn kh ng Cao 2.59 m
tc ng ln xe dao ng trong phm vi gi tr t 0.5

32
Tp ch Khoa hc v Cng ngh 116 (2017) 031-036

Hnh 1. M hnh on xe ch container 40 feet


T m hnh on xe ny, cc c tnh kh ng
Hnh 2. Chia li trn b mt thn v on xe trong
lc hc thn v xe s c tnh ton phn tch chi tit
khng gian m phng CFD
thng qua s dng cng c m phng s CFD. M
hnh c m phng trong hai trng thi vi xe 4. c tnh kh ng ca on xe ch container
nguyn bn gm, xe khng ch container v xe ch
Trong phn ny, on xe ch container nguyn
container 40 feet vi t l 1:1. M hnh tnh ton s
bn (Hnh 1) c kho st cc c tnh kh ng hc
dng trong nghin cu ny c hnh dng v kch
hai trng hp c hng v khng ch hng khi hot
thc c bn tng ng vi hnh dng kch thc
ng trong di vn tc khai thc t 40km/h n 120
on xe thc t.
km/h [1-16]. Hnh 3, 4 th hin kt qu m phng
3. M phng s CFD cc c tnh kh ng lc phn b p sut, dng bao quanh thn xe vn tc
on xe ch container 80km/h vi 2 trng hp khai thc ca on xe.
Trong nghin cu ny, cc c tnh kh ng lc Kt qu phn b p sut v dng bao quanh
hc ca on xe c tnh m phng thng qua s on xe cho thy r s thay i vn tc v p sut
dng cng c m phng s thng mi Ansys xung quanh thn xe. Vi m hnh on xe khng ch
Fluent v.14.5. Vic tnh m phng s CFD, c tin container din tch vng p sut thp gim i r rt,
hnh theo cc bc lp m hnh tnh ton, thit k khng c nh hng ca vng nhiu ng gn
min khng gian tnh ton, chia li v t cc iu container. Thng qua vic phn tch kt qu ny s
kin bin. Trong qu trnh m phng s tt c cc gip cho vic ti u ha hnh dng hay iu khin
bc thc hin u c nh hng n kt qu m dng bao quanh xe c th lm gim lc cn kh
phng. V vy vic thc hin phi tin hnh theo cc ng tc dng ln on xe.
ti liu ch dn chuyn mn do cc t chc quc t
cng b [15, 16] v da trn nhng kinh nghim tnh
ton c thc nghim kim tra cng b kt
qu [2-12]. Trong nghin cu ny qu trnh tnh m
phng s CFD c thc hin theo ti liu ch dn,
theo cc nghin cu cng b kt qu v c
kim nghim bng thc nghim m hnh ti ng th
kh ng [2-16].
Trong nghin cu ny, min khng gian tnh
ton c thit k vi chiu di 68m, chiu rng 16m
v chiu cao 8m, vi kch thc thc ca on xe nh
trong Bng 1. Chia li min khng gian tnh ton
vi kiu li khng cu trc t din c 4.7 triu
Hnh 3. Phn b p sut ng ti mt ct dc tm
li. M hnh ri k-epsilon p dng cho hm khng
on xe vn tc V=80km/h
dng c s dng, vn tc vo t cho u vo, u
ra t vi iu kin bin p sut ra [2-16]. Bng 2 th
hin cc thng s tnh ton. Hnh 2 th hin li chia
trn b mt on xe.
Bng 2: Cc thng s u vo tnh ton
Tn Gi tr n v
Vn tc vo, V 14.5 m/s
p sut ra, p 1.025 105N/m2
Khi lng ring ca
1.225 kg/m3
khng kh,
nht ng hc, 1.789 10-5kg/ms
Hnh 4. Vn tc dng bao quanh than xe trong trng
thi on xe ch container 40 feet

33
Tp ch Khoa hc v Cng ngh 116 (2017) 031-036

Hnh 5 th hin phn b p sut trn b mt thn


v xe trong hai trng thi khai thc xe. Kt qu cho
thy r s thay i v nh hng ca hnh dng thit
k ca xe n s phn b p sut trn thn xe. y l
kt qu quan trng trong vic xc nh cc nhn t
lm gia tng lc cn kh ng cho xe.

Hnh 5. Phn b p sut trn b mt thn v on xe


vn tc khai thc 80km/h
Hnh 7. M hnh on xe ch container 20 feet vi
Hnh 6 th hin th lc cn kh ng tc ng cc v tr t container khc nhau, N1, N2, N3
ln on xe theo vn tc khi xe c v khng ch Trn c s tnh ton m phng s, cc m hnh
container. T kt qu tnh ton lc cn kh ng tc
xe ny c thc hin m phng s nh trnh by
ng ln on xe cho thy khi vn tc chy xe cng
trn [1-16]. kho st cc c tnh kh ng lc
ln th lc cn kh ng tc ng ln xe cng tng
hc thn v xe. Trong nghin cu ny, cc m hnh
cao. H s lc cn kh ng tc ng ln on xe khi
c kho st c thc hin vi vn tc khai thc
khng ch container xp x bng nhau v dao ng tng ng ca xe l 80 km/h.
quanh gi tr 0.75, h s lc cn kh ng ca on xe
khi ch container 40 feet xp x 1.2 trong di vn tc Kt qu m phng th hin trn hnh 8, 9 v 10
kho st 40km/h 120km/h. th hin kt qu phn b p sut v dng bao quanh
on xe ti mt ct dc tm, khi thay i v tr xp
container 20 feet. S thay i v tr container lm
thay i phn b p sut v dng bao quanh on xe
r rt. Din tch cc vng nhiu ng dng, vng p
sut ng thp ti khu vc gia u xe v container,
ti pha sau on xe gim i khi khong cach tng
i gia u xe v container gim i. Kt qu ny cho
thy lc kh ng tc ng ln on xe c th thay
i ty theo v tr ca container 20 feet.

Hnh 6. th h s lc cn kh ng theo vn tc
ca on xe
5. nh hng ca v tr xp container 20 feet n
c tnh kh ng lc on xe
Trong phn ny, vic nghin cu nh hng ca
v tr t container 20 feet n cc c tnh kh ng
lc on xe c thc hin da trn c s so snh,
phn tch cc kt qu m phng s on xe trong 3
trng hp b tr container 20 feet khc nhau khi vn
chuyn hng ca on xe. Hnh 7 th hin m hnh Hnh 8. Phn b p sut v vn tc dng bao quanh
tnh ton m phng 3 trng hp xp container trn xe ti mt ct dc tm, N1
xe vi cc v tr khc nhau tng ng N1, N2 v N3.

34
Tp ch Khoa hc v Cng ngh 116 (2017) 031-036

h s lc cn kh ng c xc nh theo cng thc


(1).

(1)
Trong : R l lc kh ng tc dng ln xe, N
V l vn tc chuyn ng, m/s
S l din tch mt hng gi, m2
Hnh 12 th hin kt qu so snh h s lc cn
kh ng trong cc trng hp xe ch container 40
feet v xe ch container 20 feet. Kt qu so snh chi
Hnh 9. Phn b p sut v vn tc dng bao quanh tit c th hin trong bng 3. T kt qu ny cho
xe ti mt ct dc tm, N2 thy, h s lc cn kh ng tc ng ln thn v
on xe xp x gi tr bng 1. Tuy nhin c s khc
bit r rt v cng sut tiu hao trong cc trng hp
xe ch theo container v xe khng ch theo container
nh th hin trn biu lc cn hnh 12 v bng so
snh cng sut Bng 3.
Bng 3. H s lc cn kh ng v cng sut tiu hao
cho thnh phn lc cn kh ng
Phng n ch
Cx Pw, CV %Pw
container
Khng ch
0.724 48.33 -52.9
container
20 feet 1.100 98.55 -3.9
40 feet 1.145 102.55 0.0
Hnh 10. Phn b p sut v vn tc dng bao quanh
xe ti mt ct dc tm, N3

Hnh 11. H s lc cn kh ng tc ng ln on xe
ti vn tc khai thc 80km/h Hnh 12. Lc cn kh ng tc ng ln xe

Hnh 11 th hin kt qu tnh lc cn kh ng 6. Kt lun


tc ng ln on xe vn tc khai thc 80km/h. Kt Trong bi bo ny, tc gi trnh cc kt qu
qu cho thy vic thay i v tr container 20 feet nghin cu v c tnh kh ng ca on xe ch
lm thay i lc cn kh ng tc ng ln on xe. container. Trn c s phn tch kt qu tnh ton ca
Nh vy. khi b tr container ti v tr th 3 s gip m hnh on xe nguyn bn, bi bo trnh by kt
gim c lc cn kh ng thn v on xe. qu nghin cu v s nh hng ca v tr t
Trong nghin cu lc cn kh ng, lc cn kh container 20 feet trn on xe n cc c tnh kh
ng tng c th c phn chia thnh hai thnh phn ng on xe. Vi gii hn ni dung nghin cu v
lc cn kh ng do p sut, nhiu ng dng gy ra c tnh kh ng hc v lc cn kh ng on xe,
v lc cn kh ng do ma st gia khng kh v di y l mt s kt lun ca bi bo ny:
thnh tc dng gy ra. c trng cho hai thnh phn - Vic s dng cng c m phng s gip nh nghin
ny l cc h s lc cn kh ng p sut Cp v h s cu c th hiu r c s phn b dng, p sut tc
lc cn ma st Cf, h s lc cn kh ng tng Ct. Cc ng ln thn on xe. y l vic c th thc hin

35
Tp ch Khoa hc v Cng ngh 116 (2017) 031-036

c bng thc nghim, tuy nhin tn km hn rt Bluff bodies aerodynamic and applications, Milano,
nhiu. Italy (2008), pp.1-14.

- Thng qua kt qu ca bi bo cho thy, khi xe lu [6] Ngo.V. H, Y. Ikeda. A Study on Interaction Effects
thng vi vn tc cao lc cn kh ng tng nhanh between Hull and Accommodation on Air Resistance
of a Ship. Proceeding of the JASNAOE, Hiroshima,
theo tc khai thc. Vic b tr xe chy khng ch Japan (2013), Vol.16, pp.278-281.
theo container v xe ch ch 1 container 20 feet vi
cc v tr t khc nhau c nh hng n lc cn kh [7] K. Mizutani, D. Arai, N.V. He, Y. Ikeda. A Study on
ng tc ng ln on xe. Ngoi vic nghin cu v Reduction of the Wind Resistance Acting on a Wood
v tr xp container c li nht v gim lc cn kh Chip Carrier. Proc. of the JASNAOE, Hiroshima,
Japan (2013), Vol.16, pp.282-285.
ng, cn thit phi nghin cu thm v nh hng
ca vic xp container n tnh an ton cho xe khi [8] K. Mizutani, Y. Akiyama, N.V. He, Y. Ikeda. Effects
quay vng, i hng xe c th c kt lun c th of cargo handling equipment on wind resistance
v vic p dng gii php k thut ny. Vn ny acting on a wood chip carrier. Proceeding of the
cn lin quan n cc quy nh v lut xp hng khi JASNAOE, Hiroshima, Japan (2014), Vol.18, ISSN:
2185-1840, pp.421-424.
lu thng xe trn ng. Vi hn ch v ni dng
nghin cu, trong bi bo ny tc gi cha thc hin [9] Ngo. V.H, K. Mizutani, Y. Ikeda. Reducing air
nghin cu ni dng ny. resistance acting on a ship by using interaction effects
between the hull and accommodation. Proceeding of
- Trn c s phn tch kt qu tnh m phng s CFD the 7th AUN/SEED-Net RCMME 2014, Hanoi,
nh phn b p sut v lc tc ng ln on xe Vienam, ISSN: 978-604-911-942-2, pp.497-501.
cho thy nguyn nhn lm tng hay gim lc cn kh
[10] Ngo. V.H, Phan. A.T, Luong. N.L, Y. Ikeda. A Study
ng tc ng ln thn xe. Cc kt qu nghin cu v on interaction Effects on air resistance acting on a
s nh hng ny s l c s ti u hnh dng kh ship by shape and location of the accommodation.
ng cho on xe c li nht v lc cn kh ng. Journal of Science and Technology, Vietnam (2015),
y chnh l c s gim tiu hao nhin liu cn Vol 27, ISSN:1859-3585, pp. 109-112.
thit cho on xe v nng cao hiu qu kinh t khai
[11] Ngo V. H, Mizutani. K, Ikeda. Y. Reducing air
thc on xe. resistance acting on a ship by using interaction effects
Ti liu tham kho between the hull and accommodation. Ocean
Engineering Journal (2015), Vol. 111, pp. 414-423.
[1] K. Salari. DOEs Effort to Improve Heavy Vehicle
Aerodynamics though Joint Experiments and [12] Ng Vn H, L Quang (2015). Nghin cu nh
Computations. DOE annual merit review, Lawrence hng ca hnh dng thn v n c tnh kh ng
Livermore National Laboratory (2013). on xe ch container. Tp ch giao thng vn ti
(2015), s 56, pp.194-196.
[2] European Federation for Transport and Enviroment
AISBL. The case for the exemption of aerodynamic [13] Trn S Phit, V Duy Quang. Thy kh ng lc hc
devices in future type approval legislation for heavy k thut (1979). NXB H v TH CN H Ni.
goods vehicles (2010), pp. 1-25. [14] Nguyn Phc Hong ( Ch bin), Phm c Nhun,
[3] H. Chowdhury, H. Moria, A. Ali, I. Khan, F. Alam, S. Nguyn Thc Tn. Thy lc v my thy lc. NXB
Watkins. A study on aerodynamic drag of a semi i hc v trung hc chuyn nghip, H ni 1979.
trailer truck. Journal of Procedia Engineering (2013), [15] ITTC (2008), The proc. of the 25th International
Vol.56, pp. 201-205. Towing Tank Conference, Fukuoka, Japan, Website:
[4] Ch. Hakansson, M.J. Lenngren. CFD analysis of http://ittc.sname.org/proc25/assets/documents/V
aerodynamic trailer devices for drag reduction of olumeI/Proceedings.
heavy duty trucks. Master thesis of Chalmers
University of technology, Sweden (2010). [16] ITTC (2011), The proc. of the 26th International
Towing Tank Conference, Rio de Janeiro, Brazil,
[5] GM.R. Gandert, V. Raemdonck, J.L. Michel, V. Website:
Tooren. Design of an aerodynamic aid for the http://ittc.sname.org/proc26/assets/documents/V
underbody of trainler within a tractor-trailer olumeI/Proceedings.
combination. BBAA VI International colloquium on

36
Tp ch Khoa hc v Cng ngh 116 (2017) 037-041

Nghin cu nh hng ca gc ln ci
n qu trnh dp thy tnh phi tm kim loi
Effect of the Die Conner Radius on the Sheet Metal Hydroforming Process

L Trung Kin*, Phm Vn Ngh


1
Trng i hc Bch khoa H Ni, S 1, i C Vit, Hai B Trng, H Ni, Vit Nam
n Ta son: 12-5-2016; chp nhn ng: 20-12-2016

Tm tt
Nguyn cng dp vut c s dng rt nhiu trong qu trnh to hnh cc chi tit phc tp trong bao
gm c cng ngh dp vut truyn thng, dp vut thy c, dp vut thy tnh. Mi cng ngh c nhng u
im khc nhau v ng dng ph thuc vo vt liu, sn phm, iu kin sn xut ... Cng ngh dp thy
tnh c s dng cho nhng chi tit cn c bn knh gc ln chi tit nh m cc phng php khc kh
hoc khng th ch to. Mc tiu ca nghin cu ny l xc nh nh hng ca bn knh gc ln ci
trong qu trnh dp thy tnh chi tit tm n kh nng to hnh v thng s lc chn. Nghin cu c thc
hin vi thp ZAM dy 0,8 mm vi cc bn knh gc ln ci 2mm, 3mm, 4 mm, 5 mm v 6mm..
T kha: Dp thy tnh, Bin mng, Nhn, Rch
Abstract
Drawing is used a lot in the process of the intricate part shaping including traditional drawing, hydro-
mechanical deep drawing, and hydrostatic deep drawing. Each technology has different advantages and
applications that depend on the materials, products and production conditions... Hydrostatic deep drawing is
used for the products, required die shoulder and die radius little, that is difficult or impossible to fabricate by
other method. The objective of the present study is to determine the influence of work piece materials on die
shoulder radius in sheet hydrostatic forming process. The die shoulder radius plays a vital role in
manufacturing the product in deep drawing process to formability and holder force. The present work deals
with ZAM steel blank of 0,8 mm in thickness, and 2mm, 3mm, 4 mm, 5 mm and 6mm for corner radii of the
die.
Keywords: Hydrostatic Forming, Thinning, Wrinkle, Crack

1. t vn * gc ln ci, bn knh gc ln y chi tit. Do vy,


nhm nghin cu trin khai cng vic kho st nh
c nhiu nghin cu v qu trnh v ti u
hng ca bn knh gc ming ln ming v y ci
cc thng s cng ngh khi dp vut truyn thng [1-
n qu trnh hnh thnh v bin dng chi tit dng
3]. Cc c ch bin dng, h s dp vut, mc
cc tr vi vt liu thp ZAM dy 0,8 mm. Phng
bin dng ti a, s bin mng thnh hoc nhng
php nghin cu c thc hin bng m phng s
dng hng chi tit c nghin cu, cng b v p
kt hp thc nghim. Cc kt qu m phng c
dng vo sn xut cng nghip. Tuy nhin, cng ngh
kim chng bng mt trng hp tng ng vi bn
dp vut truyn thng cn c rt nhiu cc nhc
knh gc ln ming ci rC = 4mm v bn knh y
im nh: kh ch to c cc chi tit c hnh dng
ci rct = 2mm.
phc tp, tn kinh ph khi phi to c chy v ci nn
kh ch to khi sn lng nh ... Cng ngh dp thy 2. M phng qu trnh dp chi tit cc tr vi bn
tnh c pht trin v ng dng khc phc nhng knh gc ln ci khc nhau.
nhc im ca cng ngh dp vut truyn thng.
Cng ngh ny vi cc u im: Bn knh gc ln
nh, hnh dng hnh hc chnh xc, nng sut cao, tit
kim chi ph do ch ch to ci thy tnh [4]. Hai
cng ngh ny c nhiu nhm nghin cu thc
hin v a ra cc so snh vi cc u nhc im
khc nhau [5,6]. Mt trong nhng yu t hnh hc ca
khun quyt nh s hnh thnh chi tit l bn knh

*
Corresponding author: Tel.: (+84) 915021575 Hnh 1. S nghin cu
Email: kien.letrung@hust.edu.vn
37
Tp ch Khoa hc v Cng ngh 116 (2017) 037-041

S nghin cu nh hnh 1. Phi 1 c t 2.3. Kt qu m phng


vo gia tm chn 2 v ci thy tnh. Khi cht lng
Bng phng php tim cn le, tin hnh chy
c bm vo trong lng ci tc dng trc tip ln b
cc bi ton trn my tnh, sn phm to hnh t
mt phi s lm bin dng phi theo hnh dng ci.
yu cu v hnh dng, kch thc.
2.1. Vt liu nghin cu
Xt trng hp bn knh gc ln ming ci
Vt liu s dng nghin cu l thp cn nng thy tnh rc = 2mm; ln lt bn knh y chi tit rct =
c ph lp kim loi (ZAM) vi thnh phn v tnh 1mm, 2mm, 3mm, 4mm v 5 mm. Quan h lc chn
cht nh sau [8]: v mc in y gc ln chi tit c ch trong
bng 2.
Bng 1. Thnh phn ho hc lp ph thp ZAM (%)

Zn Al Mg
91% 6% 3%
Bng 2.Thnh phn ho hc thp cn nng SPHC(%)

C Mn P S
0.15 0.60 0.050 0.050 Hnh 4. Chi tit hnh thnh khi rc = 2mm, rct = 2mm.
Gii hn chy ca vy liu thp ZAM c c Khi bn knh gc ln ming ci rc = 2mm,
nh th nghim ko trn my MTS809. tt c cc trng hp vi cc di lc chn khc nhau
Axial/Torsional Test System: u gy nn rch phi, khng in y c.

rc Lc chn Lc chn rct Tnh trng chi


(mm) nh nht ln nht (mm) tit
Q1 (kN) Q2 (kN)
0 25 1 khng y, rch
0 25 2 khng y, rch
2 0 25 3 khng y, rch
0 25 4 khng y, rch
Hnh 2. Th nghim ko mu vt liu v th quan 0 25 5 khng y, rch
h ng sut bin dng ca vt liu khi ko
Kt qu ko cho c = 300 MPa = 30kG/mm2
2.2. Xy dng m hnh hnh hc
Phng php phn t hu hn gn y c
pht trin phn tch v d on cc qu trnh, ng
sut v bin dng khi to hnh. Do , nhiu nghin
cu c thc hin bng cch s dng phng Hnh 5. Chi tit khi rc = 2mm, rct = 1mm, Q = 25kN
php phn t hu hn.
Khi bn knh gc ln ming ci rc = 3mm,
rct = 1mm, 2mm, 3mm chi tit khng th in y y
ci v b rch ti ming ci (hnh 5). Vi bn knh
y chi tit rct = 4mm v 5mm, chi tit to hnh t
kch thc v hnh dng yu cu, lc chn Q = (12
25) kN.

Hnh 3. Xy dng m hnh hnh hc


M hnh hnh hc c xy dng nh hnh 3.
ng knh chi tit 60 mm, chiu dy phi 0,8mm,
chiu su chi tit 25mm.
Hnh 6. Chi tit khi rc = 3mm, rct = 5mm, Q = 25 kN

38
Tp ch Khoa hc v Cng ngh 116 (2017) 037-041

Nhm thun li cho qu trnh thc nghim sau


ny, ta chuyn i p lc chn ln chi tit sang thng
s p sut trong lng xilanh chn. H thng thc
nghim c thit lp trn my p thy lc 125 tn
vi ng knh xi lanh cng tc 220mm. Trong qu
trnh thc nghim, ta s thit lp p lc chn theo
thng s p sut ny. Tin hnh iu chnh p sut xi
lanh chn P (gi tr P c h thng o p sut hnh
Hnh 7. Chi tit khi rc = 4mm, rct = 3mm. Q = 30 kN
trnh o v lu gi kt qu).
Trong tt c cc trng hp, khi bn knh chi
tit nh rct = 1mm khng th in y c ti gc
y chi tit, vi cc trng hp bn knh y chi tit
rct > 2mm th chi tit in y r dng hn.
Bng 3. Quan h gia lc chn v bn knh rct tng
ng vi cc gi tr bn knh gc ln ming ci rc.
Hnh 8. Chi tit khi rc = 5mm, rct = 3mm. Q = 40 kN rc Q1 P 1 Q2 P 2 rct Tnh trng chi
(mm) (kN) (bar) (kN) (bar) (mm) tit
0 0 25 5,3 1 khng y, rch
0 0 25 5,3 2 khng y, rch
2 0 0 25 5,3 3 khng y, rch
0 0 25 5,3 4 khng y, rch
0 0 25 5,3 5 khng y, rch
10 2,6 25 5,3 1 rch gc ln
Hnh 9. Chi tit khi rc = 6mm, rct = 3mm. Q = 50kN 10 2,6 25 5,3 2 rch gc ln
3 10 2,6 25 5,3 3 rch gc ln
12 3,2 25 5,3 4 t
12 3,2 25 5,3 5 t
19 5,0 30 7,9 1 Nhn, khng
in y
19 5,0 32 8,4 2 t
4
20 5,3 33 8,7 3 t
a - Min lm vic ca lc chn nh nht 20 5,3 35 9,2 4 t
20 5,3 35 9,2 5 t
22 5,8 45 11,8 1 Nhn, khng
in y
23 6,1 47 12,3 2 t
5
23 6,1 47 12,3 3 t
23 6,1 48 12,6 4 t
23 6,1 50 13,2 5 t
b - Min lm vic ca lc chn ln nht 35 9,2 50 13,2 1 Nhn, khng
Hnh 10. Min lm vic ca lc chn in y y
35 9,2 55 14,4 2 t
Ln lt thc hin vi cc bn knh gc ln 6
ming ci rc= 3mm, 4mm, 5mm v 6mm tng ng 35 9,2 55 14,4 3 t
vi bn knh gc ln y chi tit rct= 1mm, 2mm, 35 9,2 58 15,3 4 t
3mm, 4mm v 5mm ta c cc gi tr trong bng 3.
35 9,2 58 15,3 5 t

39
Tp ch Khoa hc v Cng ngh 116 (2017) 037-041

T cc kt qu bng 3, ta xy dng c min


lc chn ti thiu v min lc chn ti a ph thuc
vo bn knh gc ln ming ci rc v bn knh gc
ln chi tit rct. Min lm vic ca lc chn khi bn
knh gc ln ci, bn knh gc ln chi tit thay i
nm trong mt gii hn trn v mt gii hn di ca
cc mt lc chn nh nht v ln nht (hnh 10).
T hnh 10 ta thy rng bn knh gc ln chi
tit cng ln th min lc chn cng c m rng,
ng thi gi tr lc chn Q cng tng ln trnh
hin tng nhn do kh nng ko phi vo trong lng
ci d dng hn (ng sut hng knh gim i nh
vy theo Huber Mises th ng sut chn z phi tng
ln).
4. Thc nghim
Nhm kim chng cc kt qu m phng, thc
nghim c tin hnh cho trng hp bn knh ln Hnh 11. H thng thc nghim kim chng
ci rc = 4mm v bn knh chi tit rct = 2mm.
H thng thc nghim tin hnh trn my p
thy lc 125 tn cng vi h thng cp cht lng cao
p, cc thit b thu thp kt qu o v x l tn hiu.
Khun th nghim c tc gi ch to vi kch
thc lng ci nh trong bi ton m phng.
a - lch b -nhn vnh
ng knh lng ci: 60 mm
Bn knh gc ln ming ci: rc = 4 mm
Bn knh gc ln y: rct = 2 mm
Chiu su lng ci: 25 mm
H thng o p sut hnh trnh bao gm cm
bin K1 o p sut trong ci thy tnh, cm bin K2 o
p sut trong xilanh chn my p, cm bin hnh c - chi tit vi cc mc bin dng khc nhau
trnh o hnh trnh to hnh chi tit trong lng ci.
Cc tn hiu o c thu thp v x l tn hiu bng
my tnh.
t lc chn tng ng p sut xi lanh chn P 1
= 8 bar tng ng lc chn 30 kN.
Trn hnh 12a l hin tng lch do dng kim
loi khi ko vo lng ci khng u; trn hnh 12b l
hin tng nhn vnh v hnh dng phi cha t
c theo thit k do lc chn thp.
Trn hnh 12c th hin s thay i hnh dng
phi tng ng vi mi mc p sut khc nhau ln d - thu thp v x l tn hiu cc thng s p sut
lt l 300bar, 330 bar, 430 bar. Vi p sut 430 bar, hnh trnh
chi tit t yu cu to hnh in y gc chi tit, cn
hai trng hp p sut cn li do gi tr thp nn cha Hnh 12. Mt s hnh nh to hnh chi tit
t c v hnh dng yu cu. 5. Kt lun
Thc nghim cho thy kt qu tng ng vi Cc kt lun t nghin cu nh sau:
cc kt qu m phng. Mi quan h gia gi tr bn
knh gc ln ci, bn knh gc ln y chi tit v 1. Khi tng bn knh gc ln ming ci r c, lc
lc chn trong m phng l gi tr tham kho trong chn cn thit ti thiu v ti a tng sp x 45% khi
thc tin nhm gim cc bc tm cc bn knh ti u bn knh rc tng 1 n v. Nguyn nhn bao gm:
khi sn xut.

40
Tp ch Khoa hc v Cng ngh 116 (2017) 037-041

- Mt l do khi bn knh rc tng ln lm kh [3] A.G. Mamalis, D.E. et al., On the finite element
nng ko phi vo trong ci r dng hn, cn bng modelling of the deep-drawing of square sections of
ng sut bt buc phi tng ng sut chn ln. coated steels, Journal of Materials Processing
Technology 58 (1996), 153159.
- Hai l s mt n nh ti bn knh gc ln
[4] Taylan Altan (2006), Processes for hydroforming
ca ci gy nhn ti phn vnh khi tng rc, khng sheet metal 1,Stamping Journal, (Feb 2006), 40-41
mt n nh th phi tng gi tr lc chn khi tng rc.
[5] R. Narayanaswamy et al., A comparative study of
2. Vi bn knh gc ln y chi nh (1mm), deep drawing with conventional, isostatic, and
s in y l rt kh (do t s S/D ti bn knh gc hydrostatic pressure, Journal of Mechanical Working
ln ln). Khi tng bn knh gc ln chi tit rct ln Technology, 6 (1982) 227-234
mt n v, gi tr lc chn y thay i khng
[6] S.A. Zahedi et al., Investigation of conventional deep
ng k. in y cc bn knh gc ln chi tit th drawing and hydroforming deep drawing via
cn tng p sut cht lng trong lng ci p0. experimental and finite element simulation, Indian
Journal of Science and Technology, Vol. 3 No. 9 (
Ti liu tham kho
2010), 1009-1013.
[1] J.P. Fan et al., 3D finite element simulation of deep
[7] M. Jurkovi, I. Mamuzi, E. Karabegovi. The sheet
drawing with damage development, International
metal forming with Hydraulic fruid pressure.
Journal of Machine Tools & Manufacture 46 (2006),
Metalurgija 43 (2004), 315-322
10351044
[8] Nisshin Steel Quality Products, ZAM.
[2] Marcelo Elguela, Ductile damage analysis of sheet
metal forming, Journal of Materials Processing [9] Pha m Vn Ngh . Cng ngh d p thuy tin h, NXB
Technology 121 (2002), 148 156. Bach Khoa Ha N i, 2006.

41
Tp ch Khoa hc v Cng ngh 116 (2017) 042-046

Cng ngh ch to in cc hn
cho dy chuyn hn bn t ng xch neo tu hi qun
Welding Electrode Manufacturing Technology
for Marine Anchor Chain Flash Butt Welding Machine

Phng Tun Anh


Hc vin K thut Qun s - 236 Hong Quc Vit, Bc T Lim, H Ni.
n Ta son: 20-9-2016; chp nhn ng: 20-12-2016

Tm tt
Bi bo ny tin hnh nghin cu thc nghim ch to cc in cc hn t brng BCuNi3Si ( 1-3) cho
dy chuyn hn tip xc bn t ng xch neo tu hi qun. Thng qua thc nghim cc ch nu luyn
v nhit luyn hp kim BCuNi3Si c xc nh. Nhit c c xc nh trong khong (1170 oC -
1200 oC). Nhit ng u ha thnh phn thi c khong 90010 oC vi thi gian gi nhit 4 h. Nhit
rn phi in cc hn (750-900) oC. Sau rn, phi c kt tinh li nhit 60010 oC trong 2 h.
Nhit luyn kt thc bao gm ti v ha gi, trong , nguyn cng ti c thc hin nhit 850 oC,
ha gi nhit 450 oC vi thi gian gi nhit 4 h. Khi cng ca hp kim t 240 HV5, gii hn bn
nh nht t 757,9 MPa, gii hn chy nh nht t 559,8 MPa, gin di tng i nh nht t 8,5 %,
dn in nh nht t 35,4 % IACS. Cc in cc hn u t cht lng tng ng in cc hn
nhp khu i km theo dy chuyn hn.
T kha: in cc hn, hp kim BCuNi3Si ( 1-3), c tnh, cng, dn in.
Abstract
In this paper, a study on manufacturing technology of welding electrodes from CuNi3Si alloy for marine
anchor chain flash butt welding machine was reported. Remelting regime and heat treatment are clearly
determined through experimental process. Casting temperature was established in the range of (1170-1200)
oC. After casting, the alloy was homogenized at temperature 90010 oC for 4 hours. Forging temperature for

casting blank was in the range of (750-900) oC. After forging, the electrode blank was recrystallization
annealed at 60010 oC for 2 hours. Finish heat treatments for electrode blank consisted of solution heat
treatment and aging. The solution treatment temperature was set at 850 oC. Optimum aging temperature
appeared to be 450 oC and time at this temperature was 4 hours long. Then alloy reached the hardness of
240 HV5, minimum tensile strength of 757.9 MPa, minimum yield strength of 549.8 MPa, elongation at
fracture of 8.5 % and minimum electrical conductivity of 35.4 % IACS. Welding electrodes had absolutely
equivalent quality in comparison with accompaniment standard ones of butt welding machine.
Keywords: welding electrode, CuNi3Si alloy, mechanical properties, hardness, electrical conductivity.

1. t vn * bn v dn in cao sau nhit luyn thch hp, c


th thay th cho hp kim Cu-Be c nhc im l
Trong nhng nm gn y Vit Nam, nhu cu
nguyn t berili kh c mc d hp kim bn v
v in cc hn cho cc my hn tip xc ca cc nh
dn in cng kh cao [6,7]. Bi bo ny s tin
my ch to t, nh my c kh ngy cng ln. Ty
hnh nghin cu thc nghim v ch to in cc hn
theo nhu cu sn phm m in cc hn c cc hnh
t hp kim Cu-3,0Ni-1,0Si (BCu3NiSi) cho dy
dng khc nhau. Vt liu in cc ca cc my hn
chuyn hn tip xc bn t ng xch neo hi qun.
tip xc c ch to t cc hp kim ng bn nhit
v dn in cao hoc cc hp kim bt. Thuc v cc 2. Thc nghim
hp kim ng c th k n nh h Cu-Ni, Cu-Cr,
in cc hn ca dy chuyn thit b hn tip
Cu-Cr-Zr, Cu-Cd, Cu-Be, Cu-Ni-Si [1,2] Tuy
xc gip mi xch neo tu hi qun gm 4 chi tit c
nhin, hin nay mt hng ny ch yu c nhp
kch thc ngoi 165x85x50 mm (hnh 1), c ch
khu phc v sn xut. c mt s cng trnh
to t hp kim 1-3 (theo tiu chun Nga),
trong nc nghin cu v cc h hp kim Cu-Cr, Cu-
tng ng vi brng BCuNi3Si. y l cc chi tit
Cr-Zr.. [3-5], nhng cha c cng trnh no nghin
lm vic trong iu kin khc nghit, nhit tip
cu v hp kim h Cu-Ni-Si. y l hp kim c
xc vi chi tit hn ln n (700-900) oC nn i hi
cn c dn in cao v bn phi cao. Thnh
phn ha hc ca hp kim BCuNi3Si ch to in
*a ch lin h: Tel.: 0932.277.676;
Email: phungtuananhmta@gmail.com

42
Tp ch Khoa hc v Cng ngh 116 (2017) 042-046

cc hn c cho trong bng 1. C tnh yu cu ca mc M1 c hm lng 99,9 %, niken nguyn cht H-


sn phm in cc hn c cho trong bng 2 [1]. 1 c hm lng 99,93 %, silic nguyn cht mc 00
c hm lng 99,0 %. Trong qu trnh nu luyn, tr
dung to x bo v v tinh luyn c s dng c
thnh phn [35 % KCl + 25 % criolit (Na3AlF6) + 28
% Na2B4O7 + 10 % NaCl + 2 % than g]. Tr dung
sau khi cn theo thnh phn phi c nghin trn
u v sy kh nhit 300 oC. Lng tr dung
c dng chim khong 1 % khi lng m liu.
Than hoa (khong 2 % m liu) c ri ln b mt
kim loi lng trong qu trnh nu luyn hn ch
lng khng kh xm nhp vo bn trong kim loi
lng. Cht tinh luyn kh kh l hp kim brng
Hnh 1. B in cc hn xch neo tu hi qun photpho (Cu-P) vi hm lng P t (9-15) %. Lng
cht tinh luyn kh kh bng khong (0,1-0,3) % khi
Bng 1. Thnh phn ha hc hp kim BCuNi3Si
lng m liu. Nhit nu luyn hp kim c xc
( 1-3 theo 18175-78)
nh nm trong khong (1170-1200) oC.
Thnh phn ha hc, %
Sau khi kh kh t yu cu, tin hnh vt x v
Fe Si Mn Ni Al Pb Zn Sn Cu
iu chnh nhit kim loi lng n nh t khong
Cn
0,1 0,6-1,1 0,1 2,4-3,4 0,02 0,15 0,1 0,1 1170 oC chun b rt khun.
li
Bng 2. C tnh yu cu ca hp kim 1-3 lm
in cc hn
cng 0,2, b, , dn in,
HV5 MPa MPa % % IACS
170-220 - 500-600 6-8 34-38

Bng 3. Thnh phn ha hc trung bnh ca m nu


hp kim nghin cu

Zn Pb Sn Fe Ni Si Cr Al Ti Cu
0,10 0,01 0,01 0,05 3,07 1,00 0,01 0,03 0,02 95,7
Hnh 2. T chc t vi hp kim BCuNi3Si sau c
Qu trnh thc nghim bt u bng vic tnh
ton phi liu, nu luyn v c thi hp kim
BCuNi3Si trong l nu in tr Nabertherm (c).
Phi c sau khi ct u rt c ng u ha
thnh phn, sau tin hnh rn nng v kt tinh
li chun b t chc cho nghin cu xc nh ch
nhit luyn kt thc. Sau nhit luyn, tin hnh gia
cng c kh ch to hon chnh b in cc hn cho
thit b hn xch neo tu hi qun. Phng php
nghin cu ch yu gm o cng HV5 (c xc
nh trn my o cng Vickers Wilson Wolpert
Trung Quc), o dn in (c xc nh thng Hnh 3. T chc t vi hp kim BCuNi3Si sau ng
qua o in tr ca mu trn thit b Megger Digital nht
Microhmmeter DLRO-10 Anh Quc) v th ko
xc nh cc ch tiu c tnh (c tin hnh trn my Khun kim loi c chun b sn v sy
th ko nn vn nng 60T Trung Quc). trc t nhit (300-400) oC. Qu trnh rt phi rt
t t kim loi lng in y khun v b ngt kp
3. Kt qu v tho lun thi. Do h s co ngt ca hp kim kh ln nn cn
3.1. Nu luyn v c phi in cc hn rt vi tc chm nhng lin tc trnh khuyt
tt, giai on cui tc rt cng chm cng tt
Vt t nu luyn bao gm Cu nguyn cht mc m bo lng kim loi b ngt, trnh co ngt
M1 v cc hp kim trung gian CuSi10, CuNi15 c mnh to lm co ln dn n ph phm.
sch cao c nu luyn trc t ng nguyn cht

43
Tp ch Khoa hc v Cng ngh 116 (2017) 042-046

Hp kim nu luyn c c thnh phn ha hc th hai ha tan vi mc ha tan kh t vo pha nn


nh ch ra trong bng 3, tng ng vi hp kim giu ng v cha to thnh dung dch rn qu bo
1-3 theo 18175-78. ha, cng sau ti khong 95 HV5 (hnh 5). Khi
nung ti nhit 850 oC, mc ha tan cc pha
3.2. ng u ha thnh phn thi c
th hai tng ln r rt, cng gim xung cn 90,1
Sau khi rt c xong, phi c ngui dn, sau HV5 (hnh 6), t chc mt pha kh ng u. Tng
tho khun, ct u ngt v tin hnh ng u nhit ti ln 875 v 900 oC, mc ha tan ca
ha thnh phn. Nhit ng u l 90010 oC cc pha th hai t cao nht, cng ca hp kim
vi thi gian gi nhit 4 h, sau ngui theo l. gim xung cn 85,1 v 79,8 HV5 tng ng, tuy
T chc t vi sau c v sau ng u c cho nhin cc ht tr nn th to, nh hng xu n c
trn hnh 2 v hnh 3. tnh sau cng ca sn phm. Do vy, nhit ti tt
nht nn chn l 850 C.
3.3. Rn v kt tinh li phi in cc hn
3.4.2. Xc nh nhit ha gi
Phi sau c c kch thc 195x90x55 mm
c ct u ngt v chuyn sang rn t do theo c i vi cc hp kim h Cu-Ni-Si, nhit ha
ba chiu nhm chun b t chc bin dng cho gi thng la chn trong khong (400-550) oC [8].
nguyn cng nhit luyn kt thc. Nhit bt u i vi hp kim nghin cu BCuNi3Si, xc nh
rn khong 900 oC v nhit kt thc rn khng nhit ha gi ti u, tin hnh thc nghim ha gi
di 750 oC. Sau rn ln 1, phi c kch thc cc nhit la chn l 425, 450, 475, 525 oC trong
167x98x55 mm. Tip tc nung nng tr li 900 oC v l ram, ha gi Nabertherm (c). Cc tham s nh
rn ln 2, kch thc t 170x90x59 mm. Nung nng gi cht lng ha gi bao gm cng HV5 c
tr li 900 oC v rn ln 3, sau rn phi in cc t do trn my o cng Vickers Wilson Wolpert
kch thc 180x90x55 mm. (Trung Quc) v dn in (% IACS) c o
thng qua thit b o in tr Megger Digital
Sau nguyn cng rn, phi in cc hn b bin
Microhmmeter DLRO-10 (Anh).
cng v tn ti ng sut d ln. Cn tin hnh kt
tinh li kh ng sut d do rn v to t chc tt
nht cho nhit luyn kt thc. Nhit kt tinh li
l 60010 oC vi thi gian gi nhit l 2 h. T chc t
vi hp kim sau kt tinh li c ch ra trn hnh 4.

Hnh 5. T chc t vi mu hp kim khi ti nhit


825 oC

Hnh 4. T chc t vi hp kim sau kt tinh li


60010 oC
3.4. Nhit luyn kt thc in cc hn
3.4.1. Xc nh nhit ti
i vi cc hp kim h Cu-Ni-Si, ty thuc vo
thnh phn c th ca tng hp kim m la chn
nhit ti thch hp, tuy nhin, khong nhit
c la chn thng nm trong khong (800-900) Hnh 6. T chc t vi mu hp kim khi ti nhit
o
C [8]. i vi vt liu ch to chi tit in cc hn 850 oC
t hp kim BCuNi3Si, xc nh nhit ti ti u, Khi ha gi nhit 425 oC, cng ca mu
tin hnh thc nghim ti cc nhit 825, 850,
hp kim tng dn theo thi gian v t gi tr cc i,
875 v 900 oC trong l ti Nabertherm (c). Thc
sau gim xung, tng ng vi giai on thi bn.
nghim cho thy, khi ti nhit 825 oC, cc pha

44
Tp ch Khoa hc v Cng ngh 116 (2017) 042-046

Trn hnh 7, gi tr cc i cng ca mu t


255 HV5 khi ha gi 425 oC sau 4,5 h.
Khi ha gi cc nhit cao hn 425 oC,
cng ca hp kim vn tng ln theo thi gian v t
nh cc i sm hn, nhng gi tr cc i cng
khi ha gi nhit cao u thp hn v gim dn.
nhit 450 oC, cc i cng t 240 HV5 sau
4 h ha gi, 475 oC t 221 HV5 sau 3h ha gi.
525 oC, cc i cng t 196 HV5 sau 2 h ha gi.
S thay i dn in ca hp kim sau ha gi
cc nhit v thi gian khc nhau c ch ra trn
Hnh 7. cng ca hp kim sau ti 850 oC v ha hnh 8. cng nhit ha gi, dn in tng ln
gi cc nhit khc nhau theo thi gian ha gi v sau khi t gi tr cc i,
dn in li gim xung. Khi ha gi 425 oC,
cc i dn in t 36,3 % IACS sau 8h ha gi.
450 oC, dn in t cc i 36,7 % IACS sau 6
h ha gi. dn in t gi tr cao nht 37,8 %
IACS khi ha gi 475 oC sau 8 h ha gi do s tit
ra pha ha bn -Ni2Si vi s lng nhiu. Chnh
iu ny lm cho nn ng tr nn sch hn dn n
dn in ca hp kim tng ln. Tuy nhin 500 oC
v ln hn, ngoi cc pha -Ni2Si cn c lng nh
pha -Ni5Si2 c tit ra, dn in ca hp kim li
gim xung [9]. 525 oC dn in t cc i
36,1 % IACS sau 6 h ha gi.

Hnh 8. dn in ca hp kim sau ti 850 oC v Nh vy c th thy, cng ca hp kim


ha gi cc nhit khc nhau BCuNi3Si t gi tr cao nht khi ha gi 425 oC
sau 4,5 h, cn dn in t gi tr cao nht khi ha
gi nhit 475 oC sau 8 h. La chn ch nhit
luyn thch hp cho cc chi tit ch to t hp kim
ny s c cn c vo iu kin lm vic c th ca
chi tit . Khi p dng i vi chi tit in cc hn
cho dy chuyn hn xch neo, yu cu v tnh bn
nhit c t ln cao hn do in cc thng xuyn
tip xc vi chi tit c nhit ln n (700-900) oC,
bn cnh tnh dn in cng phi cao, do
nhit ha gi la chn tt nht l 450 oC vi thi
gian gi nhit nhit ha gi l 4 h. Khi ,
cng hp kim t 240 HV5, dn in tng ng
Hnh 9. T chc t vi ca hp kim in cc hn khi t gi tr 36,5 % IACS.
ha gi 450 oC sau 4 h
T chc t vi v nh nhiu x tia X ca hp kim
in cc hn khi ha gi 450 oC sau 4 h c ch ra
trn hnh 9 v 10. Theo [9], khi ha gi nhit
(425-475) oC, pha ha bn tit pha trong hp kim
BCuNi3Si hon ton l pha -Ni2Si. Phn tch nh
nhiu x tia X (hnh 10) cho thy, trong t chc ca
hp kim ch thy xut hin pha -Ni2Si, khng thy
s c mt ca cc pha -Ni3Si2 v -Ni5Si2.
Cc ch tiu c tnh v dn in ca hp kim
BCuNi3Si sau ti 850 oC v ha gi 4 h 450 oC
c cho trong bng 4 v u tha mn yu cu i
vi in cc hn (xem bng 2) khi th nghim trn
Hnh 10. Gin nhiu x tia X ca hp kim in thit b hn xch neo tu hi qun.
cc hn khi ha gi 450 oC sau 4 h

45
Tp ch Khoa hc v Cng ngh 116 (2017) 042-046

Bng 4. C tnh v dn in ca in cc hn sau Ti liu tham kho


nhit luyn
[1]. . ., . .
cng 0,2, b, , dn in, . .:
TT Mu , 1972.
HV5 MPa MPa % % IACS
1 M1 231,4 560,4 778,7 8,5 35,4 [2]. Hongyan Zhang , Jacek Senkara. Resistance
2 M2 228,0 551,1 765,5 9,2 36,3 Welding: Fundamentals and Applications. CRC
3 M3 234,5 549,8 757,9 10,0 36,2 Press, Second Edition, 2011.
4 M4 240,0 555,1 769,5 9,0 35,7 [3]. Nguyn Vn Chin. Nghin cu v sn xut cc loi
hp kim ng bn nng lm bnh xe hn v cc
4. Kt lun hn. Bo co tng kt ti cp B Cng thng
Trn c s nghin cu thc nghim nu 2004.
luyn c mc vt liu BCuNi3Si tng ng vi [4]. Phm B Kim. Nghin cu cng ngh sn xut hp
mc hp kim 1-3 ( 18175-78) t cc kim trung gian Cu-Zr-Mg, Cu-Cr bng phng php
nguyn vt liu sn c trong nc l Cu nguyn cht, nhit nhm. Bo co tng kt ti cp B Cng
Ni nguyn cht, Si nguyn cht v ch to b in thng 2006.
cc hn cho thit b hn xch neo tu hi qun. Cng [5]. Phm B Kim. D n sn xut th nghim in cc
ngh ch to c th nh sau: hn t hp kim ng bn nhit h Cu-Cr-Zr. Bo co
- Nhit c: (1770-1200) oC. tng kt d n cp B Cng thng 2009.
- Nhit ng u ha thnh phn: 900 oC.
[6]. H. Tsubakino, R. Nozato, A. Yamamoto.
- Nhit rn phi: 900 oC. Precipitation sequence for simultaneous continuous
- Nhit kt tinh li sau rn: 600 oC. and discontinuous modes in CuBe binary alloys.
- Nhit luyn kt thc bao gm ti 850 oC v Materials Science and Technology, Volume 9, Issue 4
ha gi nhit 450 oC vi thi gian gi nhit 4 h. (1993), pp. 288-294.
Sau nhit luyn kt thc, cng ca hp kim
[7]. Djuric B, Jovanovic M, Drobnjak DJ. A study of
t 240 HV5, gii hn bn (min.) t 757,9 MPa, gii precipitation in Cu-Be alloys. Metallography, 13
hn chy (min.) t 549,8 MPa, gin di tng i (1980), pp.235-247.
(min.) t 8,5 %, dn in nh nht t 35,4 %
IACS. [8]. Corson M. G. Electrical conductor alloys [J].
Electrical World, 89 (1927), pp. 137-139.
in cc c lp t v lm vic lin tc
[9]. Lu, De-ping, Wang, Jun, Atrens, A., Zou, Xing-quan,
trn dy chuyn hn tip xc bn t ng xch neo Lu, Lei and Sun, Bao-de. Calculation of Cu-rich part
trong mt thi gian di trong iu kin khc nghit, of Cu-Ni-Si phase diagram (J). Transactions of
nhit tip xc vi chi tit hn ln n (700-900) oC Nonferrous Metals Society of China, 17 (2007), pp.
m vn cha thy hin tng hng hc, bin dng 12-15.
hay thi bn. Cht lng in cc hn ch to c
hon ton tng ng vi in cc hn nhp khu i
km theo dy chuyn thit b hn.

46
Tp ch Khoa hc v Cng ngh 116 (2017) 047-051

Numerical Investigation of Solidification around a Circular Cylinder with


the Presence of the Free Surface in a Rectangular Cavity
Nghin cu m phng s qu trnh ha rn xung quanh tr trn vi s hin din ca mt thong trong
mt khoang hnh ch nht

Vu Van Truong*, Truong Viet Anh


Hanoi University of Science and Technology, No. 1, Dai Co Viet, Hai Ba Trung, Hanoi, Viet Nam
Received: June 06, 2016; accepted: December 20, 2016

Abstract
This paper presents numerical simulation of solidification around a cooled circular cylinder with the presence
of a free surface in a rectangular cavity. The free surface is introduced to account for volume change due to
density difference between the solid and liquid phases during solidification. Pure tin with the solid-to-liquid
density ratio sl = 1.05 (shrinkage) is investigated as a phase change material. The front-tracking method
combined with an interpolation technique, in which the interface separating two phases is represented by
connected elements laid on a stationary grid, is used for solving the problem. The case of no volume change,
i.e., sl = 1.0, is also calculated and compared with the case of sl = 1.05 to see how volume shrinkage
affects the solidification process. The numerical results show that shrinkage reduces the solidification rate,
and thus results in a decrease in the form, i.e., the area, of the solid layer around the cylinder. In addition,
the liquid level decreases in time due to volume shrinkage upon solidification.
Keywords: Numerical simulation, Front-tracking, Solidification, Shrinkage, Circular cylinder
Tm tt
Bi bo gii thiu m phng s qu trnh ha rn xy ra xung quanh mt tr trn c lm lnh vi s hin
din ca mt thong trong mt khoang hnh ch nht. Mt thong c a vo b vo s thay i v
th tch do s khc nhau v khi lng ring gia pha lng v pha rn trong qu trnh ha rn. Thic
nguyn cht vi t s khi lng ring gia pha rn v pha lng sl = 1.05 (co th tch) c nghin cu nh
l mt vt liu chuyn pha. Phng php theo du bin kt hp vi k thut ni suy m bin phn cch
gia hai pha c biu din bi cc on thng lin kt, c s dng cho vic gii bi ton. Trng hp
khng c s thay i v tch vi sl = 1.0 cng c tnh ton v so snh vi sl = 1.05 thy c nh
hng ca s co th tch n qu trnh ha rn. Kt qu m phng cho thy, s co th tch lm gim tc
ha rn, v ko theo gim s hnh thnh ca min rn xung quanh tr. Thm vo , mc mt thong gim
dn theo thi gian do s co li v th thch trong qu trnh ha rn.
T kha: M phng s, Theo du bin, Ha rn, Co th tch, Tr trn

1. Introduction* complicated system in which there exist three or more


cylinders has been investigated by Sugawara and
Solidliquid phase change finds application in
Beer [2]. In another work [3], an enthalpy
many systems and in nature including latent heat
formulation-based fixed-grid approach was employed
energy storage, metallurgy, and food and
to investigate the solidification around a number of
pharmaceutical processing. Solidification around
staggered cylinders. However, in the above-
cooled cylinders appears in thermal energy storage
mentioned papers, the results were restricted to
systems, metal casting and others. Therefore,
indentical densities of the solid and liquid phases. It
understanding solidification heat transfer around
has been reported that density differerence between
cooled cylinders plays an important role in designing
the solid and liquid phases, which causes volume
and operating such systems. Accordingly, there have
change upon solidification, may have strong effects
been many works concerned with solidification
on the final solidified products [4,5]. To account for
around cylinders. Sasaguchi and co-workers [1]
this effect, it is neccessary to include a gas phase to
presented a numerical method for the solidliquid
the problem, i.e., there is the presence of the free
phase change around a single cylinder and two
surface. The investigations considering such above-
horizontal cylinders in a rectangular cavity. A more
mentioned aspects have not been reported in
liturature.
*
Corresponding author: Tel.: (+84) 915.058.146
Email: truong.vuvan1@hust.edu.vn
47
Tp ch Khoa hc v Cng ngh 116 (2017) 047-051

In the present study, we present numerical of the one-fluid representation, the momentum and
investigations for solidification around a cooled thermal energy equations are
cylinder with natural convection and with the
presence of the free surface. The method utilizes the u t uu p ( u uT )
front tracking technique [6] to represent the solid
liquid interface and an interpolation technique, i.e., an +f n f ( x x f )dS g T Tm (1)
f
immersed boundary method, to deal with the no-slip
and constant isothermal temperature boundary C pT t C pTu k T
conditions [4]. Pure tin with the solid phase denser
q x x f dS C p h
than the liquid phase, i.e., with volume shrinkage
(2)
upon solidification, is used as an investigated phase f
change material.
2. Numerical problem and method u 1 s 1 l x x f qdS Lh (3)
f

Fig. 1 shows the investigated problem, a Here, u is the velocity vector, p is the pressure, g is
solidification layer forming around a cooled circular the gravitational acceleration, and t is time. T and the
cylinder held at temperature Tc with a free surface in superscript T denote the temperature and the
a rectangular cavity. The diameter of the cylinder is transpose. D/Dt is the material derivative. f is the
denoted by d. The fusion temperature of the liquid (or momentum forcing term used to impose the no-slip
melt) is Tm greater than Tc. Initially, the gas and liquid condition on the solidliquid interface, and h is the
phases are at temperature T0 (T0 Tm). To save the energy forcing term used to impose a constant
computations, the half of the physical domain is temperature on the cylinder boundary [4]. The fourth
investigated as shown in term on the right-hand side of Eq. (1) accounts for the
Fig. 1a. The fluid and thermal properties of each interfacial tension force at the free surface [7]. The
phase are assumed constant, and the presence of the last term in Eq. (1) is the Boussinesq approximation
gas phase (i.e., free surface) is to account for volume for density changes due to thermal gradients [8],
change due to density difference between the solid and is the thermal expansion coefficient of the
and liquid phases during solidification. The fluids fluids. At the interfaces, denoted by f, is the
assumed incompressible are driven by buoyancy- interfacial tension acting on the liquidgas front. is
induced natural convection, i.e., Bussinesq twice the mean curvature, and nf is the normal vector
approximation. We treat all phases as one fluid with to the interface. The Dirac delta function (x xf) is
variable properties such as density , viscosity , zero everywhere except at the interfaces xf. q is the
thermal conductivity k and heat capacity Cp. In terms heat source at the solidification interface, given as

Fig. 1. Solidification around a cooled cylinder with the free surface in a rectangular cavity: (a) computational
domain; and (b) front-tracking representation for the solidification and free surface interfaces.

48
Tp ch Khoa hc v Cng ngh 116 (2017) 047-051

T T Accordingly, the values of the material property


q ks kl sVn Lh (4) fields at every location are given as
n s n l

where the subscripts s, l and g (when available) g I l 1 I l l I s 1 I s s (7)


represent solid, liquid and gas, respectively. Vn is the
velocity normal to the solidification front and Lh is where stands for , Cp, or k. A more detailed
the latent heat. description of the method used in this study can be
found in [4].
These above-mentioned equations are solved by
the front-tracking method combined with 3. Numerical parameters
interpolation techniques on a staggered grid with We choose the diameter d of the cylinder as a
second order accuracy in time and space [4]. The scaling length, and c l Cl d 2 kl as the
momentum, energy and mass conservation equations
characteristic time scale. The characteristic velocity
are discretized using an explicit predictor-corrector
time-integration method and a second-order centered scale is taken to be U c d c . With these above
difference approximation for the spatial derivatives. choices, the dynamics of the problem is governed by
The discretized equations are solved on a fixed, the following dimensionless parameters: Prandtl
staggered grid using the MAC method [9]. The number Pr, Stefan number St, Rayleigh number Ra,
interface between two phases is represented by finite Weber number We, initial dimensionless temperature
discrete points, on a stationary grid as shown in of the liquid 0, density ratios sl and gl, viscosity
Fig. 1b, that are updated by ratio gl, thermal conductivity ratios ksl and kgl, heat
capacity ratios Cpsl and Cpgl, and expansion
xnf 1 xnf n f V t (5) coefficient ratio gl:
where the superscripts n and n+1 are the current and C C T T g l ( Th Tm )d 3C pl 2
Pr pl l ,St pl m c ,Ra , l

next time levels. V is the velocity interpolated from kl Lh l kl


the fixed velocity field for the points on the liquid lU c2 d T T
gas interface, and Vn for the points on the solidifying We , 0 0 c , sl s , gl g ,
Tm Tc l l
interface given by Vn q f s Lh . Positions of the g kg C ps g g
k
liquidgas points are used to determine an indicator gl ,ksl s ,k gl ,C psl , gl (8)
l kl kl C pl l l
function Il which is zero in the liquid and one in the
gas, and positions of the solidliquid points are used The temperature is non-dimensionalized as
to determine an indicator function Is which is zero in T Tc Tm Tc . The dimensionless time is =
the solid and one in the liquid. The general equation t/c.
for reconstructing Is,l is

I x x f n f dS (6)
f

Fig. 2. Evolution of the solidification layer around the cooled cylinder with sl = 1.05. In each frame, the left
shows the velocity field normalized by Uc, and the right shows the isotherms plotted every = 0.1

49
Tp ch Khoa hc v Cng ngh 116 (2017) 047-051

As previously mentioned, in this study, we focus large, resulting in a high solidification rate, i.e., high
only on the effects of volume change (sl) and thus Vn , and high Nusselt number (Fig. 3). When the
other parameters are kept constant, i.e., Pr = 0.01, St temperature in the liquid phase decreases and reaches
= 0.02, Ra = 1104, We = 510-4, 0 = 1.42, gl = gl the fusion temperature m, the temperature gradient
= 0.05, ksl = 1.0, kgl = 0.005, Cpsl = Cpgl = 1.0, and gl
= 0.003. The values of these parameters correspond to drops down, and Vn and Nu decrease (Fig. 3).
pure tin with the cylinder diameter d of a few
centimetres. The computational domain is WH =
2d7d with a grid resolution of 64224. The cylinder
center is at x = 0, y = 2.5d, and the initial level of the
liquid is 5.5d. Method validations have been
extensively carried out in our previous works [4,7],
and thus are not presented in this paper.
4. Results and discussion
Fig. 2 shows the temporal evolution of the
solidifying and liquidgas fronts with the temperature
and velocity fields. The density ratio sl is set to 1.05.
This density ratio is for tin. At early times of the
solidification process, downward flow arises along
the solidliquid interface, at which the temperature is
m = 1.0, because the density of the liquid increases Fig. 3. Variations of the average solidifying velocity
with a decrease in the temperature. As shown in the and of the space-average Nusselt number at the
left frame ( = 0.6) of Fig. 2, the downward flow is solidification interface with respect to time ( sl =
strong with the cooled liquid accumulating at the 1.05).
bottom part of the cavity. As a result, a thermally
stratified region is formed. At later time = 4 (middle
frame of Fig. 2), the flow decreases and three
circulations with the strongest one at the bottom form.
These circulations are induced by buoyancy, i.e., the
last term in Eq. (1). As time progresses, the
temperature of the liquid phase decreases to near the
fusion temperature m. Consequently, the flow is
suppressed. At = 56 (right frame of Fig. 2), the
liquid temperature is uniform in the entire cavity, and
almost no flows are evident at this time, and the
solidification process is merely controlled by
conduction.
For tin, the solid is denser than the liquid, i.e.,
sl = 1.05, and this causes volume shrinkage during
solidification. Accordingly, looking at the level of the
liquid in the cavity, we can see that it decreases with
time as shown in Fig. 2.
Fig. 3 shows the temporal variations of the
average of the normal velocity of the solidifying
Fig. 4. Solidifying front and free surface location at
interface, and of the space-averaged Nusselt number,
= 60 for sl = 1.0 (left) and sl = 1.05 (right).
at the sodifying interface, defined as
Lf
To consider how volume change affects the
1 solidification process, we also perform simulation of
Nu
Lf
0
dl
n f
(9)
a case with no density difference, i.e., sl = 1.0, and
compare its results with those for sl = 1.05, as shown
where Lf is the length of the solidifying interface. in
During the initial stages of solidification, the
temperature gradient at the solidifying interface is

50
Tp ch Khoa hc v Cng ngh 116 (2017) 047-051

Fig. 4. We can see that at this time as sl solidication rate, and thus results in a decrease in the
decreases from 1.05 to 1.0 the solid layer forming form, i.e., the area, of the solid layer around the
around the cylinder is wider. This indicates that the cylinder. In addition, the liquid level decreases in
solidification rate decreases as sl increases. This is time due to volume shrinkage. The results for sl =
confirmed by Fig. 5, in which the area of the solid 1.2 are also presented.
phase increases with a decrease in sl from 1.2 to 1.0 Acknowledgments
(one more case of sl = 1.2 has been calculated to
show the effects of volume shrinkage). This is This research is funded by Vietnam National
understandable since there is flow induced by density Foundation for Science and Technology
difference between the solid and liquid, coming to the Development (NAFOSTED) under grant number
solid layer to compensate [7,10] for sl = 1.05 and 1.2 107.03-2014.21.
(volume shrinkage). This flow reduces the References
solidification rate. Accordingly, the solid layer
forming around the cylinder decreases for the case of [1] K. Sasaguchi, K. Kusano, R. Viskanta, A numerical
shrinkage. In addition, as prevously mentioned, the analysis of solid-liquid phase change heat transfer
around a single and two horizontal, vertically spaced
level of the liquid phases decreases with time for the
cylinders in a rectangular cavity, Int. J. Heat Mass
case of shrinkage while it does not change in the case Transfer. 40 (1997) 13431354.
of no volume change, i.e. staying at 5.5d, as shown in
Fig. 5. Fig.5 also indicates that increasing this density [2] M. Sugawara, H. Beer, Numerical analysis for
ratio results in a faster decrease in the liquid level. freezing/melting around vertically arranged four
cylinders, Heat Mass Transfer. 45 (2009) 12231231.
[3] Y.-C. Shih, H. Chou, Numerical study of solidification
around staggered cylinders in a fixed space, Numer.
Heat Tr. A-Appl. 48 (2005) 239260.
[4] T.V. Vu, A.V. Truong, N.T.B. Hoang, D.K. Tran,
Numerical investigations of solidification around a
circular cylinder under forced convection, J. Mech.
Sci. Technol. 30 (2016) 50195028.
[5] S. Sablani, S.P. Venkateshan, V.M.K. Sastri,
Numerical study of two-dimensional freezing in an
annulus, J. Thermophys. Heat Tr. 4 (1990) 398400.
[6] T.V. Vu, G. Tryggvason, S. Homma, J.C. Wells, H.
Takakura, A front-tracking method for three-phase
computations of solidification with volume change, J.
Chem. Eng. Jpn. 46 (2013) 726731.
[7] T.V. Vu, G. Tryggvason, S. Homma, J.C. Wells,
Fig. 5. Temporal variations of the level of the liquid Numerical investigations of drop solidification on a
phase and the area of the solid layer As around the cold plate in the presence of volume change, Int. J.
Multiphase Flow. 76 (2015) 7385.
cylinder for sl = 1.0, sl = 1.05, and sl = 1.2. Ac is
the area of the cylinder. [8] H. Gan, J. Chang, J.J. Feng, H.H. Hu, Direct
numerical simulation of the sedimentation of solid
5. Conclusion particles with thermal convection, J. Fluid Mech. 481
(2003) 385411.
We have presented the numerical results of
solidification around a cooled cylinder in a cavity [9] F.H. Harlow, J.E. Welch, Numerical calculation of
with the presence of volume shrinkage. To account time-dependent viscous incompressible flow of fluid
for volume change during solidification, a gas phase with free surface, Phys. Fluids. 8 (1965) 21822189.
was introduced at the top of the domain. Tin with sl [10] V.V. Truong, Direct numerical simulation of
= 1.05 was considered as a phase change material. solidification with effects of density difference,
The case of no volume change, i.e., sl = 1.0, was also Vietnam Journal of Mechanics. 38 (2016) 193204.
calculated and compared with the case of volume
change to demonstrate the effect of volume change on
the solidication process. The front-tracking method
combined with the interpolation technique [4] was
used for solving the problem. The numerical results
show that the presence of shrinkage reduces the

51
Tp ch Khoa hc v Cng ngh 116 (2017) 052-057

Nghin cu kho st kh nng phn tch ph liu da thuc


ca sn xut giy thnh vt liu c cu trc dng x
Primarily Study on Spliting Ability of Scrap Leather of Shoe Manufacturing into Fiber Form Materials

on Anh V 1*, Dng Th Hon 1,2


1
Trng i hc Bch khoa H Ni, S 1, i C Vit, Hai B Trng, H Ni, Vit Nam
2
Trng i hc cng nghip Dt May H Ni, L Chi, Gia Lm, H Ni, Vit Nam
n Ta son: 24-8-2016; chp nhn ng: 20-12-2016

Tm tt
Bi bo nghin cu kh nng phn tch ph liu da thuc dng mnh hnh thnh trong qu trnh sn xut
giy da thnh cc dng vt cht c cu trc x bng cc phng php khc nhau. Loi ph liu c la
chn nghin cu l da b ct v da b vng c s dng rng ri trong sn xut giy ti Vit Nam. Cc
cng ngh phn tch p dng l: nghin x kh trc tip bng phng php c hc s dng my nghin
ba v nghin x t c tin x l bng NaOH v H2SO4 trong cc iu kin nng v thi gian khc
nhau. Kt qu nghin cu thu c cho thy c hai loi da nu trn u c kh nng phn tch thnh cc
dng vt cht dng x bng c hai phng php nghin kh v nghin t. Phng php nghin x t s
dng tin x l bng H2SO4 c kh nng to thnh x vi ng knh nh hn 100 m v chiu di ti vi
cm. Trong khi , tin x l bng NaOH ch ph hp vi da vng v ch nn c s dng nng thp
v thi gian x l ngn. Phng php nghin x trc tip bng my nghin ba c tc nghin nhanh, x
thu c c ng knh nh (nh hn 0.1mm) v ng u nhng chiu di ngn hn so vi phng php
s dng H2SO4. Cc kt qu thu c l c s quan trng la chn phng php nghin ph hp nhm
a cc ph liu da thuc dng mnh thnh dng x ng dng trong vic ch to cc loi vt liu ti
ch.
T kha: X da, Nghin x da thuc, Da thuc ph liu
Abstract
In this research, methods for dissociation of leather fibres from scrap leather pieces of shoe manufacturing
are studied. The types of scrap used are grain and corium cow leathers which are materials for common
shoe making in Vietnam. Dissociation techniques used include: (1) dry crushing by mechanical methods
using a hammer mill and (2) chemical pretreatment - assisted wet milling using NaOH and H2SO4 at various
concentrations and retention time. Experimental results showed that both types are able to dissociate into
fiber form materials by the wet and dry grinding methods. Wet grinding method using the pretreatment in
H2SO4 is capable of forming fibers with less than 100 micron in diameter and up to several centimeters in
length. Meanwhile, pretreatment with NaOH is only suitabe with curium leather and should only be used in
low concentrations and short processing time. Grinding directly by hammer mill is fast and helped obtained
fibres with small diameter (less than 0,1mm) but the length is shorter than those obtained from the H 2SO4
method. These results are important for choosing the suitable crushing method in order to transform scrap
leather into fiber form to be used for recycle materials production.
Keywords: Leather fiber, Leather grinding, Scrap leather

1. Tng quan nhin no c c nh tnh n hi, tnh do, bn,


gin v cc tnh cht v sinh.
Trn*th gii, vic ti s dng cc ph thi ca
vt liu t nhin dng x lm cht n cho cc loi Da thuc trong sn xut giy thng ch yu l
vt liu t hp ang l mt xu hng c quan tm. da b ct v da b vng [3]. Cc loi da thuc ph
y chnh l bin php c bn nht ang s dng liu thng dng mnh vi kch thc ln (c cm)
gii quyt ti ch ph liu da thuc ca cng on sn v khng ng u. Chnh v vy, trc khi s dng
xut giy [1-3]. Gii php ny khng nhng gii phi trn vi cc nn polime to vt liu t hp th
quyt c vn mi trng m cn tn dng c chng phi c nghin x thnh dng kch thc
x da vi cc c tnh u vit m khng c loi x t nh (dng x, dng ht, dng bt). Cc nhm nghin
cu trn th gii tin hnh nhiu phng php
chuyn ha da ph liu thnh cu trc dng x.
*
a ch lin h: (+84) 936 270 437
Nhm nghin cu ca Olszewska [4] tin
Email: vu.doananh@hust.edu.vn
52
Tp ch Khoa hc v Cng ngh 116 (2017) 052-057

hnh phn r da thuc crom theo nhiu giai on khc v Cng ty Giy Thy Khu. Cc ha cht c bn
nhau thu c cc bo da v ht da mi lm c s dng lm tc nhn tin x l da trc khi
nguyn liu ch to cc vt liu polime compozit c nghin l NaOH v H2SO4 c xut x Trung Quc.
kh nng phn hy sinh hc.
2.2 Ni dung nghin cu v qui trnh thc nghim
Santana v Moreno [5] tin hnh nghin x
2.1.1 Nghin x da theo phng php t:
ph liu da nappa ca qu trnh sn xut giy bng
my nghin ba c kch thc mt sng l 1,5 mm Trc tin cc mu da ph liu c s loi v
thnh cc x da. Cc x da thu c tip tc c s ct ng u ha s b v kch thc sau c
dng ch to vt liu lai ha. tin hnh ngm trong mi trng ha cht cc iu
kin nng v thi gian khc nhau. Mi trng tin
Trong mt nghin cu khc, Madera Santana v
x l trc khi nghin s dng l axit (H2SO4) v
cng s [5], tin hnh nghin da thuc crom thnh
kim (NaOH). Thit b nghin c s dng l thit
cc b vi x v dng lm cht n ch to cc chi
b hot ng theo nguyn l dao ct.
tit giy ti ch.
Tin x l c thc hin dung t 1:50 trong
Nhm nghin cu ca Nahar thuc i hc
iu kin nhit thng. Thi gian lu ca mu
Malaya, Malaysia [6] tin hnh ti ch cc loi da
c thc hin 3 mc khc nhau l 2h, 3h v 4h.
thuc bng cc cht thuc khc nhau bng cch
Vi mi ha cht tin x l tin hnh vi 3 nng
phi trn chng vi polyeste. Trc khi phi trn, cc
khc nhau c th l: NaOH (20 g/l, 30 g/l, 40 g/l);
da thuc ph liu c nghin hai ln bng my mi
H2SO4 (1.5 M, 2 M, 2.5 M).
nhm thu c cc ht da c kch thc 300 - 500
micron. Cc mu sau tin x l c tin hnh nghin
trong cng iu kin cc thi gian nghin khc
Nhm nh sng ch ca Nht do Masahiro Ueda
nhau. Tip theo mu s c lc qua cc sng Inox c
ng u pht kin ra tng ti s dng x
ng knh mt li l 1 mm v c git trung ha,
colagen ca da thuc sn xut cc vt liu c kh
git sch trc khi em sy kh. Qu trnh sy c
nng chu nhit dng lm tc gi (United States
thc hin bng thit b sy gi nng nhit 100 oC
Patent, 2004). thu c cc x colagen th cc
trong 24h.
mnh da thuc c x l trong mi trng axit
v mi trng kim vi cc phng n khc nhau. [7] 2.1.2 Nghin x da theo phng php kh:
C th thy rng, trong tt c cc nghin cu Vi phng php nghin x kh th sau khi
c cng b th trc khi ti s dng ph liu da c ng u ha v mt kch thc, da c sy s
giy u phi tri qua cng on nghin x. Cc b nhit 60oC trong 24h trc khi tin hnh
phng php c nghin cu nghin x rt a nghin. Thit b nghin kh c s dng trong
dng nhng nhn chung c tng hp thnh hai nghin cu l thit b nghin ba hai tng c cng
nhm l: (1) nghin x c hc khng s dng ha sut ng c 15kWh, cng sut nghin ti a 50kg/h.
cht v (2) nghin x c tin x l bng ha cht. Tuy Tc nghin c la chn l khong xp x 1500
nhin cc phng php nghin x ny ch mang tnh vng/pht.
gii thiu m khng c thng tin chi tit trn cc
ti liu v cng b quc t trong lnh vc c lin 2.3 Phng php phn tch
quan. Trc ht, nh gi tnh i din ca mu da
Chnh v vy, vic nghin cu kh nng nghin s dng trong nghin cu th cc tnh cht c bn ca
da ph liu c kim tra theo cc tiu chun sau:
x ph liu da thuc dng mnh thnh cc vt cht
dng x l bc nghin cu cn thit nhm hng ti - dy c kim tra trn thit b o dy
vic ch ng c cng ngh ti s dng ph liu da (VEB Werkstottpfilfi maschmen Leipzig) vi p lc
thuc sn xut cc vt liu mi. ti trng l 500 g, theo tiu chun TCVN 5071-90.
2. Thc nghim - bn ko t v gin t c tin hnh
kim tra trn thit b Tensilon RT- 1250A, theo tiu
2.1. i tng nghin cu
chun EN ISO 3376:2002,.
Mc ch ca nghin cu l kho st kh nng
- bn x c kim tra trn thit b Tensilon
cng ngh nghi n ph liu da thuc ca sn xut giy
RT- 1250A, theo tiu chun EN ISO 3377-2: 2002.
nhm nhn c hn hp sau nghin c nho,
u, ti xp. Xut pht t mc tiu nghin cu, i Hiu qu ca qu trnh nghin x c nh gi
tng nghin cu c la chn nghin x l ph thng qua trng thi mu v hnh dng cng nh kch
liu da b ct v da b vng ca qu trnh sn xut thc ca x sau nghin. Cc mu x sau nghin
giy. Da ph liu c thu nhn t cng ty da i Li c quan st trn knh hin vi in t chp nh vi

53
Tp ch Khoa hc v Cng ngh 116 (2017) 052-057

nh sng phn cc. Thit b c tch hp phn mm th l gii l do da c cu trc protein v cha cc
dinocapture 2.0 t ng xc nh kch thc i nhm (-COOH) trong phn t do vy chng khng
tng o ng knh v chiu di x thu c. bn vi kim. Kt qu l, trong iu kin x l kim,
m bo tnh so snh, phng i c c nh l trc khi din ra s phn tch cc x colagen khi
50 ln cho tt c cc mu. Cc thng s v ng cu trc da th xy ra qu trnh ha tan cc thnh
knh v chiu di x l c s so snh hiu qu ca phn protein v chuyn ha chng thnh cu trc gel.
cc phng php nghin. Do cu trc x ca lp ct rt bn chc do vy tc
phn tch x thp hn nhiu so vi qu trnh ha tan
3. Kt qu v bn lun
lm cho mu c nht ln. Kt qu ny cho thy
3.1 Kt qu kim tra cc c trng da mu vic tin x l da ct trong mi trng kim khng
em li hiu qu v khng p dng c thc y
Cc c trng, tnh cht v dy, bn ko
qu trnh phn tch cc b x colagen ln thnh cc
t, gin t v bn x ca da ph liu c
b x c cu trc mnh hn hoc x n.
kim tra theo cc tiu chun quc t. Cc kt qu v
tnh cht da c tng hp trn bng 1.
Bng 1. Mt s c trng tnh cht ca da ph liu
dng lm nguyn liu nghin x

c trng Da ct Da vng
dy (mm) 1.76 1.23
bn t (N/mm ) 2
15.27 7.44
gin t (%) 22.66 11.55
Lc x ln nht (N) 36.88 29.73

Kt qu th nghim cho thy, cc ch tiu


bn t, bn x, gin t ca mu da ct u
cao hn hn mu da vng. Cc gi tr v dy,
bn ko t, gin t v bn x ca cc mu s
Hnh 1. Hnh dng mu thu c sau nghin ca da
dng trong nghin cu ny nm trong khong trung
ct vi cc iu kin tin x kim cc nng khc
bnh ca cc loi da thuc dng sn xut giy [1,2].
nhau: (1) 20 g/l; (2) 30 g/l; (3) 40 g/l v cc thi
iu cho thy cc mu da la chn nghin
gian khc nhau (a) 2h; (b) 3h; (c) 4h.
cu l tnh i din cho ph liu da thuc ca qu
trnh sn xut giy. 3.2.2 nh hng ca x l kim ti kh nng nghin
x da vng
3.2 Kt qu nghin cu nghin x theo phng
php t i vi da vng c x l kim c mt nhn
xt chung l tt c cc mu th nghim sau khi
3.2.1 nh hng ca x l kim ti kh nng nghin
nghin khong 30 - 45 giy ming da b ph hy
x da ct
khong 50% v sau khong 2 pht hu nh tt c cc
Hnh nh ca mu da ct c nghin x bng ming da b nghin hon ton. Kt qu cho thy
phng php t sau khi tin hnh tin x l kim tc nghin ca da vng sau khi x l kim nhanh
cc iu kin nng v thi gian khc nhau c hn hn so vi da ct. iu ny c th l gii l do
tp hp trn hnh 1. Cc hnh nh thu c cho thy cu trc lng lo ca lp vng trong da. Hnh nh ca
vi nng x l l 20 g/l trong 2h th mu sau mu sau nghin c tp hp trn hnh 2.
nghin c nhn thy hnh dng x nhng lp mng
Vi mu tin x l 20 g/l trong 2h. C th
lin kt x cha b phn r. Khi tng thi gian x l
nhn thy mnh da c phn tch thnh dng cc
nng ny ln 3h th x bt u c hin tng phn
x mt cch r rng vi chiu di trong khong 10
tch nhng vn dng mng kt dnh vi kch thc
mm n 30 mm v ng knh l 0,035 mm n
ln ti 5 mm. Nu tip tc tng thi gian x l ln
0,191 mm. nng ny nu tng thi gian tin x l
thnh 4h th hnh nh x tr nn r nt hn tuy nhin
ln 3 h th x thu c c chiu di gim cn khong
quan st thc t cho thy mu c nht rt cao, x
1025 mm v ng knh l 0,0520,321 mm. Nu
trng thi dnh bt vo nhau.
tip tc tng thi gian ln mc 4h, chiu di x tip
Khi nng x l kim tng ln 30 g/l hoc 40 tc gim cn 820 mm v ng knh t 0,061
g/l th ngay c thi gian x l ngn l 2h cng 0,748 mm. Bn cnh vic thay i kch thc th khi
khng thu c cu trc x sau nghin. iu ny c tng thi gian ngm, mu sau nghin c nht tng

54
Tp ch Khoa hc v Cng ngh 116 (2017) 052-057

ln, khi lng x thu c sau khi lc v sy gim T cc kt qa so snh trn c th thy vi da
i. iu ny c ngha l mt lng x da b ha vng khi tin x l kim nng thp v thi gian
tan bi kim trong qu trnh nghin. ngn c th phn tch c thnh dng x sau
nghin. Tuy nhin vic tng thi gian hoc nng
Vi cc mu tin x l nng 30 g/l hnh
kim khi tin x l lm thu ngn chiu di x sau
nh thu c sau nghin vn c dng x tuy nhin
nghin. Tr mu da vng tin x l nng 20 g/l
khi lng thu c t hn nhiu so vi mu tin x
trong 2 h, cc mu cn li u cho thy mu sau
l 20 g/l. iu ny l do khi nng kim cng
nghin c nht cao, lng da b ha tan trong qu
cao th phn ng phn hy cu trc protein ca da
trnh nghin ln. V vy, nu dng phng php x l
din ra cng mnh. Ngoi ra, x thu c cng hn,
kim cho da vng th ch nn dng li mc khong
v vn cn mt phn keo nht bm dnh. c bit vi
20 g/l.
mu ngm trong 4h phi git bng axit mi c th
loi b hon ton lp vt liu nht. Vi iu kin tin 3.2.3 nh hng ca x l axit ti kh nng nghin
x l nng 40 g/l, sau khi nghin mu c x da ct
nht rt cao, k c thi gian ngm ch l 2 gi. Cc
Quan st s thay i th tch ca cc mu da
x thu c c kch thc gim i r rt.
trong qu trnh nghin c th thy r tc ph hy
4.1a 2.1a 4.1b 2.1b 4.1c 2.1c mu da ph thuc nhiu vo hm lng v thi gian
x l axit. Khi tng nng axit, tc phn tch x
din ra nhanh, tuy nhin bng quan st trc tip c
th nhn thy x b cng. Hnh dng mu da ct sau
nghin x c tin x l bng axit th hin trn hnh 3.
4. 2a 2. 2a 4.2b 2.2b 4.2c 2.2c C th nhn thy, khi tin x l bng axit tt c
cc mu thu c sau qu trnh nghin u c hnh
dng x r rng hn hn s vi x l bng kim. Tuy
vy cc x ny vn dng cu trc th v bt dnh,
khng ti xp, gia cc x vn cn mng bm dnh.
4.3a 4.3b 4.3c
2.3a 2.3b 2.3c iu ny l do trong mi trng axit da khng b ha
tan m ch b trng n lm cho lin kt lin phn t
gia cc chui mch polypeptit ca colagen yu i.
Do vy di tc ng ca lc x v ct ca qu trnh
nghin th s phn tch cc x chim u th so vi s
Hnh 2. Hnh dng mu thu c sau nghin ca da ct ngn mch.
vng vi cc iu kin tin x kim cc nng
Khi nng x l axit tng ln, tc ph hy
khc nhau: (1) 20 g/l; (2) 30 g/l; (3) 40 g/l v cc
chung ca mu c tng ln ng k tuy nhin kh
thi gian khc nhau (a) 2 h; (b) 3 h; (c) 4 h.
nng phn tch cc x khng c s khc bit nhiu.
3.1a 3.1b Hnh nh cc mu cho thy cu trc dng x c chiu
3.1c
di tng ln nhng khi cng ca cc b x thu
c cng tng ln. Cc kt qu ny cho thy, i vi
da ct th tin x l bng axit gip cho kh nng phn
tch x tt hn nhiu so vi x l kim. Mu thu
3. 2a 3.2b 3.2c c khng c dng nht m cng. Tuy nhin cc x
thu c khng ti xp.
3.2.3 nh hng ca x l bng axit ti kh nng
nghin x da vng
3.3a 3.3b 3.3c Thc nghim cho thy, cc mu da vng b ph
hy (khng cn hnh dng ming) trong khong thi
gian rt ngn. Hu ht kch thc cc mnh da u
gim i 50% sau khong thi gian nghin l 1 pht v
hon ton khng cn cu to dng ming sau thi
Hnh 3. Hnh dng mu thu c sau nghin da ct gian nghin l 2 pht. iu ny c ghi nhn vi tt
vi cc iu kin tin x axit cc nng khc c cc mu da vng c x l trong mi trng axit
nhau: (1) 1.5 M; (2) 2 M; (3) 2.5 M v cc thi gian cc iu kin nng v thi gian khc nhau. Hin
khc nhau (a) 2h; (b) 3h; (c) 4h tng ny c th l gii l do cu trc lng lo ca
lp vng da, lm cho kh nng thm thu ca cc
phn t axit vo khong th tch t do gia cc chui

55
Tp ch Khoa hc v Cng ngh 116 (2017) 052-057

mch polypeptit din ra nhanh hn, thc y qu ba. Hnh nh thu c sau nghin ca cc mu da
trnh trng n v lm mm da ngay c nng thp ct v da vng c th hin trn hnh 5.
vi thi gian x l ngn. Hnh nh v hn hp x da
C da ct v da vng th mu thu c sau khi
thu c sau nghin x cc mu da vng qua x l
nghin c dng x r nt. Vi da ct th x thu c
bng axit sunfuric c th hin trong hnh 4.
c chiu di 0,2 mm n 10 mm (ngn hn so vi cc
x thu c bng phng php nghin c tin x l
4.1a 4.1b 4.1c axit) v ng knh 0,020,07 mm. Mu sau nghin
x thu c da mn, an xen c hc vo nhau.
Vi mu da vng, x thu c sau khi nghin
rt mm, mn v ng u. ng knh cc x tp
4. 2a 4.2b 4.2c trung trong khong 0,020,05 mm. Chiu di ca x
gim i so vi cc x thu c khi nghin da ct. Mt
khc, tc nghin i vi da vng nhanh hn so vi
da ct. Thi gian cn thit tch x ch khong 30
giy.
4.3a 4.3b 4.3c
(a) (b)

Hnh 4. Hnh dng mu thu c sau nghin da vng


vi cc iu kin tin x axit cc nng khc
nhau: (1) 1.5 M; (2) 2 M; (3) 2.5 M v cc thi gian
khc nhau (a) 2h; (b) 3h; (c) 4h Hnh 5. Hnh dng sau nghin ca cc mu (a) da ct
Nhn chung cc mu sau nghin cho thy x (b) da vng bng phng php nghin ba
c phn tch tt, trng thi x xp v mn, khng Nh vy, phng php nghin kh bng my
c hin tng cng nh khi nghin x da ct. Vi nghin ba c tc nghin nhanh. Vi c hai loi da
nng axit tin x l l 1.5 M th kch thc x thu ct v da vng u c th thu c x mn v ng
c sau nghin t ng knh khong 0.15 mm v nht. Mc d chiu di x nhn c ngn hn so vi
chiu di 15 mm. Khi tng thi gian hu nh ng phng php nghin c tin x l bng axit nhng
knh x khng thay i nhng chiu di tng ln ng knh x li nh hn hn.
khong 10-15%. Khi tng nng axit tin x l th
ng knh x thu c gim v chiu di x c xu Kt qu ny hon ton ph hp vi nguyn l
hng tng ln. ng knh x sau nghin t mc hot ng ca my nghin ba. Trong qu trnh
nh hn 100 micron trong iu kin x l tin x l nghin, cc cnh ba c quay vi cc hnh trnh
axit nng 2 M trong 4h hoc 2.5 M ch trong 3h. khc nhau, v tr tng i gia cc cnh ba, gia
Chiu di x thu c sau nghin vi cc mu x l cnh ba v thnh ca bung nghin thay i lin tc.
nng 2 M l khong 20 mm v vi nng 2.5 iu ny lm thay i v tr tng i ca cc mnh
M l 25 mm. da so vi cc c cu ca my. Do vy, trong qu trnh
nghin, ty theo v tr trong bung nghin m da s
Kt qu ny c c l do khi nng axit ca ng thi chu tc ng ca nhiu lc c hc nh lc
qu trnh tin x l cng cao th kh nng trng n x, lc ct, lc ko gin, lc b un khc nhau. Chnh
hay ni khc i l th tch t do gia cc chui mach s tng hp ca cc lc c hc ny lm cho da c th
polypeptit cng tng v lc lin kt lin phn t cng d dng phn tch cc x mnh v mn.
yu. Vi cng mt lc nghin x nh nhau th tc
phn tch ca x s tng lm cho ng knh ca x 4. Kt lun
gim. ng thi, khi thi gian phn tch x ngn th Bi bo trnh by kt qu nghin cu kho st
cng ng ngha vi vic thi gian chu tc ng ct kh nng nghin x nhm chuyn ha ph liu da b
mch ca x cng gim v do vy x c th gi c ct v da b vng ca sn xut giy thnh cc vt cht
chiu di ln. c cu trc dng x bng cc phng php nghin
3.3 Kt qu nghin cu nghin x theo phng khc nhau: (1) nghin x t c tin x l bng
php kh NaOH v H2SO4 cc iu kin nng v thi gian
thay i; (2) nghin x kh bng my nghin ba
nghin cu kh nng nghin x theo phng khng qua x l ha hc. Kt qu ch ra c kh
php khng tin x l bng ha cht, cc mnh da ct nng v mc phn tch x ca tng phng php
v da vng c tin hnh nghin trn my nghin nghin. y l c s khoa hc xy dng phng

56
Tp ch Khoa hc v Cng ngh 116 (2017) 052-057

php chuyn ha cc ph liu da thuc thnh cc vt Ti liu tham kho


cht c cu trc dng x. Cc x thu c t qu
[1] M. Kate, R. Thomson, Conservation of Leather and
trnh nghin x s tip tc c x l hng ti s Related Materials; Elservier, Oxford, 2006.
dng lm nguyn liu ch to cc vt liu ti ch
trong cc nghin cu tip theo. [2] Hip hi Da - Giy Vit Nam. Hin trng pht trin
ca ngnh da giy Vit Nam v cc vn mi trng
Li cm n pht sinh. Bo co Hi tho: ng dng sn xut sch
trong ngnh Da - Giy Vit Nam, 2010.
Nhm tc gi xin c cm n B mn Vt liu
v Cng ngh Ha dt, Vin Dt May-Da giy v [3] J. Kanagaraj, K. C. Velappan, N. K. Chandra Babu
Thi trang; Phng th nghim trng im v Vt liu and S. Sadulla, Solid wastes generation in the leather
polime v compozit, Trng i hc Bch Khoa H industry and its utilization for cleaner environment A
review, Journal of Scientific & Industrial Research. 66
Ni; Trung tm nghin cu ch bin g, Trng i
(2006) 541-548.
hc Lm nghip; Cng ty da i Li v Cng ty Giy
Thy Khu h tr trong vic thc hin nghin cu [4] K. C. Olszewska, A. Przepiorkowska, A Mixture of
ny. Nghin cu c thc hin bng ngun kinh ph Buffing Dust and Chrome Shavings as a Filler for
t ti 01C-03/1-2014-2 ca S Khoa hc v Cng Nitrile Rubbers, Journal of Applied Polymer Science,
122 (2011) 28992906.
ngh H Ni.
[5] T. J. Madera-Santana, F. V. Moreno, Graft
polymerization of methyl methacrylate onto short
leather fibers, Polymer Bulletin 42(1999) 329-336.
[6] S. Nahar, M. A. Khan, R. A. Khan, E. C. B. Abdullah,
M. J. H. Khan, R. Islam, F. Karim, M. Rahman, A.
Rahman, A. A. Mahmood, A. K. Deb, U. H. B. Nahar,
An Approach to Utilize Crust Leather Scrapes,
Dumped into the Land, for the Production of
Environmental Friendly Leather Composite, Eng.
Journal, 17 (3), 2013.
[7] Ueda, Regenerated Collagen Fiber with Excellent Heat
Resistance, United States Patent, 2004.

57
Tp ch Khoa hc v Cng ngh 116 (2017) 058-062

Effects of Milling Time on the Properties of In-Situ Binary Niobium-


Titanium-Carbide Reinforced Cu Based Composite
nh hng ca thi gian nghin n tnh cht ca compozit
nn ng ct ht in-situ lin ccbit titan niobium

Le Minh Hai*, Tran Duc Huy


Hanoi University of Science and Technology No. 1, Dai Co Viet Str., Hai Ba Trung, Ha Noi, Viet Nam
Received: August 23, 2016; accepted: November 26, 2016

Abstract
Mechanical alloying was used to synthesize in-situ copper based composite reinforced by binary niobium-
titanium-carbide from Cu, Nb, Ti and graphite powder mixture. The nominal composition was correponded to
Cu-30 vol.% (Nb,Ti)C. XRD patterns showed that (Nb, Ti)C was not formed in the as-milled powder after 5
hours of milling but was precipitated with a subsequent sintering at 900 oC. Milling time has showed a great
influence on both mechanical and physical properties of the sintered composite pellets. Increasing milling
time leads to an increase of the microhardness of the composite due to a higher degree of deformation that
enhanced hardening. On the other hand, the electrical conductivity decreases considerably when the milling
time increases. This phenomenon could be atrributed to the increase of density of grain boundaries, which
acts as a centre of electron scattering, with milling time.
Keywords: Cu, (Nb, Ti)C, Mechanical alloying, Sintering.
Tm tt
Phng php hp kim ha c hc c s dng tng hp vt liu compozit nn ng ct ht cacbit hp
kim (Nb, Ti)C t sinh t hn hp bt ca cc nguyn t thnh phn bao gm Cu, Nb, Ti v graphit. Ph
nhiu x tia Rnghen ca hn hp bt vi thnh phn tng ng vi 30% th tch (Nb,Ti)C cho thy pha
ccbit cha c to thnh sau 5h nghin nhng xut hin sau khi thiu kt 900 oC trong mi trng kh
argon. Thi gian nghin nh hng mnh n c tnh cht c hc v tnh cht vt l ca vt liu compozit.
Ko di thi gian nghin lm tng cng ca vt liu compozit do s tng mt khuyt tt trong mng
tinh th ca vt liu. Mt khc, tng thi gian nghin lm gim dn in ca vt liu do s tng ca mt
bin gii ht tinh th, qua lm tn x s chuyn ng ca cc in t trong vt liu.
T kha: ng, Cacbit hp kim (Nb, Ti)C, Nghin nng lng cao, Hp kim ha c hc, Thiu kt.

1. Introduction1 In our previous work [8], copper based


reinforced in-situ binary niobium-titanium-carbide
In an in-situ reinforced metal matrix composites,
(Nb,Ti)C composite powders have been succesfully
the reinforcements are formed within the metal
synthesized by mechanical alloying. We investigated
matrix during the fabrication of the composite by
the influence of the milling time on the formation of
some chemical reactions [1]. The in-situ reinforced
the in-situ carbide in the copper matrix. The obtained
MMCs have more advantages over conventional ex-
results showed that the maximum volume fraction of
situ composites such as thermaldynamic stability of
the carbide was reached after 20 hours of milling. The
the reinforcing phases, finer reinforcing particle size
as-milled powder exhibited a good dispersion of (Nb,
with clean particle-matrix interfaces and good
Ti)C particles within copper matrix with an excellent
mechanical properties [1-3]. In-situ copper-based
interfacial bonding. The in-situ carbide (Nb,Ti)C
composite reinforced by carbide dispersed particles
particle size ranged from 20 to 80 nm.
has now emerged as a promising candidate for high
performance electrical materials for such applications However, milling time influences not only the
as sliding electrical contacts. Particle reinforced formation of the in-situ carbides in the copper matrix
copper matrix composites present high-specific but also the properties of the bulk in-situ composite.
strength and good wear resistance while maintaining In the present work, the in-situ copper nanocomposite
its high electrical conductivity [4,7]. reinforced with 30 vol.% (Nb,Ti)C was synthesized
by mechanical alloying. The milling time was varied
to investigate the microstructure and the morphology
*
evolution of the formed binary niobium-titanium
Corresponding author: Tel.: (+84) 912.098.484 carbide of the bulk composite after sintering.
Email: hai.leminh@hust.edu.vn
58
Tp ch Khoa hc v Cng ngh 116 (2017) 058-062

2. Experimental procedure 10000


C
The starting powders were pure elemental Cu 9000
u
(99.8%), Nb (99.9%), Ti (99.9%) and graphite 8000

(a.u.)
C
(99.99%), purchased from Sigma Aldrich, with 7000

Lin (Counts)
mixture composition corresponding to Cu-30vol.% 6000

(N

Counts
5000
(N (N (N
(Nb,Ti)C. The mixture of powders was milled using a b, b, b, b, C
Fritsch Pulverisette 6 planetary ball milling in Ti
4000
Ti Ti Ti u
(d) )C )C
3000

argon atmosphere with a rotation speed of 400 rpm. )C )C


2000
(c)
The ball-to-powder ratio used was 10:1 with 10mm- 1000
(b)
diameter stainless steel balls. After 5, 10, 20, and 30 0
(a)
hours of milling, the as-milled powders were 30
30
40
40
50
50
60 60
70
70
80
80

extracted. The as-milled powders were uniaxially 2-theta (o)


2-Theta - Scale

compacted in a cylindrical steel mould at 800 MPa Fig. 1. XRD patterns of sintered samples at 900oC/1h
and then sintered in vacuum at 900oC for 1 hour. The from the powders of different milling times: (a) 5, (b)
density of the sintered in-situ (Nb,Ti)C-Cu composite 10, (c) 20 and (d) 30 hours
was determined based on Archimedes principle using
a Satorious electronic analytical balance. Micro- Copper crystallite size was determined by the
hardness and electrical conductivity of the composite Williamsons-Hall method from their corresponding
were measured using a Shimadzu Vickers micro- XRD patterns acquired on the sintered samples of
hardness tester at a load of 100 g and a four-point different milling times. The variations in the average
probe Changmin Tech CMT-SR2000N, respectively. crystallite size of Cu (DCu) in both as-milled powders
and sintered pellets for different milling times are
3. Results and discussion presented in Figure 2. The crystallite size decreases
According to our previous work [8], the as- rapidly, from 41 nm of starting copper powder at the
milled powder showed the diffraction peaks of the initial state of MA to 22 nm after 5 hours of milling.
starting elemental Nb and Ti powders after 5 hours of The average crystallite size of Cu drops slightly from
milling. From 10 hours to 30 hours of milling the 10 to 20 hours of milling time, and after 20 hours of
peaks of Nb and Ti powders are no longer existed milling the crystallite size of Cu decreases to 17 nm.
while almost all of the (Nb, Ti)C major reflections No change of DCu value occurs after 20 hours of
(111), (200) and (220) are detected. milling, indicating that steady-state is attained at 20
hours of milling.
Figure 1 shows the XRD patterns of the in-situ
sintered composites. The peaks of (Nb, Ti)C in the
XRD patterns of sintered samples of 5-hour as-milled
powder (Fig. 1a) are clearly visible. (Nb, Ti)C were
not formed in the as-milled powder after 5 hours of
milling but was precipitated with a subsequent
sintering at 900oC. According to [9], the reaction
temperatures for the formation of the carbide from the
elements Ti, Nb and carbon is higher than 1300oC.
The precipitation of (Nb, Ti)C in this present work
occurred at a much lower temperature with the
enhanced diffusivity of atoms due to the MA process.
The refinement of the grain size during MA increased
the number of grain boundaries. The numerous
interfaces provided a high density of short-circuiting
diffusion paths [10].
In the case of others composites (Fig. 1b-d), the Fig. 2. Copper crystallite size measured from XRD
diffraction peaks from the sintered in-situ composite, pattern for as-milled powders and sintered composite
compared to those of the as-milled powders, are more with different milling times
intense and well-defined than the peaks of as-milled At this stage, a balance was achieved between
powder. This phenomenon indicates that heat the rate of welding, which tends to increase the
treatment recovered considerable internal strains and average particle size, and the rate of fracturing, which
made the crystallite size increase remarkably. tends to decrease the average composite particle size
[10]. Compared to the crystallites of Cu in as-milled
powders, the crystallites of Cu in sintered pellets are

59
Tp ch Khoa hc v Cng ngh 116 (2017) 058-062

larger and follow a similar increasing trend. It is due [10]. The low density of sintered composite after the
to the heat-treatment results in recrystallization and initial milling time may be also due to the low-
crystallite growth. uniform distributions and the larger size of Nb and Ti
particles in 5-hour-as-milled powder.
In contrast to crystallite size, the internal strain
of Cu is increased with increasing milling time as Furthermore, the refined microstructural
shown in Figure 3. At the beginning of milling the features decrease the diffusion distances [10]. The
internal strain in the Cu lattice structure increases mechanisms can easily be understood, the finer
rapidly due to the dissolution of carbon in the copper particle size results in a higher surface energy for a
matrix. After 20 hours of milling, the lattice strain of compact, thus a higher driving force for grain growth
copper increases slightly, possibly because during the (growth of crystallites) and densification to reduce
MA powder particles are subjected to high-energy the system's Gibbs energy [12]. Furthermore, the
collisions, causing a heavy plastic deformation that is higher amount of contact points between the particles
associated with a high density of defects, such as activated the transport of matter leading to a high
dislocations and stacking faults [11], which is the number of necks between particles, motivating the
main contributor to the increase in lattice strain. The diffusion and evaporationcondensation of the matter
internal strain for Cu in the sintered in-situ composite on surfaces with consequent bulk densification [13].
is lower than that in the as-milled powder, probably
because the stored energy in the as-milled powder
particle is released because of a recovery or
relaxation process within the boundaries during the
sintering process.

Fig. 4. Variation in sintered density of in-situ Cu-


(Nb,Ti)C composites with different milling times

Fig. 3. Internal strain of Cu measured from XRD


pattern for as-milled powders and sintered composite
with different milling times
The change in density of the bulk Cu-(Nb,Ti)C
composite as as function of milling time is shown in
Figure 4. As can be seen, the density of the sintered
Cu-(Nb,Ti)C composite is significantly influenced by
duration of MA. Sintered density increases with
prolonged milling time, i.e. from 6.45 g/cm3
[corresponding to 85.10% of theoretical density
(TD)] after 5 hours of milling to 6.87 g/cm3
(corresponding to 90.72% of TD) after 30 hours. A
possible explanation for the increase in density is that
a variety of crystal defects such as dislocations,
Fig. 5. Variation on microhardness of in-situ Cu-
vacancies, and stacking faults as well as the number
(Nb,Ti)C composites with different milling times
of grain boundaries increases when extending the
milling time, and the presence of this defect structure The results of Vickers microhardness
enhances the diffusivity of atoms during sintering measurements performed on polished consolidated

60
Tp ch Khoa hc v Cng ngh 116 (2017) 058-062

pellet as a function of milling time of the sintered Cu- formation of (Nb,Ti)C, and the porosity of the
-(Nb,Ti)C composite is shown in Figure 5. The composite. As can be seen in Figure 6, the electrical
microhardness value increases from 359 HV to conductivity increases rapidly from 6.02 x 10 8 (m)-1
431 HV as the milling time increases from 5 to 30 after 5 hours of milling to 9.09 x 10 8 (m)-1 after 10
hours. This is to be expected since during MA the hours of milling. It is due to a considerable reduction
crystallite size was regularly refined to a nanometer in the large degree of porosity that had been found in
level, allowing a higher degree of deformation that the 5-hour composite. The electrical conductivity
produced lattice distortion in the matrix copper. This decreases considerably when the porosity increases.
lattice distortion then created lattice strain and The decrease of electrical conductivity with milling
increased the dislocation which enhanced hardening. time is confirmed by the density results. From 10 to
The ultra-fine particles of (Nb,Ti)C increased the 30 hours of milling the electrical conductivity slightly
amount of interfacial bonding between the decreases to 8.17 x 108 (m)-1. The possible cause of
reinforcement and Cu matrix, which also contributed this slight decrease is the increase of density of grain
to the composites enhanced mechanical properties boundaries, which acts as a centre of electron
[14]. scattering, with milling time. According to Murty et
As shown in Figure 5, the microhardness value al. [16], with an increasing amount of grain
rose rapidly between 5 and 10 hours of milling. At boundaries, the mean free conductive path decreases,
this stage, the effect of dislocation is not the main resulting in increased resistivity.
factor in the increased microhardness, instead, the
major influence is the formation of the carbide
(Nb,Ti)C in the Cu matrix. Furthermore, when the
milling time exceeds 20 hours, the Vickers hardness
variation is negligible, suggesting that the MA
process may have reached steady-state by 20 hours of
milling.
The mechanism of strengthening can be
explained using Orowans mechanism. In Orowans
mechanism [15], impenetrable precipitates in the
matrix interrupt dislocation migration and thus plastic
deformation via interaction with dislocations, which
results in an increase in the matrix strength.
The strengthening of the metal matrix by rigid
particles is achieved as follows: Fig. 6. Variation on electrical conductivity of Cu-
(Nb,Ti)C composites with different milling times
(1)

where is the external stress, is the modulus of


rigidity of the matrix metal, b is the magnitude of
Burgers vector and L is the interparticle distance. It is
therefore proposed that the precipitation of in-situ
(Nb,Ti)C nanometric particles, which act as a barrier
to dislocation motion and are too hard to be cut by
dislocations, results in strengthening of the copper
matrix. Following Equation 1, when the in-situ
carbides particles were refined with milling time,
corresponding to a decrease in internal particle
distance L, the external stress increases leading to the
rise of the microhardness.
It is well known that the physical properties of
metallic materials are influenced by defects such as Fig. 7. Microhardness versus electrical conductivity
grain boundaries, solute atoms, dislocations, of Cu-(Nb,Ti)C composites at different milling times
porosities and second phases. The electrical A plot of microhardness versus electrical
conductivity of the sintered composites was found to conductivity in Figure 7 indicates that the in-situ Cu-
depend on the number of grain boundaries, the (Nb,Ti)C composite reached a good combination of

61
Tp ch Khoa hc v Cng ngh 116 (2017) 058-062

microhardness and electrical conductivity after 20 [4] T. Takahashi, Y. Hashimoto, Mater. Sci. Forum. 88
hours of milling, where the microhardness and (1992) 175 182.
conductivity are 420 HV and 8.62 x 108 (m)-1, [5] M. T. Marques, V. Livramento, J. B. Correia, A.
respectively. This finding suggests that to produce Almeida, R. Vilar, Materials Science and Engineering
Cu-(Nb,Ti)C composite with high microhardness and A 399 (2005) 382-386.
high electrical conductivity, in addition to lower [6] M.T. Marques, A.M. Ferraria, J.B. Correia, A.M.
power consumption, the optimum milling duration is Botelho do Reg, R. Vilar, Materials Chemistry and
20 hours. Physics 109 (2008) 174180.
4. Conclusion [7] Z. Hussain, R. Othman, Bui D. L., Minoru U., Journal
of Alloys and Compounds 464 (2008) 185-189.
The in-situ Cu-(Nb, Ti)C nanocomposite pellets
have been successfully synthesized via mechanical [8] L.M. Hai and T.D. Huy, Journal of Science and
alloying and powder metallurgy. Milling time Technology 112 (2016) 80-84.
exhibited a great influence on both the mechanical [9] L.E. Toth, Transition metal carbides and nitrides,
and physical properties of the sintered composite Academic Press, New York (1971) 13.
pellets. Increasing milling time leads to an increase of
[10] C. Suryanarayana, Mechanical Alloying and Milling,
the microhardness of the composite due to a higher
Marcek Dekker, New York, USA (2004) 59-66, 83-
degree of deformation that enhanced hardening. On 87.
the other hand, the electrical conductivity decreases
considerably when the milling time increases. It could [11] M.S El-Eskandarany, Mechanical alloying for
be atrributed by the increase of density of grain fabrication of advanced engineering materials, Noyes
Publications, New York, USA (2001) 16-18.
boundaries, which acts as a centre of electron
scattering. Our results indicated that the in-situ Cu- [12] Q. Jiang, S.H. Zhang, J.C. Li, Solid State
(Nb,Ti)C composite reached a good combination of Communications 130 (2004) 581584.
microhardness and electrical conductivity after 20 [13] C. Santos, M.H. Koizumi, J.K.M.F. Daguano, F.A.
hours of milling, where the microhardness and Santos, C.N. Elias, A.S. Ramos, Materials Science
conductivity are 420 HV and 8.62 x 108 (m)-1, and Engineering A 502 (2009) 6-12.
respectively.
[14] H. Zuhailawati, Y. Mahani, Journal of Alloys and
References Compounds 476 (2008) 142-146.

[1] L. Froyen, J.D. Wilde, Materials Science Forum Vols [15] E. Orowan, Symposium on International Stresses,
437-438 (2003) 141-144. Institution of Metal, London (1947) 451.

[2] M. Krasnowski, T. Kulik, Journal of Alloys and [16] B.S. Murty, T. Venugopal, K.P. Rao, Acta
Compounds 448 (2008) 227-233. Metallugica 55 (2007) 4439-4445.

[3] Zhang. X., Wang H., Liao. L., Ma. N., Composites
Science and Technology 67 (2007) 720-727.

62
Tp ch Khoa hc v Cng ngh 116 (2017) 063-067

Cu trc li/v v s pht hunh quang ca dy nan silic


Core/Shell Structure and Photoluminescence of Silicon Nanowires

Nguyn Th Thy1,2,*, Nguyn Quang Huy1, Nguyn Khc Tng1,


Vng Tun Dng1, Nguyn Hu Lm1
1
Trng i Trng i hc Bch Khoa H Ni, s 1 i C Vit, H Ni, Vit Nam
2
Trng i hc S Phm K Thut Hng Yn, Hng Yn, Vit Nam
n Ta son: 20-6-2016; chp nhn ng: 20-12-2016

Tm tt
Dy nan silic (SiNWs) c tng hp bng phng php bc bay nhit ti nhit cao trong khong t
1100 0C n 1200 0C trn Si (111) s dng vt liu ngun l hn hp bt Si:C. Kt qu nh hin vi in
t qut cho thy kch thc ca SiNWs thu c c ng knh vi chc nanomt. Cu trc li/v ca dy
Si c quan st bng knh hin vi in t truyn qua phn gii cao. Ph pht x hunh quang ca dy
nan silic nhit phng c lin quan n hiu ng giam gi lng t khi thu nh kch thc ca dy.
T kha: SiNWs, phng php bc bay nhit, cu trc li/v;
Abstract
Silicon nanowires (SiNWs) were synthesized on Si (111) surfaces using the vaporliquidsolid technique at
high temperature ranging from 1100 0C to 1200 0C. Si:C mixture powders were used as the material
sources. Scanning electron microscope images were revealed that the Si nanowires had few tens
nanometer of diameter. The Si-core/SiOx-shell structure of the nanowires was investigated via transmission
electron microscopy. The photoluminescence of the nanowires at room temperature demonstrated a
quantum confinement effect because of the reduced diameter of the nanowires.
Keywords: SiNWs, thermal evaporation method, core/shell structure;

1. Gii thiu* Ging nh cc vt liu cu trc nan khc th


dy nan Si cng c rt nhiu phng php ch to,
Silic (Si) l vt liu ph bin v c s dng
nh phng php lng ng pha hi ha hc (CVD)
ch yu trong ch to linh kin in t v vi c in
[5], phng php bc bay c s h tr ca laser (laser
t. dng cu trc khi, cc tnh cht ca Si c
ablation) [6], phng php n mn ha hc [7] ....
nghin cu kh c th v chi tit. Tuy nhin, khi kch
Trn c s iu kin phng th nghim ti Vin Vt
thc ca cu trc thu nh ti kch c vi nanomt,
l k thut - Trng i hc Bch Khoa H Ni,
ni m hiu ng lng t xy ra, th chng c nhng
chng ti la chn phng php bc bay nhit
tnh cht ht sc mi l. Do , tim nng ng dng
tin hnh ch to dy nan silic. Vic hnh thnh dy
ca Si c cu trc nan trong cc ngnh cng ngh
nan Si c gii thch theo c ch hi lng rn
cao nh nng lng sch, vt liu trong pin nhin
(VLS) [8, 9].
liu, v s dng lm vt liu trong cm bin kh rt
ln [1-4]. Dy nan Si l mt dng cu trc thp 2. Thc nghim
chiu vi kch thc ng knh rt nh (kch thc
Trc tin, phin Si (111) c s dng lm b
nm trong khong nanomt), cn gi l cu trc mt
mt mc dy nan Si. Vic la chn loi ny
chiu. Vic tng hp cu trc Si mt chiu cng nh
c lin quan n nng lng lin kt cc nguyn t b
cc nghin cu v cu trc, s lin quan ti tnh pht
mt v s nh hng ca tinh th trong qu trnh
quang, tnh cht in ca loi vt liu ny lun l ch
mc dy Si. Phin Silic c ng knh 4 inch c
quan tm ca cc nh nghin cu. Trong bi bo
ct thnh cc tm nh kch thc (2x1) cm. Cc tm
ny, chng ti tm hiu vic tng hp dy nan silic
ny c lm sch b mt bng phng php ha hc
bng phng php bc bay nhit, cu trc ca chng
s dng cc ha cht nh cn, axtn, nc ct hai
v s lin quan ca cu trc ny n vic pht hunh
ln, kt hp rung siu m loi lp bi b mt, cc
quang ca dy Si o nhit phng.
tp cht hu c bm dnh b mt. Dung dch axt HF
1% c s dng loi b lp xt th ng ban
u do mi trng gy ra. Cc tm ny sau c
*
Lin h tc gi: Tel: 0962490411; ra bng nc ct hai ln v lm kh trong mi
Email: thuyiop@gmail.com; lam.nguyenhuu@hust.edu.vn

63
Tp ch Khoa hc v Cng ngh 116 (2017) 063-067

trng kh nit. Tip theo, mt lp mng vng (Au) Hnh 1 m t c ch VLS ca qu trnh hnh
vi dy 2 nm c ph ln b mt Si bng thnh dy nan Si. Vi mt lp mng Au, nhit
phng php bc bay bng chm in t lm xc cao s lin kt mng b ph v, cc nguyn t s co
tc. H bc bay s dng l Boc-Edward Auto 500 vi cm to thnh cc ht Au nh c ng knh c
chn khng ban u t ~ 10-6 mbar. nanomt. Cc ht kim loi nhanh chng kt hp vi
Si to thnh hp kim Au-Si. Khi c cp ngun
Cc tm Si(111) c ph mng Au ny sau
hi do s bc bay nhit ca bt Si, cc nguyn t Si
c t vo b g mu v chuyn nhanh vo l ca
c th bm vo v khuch tn xung quanh cc ht
h bc bay nhit thc hin qu trnh hnh thnh
nan Au to trng thi qu bo ha. Cc nguyn t Si
dy nan Si. Ngun vt liu bay hi l hn hp bt Si
tip tc khuch tn vo vng hp kim lng Au/Si qu
(Testbourne 200 mesh) v bt C trn vi t l 1:1
bo ha nu trn, sau kt tinh to cu trc mt
[10], c t trong cc ng vt liu bng xt
chiu l dy Si.
nhm gia l ni c nhit c xc nh chnh
xc bng cp nhit. Khong cch gia cc ng vt Hnh 2 th hin cc kt qu ca s to ht nan
liu v Si l 5 cm, m bo nhit bng nhit Au v dy nan Si cc iu kin ch to khc nhau.
tm l nhit. Tc nng nhit, thi gian nng Hnh 2.a l nh SEM ca Si c cha cc ht nan
nhit c iu khin thng qua b iu khin nhit Au khi nhit ti nhit 900 0C i vi mng Au
. Kh Ar tinh khit (99,9%) c a vo bung dy 2 nm. C th thy lp mng vng di tc dng
phn ng vi lu lng kh c gi n nh ~500 ca nhit co cm li thnh cc ht kim loi xc
sccm. Nhit trong l c nng ln n nhit tc, cc ht nan Au ny c kch thc nh vi chc
mc dy Si trong khong t 1100 0C n 1200 0C vi nanomt v c nh hng n ng knh dy Si.
tc nng nhit 10 0C/min. Ti nhit cao, qu Theo c ch pht trin dy VLS, nu kch thc ht
trnh to dy nan Si hnh thnh v thi gian mc l xc tc ln, ng knh dy Si nhn c s ln. Khi
30 pht. kch thc ht xc tc nh th ng knh dy s b.
Tuy nhin, kch thc, s ng u cng nh phn b
Kt thc qu trnh, cc mu c lm ngui t
ht xc tc cng ph thuc vo b dy ca mng
nhin n nhit phng trong mi trng kh tr.
mng Au. Trong mt s nghin cu trc, chng ti
Mu dy Si sau khi ch to s c kho st mt s
cp [11].
tnh cht v cu trc v tnh cht quang thng qua cc
php o hin vi in t qut pht x trng (FESEM-
S4800 Hitachi) kt hp ph tn sc nng lng tia X
(EDX), hin vi in t truyn qua phn gii cao
(HRTEM-JEM 2100 Jeol), v ph pht x hunh
quang (PL - Jobin Yvon) dng ngun kch thch laser
c bc sng 325 nm o nhit phng.
3. Kt qu v tho lun
Trong phng php ch to dy nan Si, c ch
hi-lng-rn (VLS) ng vai tr quan trng trong qu
trnh hnh thnh cu trc nan mt chiu. ng knh
dy Si ph thuc vo kch thc ht xc tc.

Hnh 2. nh SEM b mt Si ti cc iu kin ch


to khc nhau: S hnh thnh ht nan vng ti nhit
900 0C (a), dy nan Si hnh thnh ti cc nhit
1100 0C (b), 1150 0C (c), v 1200 0C (d).
S hnh thnh dy nan Si cc iu kin nhit
khc nhau c kho st. Kt qu cho thy dy
nan Si s kh hnh thnh trn nu nhit bc
bay nh hn 1000 0C v ph thuc vo nhit
mc dy [12]. Hnh 2.b l nh SEM ca c cha
Hnh 1. Qu trnh mc dy theo c ch VLS, theo SiNWs mc nhit 1100 0C, dy c kch thc
Si s khuch tn vo vng cht lng qu bo ha kh ng u vi ng knh dy vo khong 25 nm,
ca hp kim Au-Si, pht trin nh hng mt chiu chiu di dy kh ln. Quan st trn nh c th thy
vi ht xc tc nm trn u dy. c cc ht kim loi (mu sng) nm u dy,
iu ny chng t SiNWs c hnh thnh theo c

64
Tp ch Khoa hc v Cng ngh 116 (2017) 063-067

ch VLS. Hnh 2.c v 2.d l cc nh SEM ca b mt ca SiOx v SiO ni trn. Khi Si khuch tn vo
cha dy nan Si tng hp tng ng cc nhit vng qu bo ha ca hp kim Au-Si v pht trin
1150 0C v 1200 0C. theo hng xc nh v b bao bc bi lp v v nh
hnh SiOx (bao gm c SiO2, SiO).
Khi nhit mc dy tng ln, kch thc ca
dy Si khng ng u. Cc dy Si c ng knh ln Kt qu chp ph tn sc nng lng (EDX) ca
70-90 nm nm xen k cc dy c ng knh nh dy Si th hin trn hnh 4 cho thy ph hp vi kt
~20-30 nm. C th l gii iu ny l do s tip tc qu nh HRTEM nhn c v cu trc li/v. Theo
co cm ca mt s ht xc tc kch thc nh to , nguyn t silic chim 75,5 % khi lng (tng
thnh cc ht c kch thc ln hn khi nhit ng 63,7 % v nguyn t), nguyn t xi chim 24,5
cao gim thiu nng lng b mt, do c s % khi lng (ng 36,3 % nguyn t), s hin din
phn b li v kch thc v mt ht Au. Chnh s ca nguyn t Au gn nh khng c do qu t.
thay i ny dn n s thay i v kch thc v s
khng ng u ca dy nan Si trn b mt
Si(111). S thay i v kch thc ca dy Si ph
thuc vo kim loi xc tc cng c mt s
nghin cu khc cp n [13, [14].

Hnh 3. nh HRTEM ca dy nan Si mc trn


Si (111). C th quan st thy cu trc li/v ca Hnh 4. Ph EDX ca mng cha dy nan Si vi t
dy Si. Vi dy c kch thc 90 nm th li Si c l nguyn t Si chim 75,5% khi lng v nguyn
ng knh ~52 nm v bao bc bi lp v xt v t O chim 24,5% khi lng, kt qu cho thy dy
nh hnh (a), vi dy nh hn c kch thc 21,5 Si chim t l Si kh nhiu trong cu trc.
nm th li c ng knh 8,5 nm (b). Khi kch thc ca dy nan Si thu gim ti
Hnh 3 th hin nh hin vi in t truyn qua mc gn gi tr ca bn knh Bohr (vi Si tinh th gi
phn gii cao (HRTEM) c trng ca hai cu trc ny ny vo khong 5 nm), hiu ng giam gi lng
dy nan Si tng hp nhit cao. C th quan st t mnh s xy ra trong cu trc. Vng nng lng
r nt cu trc li/v ca dy nan Si. Vi dy Si c ca cu trc s thay i t cu trc vng cm xin
kch thc ln khong 90 nm (hnh 3.a), li Si tinh (ng vi bn dn khi) sang vng cm thng (cho cu
th c ng knh 52 nm c bao bc bi lp v trc thp chiu). B rng vng cm ca dy nan Si
xt silic kh dy. Trong khi dy Si c kch thc nh s thay i ph thuc vo kch thc ca dy. ng
21,5 nm (hnh 3.b) th ng knh li ca Si tinh th knh dy Si cng gim, b rng vng cm cng tng
khong 8,5 nm. S hnh thnh cu trc li/v nu trn ln [16, 17].
c lin quan n qu trnh hnh thnh dy Si vi mt Hnh 5 th hin ph pht x hunh quang ca
s phn ng ha hc xy ra. R rng, vt liu ngun cu trc li/v dy nan Si o nhit phng. Ph
Si ban u lun b xi ha trong mi trng khng hunh quang th hin hai vng: Vng c bc sng
kh. Khi , C ng vai tr xc tc s tham gia qu t 400 nm n 700 nm v vng pht nh sng vi
trnh kh SiO2 thnh SiO v tham gia vo phn ng nh ph gn bc sng 850 nm. Ngun gc s pht
phn tch to dy Si. nhit cao ln hn 1000 0C, x ca nh sng trong vng bc sng thp (ng vi
xy ra cc phn ng sau [10, 15]: nng lng cao) c xem xt do cc yu t vi s
2SiO2 + C 2SiO + CO2, tham gia ca cc nt khuyt xi c trong lp v v
nh hnh SiOx (cc nh ph ti 443 nm v 540 nm),
SiOx Si1-x + (SiO)x, ng thi do s ti hp ca cc tm ht ti ti phn
2SiO Si + SiO2. bin ca cu trc li v Si/SiOx (cc nh tng ng
bc sng 600 nm v 650 nm) [18].
Trong qu trnh hnh thnh dy nan Si, vt liu
ngun l bt Si bao quanh bi lp xt (SiOx) ti Trong kh , nh ph hunh quang quan st
vng c ht xc tc kim loi l ht nan Au, ni qu c vng nh sng c lin quan n hiu ng
trnh mc theo c ch VLS xy ra. Dy nan Si mt giam gi lng t ca dy nan Si. Nh trn nh
chiu hnh thnh l kt qu ca phn ng phn tch HRTEM trn, dy nan Si c cu trc li/v, trong
li Si tinh th bao bc bi lp xt v nh hnh.

65
Tp ch Khoa hc v Cng ngh 116 (2017) 063-067

Vi trng hp dy c kch thc ln, s tham gia thc ln vi cc dy Si nh hn. Kt qu chp nh


vo qu trnh pht quang do hiu ng lng t gy ra HRTEM v ph EDX cho thy dy Si c cu trc
l khng ng k. Trong kh cc dy Si nh c ng li/v, theo li tinh th Si c bao bc bi lp
knh li l Si tinh th ~8 nm, gn vi gi tr bn knh xt v nh hnh SiOx. S pht quang ca nh sng
Bohr, hiu ng giam gi lng t cc ht ti in s trong ph pht x hunh quang c lin quan n
xy ra v khi dy nan Si s pht quang khi b hiu ng giam gi lng t ca cc ht ti in trong
kch thch bng ngun laser c bc sng 325 nm. li Si tinh th c kch thc nh gn gi tr bn knh
Bohr i vi tinh th Si.
Li cm n
Nghin cu ny c ti tr bi Qu Pht trin
khoa hc v cng ngh Quc gia (NAFOSTED) trong
ti m s 103.02-2015.05.
Ti liu tham kho
[1] Y. Wan, J. Sha, B. Chen, Y. Fang, Z. Wang, and Y.
Wang, Nanodevices based on silicon nanowires.,
Recent Pat. Nanotechnol., vol. 3, no. 1, pp. 19, Jan.
2009.
[2] S. Chen, A. van den Berg, and E. T. Carlen,
Sensitivity and detection limit analysis of silicon
nanowire bio(chemical) sensors, Sensors Actuators B
Chem., vol. 209, pp. 486489, 2015.
Hnh 5. Ph hunh quang ca dy nan Si o nhit [3] C. H. Peters, a. R. Guichard, a. C. Hryciw, M. L.
phng, trong vng pht quang bc sng t Brongersma, and M. D. McGehee, Energy transfer in
400 nm n 700 nm ng vi s ti hp pht quang nanowire solar cells with photon-harvesting shells, J.
do cc tm pht x ti lp xt hoc ti hp vng Appl. Phys., vol. 105, no. 12, p. 124509, 2009.
bin Si/SiOx, trong khi nh pht x ti bc sng [4] C. K. Chan, H. Peng, G. Liu, K. McIlwrath, X. F.
~850 nm do s giam gi lng t ca li Si tinh th Zhang, R. a Huggins, and Y. Cui, High-performance
gy ra. lithium battery anodes using silicon nanowires., Nat.
Nanotechnol., vol. 3, no. 1, pp. 315, Jan. 2008.
T mi quan h gia s pht x hunh quang v
kch thc tinh th nan Si do hiu ng giam gi [5] D. W. Kwak, H. Y. Cho, and W.-C. Yang,
lng t gy ra, c th tnh c kch thc ca li Si Dimensional evolution of silicon nanowires
theo cng thc [19,20]: synthesized by AuSi island-catalyzed chemical vapor
deposition, Phys. E Low-dimensional Syst.
C Nanostructures, vol. 37, no. 12, pp. 153157, Mar.
E g E g0 2007.
d
[6] X. T. Zhou, J. Q. Hu, C. P. Li, D. D. D. Ma, C. S. Lee,
Trong , E g v E g0 tng ng l b rng vng and S. T. Lee, Silicon nanowires as chemical
cm ca Si cu trc nan v cu trc khi, d l sensors, Chem. Phys. Lett., vol. 369, no. 12, pp.
220224, Feb. 2003.
ng knh dy Si, C v l tha s cu trc xc
nh bng thc nghim. Vi dy nan Si, cc gi tr C [7] Fei Zhao, Dan-dan Zhao, Shao-long Wu, Guo-an
= 3,73 v = 1,39. T , kch thc li tinh th theo Cheng and Rui-ting Zheng, Fabrication and Electron
tnh ton l ~ 6,5 nm cho nh ph ti bc sng 850 Field Emission of Silicon Nanowires Synthesized by
nm. Gi tr ny thc t nh hn kch thc o c Chemical Etching, J. Korean Phys. Soc., vol. 55, no.
trn nh HRTEM l 8,5 nm. Tuy nhin, nh trn nh 61, p. 2681, Dec. 2009.
HRTEM nhn c, phn bin tip xc Si/SiOx thc [8] H. Fang, Y. Wu, J. Zhao, and J. Zhu, Silver catalysis
t cha c tnh n. in the fabrication of silicon nanowire arrays,
Nanotechnology, vol. 17, no. 15, pp. 37683774, 2006.
4. Kt lun
[9] E. Zhang, Y. Tang, Y. Zhang, and C. Guo, Synthesis
Dy nan Si tng hp c bng phng and photoluminescence property of silicon carbon
php bc bay nhit s dng ngun xc tc l bt Si:C. nanowires synthesized by the thermal evaporation
Ty thuc iu kin ch to nh lp xc tc v nhit method, Phys. E Low-dimensional Syst.
, cng nh thnh phn hn hp ngun m dy Si Nanostructures, vol. 41, no. 4, pp. 655659, Feb.
nhn c hoc c kch thc kh nh 20-30 nm 2009.
ng u, hoc c s phn b xen k cc dy c kch

66
Tp ch Khoa hc v Cng ngh 116 (2017) 063-067

[10] G. Gundiah, F. L. Deepak, a. Govindaraj, and C. N. R. and chemical analysis of silicon nanowires, Appl.
Rao, Carbon-assisted synthesis of silicon nanowires, Phys. Lett., vol. 81, no. 15, p. 2866, 2002.
Chem. Phys. Lett., vol. 381, no. 56, pp. 579583,
Nov. 2003. [16] a. D. Yoffe, Advances in Physics Low-dimensional
systems: Quantum size effects and electronic
[11] T. Nguyen, T. T. Nguyen, A. X. Vuong, L. D. Mai, T. properties of semiconductor microcrystallites ( zero-
H. Nguyen, C. D. Nguyen, and L. H. Nguyen, dimensional systems ) and some quasi-two-
Growth of silicon nanowires by sputtering and dimensional systems, Adv. Phys., vol. 51, no. January
evaporation methods, Phys. Status Solidi Appl. 2015, pp. 799890, 2002.
Mater. Sci., vol. 210, no. 7, pp. 14291432, 2013.
[17] G. Belomoin, J. Therrien, A. Smith, S. Rao, R.
[12] Z. W. Pan, Z. R. Dai, L. Xu, S. T. Lee, and Z. L. Twesten, S. Chaieb, M. H. Nayfeh, L. Wagner, and L.
Wang, Temperature-Controlled Growth of Silicon- Mitas, Observation of a magic discrete family of
Based Nanostructures by Thermal Evaporation of SiO ultrabright Si nanoparticles, Appl. Phys. Lett., vol. 80,
Powders, J. Phys. Chem. B, vol. 105, no. 13, pp. no. 5, pp. 841843, 2002.
25072514, 2001.
[18] J. A. Rodrguez and M. Aceves-Mijares, Emission
[13] M. Lajvardi, H. Eshghi, M. E. Ghazi, M. Izadifard, Mechanisms of Si Nanocrystals and Defects in SiO 2
and a. Goodarzi, Structural and optical properties of Materials, J. Nanomater., vol. 2014, pp. 117, 2014.
silicon nanowires synthesized by Ag-assisted chemical
etching, Mater. Sci. Semicond. Process., vol. 40, pp. [19] H. Scheel, S. Reich, and C. Thomsen, Electronic
556563, 2015. band structure of high-index silicon nanowires, Phys.
status solidi, vol. 242, no. 12, pp. 24742479, Oct.
[14] A. Kramer, T. Boeck, P. Schramm, and R. Fornari, 2005.
Investigation of Au and In as solvents for the growth
of silicon nanowires on Si(111), Phys. E Low- [20] G. Ledoux, J. Gong, F. Huisken, O. Guillois and C.
dimensional Syst. Nanostructures, vol. 40, no. 7, pp. Reynaud, "Photoluminescence of size-separated
24622467, May 2008. silicon nanocrystals: confirmation of quantum
confinement", Appl. Phys. Lett., vol. 80, pp. 4834-
[15] R. J. Barsotti, J. E. Fischer, C. H. Lee, J. Mahmood, C. 4836, 2002.
K. W. Adu, and P. C. Eklund, Imaging, structural,

67
Tp ch Khoa hc v Cng ngh 116 (2017) 068-071

Tnh cht nhy kh H2S ca cm bin mng mng SnO2/NiO


Fabrication of H2S Gas Sensor bsed on SnO2/NiO Thin Film

Nguyn Vn Ton, Nguyn Vn Duy, Nguyn Vn Hiu*


Trng i hc Bch khoa H Ni S 1, i C Vit, Hai B Trng, H Ni
n Ta son: 25-10-2015; chp nhn ng: 20-12-2016

Abstract
H2S gas sensor based on SnO2 (40 nm)/ NiO (20 nm) thin film was fabricated by DC sputtering method in
combination with photolithography technique. Morphology, crystal structure, and composition of the
synthesized thin film were characterized by SEM, EDS and XRD. The gas-sensing characteristics of the
fabricated sensor were studied by real time measurement of resistance change in air and different
concentrations of H2S gas. Results show that the sensor can measure low concentrations of H2S (2,5 to 10
ppm) at various temperatures ranging from 250 to 400 oC with fast response time (about 13 - 33 seconds)
and fulfill the requirements in air monitoring.
Keywords: SnO2/NiO thin film, Gas sensors, H2S
Tm tt
Bi bo ny gii thiu cc kt qu nghin cu v cm bin kh H2S trn c s mng mng SnO2/NiO (chiu
dy 40 nm/ 20 nm) bng phng php phn x hot ha. Vi cu trc v tnh cht ca vt liu SnO2/NiO
c kho st bng nh hin vi in t qut, ph tn xc nng lng v gin nhiu x tia X. Tnh cht
nhy kh ca cc cm bin c nghin cu mt cch c h thng trong gii nng kh H2S t 2.5 10
ppm v trong gii nhit 250 - 400 oC theo thi gian. Cc kt qu nghin cu cho thy cm bin c thi
gian p ng nhanh (t 13 33 giy) v p ng c yu cu ng dng trong quan trc nhim mi
trng kh.
T kha: mng mng SnO2/NiO, cm bin kh, H2S

1. Gii thiu nim mc, v c th gy hn m hoc t vong ty


thuc vo nng kh tip xc. Gii hn cho php
nhim khng kh gy bi cc kh c khng
*
i vi kh H2S trong mi trng cng nghip l 10
nhng lm nh hng tiu cc n sc khe con
ppm vi thi gian tip xc ngn di 8h lm vic. Do
ngi m cn c th hy hoi mi trng sng cng
, vic pht hin v kim tra nng kh H2S
nh h sinh thi. Cc loi kh c bao gm H2S, NO2,
nng c ppm l vn rt quan trng nhm bo
NH3 c th c thi ra t cc ngun gy nhim
v cuc sng con ngi [2].
nh cc nh my, cc khu cng nghip, cc loi
phng tin giao thng vn ti, v cc hot ng khai C rt nhiu loi cm bin kh khc nhau
thc hm m v chn nui v.v. [1]. Trong s cc kh c pht trin nhm ng dng trong quan trc
c k trn, kh hydrogen sulfide (H2S) c bit n nhim mi trng kh; Th d nh cm bin kh hot
nh l mt cht kh cc k c hi, c th gy nh ng da trn s thay i tnh cht quang ca vt liu
hng trc tip n sc khe con ngi ngay c trong mi trng kh [3]-[4], [9] cm bin kiu in
nng thp c vi phn triu (ppm). Trong t nhin, ha [5] v cm bin o dn [6], [12]-[13]. So vi
kh H2S c sinh ra do cc cht hu c b phn hy, cc cm bin kh s dng tnh cht quang v cm bin
v c th tm thy trong cc bi rc thi, ao h cn, in ha th cm bin o dn trn c s mng
cng rnh hay hm l khai thc than v du m. mng xit kim loi bn dn t ra c nhiu u vit do
thit k n gin, c th hot ng lin tc trong
Kh H2S vi mi c trng ca trng thi rt
khong thi gian di, v c p ng kh cao [1],
c i vi sc khe con ngi. Con ngi c th
[10]. C ch hot ng ca cm bin s dng vt liu
cm nhn c mi ca kh H2S nng rt thp
xit kim loi bn dn da trn s thay i in tr
c 0.13 ppm. Tuy nhin kh nng mi ngi pht
(hay dn in) ca cc lp xit kim loi bn dn
hin mi ca kh H2S b suy gim khi tip xc trong
khi tip xc vi kh cn phn tch [6]. Cm bin kh
mt thi gian di. Khi ht phi kh H2S vi nng
loi ny c u im l thit k n gin, kch thc
thp s gy nh hng n ng h hp, gic mc,
nh, d ch to, in nng tiu th thp, gi thnh r
v c kh nng lm vic trong thi gian di [7]. Mc
*a ch lin h: Tel: (84-4)38680787 d vy, cm bin kh truyn thng trn c s mng
Email: hieu@itims.edu.vn
68
Tp ch Khoa hc v Cng ngh 116 (2017) 068-071

xit kim loi thun khit thng c p ng khng bia: 5 cm, chiu dy bia: 5 mm) phn x mng
cao v c chn lc kh km [8]. Do , nghin cu NiO dy 20 nm (11). S dng cng ngh Liff-off
ch to cm bin kh H2S c nhy cao, gii hn o ty b phn NiO khng s dng (12). Cui cng ta
thp v c chn lc cao vn ang l mt vn cho c phin in cc ch to vo trong mi
thch thc gii nghin cu trn ton th gii. trng khng kh nhit 400oC/2h. Hnh thi v
vi cu trc ca mng mng lp nhy kh c kho
Trong bi bo ny chng ti la chn vt liu
st bi nh hin vi in t qut pht x trng (FE-
mng mng SnO2/NiO (dy 40/20 nm) bng phng
SEM, JEOL 7600) v nhiu x tia X (XRD) v ph
php phn x ch to cm bin o kh H2S. Vic
tn sc nng lng EDS. Tnh cht nhy kh ca cm
thit k v a ra cc quy trnh cng ngh ch to
bin c o c bi h kho st kh t to ca nhm
cm bin trn quy m kch c phin silic (wafer)
iSensor-Vin ITIMS.
c chng ti tp trung nghin cu nhm ch to
c cm bin c p ng cao, thi gian p ng 3. Kt qu v tho lun
nhanh phc v cho vic quan trc nhim mi
Sau khi ch to c th thu c phin Si gm
trng khng kh.
trn 350 cm bin nh trn Hnh 2(a). Hnh dng v
2. Thc nghim kch thc ca cm bin c th thy trn Hnh 2(d),
trong chip cm bin ch to c kch thc 33
Thit k v quy trnh ch to c th hin trn
mm2, trong din tch lp mng mng nhy kh l
Hnh 1. C th, phin Silic loi p (100) kch thc 4
260260 m. Mt v kch thc mng mng SnO2
inch c in tr 1-10 cm c ra sch theo cng
c th quan st trn Hnh 2(c). nh FE-SEM b mt
ngh tiu chun ca cng ngh vi in t (1). Tip
ca mng mng SnO2 sau khi nung nhit 400
theo phin c oxi ha to lp SiO2 dy o
C/2 gi, qua Hnh 2(c) cho thy b mt mng c
ng u cao, cc ht mn nh v c kch thc c 10
(1) (6) n 20 nm. Mc d vy c th thy cc vt dn v
trn b mt mng, y c th l do ng xut ca mng
trong qu trnh ch to.
(2) (7) (a) (b)

(3) (8)

(4) (9) 100 m

(c) (d)

(5) (10)
5 m
Hnh 1. Quy trnh ch to chp cm bin
1 m lm lp cch in bng cng ngh oxi ha 100 nm
m (1). Sau tin hnh ph lp nhy quang v s
dng mt n th nht tin hnh quang khc hnh Hnh 2. Hnh nh cm bin trn phin silic 4 inch (a); nh
dng ca in cc (2, 3). Tin hnh phn x lp Cr c mt chp cm bin (b); nh SEM mng mng SnO2/NiO
chiu dy 5 nm v lp Pt c chiu dy 300 nm lm sau khi ch to (c); v ph EDS ca mng mng SnO2/NiO
in cc (4). Sau khi phn x ta dng cng ngh liff- (d).
off ty b phn Cr/Pt (5). Tip theo ta tin hnh
Trn Hnh 3 l gin nhiu x tia X ca mng
quang khc mt n th 2 m ca s cho lp nhy
SnO2 c x l ti 400 oC/2 gi. Gin nhiu x
ca vt liu (6, 7). Sau dng bia Sn ( sch ca
tia X cho thy xut hin cc nh nhiu x cng
bia t 99,99%, ng knh ca bia: 5 cm, chiu dy
bia: 5 mm) phn x mng SnO2 dy 40 nm trong mnh nht ti 2 = 26,65o ng vi mt (110) v cc
mi trng kh Ar/O2 vi t l 1:1 (8). S dng cng nh ti gc 2 l 33,7o v 51,7o tng ng vi mt
ngh Liff-off ty b phn SnO2 khng s dng (9). (101) v (211) ca SnO2 cu trc t din (JCPDS, 41-
Sau khi ch to mng SnO2 ta tin hnh quang khc 1445).
mt n th 3 m ca s cho lp xc tc (10). Dng Cc nh nhiu x tri rng chng t kch thc
bia NiO ( sch ca bia t 99,99%, ng knh ca ht tinh th ca mng mng kh nh. Theo cng thc

69
Tp ch Khoa hc v Cng ngh 116 (2017) 068-071

thc nghim ca Scherrer c th tnh c kch thc p ng ca cm bin tng ng vi nng kh H2S
tinh th trung bnh d= k/cos. Trong k ~ 0,9 l ti nng 2,5; 5; v 10 ppm ln lt c cc gi tr l
hng s thc nghim, l bc sng ca tia X (i 2,23; 2,63 v 3,31 ln. Tip tc tng nhit vi cc
vi bc x CuK: = 0,154056 nm), l rng ti gii nhit l 300; 350 v 400 oC ta thy nhit
na cao ln nht (Full Wide at Half Maximum) 400 oC p ng ca linh kin l cc i, ng vi
ca nh ph tnh theo radian, l gc nhiu x ca tt c cc nng kh kho st. Ln lt l 4,02; 6,25
nh ph . Gi tr c tnh kch thc tinh th trung v 8,67. iu cho thy cm bin c mng mng
bnh ca mng mng SnO2 l khong 12 nm. Mc d SnO2/NiO ch to bng phng php phn x lm
vy khng pht hin c s sut hin nh nhiu x vic tt nht gii nhit 400 oC. Qua Hnh 4(b) ta
ca NiO trn gin nhiu x tia X. iu ny c th thy nhy ca mng mng SnO2/NiO c nhy
gii thch do mng NiO qu mng, nn tn hiu ca cao nht 400 oC v nhy tng dn u khi ta tng
NiO b ln t bi tn hiu ca SnO2. Tuy nhin qua nng kh. nhy cao nht t 8,67 ln ng vi
ph tn sc nng lng EDS ca mng mng (Hnh nhit 400 oC vi nng kh l 10 ppm kh H2S.
2(d)) cho thy hp phn ca cc nguyn t c mt 2.5 ppm 5 ppm 10 ppm
trong mu vi cc nguyn t chnh l Sn, O, NiO, Si. 120 (a)
10 o
250 C

Ngoi tr Si l tn hiu t nn, cc nguyn t Sn, O,


o
300 C (b)

400 C
80 o
350 C

o
NiO l cc nguyn t m chng ta ch to. 40
8
o
400 C

105

in tr ()
SnO2 (110)

p ng (Ra/Rg)
Tetragonal SnO2 70

350 C
o
35 6
JCPDS, No. 41 - 1445
C-ng (.v.t.y.)

120
SnO2 (101)

80

300 C
o
SnO2 (211)

4
40
SnO2 (200)

105

250 C
70 2
SnO2 (210)

o
35

0 250 500 750 1000 1250 2,5 5,0 7,5 10,0


Thi gian (s) Nng kh (ppm)

Hnh 4. (a) p ng kh ca cm bin theo thi gian ti cc


25 30 35 40 45 50 55
o nhit v nng kh khc nhau; (b) p ng ph
Gc qut 2 ( .) thuc nng kh.
Hnh 3. Gin nhiu x tia X. Ta nhn thy vt liu NiO l cc xit kim loi
nh gi c trng nhy kh ca mng ta da bn dn loi p. Khi bin tnh trn b mt mng mng
vo cng thc S = Ra/Rg, Ra l in tr ca cm bin SnO2, (l bn dn loi n) to ra tip xc p-n. Di tc
trong mi trng khng kh, Rg l in tr ca cm dng ca xc tc l mng mng NiO, cc n nguyn
bin trong mi trng kh o.Qua cng thc ny ta t hydro tch ra t phn t H2S s d dng phn ng
tnh c c trng nhy kh ca mng. Tin hnh vi oxi hp ph trn b mt SnO2 [14]. Phn t oxi
kho st c trng nhy kh ca cm bin vi mng hp ph c gii phng, tr li in t cho mng
SnO2/NiO chng ti cp in p cho l vi nhit v mng, lm gim in tr ca mng mng t lm
xc nh in tr ca mng nhy SnO2/NiO. in p thay i bn cht ca tip xc p-n gia NiO v SnO2.
cp vo l vi nhit c hng chc V, tng ng t Thi gian p ng (res) v thi gian hi phc
c cc nhit l 250 400 oC. Nng kh H2S (rec) l nhng thng s quan trng khc nh gi
kho st trong di t 2,5 n 10 ppm. S thay i cm bin kh. Thi gian p ng c tnh l thi
in tr ca cm bin khi c s thi/ngt kh H2S gian in tr ca cm bin gim n 90% ca gi
c ghi li trn Hnh 4(a). Ti cc nhit kho st, tr in tr ban u tnh t thi im o kh H2S. Thi
in tr ca cm bin gim i, iu ny chng t vi gian hi phc l thi gian in tr cm bin tr v
bn cht ca cht bn dn loi n khi c s p ng 90% ca gi tr in tr ban u (trong mi trng
vi cc loi kh kh. Ta thy c c trng p ng khng kh). Thng s c th c tnh trn d liu v
cm bin sau khi cho kh H2S, in tr mng nhy khi in tr theo thi gian ca cm bin ti lm vic theo
c kh cng t c trng thi n nh. Khi ngt kh nhit c th hin trn Hnh 5. Kt qu cho thy
H2S, in tr mng nhy phc hi gn 100% v gi s i ca thi gian p ng v thi gian hi phc
tr in tr ban u. iu cho thy mng mng ca cm bin theo nng kh H2S ti nhit lm
SnO2/NiO ch to c kh n nh. p ng ca vic 250- 400 oC. Thi gian p ng ca cm bin
cm bin tun theo gi tr tuyn tnh khi c s thay mng mng SnO2/NiO l kh ngn, di 35 giy; cn
i nng kh thi v khng theo quy lut khi thi gian hi phc cng kh ngn, di ba pht ty
thay i nhit lm vic. Ti nhit 250 oC

70
Tp ch Khoa hc v Cng ngh 116 (2017) 068-071

thuc vo nng kh a vo. Ta thy khi nng Chromatographia 71 (2009) 259265.


kh H2S tng t 2,5 ppm n 10 ppm, kt qu l thi doi:10.1365/s10337-009-1434-z.
gian p ng gim dn khi nhit tng ln v thi [4] H. Nguyen, C.T. Quy, N.D. Hoa, N.T. Lam, N. Van
gian hi phc th c xu hng ngc li. Thi gian Duy, V. Van Quang, et al., Controllable growth of
p ng v thi gian hi phc ca cm bin s ZnO nanowires grown on discrete islands of Au
dng ngn c th ng dng trong thc t. catalyst for realization of planar-type micro gas
sensors, Sens. Actuators B 193 (2014) 888894.
400 C doi:10.1016/j.snb.2013.11.043.
350 C
300 C
(a) (b)
250 C [5] N.D. Hoa, N. Van Quy, M. An, H. Song, Y. Kang, Y.
100 100
Cho, et al., Tin-Oxide Nanotubes for Gas Sensor
Thi gian hi phc (s)

Application Fabricated Using SWNTs as a Template,


Thi gian p ng (s)

J. Nanosci. Nanotechnol. 8 (2008) 55865589.


doi:10.1166/jnn.2008.1387.

400 C [6] P. Samarasekara, N.T.R.N. Kumara, N.U.S. Yapa,


350 C Sputtered copper oxide (CuO) thin films for gas
300 C
250 C sensor devices, J. Phys. Condens. Matter. 18 (2006)
24172420. doi:10.1088/0953-8984/18/8/007.
10 10
2,5 5,0 7,5 10,0 2,5 5,0 7,5 10,0

Nng kh (ppm) Nng kh (ppm) [7] H. Liu, S.P. Gong, Y.X. Hu, J.Q. Liu, D.X. Zhou,
Properties and mechanism study of SnO2 nanocrystals
Hnh 5. Thi gian p ng v hi phc ca cm bin. for H2S thick-film sensors, Sens. Actuators B 140
(2009) 190195. doi:10.1016/j.snb.2009.04.027.
4. Kt lun
[8] D.J. Yoo, J. Tamaki, S.J. Park, N. Miura, N.
Cm bin kh H2S trn c s mng mng Yamazoe, H2S sensing characteristics of SnO2 thin
SnO2/NiO c ch to thnh cng. Cng ngh film prepared from SnO2 sol by spin coating, J.
ny cho php ch to quy m ln cc chp (~400 Mater. Sci. Lett. 14 (1995) 13911393.
chp/1 phin Si 4-inch) cm bin bng s kt hp doi:10.1007/BF00270739.
gia phng php phn x hot ha v quang khc.
[9] S.-W. Choi, A. Katoch, J. Zhang, S.S. Kim,
nh hng ca mng mng SnO2/NiO ln tnh nhy Electrospun nanofibers of CuO/SnO2 nanocomposite
kh H2S trong gii nng t 2,5 10 ppm v trong as semiconductor gas sensors for H2S detection, Sens.
gii nhit t 250 400 oC theo thi gian c Actuators B 176 (2013) 585591.
kho st. Cm bin cng c th lm vic c trong doi:10.1016/j.snb.2012.09.035.
iu kin nhit thp l 250 oC vi p ng t
2,23 ln vi nng 2,5 ppm kh H2S. Thi gian p [10] G.J. Fang, Z.L. Liu, C.Q. Liu, K.L. Yao, Room
temperature H2S sensing properties and mechanism of
ng ca cm bin nhanh trong khong t 13-33 giy 2CeOSnO solgel thin films, Sens. Actuators B, 6
ty thuc vo nhit v nng kh o. D trn (2000) 46.
quy trnh cng ngh ch to ny hon ton c th pht
trin ch to c s lng ln cm bin o kh [11] Mukta V. Vaishampayan, Rupali G. Deshmukh,
H2S quy m cng nghip. Pravin Walke, I.S. Mulla, Fe-doped SnO2
nanomaterial: A low temperature hydrogen sulfide
Li cm n. Cng trnh ny c thc hin vi s ti gas sensor, Materials Chemistry and Physics 109
tr ca ti cp Trng m s: T 2015 - 068 (2008) 230234.
doi:10.1016/j.matchemphys.2007.11.024
Ti liu tham kho
[12] D.-L. Tang, S. He, B. Dai, X.-H. Tang, Detection H2S
[1] S.K. Pandey, K.-H. Kim, K.-T. Tang, "A review of mixed with natural gas using hollow-core photonic
sensor-based methods for monitoring hydrogen bandgap fiber, Opt. - Int. J. Light Electron Opt. 125
sulfide", TrAC Trends Anal. Chem. 32 (2012) 8799. (2014) 25472549. doi:10.1016/j.ijleo.2013.10.097.
doi:10.1016/j.trac.2011.08.008.
[13] D.D. Vuong, G. Sakai, K. Shimanoe, N. Yamazoe,
[2] Y. Guan, C. Yin, X. Cheng, X. Liang, Q. Diao, H. Hydrogen sulfide gas sensing properties of thin films
Zhang, et al., Sub-ppm H2S sensor based on YSZ and derived from SnO2 sols different in grain size, Sens.
hollow balls NiMn2O4 sensing electrode, Sens. Actuators B 105 (2005) 437442.
Actuators B 193 (2014) 501508. doi:10.1016/j.snb.2004.06.034.
doi:10.1016/j.snb.2013.11.072.
[14] N. Van Hieu, P. Thi Hong Van, L. Tien Nhan, N. Van
[3] J.-Z. Dong, S.M. DeBusk, GCMS analysis of Duy, N. Duc Hoa, Giant enhancement of H2S gas
hydrogen sulfide, carbonyl sulfide, methanethiol, response by decorating n-type SnO2 nanowires with
carbon disulfide, methyl thiocyanate and methyl p-type NiO nanoparticles, Appl. Phys. Lett. 101
disulfide in mainstream vapor phase cigarette smoke, (2012) 253106. doi:10.1063/1.4772488.

71
Tp ch Khoa hc v Cng ngh 116 (2017) 068-071

72
Tp ch Khoa hc v Cng ngh 116 (2017) 072-076

nh hng ca kim loi xc tc khi tng hp ng nano ccbon


bng phng php CVD nhit
The Role of Catalyst Metal in Synthesis of Carbon Nanotubes by Thermal CVD Method

Nguyn Cng T*, Nguyn Hu Lm


Trng i hc Bch khoa H Ni, S 1, i C Vit, Hai B Trng, H Ni
n Ta son: 20-6-2016; chp nhn ng: 20-12-2016

Tm tt
ng nano ccbon c tng hp bng phng php lng ng nhit ha hc t pha hi vi kh ngun
ccbon l axilen (C2H2), kim loi xc tc l hp kim permalloy (Fe19Ni81). S hnh thnh, kch thc v hnh
thi ca ng nano ccbon ph thuc vo lp kim loi xc tc v nhit . 750 oC, vi mng kim loi xc
tc dy 10 nm, ng nano ccbon thu c c nh hng thng ng, tuy nhin nu b dy mng kim loi
xc tc ln hn 20 nm, ng nano ccbon khng th hnh thnh. Trong vng nhit 650 oC - 850 oC, nhit
kim loi xc tc cng cao, ng knh ca ng nano ccbon thu c cng ln v mt gim.
T kha: ng nano ccbon, c ch VLS, CVD nhit, kim loi xc tc
Abstract
Carbon nanotubes were synthesized by thermal chemical vapor deposition method using acetylene (C 2H2)
as carbon precursor, permalloy (Fe19Ni81) as catalyst. The formation, dimension and morphology of
nanotubes were strongly depended on the parameters of catalyst thin film and sintering temperature. At
750oC, with 10-nm thickness catalyst film, carbon nanotubes were aligned vertically, but when catalyst film
was thicker than 20 nm, no CNT was observed. In the range from 650 oC to 850 oC, at higher sintering
temperature, the obtained carbon nanotubes had larger diameter.
Keywords: carbon nanotubes, VLS mechanism, thermal CVD, catalyst metal.

1. Gii thiu1 VLS, ht kim loi xc tc ng vai tr ct li.


mc CNT, cc kim loi xc tc c s dng a phn
ng nano ccbon (Carbon Nanotube - CNT), vi
l kim loi chuyn tip v phi tha mn mt s yu
nhng tnh cht ni tri v c, in, thu ht rt nhiu
cu sau: c kh nng ha tan ccbon to thnh hp
s quan tm ca cc nh khoa hc trn th gii. Cc
cht ccbit; dng lng c kh nng ha tan ccbon
nghin cu v tng hp CNT cng nh cc nghin cu
ln hn so vi dng rn; p sut hi bo ha ca
v pht trin ng dng ca CNT vn ang l cc ch
kim loi hay hp kim xc tc thp khng b bay
hp dn [1-5]. Trong cc phng php tng hp CNT
hi trong qu trnh mc CNT; tr vi phn ng phn
ph bin nh nghin bi, bc bay bng chm laser,
ng ha hc nu khng tnh xc tc ca n s b th
phng php lng ng ha hc t pha hi (Chemical
ng ha do phn ng; khng tc thi to thnh pha
Vapor Deposition CVD), th phng php lng ng
rn lm v hiu tnh xc tc ca kim loi; v c th l
nhit ha hc t pha hi (Thermal CVD) hay CVD nhit
kim loi xc tc cho phn ng phn hy nhit ca kh
l phng php c s dng rng ri nht. u im
ngun ccbon [12-14]. Cc kim loi xc tc c s
ca phng php ny l d dng iu khin c hnh
dng ph bin l Fe, Ni, Co hay hp kim permalloy
thi ca CNT thng qua vic iu khin cc thng s
(Fe, Ni), Co-Mo Cc thng s k thut ca kim loi
ca qu trnh tng hp nh thi gian phn ng, b dy
xc tc nh b dy mng kim loi xc tc, thm
mng xc tc, nhit phn ng, v c th mc CNT ti
thu ccbon khng nhng nh hng ln ti tc
v tr chn lc [6-11].
phn ng phn hy nhit, tc mc m cn nh
gii thch cho s hnh thnh ca CNT tng hng ti kh nng mc nh hng thng ng ca
hp bng phng php CVD nhit, cc nh khoa hc cu trc nano mt chiu [12-18].
s dng c ch Hi-Lng-Rn (VaporLiquidSolid -
Trong bi bo ny chng ti s trnh by nh
VLS) - c ch ph bin gii thch cho qu trnh
hng ca kim loi xc tc ti hnh thi, tnh nh
hnh thnh cc cu trc mt chiu. Trong c ch
hng ca CNT tng hp bng phng php CVD
nhit vi kh ngun l C2H2. Kim loi xc tc c s
dng l permalloy (Fe19Ni81). Cc kt qu thu c s
1
a ch lin h: Tel.: (+84) 985.450.355 c nh gi v so snh vi cc kt qu ca cc nhm
Email: tu.nguyencong@hust.edu.vn
72
Tp ch Khoa hc v Cng ngh 116 (2017) 072-076

nghin cu khc a ra nh gi v nh hng v vai 3. Kt qu v tho lun


tr ca kim loi xc tc. Hnh thi ca CNT s c
Trong qu trnh hnh thnh CNT theo c ch
kho st bng knh hin vi in t qut (Scanning
VLS, ng knh ngoi ca CNT c xc nh bi
Electron Microscopy - SEM).
kch thc ca ht kim loi xc tc, v do n nh
hng ti hnh thi cng nh tnh cht ca CNT.
CNT n vch hay hai vch s u tin mc t cc ht
kim loi xc tc c kch thc nh c mt vi nano
mt hoc nh hn [14,16]. Vi cc ht xc tc c
kch thc ln, CNT a vch s hnh thnh [14,18].
Tuy nhin khng phi kch thc no ca ht kim
loi xc tc cng h tr cho CNT hnh thnh. hnh
thnh CNT, kch thc ht kim loi xc tc phi nh
hn chiu di khuch tn ca phn t ccbon [6,19].
Nh vy kch thc ca ht kim loi xc tc l mt
thng s quan trng nh hng ti vic hnh thnh v
ti hnh thi ca CNT.
(a)
Vic iu khin kch thc ht kim loi xc tc
l rt phc tp, n ph thuc vo nhiu yu t nh b
dy mng kim loi xc tc, bn cht kim loi, nhit
, p sut Bn knh nh nht ca ht kim loi xc
tc th lng c xc nh theo cng thc sau:
2Vl
Rmin lv (1)
RT ln s

Trong : Rmin l bn knh nh nht c th; Vl l th


tch ca 1 mol cht lng kim loi xc tc, R l hng
(b) s kh, T nhit tuyt i ca , s l qu bo
Hnh 1. S tng qut ca h CVD nhit ch to ha pha hi, lv l nng lng b mt gia hai pha
CNT (a) v m hnh mng kim loi xc tc trn lng-kh ca kim loi [13]. Trong bi bo ny, chng
SiO2/Si (b) ti nghin cu nh hng ca b dy lp xc tc v
2. Thc nghim nhit x l (T) ti vic hnh thnh cc ht kim
loi xc tc v ti hnh thi ca CNT.
CNT c tng hp bng phng php CVD
nhit vi h l ngang (Hnh 1.a). s dng l 3.1. B dy mng
Si(100) c xi ha to mt lp SiO2 dy Chng ti tin hnh tng hp CNTs vi cc
1m. Trn SiO2/Si ph mt mng mng kim loi mng xc tc permalloy c b dy khc nhau t 1 nm
xc tc permalloy (Hnh 1.b) bng h bc bay bng n 30 nm 750 oC. Vi cc mng xc tc c b dy
chm in t (BOC Edwards Auto 500 Electron nh hn 20 nm, CNT thu c trong tt c cc th
Beam Evaporation System). B dy mng kim loi nghim. Trn hnh 2 l nh SEM ca CNT mc t
xc tc c o chnh xc ti 0,1 nm bng b vi cn mng permalloy dy 10 nm (Hnh 2.a) v 15 nm
tinh th thch anh (Quart Crystal Microbalance - (Hnh 2.b) 750 oC. CNT thu c c ng knh c
QCM) tch hp trong h bc bay bng chm in t. vi chc nm, c ln vi ccbon v nh hnh trn b
Kh N2 c s dng to mi trng tr cho qu mt v l CNT a vch nh cc kt qu cng b
trnh nng nhit, qu trnh phn ng cng nh qu [10]. Vi mng kim loi xc tc c b dy ln hn 20
trnh h nhit sau phn ng. Kh N2 cng ng nm, chng ti khng thu c CNT m ch thu c
thi to p sut dng y cc sn phm ca cc si ccbon c kch thc ln ~ 300 nm trn lp
phn ng phn hy nhit i ra ngoi. Kh NH3 c ccbon v nh hnh (hnh nh khng th hin trong
s dng kh cc ht kim loi xc tc trong 30 pht bi bo ny). Nh vy 750 oC, b dy ti hn ca
qu trnh nhit - trc khi a kh ngun ccbon mng permalloy h tr cho s hnh thnh CNT
C2H2 vo phn ng. Kh C2H2 a vo bung phn trn SiO2/Si l 20 nm. Chiu dy ti hn ca mng
ng vi lu lng 50 mL/pht cng vi 400 mL/pht xc tc cho qu trnh tng hp CNT c l gii l do
kh N2 ng vai tr kh mang. Chi tit ca qui trnh kch thc ti hn ca cc ht kim loi xc tc. Khi
phn ng c th tm thy trong cc cng b khc ca x l nhit mng kim loi xc tc trc khi a kh
nhm [10,11]. ngun ccbon vo phn ng, do sc cng b mt,
mng kim loi s tr thnh cc o, cc m kim loi

73
Tp ch Khoa hc v Cng ngh 116 (2017) 072-076

hay cc ht kim loi. cng mt nhit x l, kch [13]. Tnh nh hng ca cc CNT l do tng tc
thc cc ht kim loi xc tc tng tuyn tnh vi b vt l gia cc CNT lc Van der Waals [11]. Khi
dy mng [16,20]. V vy khi b dy ln, cc ht cc CNT cng ng u v cng st nhau (mng kim
kim loi xc tc c kch thc ln hn di khuch loi xc tc mng ~ 10 nm) mt CNT cao lc
tn ca ccbon v do n khng h tr cho s hnh tng tc cng ln, v trong qu trnh mc cc CNT
thnh ca CNT [6,19]. ta vo nhau mc thng ng (Hnh 3.a).
Vi mng kim loi xc tc c b dy ln, cc
ht kim loi xc tc to ra c kch thc trung bnh
ln hn. Tuy nhin cc ht to ra c kch thc
khng ng u, n gm cc ht to nm xen k vi
cc ht nh. Cc ht c kch thc ln hn chiu di
khuch tn ca ccbon s khng h tr CNT hnh
thnh, ch cc ht c kch thc nh hn chiu di
khuch tn ca ccbon mi ph hp lm mm cho s
hnh thnh ca CNT. Cc CNT hnh thnh t cc ht
kim loi xc tc nm xen k gia cc o kim loi
ln, v cch xa nhau, do chng gn nh khng
tng tc vi nhau mc nh hng (Hnh 3.b).

(a) (b)

Hnh 2. nh SEM ca mng CNT mc vi lp kim


loi xc tc permalloy dy 10 nm (a) v 15 nm (b). (c)
Hnh nh tng ng vi nh SEM chp ct ngang
mu.
Hnh 3. M hnh gii thch cho s hnh thnh ca
Cc nh nh trn cc gc ca hnh 2.a v 2.b l rng CNT nh hng thng ng (a); s hnh thnh
nh chp ct lp tng ng ca cc mu. Ta thy ca mng CNT nh hng thp (b); Hnh SEM
rng vi CNT mc trn mng dy 10 nm (Hnh 2.a) chp ct lp ca mu CNT mc nghing (c). Cc
c nh hng thng ng. Cc kt qu tng t ng nt t trong hnh c ch r hn hng
cng thu c vi cc mng xc tc dy 5 nm v 7 nghing ca CNT trong tng khu vc.
nm [10]. Trong khi vi mng dy 15 nm (Hnh 2.b),
Lc tng tc Van der Waals gia cc CNT cn
CNT nh hng ngu nhin v kch thc khng
dn ti h qu l cc CNT mc pha ngoi ca
ng u. Nh vy b dy mng xc tc khng ch
mng c tnh nh hng thp hn hay b nghing
nh hng ti kh nng hnh thnh CNT m cn nh
nhiu hn do ch c tng tc vi cc CNT bn
hng ti tnh nh hng ca CNT thu c. Khc
trong mng. Suy on ny c khng nh khi
vi cc cu trc mt chiu khc nh si hay thanh
chng ti quan st nh SEM chp ct lp phn mp
nan mc nh hng do tnh tng thch gia cu
ca mng CNT mc 750 oC (Hnh 3.c). nh SEM
trc tinh th ca vt liu nh ZnO, Si vi vt liu

74
Tp ch Khoa hc v Cng ngh 116 (2017) 072-076

cho thy xu hng gim nghing hay s tng ca khi tng nhit x l mng kim loi xc tc, chng
nh hng thng ng ca cc CNT khi i t mp ti thu c CNT c ng knh ln hn, v mt
ca mng CNT (pha bn phi) vo trong mng CNT xp kht thp hn. trn 900 oC, chng ti ch thu
(pha bn tri). Hirose v cc cng s s dng s c si ccbon c kch thc ln. Hnh 4 l nh
thay i lc tng tc Van der Waals theo v tr ny SEM chp ct lp ca CNTs mc 750 oC (Hnh 4.a)
iu khin nh hng ca mng CNT [21]. v 850 oC (Hnh 4.b). T nh SEM c th cho thy
rng nhit 750 oC, ng CNT hnh thnh c
ng knh nh hn v mt xp kht cao hn so
vi CNT nhn c nhit 850 oC. Nh vy, khi
tng nhit , ng knh ca CNT tng v xp
kht ca cc CNT thng ng gim. Kt qu ny ca
chng ti ph hp vi kt qu m Siegel v cng s
thu c [8].
S tng kch thc theo nhit c l gii
l do, khi tng nhit , kch thc trung bnh ca
ht kim loi xc tc tng dn, khi tng n kch thc
ti hn (ln hn chiu di khuch tn tng ng ca
ccbon) th cc si ccbon hnh thnh thay cho CNT.
Nu tip tc tng nhit , kch thc trung bnh
tip tc tng, nhng lc ny xut hin ng thi cc
ht kim loi xc tc rt nh (Rmin ~ mt vi nano mt)
nm xen k gia cc ht kim loi rt ln, cc ht ny
c kch thc nh h tr s hnh thnh ca
CNT n vch [14,15,18]. V vy tng hp CNT
n vch t cc mng kim loi xc tc, cc nhm
thng tng hp nhit cao.
4. Kt lun
Chng ti trnh by cc kt qu nghin cu
v nh hng ca mng kim loi xc tc ti qu trnh
tng hp CNT bng phng php CVD nhit. B
dy ti hn ca mng xc tc permalloy trn
SiO2/Si mc CNT 750 oC l 20 nm. Vi b dy
trong khong t 5 10 nm, CNT c c nh hng
thng ng. Nhit nh hng phc tp ti s
Hnh 4. nh SEM chp ct ngang ca rng CNT hnh thnh CNT. Trong di nhit t 650 oC n
mc nh hng thng ng vi mng kim loi xc 850 oC, khi tng nhit , ng knh ca CNT tng
tc permalloy dy 10 nm, tng hp nhit 750 oC v mt CNT gim.
(a) v 850 oC (b). Li cm n
3.2 nh hng ca nhit Nghin cu ny c ti tr bi Qy Pht trin
nh hng ca nhit l rt phc tp, c hai Khoa hc v Cng ngh Quc gia (NAFOSTED)
thng s nhit nh hng ti qu trnh mc CNT trong ti m s 103.02-2015.05.
l: nhit phn ng hay nhit mc CNT v nhit Ti liu tham kho
hnh thnh ht kim loi xc tc. Khi nghin cu
tch bit nh hng ca nhit phn ng v nhit [1] E. Shawat, V. Mor, L. Oakes, Y. Fleger, C.L. Pint, G.
ti vic hnh thnh CNT, cc nhm nghin cu D. Nessim, Nanoscale, 6 (2014) 1545-1551.
trn th gii cho thy nhit phn ng khng nh [2] Haider Almkhelfe, Jennifer Carpena-Nez, Tyson C.
hng nhiu ti kch thc ca CNT. Kch thc ca Back and Placidus B. Amama, Nanoscale, 8 (2016)
CNT ch b nh hng bi nhit x l mng kim 13476-13487.
loi xc tc hay nhit [19,20]. Trong bi bo [3] J. Lee, I.Y. Stein, S.S. Kessler, B.L. Wardle, Applied
ny, chng ti trnh by nh hng ca nhit ti Materials and Interfaces, 7(16), (2015) 8900-8905.
kch thc ca CNT. T cng thc (1) ta thy rng
khi tng nhit cng cao, kch thc nh nht [4] J.P. Giraldo, M. P. Landry, S.M. Faltermeier, T.P. Mc
Nicholas, N.M. Iverson, A.A. Boghossian, N.F.
ca ht kim loi xc tc cng gim. Tuy nhin, trong
Reuel, A.J. Hilmer, F. Sen, J.A. Brew , M.S. Strano,
gii nhit t 650 oC n 850 oC c nghin cu, Nature Materials, 13 (2014) 400-408.

75
Tp ch Khoa hc v Cng ngh 116 (2017) 072-076

[5] A. Lenert, D.M. Bierman, Y. Nam, W.R. Chan, I. nanostructures for optoelectronic devices processing
Celanovic, M. Soljacic, E. N. Wang, Nature characterixation and applications, Yi Guy-Chun
Nanotechnology, 9 (2014) 400-408. (Editor), ISBN: 978-3-642-22479-9 (2012) 9.
[6] Y. Y. Wei, G. Eres, V. I Merkulov, D. H. Lowndes, [14] H. U. Rashid, K. Yu, M. N. Umar, M. N. Anjum, K.
Applied Physics Letters, 78(2001) 1394-1396. Khan, N. Ahmar, M. T. Jan, Reviews on Advanced
Materials Science, 40 (2015) 235-248.
[7] S. Fan, M. G. Chapline, N. R. Franklin, T. W.
Tombler, A. M. Cassell, H. Dai, Science, 283 (1999) [15] V.L. Kuznetsov, A.N. Usoltseva, A.L. Chuvilin, E.D.
512-514. Obraztsova, J-M Bonard, Physical review B, 64
(2001) 235401-235407.
[8] M. P. Siegel, D. L. Overmyer, P. P. Provencio,
Applied Physics Letters, 80 (2002) 2171. [16] Q.A. Nerushev, S. Dittmar, R.E. Morjan, F.
Rohmund, E. E.B. Campbell, Journal of Applied
[9] K.-H. Lee, J.-M. Cho, W. Sigmund, Applied Physics Physics, 93 (7), (2003) 4185-4190.
Letters, 82 (2003) 448.
[17] Wei-Wen Liu, Azizan Aziz, Sian-Piao Chai, Abdul
[10] N C Tu, L D Huy, L H Bac, P Q Pho, N D Chien, T X Rahman Mohamed, U. Hashim, Journal of
Thang, N N Trung, N H Lam, Synthesis of multi- Nanomaterials, 2013 (2013) ID 592464.
walled and single-walled carbon nanotubes by
thermal CVD method, Proceedings of the Eleventh [18] S. B. Sinnott, R. Andrews, D. quian, A. M. Rao, Z.
Vietnamese-German Seminar on Physics and Mao, E. C. Dickey, F. Derbyshire, Chemical Physics
Engineering, Nha Trang City, from March 31st to Letters, 315 (1999) 25-30.
April 5th (2008) 85-88.
[19] O. A. Nerushev, R. E. Morjan, D. I. Ostrovskii, M.
[11] N H Lam, N C Tu, L D Huy, L H Bac, T X Thang, P Sveningsson, M. Jonsson, F. Rohmund, E. E. B.
Q Pho, N D Chien, Advances in Natural Sciences, 10 Campbell, Physica B, 323 (2002) 51-59.
(2), (2009) 215-218.
[20] Eric R. Meshot, Desire L. Plata, Sameh
[12] X. Z. Liao, A. Serquis, Q. X. Jia, D. E. Peterson, Y. Tawfick, Yongyi Zhang, Eric A. Verploegen and A.
T. Zhu, H. F. Xu, Applied Physics Letters, 82(16), John Hart, ACS Nano, 3(9) (2009) 24772486.
(2003) 2694-2696.
[21] Q. Yang, C. Xiao, W. Chen, A. K. Singh, T. Asai, A.
[13] Heon-Jin Choi, Chapter 1: VLS growth of Hirose, Diamond and related materials, 12 (2003)
semiconductor nanowires, Book: Semiconductor 1482-1487.

76
Tp ch Khoa hc v Cng ngh 116 (2017) 072-075

Xc nh hot tnh sinh hc ca hn hp tinh du v qu chanh v cam


Determination of Biological Activity of Mixture Lime and Orange Peel Oils

Nguyn Vn Li1,*, L Th Phng2


1
Trng i hc Cng nghip H Ni, Minh Khai, Bc T Lim, H Ni
2
Trng i hc Gio dc, i hc Quc gia H Ni, Xun Thy, Cu Giy, H Ni
n Ta son: 14-3-2016; chp nhn ng: 20-12-2016

Tm tt
Trong nghin cu ny xc nh kh nng khng vi khun ca tinh du v qu chanh (TDA), tinh du v
qu cam (TDB) v hn hp hai loi tinh du ny trn hai nhm vi khun Gram m Escherichia coli v Gram
dng Staphylococcus aureus. C hai loi tinh du u th hin tc dng c ch s pht trin ca chng
Escherichia coli vi ng knh vng trn khng khun l 39 2,8 mm (tinh du v qu chanh) v 32 1,5
mm (tinh du v qu cam). Vi chng Staphylococcus aureus, ng knh vng trn khng khun 43 3,5
mm (tinh du v qu chanh) v 37 1,4 mm (tinh du v qu cam). Nng c ch ti thiu (MIC) ca tinh
du v qu chanh trn c hai chng l 6,25 l/ml; tinh du v qu cam trn chng Escherichia coli: 6,25
l/ml v chng Staphylococcus aureus: 3,35 l/ml. Vi th tch tinh du v qu chanh s dng (0,1- 0,2
l/ml) v tinh du v qu cam (0,8-1,6 l/ml) cho kt qu cng hng mnh nht (FIC 0,5) trn c hai
chng vi khun Staphylococcus aureus v Escherichia coli. Bng phng php DPPH xc nh c kh
nng chng oxy ha ca hn hp tinh du v qu chanh v cam l 45,56 0,25%.
T kha: Hot tnh sinh hc, Hn hp, Tinh du v qu chanh, Tinh du v qu cam
Abstract
The aim of this study was to evaluate the antimicrobial activity of oils against food-related bacteria gram
negtive Escherichia coli and gram positive Staphylococcus aureus by using lime, orange peel oils in
individual and in mixture. Both tested oils showed effective inhibition against Escherichia coli with inhibition
zones of 39 2.8 mm (lime peel oil) and of 32 1.5 mm (orange peel oil). They also inhibited
Staphylococcus aureus with inhibition zones of 43 3.5 mm (lime peel oil) and of 37 1.4 mm (orange peel
oil). The minimum inhibitory concentrations (MIC) of lime peel oil against both tested strains were 6.25 l/ml;
orange peel oil on a strains of Escherichia coli: 6.25 l / ml and Staphylococcus aureus: 3.35 l / ml. With
volume of lime peel oil used (0.1- 0.2 l/ml) and orange peel oil (0.8-1.6 l/ml) for maximum resonance
results (FIC 0.5) on both strains of Staphylococcus aureus and of Escherichia coli. The antioxidant
activity was determined by using DPPH and it was 45.56 0.25%.
Keywords: Biological activity, Mixtures, Lime peel oil, Orange peel oil.

1. M u vic to mi thm c trng cho tinh du v qu


chanh v cam. Cc cu t to mi thm c trng
Tinh*du c s dng rng ri trong nhiu lnh
thuc nhm chc andehit, ancol, este c kh khng
vc khc nhau nh thc phm, m phm, dc
khng khun mnh trn cc chng vi khun
phm khng ch nh mi thm c trng hp dn
Staphylococcus aureus, Escherichia coli, Salmonella
m cn nh vo kh nng c ch vi khun ca mt s
typhy v Bacillus cereus [1], [2]. Hin nay trn th
cu t c trong tinh du. Tinh du v qu chanh v
gii cng nh trong nc c nhiu cng trnh
cam, c mi thm hp dn, trong hai loi tinh du ny
nghin cu v hot tnh sinh hc ca tinh du v b
c cha cc cu t to mi thm c trng thuc
sung tinh du vo thc phm. Tuy nhin cc cng
nhm terpenoid. Cc cu t to mi thm c trng
trnh nghin cu v hot tnh sinh hc ca hn hp
trong tinh du v qu cam snh Hm Yn (octanal,
tinh du v qu chanh v cam th cn rt khim tn.
nonanal, citronellal, decanal, geranial) v trong tinh
Trong nghin cu ny xc nh c kh nng
du v qu chanh giy Hm Yn (octanal,
khng khun ca hn hp tinh du v qu chanh v
citronellal, decanal, dodecanal, geranial, tridecanal)
cam trn hai nhm vi khun gram m Escherichia
[1], [2]. Trong terpenoid c cc cu t thuc nhm
coli v gram dng Staphylococcus aureus, ng thi
chc andehit, ancol, este c vai tr quan trng trong
cng xc nh c hot tnh chng oxy ha ca
hn hp tinh du ny, lm c s khoa hc cho vic
*
a ch lin h: Tel: (+84) 986592378 ng dng tinh du vo trong thc phm.
Email: loichebien@yahoo.com
72
Tp ch Khoa hc v Cng ngh 116 (2017) 072-075

2. Phng php nghin cu Sau khi xc nh c nng c ch ti thiu


MIC ca tng loi tinh du ring bit, tin hnh kim
2.1. Nguyn vt liu
tra s tng tc, tc dng tng hp v nh hng
Qu chanh giy Bc Giang (Citrus limonia ca cc loi tinh du vi nhau bng phng php pha
Osbeck) c thu hoch thi im 130 ngy k t long lin tc hn hp hai loi tinh du trong mi
khi u qu (vo thng 5 nm 2015) v qu cam snh trng lng s dng phn 96 ging [4]. Kh nng
Hm Yn (Citrus sinensis (L) Osbeck) c thu hoch sng st ca vi khun kim chng khi s dng hn
thi im 220 ngy k t khi u qu (vo thng 12 hp ca 2 loi tinh du v qu chanh v cam vi nng
nm 2014). Tn khoa hc c Th.S. V Kiu Sm, tng ng 1xMIC v 1xMIC hoc 1/2 MIC v
Trng i hc Nng lm Bc Giang gim nh. Tinh 1/2MIC; 1/4MIC v 1/4MIC; 1/8MIC v 1/8MIC...
du v qa chanh giy Bc Giang v cam snh Hm Nng c ch ring phn (Fractional Inhibitory
Yn c thu nhn bng phng php chng ct li Concentration: FIC) xc nh c kh nng tng
cun hi nc v c lm khan bng natrisunfat. tc ca tinh du v qu chanh v tinh du v qu cam
th hin qua gi tr FIC c tnh theo cng thc:
Th nghim s dng cc chng vi sinh vt kim FICTDA = MICTDA khi s dng hn hp hai loi tinh du/ MICTDA
chng Staphylococcus aureus v Escherichia coli do
khi s dng ring r
Vin Vi sinh vt v Cng ngh Sinh hc cung cp.
FIC = FICTDA + FIC TDB
Ha cht s dng l DPPH (1,1-diphenyl-2-
picrylhydrazyl), ethyl acetat, methanol v vitamin E. Trong FIC 0,5 l tng tc cng hng; 0,5 <
FIC 1,0 l tng tc b sung; 1,0 < FIC 4,0 l
2.2. Phng php nghin cu khng tng tc; 4 < FIC th hin tng tc i
2.2.1. Phng php khuych tn a thch khng [3].
Kh nng c ch ca hn hp tinh du v qu 2.2.4. Phng php xc nh kh nng chng oxy ha
chanh v cam i vi s pht trin ca tng chng vi ca hn hp tinh du
sinh vt c xc nh bng phng php khuych
Kh nng chng oxy ha ca hn hp tinh du
tn a thch khi nui cy vi khun trn mi trng v qu chanh v cam c thc hin theo phng
thch hp. Cc a giy lc tit trng c cha tinh du php DPPH (1,1-diphenyl-2-picrylhydrazyl) nh sau:
c t ln trn a thch cy chng vi khun
Mu th nghim gm 0,1 ml hn tinh du v qu
kim chng, vi khun ny c nui cy 37oC vi
chanh v cam, 2ml ethyl acetat, 1,9ml methanol v
thi gian 24 gi. Kh nng khng khun c xc
1ml DPPH. Mu trng gm 0,1ml hn hp tinh du
nh bng cch o bn knh (BK) vng c ch vi
v qu chanh v cam, 2ml ethyl acetat v 2,9ml
khun bng cng thc: D d = BK (mm), vi D: methanol. Mu kim chng gm 2ml ethyl acetat,
ng knh vng khng khun (mm), d: ng knh 2ml methanol v 1ml DPPH. Hn hp sau khi phi
l khoan thch (mm) [3], [4].
trn lc nh v yn trong bng ti nhit
2.2.2. Xc nh nng c ch ti thiu ca hn hp phng 30 pht, o hp th bc sng 517nm [6],
tinh du [7]. Th nghim c lp li 3 ln v tnh bng cng
thc %DPPH = [(Ao-(A-Ab)/Ao] 100 %, trong
Nng c ch ti thiu (minimum inhibitory DPPH: hot tnh qut gc t do (%), A o: hp th
concentration, MIC) ca hn hp tinh du v qu ca mu kim chng, A: hp th ca mu th
chanh v cam c xc nh bng phng php pha nghim, Ab: hp th ca mu trng.
long lin tc trong mi trng lng s dng phn 96
ging [4]. Hn hp tinh du vi nng th nghim Kh nng chng oxy ha ca hn hp tinh du
khc nhau c ha tan trong nc ct v trng c v qu chanh v cam c so snh i chng vi
cha Tween 80. Mi ging trong phn cha 20 l tinh vitamin E.
du, 20 l dch vi khun v 160 l mi trng MHB
3. Kt qu v tho lun
(nng cui cng ca dch vi khun l 106 cfu/ml v
th tch cui cng l 200l). Phn 96 ging c em 3.1. Kh nng khng khun ca tinh du v qu
i nui cy trong thi gian 24 gi 37oC. Nng vi chanh v cam
khun nh nht m khng quan st c s pht trin
Kh nng khng khun ca hn hp tinh du v
ca vi khun bng my c vi phin knh ti bc
qu chanh v cam c xc nh bng phng php
sng hp th 600 nm c ghi nhn l nng c
khuch tn trn a thch. Kt qu c th hin
ch ti thiu ca tinh du [3], [5].
bng 1.
2.2.3. Phng php xc nh s tng tc gia hai
Kt qu nghin cu trong bng 1 cho thy tinh
loi tinh du
du v qu chanh v tinh du v qu cam u c kh
nng khng khun mnh trn cc chng vi sinh vt

73
Tp ch Khoa hc v Cng ngh 116 (2017) 072-075

kim chng. Kh nng khng khun ca tinh du v du s dng (0,10- 0,20 l/ml vi tinh du v qu
qu chanh, vi ng knh vng trn khng khun chanh v t 0,80-1,60 l/ml vi tinh du v qu cam)
ca chng Escherichia coli l 39 2,8mm v chng s cho kt qu cng hng mnh nht (FIC 0,5).
Staphylococcus aureus l 43 3,5mm. Nng c Nh vy vic s dng hn hp tinh du v qu chanh
ch ti thiu ca tinh du v qu chanh trn c hai v cam c kh nng khng khun mnh trn chng vi
chng vi khun ny l 6,25l/ml. Kh nng khng khun Escherichia coli v Staphylococcus aureus hn
khun ca tinh du v qu cam, vi ng knh vng l khi s dng ring r tng loi tinh du. iu c
trn khng khun ca chng Escherichia coli l 32 ngha quan trng trong vic b sung hn hp tinh
1,5mm, nng c ch ti thiu 6,25l/ml, chng du ny vo thc phm; va c tc dng to mi
Staphylococcus aureus l 37 1,4 mm v nng c thm cho thc phm, c tc dng khng khun v bo
ch ti thiu 3,35l/ml. qun thc phm.
Bng 1. Kh nng khng khun ca tinh du v qu Bng 3. Nng c ch ring phn ca tinh du v
chanh v cam qu chanh v cam vi chng Staphylococcus aureus.
Tinh ng knh vng trn Nng c ch ti 1MICTDB 1/2MICTDB 1/4MICTDB 1/8MICTDB
du khng khun* (mm) thiu (MIC) ** (l/ml) **(6,25 (3,13l/ml) (1,6l/ml) (0,8l/ml)
Staphylococcus Escherichia Staphylococcus Cc gi tr l/ml) )
Escherichia coli aureus coli aureus
1MICTDA
TDA 39 2,8 43 3,5 6,25 6,25 2,51 1,54 1,34 1,16
(0,8l/ml)
TDB 32 1,5 37 1,4 6,25 3,35
1/2MICTDA
1,64 1,15 0,83 0,65
TDA: Tinh du v qu chanh, TDB: Tinh du v qu cam (0,39l/ml)
*ng knh vng trn khng khun th hin kh nng c 1/4MICTDA
1,46 0,92 0,64 0,58
ch vi khun ( 6mm: c kh nng khng khun). (0,2l/ml)
**Nng c ch ti thiu l gi tr trung bnh ca t nht 1/8MICTDA
ba ln th nghim lp li. 1,15 0,71 0,45 0,36
(0,1l/ml)
Bng 2. Nng c ch ring phn ca tinh du v **MIC: nng c ch ti thiu, FIC 0,5: Cng hng,
qu chanh v cam vi chng Escherichia coli 0,5 <FIC 1,0: cng hp, 1,0< FIC 4,0: khng tng
tc, 4,0 < FIC: i khng.
1MICTDB 1/2MICTDB 1/4MICTDB 1/8MICTDB
**(6,25 (3,13l/ml) (1,6l/ml) (0,8l/ml) Bng 4. Kh nng chng oxy ha ca hn hp tinh
Cc gi tr l/ml) du v qu chanh v cam
1MICTDA Mu th nghim Th tch (ml) % qut gc t
2,30 1,50 1,35 1,15
(6,25l/ml) do DPPH
1/2MICTDA TDA 0,10 41,25 0,12
1,60 1,10 0,85 0,68
(3,13l/ml) TDB 0,10 38,17 0,24
1/4MICTDA
1,35 0,85 0,80 0,41 Hn hp TDA v TDB 0,10 45,56 0,25
(1,6l/ml)
Vitamin E 0,10 43,38 0,17
1/8MICTDA
1,15 0,65 0,41 0,35
(0,8l/ml) 3.3. Kh nng chng oxy ha ca hn hp tinh
du v qu chanh v cam
3.2. Kh nng khng khun khi s dng hn hp Kh nng chng oxy ha ca hn hp tinh du
tinh du v qu chanh v cam v qu chanh v cam c xc nh theo phng
php qut gc t do DPPH, th nghim c tin
Tc dng cng hng, khi s dng hn hp hai hnh ti Trng i hc Cng nghip H Ni. Kt
loi tinh du v qu chanh v cam cc nng qu c trnh by bng 4.
khc nhau c nh gi bi ch s FIC, nng c
ch ring phn c xc nh bng phng php pha Kt qu nghin cu trong bng 4 cho thy hn
long lin tc hn hp hai loi tinh du ny trong mi hp tinh du v qu chanh v cam c kh nng
trng lng s dng phn 96 ging. Kt qu c chng oxy ha ln hn tinh du v qu chanh v
thnh by bng 2 v bng 3. cam khi s dng ring r. Tinh du v qu chanh v
cam khi s dng ring r, kh nng chng oxy ha
Kt qu nghin cu trong bng 2 v bng 3 cho nh hn vitamin E, nhng khi s dng kt hp hai
thy, nng 1/8 n 1/4 MIC vi mi loi tinh

74
Tp ch Khoa hc v Cng ngh 116 (2017) 072-075

loi tinh du ny th kh nng chng oxy ha li ln [3]. V Thu Trang, Lm Xun Thanh, Samira Sarter.
hn so vi vtamin E. Nghin cu hot tnh khng vi khun khi s dng kt
hp tinh du qu v mng tang. Tp ch Khoa hc v
4. Kt lun Cng ngh, tp 52 (5B) (2014) 417-422.
Kh nng khng khun ca tinh du v qu [4]. Gutierrez J., Barry-Ryan C., and Bourke P. The
chanh, vi ng knh vng trn khng khun ca antimicrobial efficacy of plant essential oil
chng Escherichia coli l 39 2,8mm v chng combinations and interactions with food ingredients.
Staphylococcus aureus l 43 3,5mm. Nng c International Journal of Food Microbiology, 124
(2008) 91-97.
ch ti thiu ca tinh du v qu chanh trn c hai
chng vi khun ny l 6,25l/ml. Kh nng khng [5]. Fei L., Liang H., Yuan Q. and Li C. In vitro
khun ca tinh du v qu cam, vi ng knh vng antimicrobial effects and mechanism of action of
trn khng khun ca chng Escherichia coli l 32 selected plant essential oil combinations against four
food-related microorganisms. Food Research
1,5mm, nng c ch ti thiu 6,25l/ml, chng
International 44 (2011) 3057-3064.
Staphylococcus aureus l 37 1,4 mm v nng c
ch ti thiu 3,35l/ml. Vi th tch tinh du v qu [6]. Molyneux P. The use of the stable free radical
chanh s dng (0,1- 0,2l/ml) v tinh du v qu cam diphenylpicryl-hydrazyl (DPPH) for estimating
(0,8-1,6l/ml) cho kt qu cng hng mnh nht antioxidant activity. Songklanakaric Journal of
Science Technology 26, (2004) 211- 219.
(FIC0,5) trn c hai chng vi khun
Staphylococcus aureus v Escherichia coli. Bng [7]. Matook S.M and Fumio H. Evaluation of the
phng php DPPH xc nh c kh nng antioxidant activity of extracts from buntan (Citrus
chng oxy ha ca hn hp tinh du v qu chanh v grandis Osbeck) fruit tissues. Food Chemistry 94
cam l 45,56 0,25%. (2006) 529-534.

Ti liu tham kho


[1]. Nguyn Vn Li, Nguyn Th Minh T, Hong nh
Ha. Nghin cu tch chit v xc nh hot tnh sinh
hc ca cc thnh phn to hng trong tinh du v
qu bi v v qu cam ca Vit Nam. Tp ch Khoa
hc v Cng ngh, tp 51(2) (2013) 153- 162.
[2]. Nguyn Vn Li, Nguyn Th Minh T, Hong nh
Ha. Nghin cu tch chit v xc nh hot tnh sinh
hc ca cc cu t to hng trong tinh du v qu
chanh giy Hm Yn- Tuyn Quang. Tp ch Ha
hc, tp 51(4) (2013) 519- 523.

75
Tp ch Khoa hc v Cng ngh 116 (2017) 076-081

S dng graphene a lp lm cht mang xc tc trong phn ng hydro ha


cinnamaldehyde nhm thu c hydrocinnamaldehyde vi chn lc cao
Highly Selective Hydrogenation of Cinnamaldehyde to Hydrocinnamaldehyde by
Using Few Layer Graphene as a Catalyst Support

Trng Hu Tr
Trng i hc Bch khoa - i hc Nng - 54 Nguyn Lng Bng - Lin Chiu - Nng
n Ta son: 25-4-2016; chp nhn ng: 20-12-2016

Tm tt
Vt liu graphene a lp (FLG) c nghin cu s dng trong nhiu lnh vc khc nhau trong hn thp
nin va qua nh vo nhng tnh cht u vit ca chng. nghin cu ny FLG c ch to t rut
bt ch bng phng php bc tch c hc v c ng dng lm cht mang cho ht nano palladium (Pd).
Xc tc Pd/FLG c nh gi cc c trng bng mt s phng php phn tch ha l hin i nh hp
ph - gii hp ph ng nhit nit v x l s liu theo l thuyt BET, knh hin vi in t qut (SEM), knh
hin vi in t truyn qua (TEM) v quang ph Raman. Kt qu ng dng xc tc cho phn ng hydro ha
cinnamaldehyde (CAL) thu c hydrocinnamaldehyde (HCAL) vi chn lc cao trn 94% khi
chuyn ha bng 80%. chn lc cao nghin cu ny c th n t hai l do khc nhau, trc ht l do
graphite ha cao ca cht mang FLG (IG/ID = 5,7), th hai c th do kch thc ca ht nano Pd mang
li.
T kha: FLG; Pd/FLG; Raman; SEM; TEM; hydro ha CAL.
Abstract
Few layer graphene (FLG) materials have been applied in different areas for over last decade thanks to their
novel properties. In this work, FLG was produced from pencil lead by mechemical exfoliation method, this
material was used as catalyst support for palladium (Pd) nanoparticles. Pd/FLG catalyst was characterised
by several techniques including nitrogen adsorption - desorption isotherms (BET), scanning electron
microscopy (SEM), transmission electron microscopy (TEM) and Raman spectrum. The catalyst was tested
for the selective hydrogenation of cinnamaldehyde (CAL) and the result showed a high selectivity towards
the C=C bond, over 94% of hydrocinnamaldehyde (HCAL) obtained at 80% of CAL conversion. The high
selectivity to HCAL in this work would be related to two different aspects, the first is the high graphitization
degrees of FLG (IG/ID = 5,7), the second is the particle size of Pd.
Keywords: FLG; Pd/FLG; Raman; SEM; TEM; Cinnamaldehyde hydrogenation.

1. Gii thiu chung* hn kh nng tn cng ln ni i C=O ca nhm


aldehyde (to sn phm COL) [3].
Phn ng hydro ha cinnamaldehyde thng to
ra hn hp cc hp cht bao gm
hydrocinnamadehyde (HCAL), ru cinnamyl
(cinnamyl alcohol: COL) v ru hydrocinnamyl
(hydrocinnamyl alcohol: HCOL). S n gin cc
giai on to thnh cc hp cht c biu din trn
hnh 1.
Hydrocinnamadehyde v ru cinnamyl l
nhng hp cht trung gian c s dng trong lnh
vc hng liu v dc phm [1], c bit HCAL l Hnh 1. S n gin cc giai on trong phn ng
hp cht trung gian s dng trong sn xut thuc hydro ha CAL.
cha bnh HIV [2]. T quan im ca nhit ng
hc, trong qu trnh hydro ha hp cht Tuy nhin, khi tin hnh phn ng hydro ha
cinnamaldehyde th kh nng tn cng ca hydro ln thng to ra ng thi cc hp cht nu trn, v vy
ni i C=C (to sn phm HCAL) s c u tin vic la chn xc tc v iu kin tin hnh phn ng
nhm to ra sn phm l COL hoc HCAL vi
chn lc cao l vn c quan tm ca nhiu
* a ch lin h : Tel: (+84) 932 445 199
nhm nghin cu. Cc kt qu cng b cho thy phn
Email: thtri@dut.udn.vn

76
Tp ch Khoa hc v Cng ngh 116 (2017) 076-081

ng ny thng c thc hin trn xc tc d th vi nhm Arai v cc cng s [13] cho thy chn lc
pha hot tnh l cc kim loi qu nh palladium (Pd), ca phn ng hydro ha CAL cn ph thuc vo
platinum (Pt), ruthenium (Ru) c phn tn trn cc dung mi s dng.
cht mang khc nhau [4-7], chn lc i vi
Qua phn tch kt qu ca nhng cng trnh
HCAL khi pha hot tnh l cc kim loi qu gim dn
c cng b cho thy chn lc i vi HCAL
theo th t Pd > Ru > Pt [8]. Nh vy Pd l pha hot
trong qu trnh hydro ha CAL ph thuc vo rt
tnh hiu qu nht c s dng khi mun thu nhn
nhiu yu t, trong cht mang cho xc tc c mt
HCAL vi chn lc cao. Trong thc t, vic s
vai tr rt quan trng. V vy, bi bo ny phn
dng Pd lm pha hot tnh cho phn ng hydro ha
tch v la chn vt liu graphene a lp (few layer
chn lc CAL nhm thu nhn HCAL c nghin
graphene: FLG) lm cht mang cho pha hot tnh l
cu bi nhiu nhm khc nhau, kt qu thu c cho
ht nano Pd trong phn ng hydro ha CAL nhm thu
thy chn lc i vi HCAL thay i trong mt
c HCAL c chn lc cao. Graphene a lp l
phm vi rt rng, t 20 n trn 90 % [1-2,7,9-12] ty
vt liu mi c nghin cu sn xut v ng dng
thuc vo xc tc s dng v iu kin tin hnh
trong hn mt thp nin qua nh vo nhng tnh cht
phn ng. Bng 1 trnh by kt qu ca cc nhm
u vit ca n nh dn in, dn nhit, bn c
nghin cu khc nhau cng b.
cao [14]. FLG l vt liu carbon nn chng kh tr v
So snh kt qu ca Li v cc cng s [9] vi mt ha hc do c th s dng lm cht mang cho
kt qu ca Liu v cc cng s [11] bng 1 cho xc tc trong mi trng acid hoc kim. Ngoi ra,
thy, khi s dng cng loi xc tc (Pd/CNTs) nhng y l vt liu khng c cc vi mao qun nn trnh
dung mi v iu kin tin hnh khng ging nhau c cc phn ng chuyn ha su to ra nhng sn
dn n chn lc i vi HCAL rt khc nhau, gi phm khng mong mun.
tr ny l 20% nghin cu ca Li so vi 90%
2. Thc nghim
nghin cu ca Liu. Trn cng loi xc tc l
Pd/SiO2, kt qu ca nhm Liu [1] thu c 81,6% 2.1. Graphene a lp - cht mang cho xc tc
HCAL trong khi nhm ca Mahmoud [7] ch thu
c 75% loi sn phm ny. Nghin cu v vi tr Cht mang cho pha hot tnh l FLG, nghin
ca cht mang xc tc trong phn ng hydro ha cu ny FLG c sn xut t rut bt ch (loi 9B)
bng phng php bc tch c hc, phng php ny
CAL, nhm nghin cu ca Liu [1] cho thy, trong
c xut bi C. Pham Huu [15]. Trc ht rut
cng iu kin tin hnh phn ng, dung mi v pha
bt ch c mi ln b mt tm thy tinh (c lm
hot tnh, th cht mang s c nh hng khng
t vt liu borosilicate) c b mt nhm nhm thu
nhng n hot tnh ca xc tc m cn nh hng c
n chn lc i vi HCAL. Ngoi ra kt qu ca c graphite vi s tm graphene t hn.
nhm Liu [1] cng nh kt qu nhm nghin cu ca

Bng 1. Kt qu nghin cu v chn lc i vi sn phm HCAL trong phn ng hydro ha CAL s dng Pd
lm pha hot tnh trn cc cht mang v dung mi khc nhau.
iu kin tin hnh phn ng chn lc
i vi Ti liu tham
Xc tc p sut H2
Dung mi Nhit ( C)
o
HCAL (%) kho
(MPa)
94 kt qu nghin
Pd/FLG dioxane 80 0,1 cu ny
Pd/SiC paraxylene 80 2 84 [1]
Pd/AC paraxylene 80 2 87 [1]
Pd/GO paraxylene 80 2 79,8 [1]
Pd/SiO2 paraxylene 80 2 81,6 [1]
Pd/-Al2O3 paraxylene 80 2 92,2 [1]
Pd/C(XC72) toluene 22 0,1 65 [2]
Pd/SiO2 - 25 0,3 75 [7]
Pd/CNTs ethanol 120 5 20 [9]
Pd/CNS isopropanol 60 1 36,4-65,3 [10]
Pd/CNTs trifluoroethanol+CO2 60 4 90 [11]
Pd/PPh3 ethanol 65 0,1 36-90 [12]

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Tp ch Khoa hc v Cng ngh 116 (2017) 076-081

Qu trnh loi b cht kt dnh trong graphite bng nh chp knh hin vi in t truyn qua (TEM)
thu c sau giai on mi c thc hin theo trn my TOPCON 022-B UHR vi phn gii cao.
hai giai on, th nht l qu trnh x l bng acid
2.4. Hydro ha chn lc cinnamaldehyde
HCl (5M), nhm mc ch tch loi Al2O3, cn giai
on th hai l qu trnh x l bng NaOH (nng Thit b phn ng c s dng cho qu trnh
20%) tch loi SiO2. Phn thu c sau qu trnh hydro ha CAL l bnh cu 3 c c th tch 250 ml,
tch loi cht kt dnh c phn tn trong ethanol v mt c c s dng sc kh hydro vo trong mi
thc hin qu trnh bc tch bng sng siu m nhm trng phn ng, c th hai cho php thot kh hydro
gim s tm graphene trong graphite, sn phm thu khng tham gia phn ng ra ngoi, c th ba c s
c chnh l graphene a lp. dng ly mu ra ngoi phn tch thnh phn cc
cht trong hn hp. Thit b phn ng c gn vi
2.2. Tng hp xc tc Pd/FLG
thit b iu khin lu lng nhm iu khin lng
Tin cht ca pha hot tnh l mui palladium kh hydro a vo mi trng phn ng. Ngoi ra h
nitrate (Pd(NO3)2.6H2O) (Strem Chemicals), xc tc thng phn ng ny cn s dng thm h thng
Pd/FLG c tng hp bng phng php tm t v khuy t nhm mc ch lm tng kh nng khuch
hm lng pha hot tnh c c nh bng 5% khi tn kh hydro vo trong mi trng phn ng.
lng ca xc tc thu c. C th qu trnh tng hp
Mi th nghim c tin hnh vi 5 ml CAL
xc tc c tin hnh theo bn giai on nh sau:
(Sigma-Aldrich) c pha long vo trong 100 ml
- a pha hot tnh ln b mt cht mang: trc dioxane (Sigma-Aldrich), lng xc tc c c nh
ht mui palladium nitrate c ha tan trong dung 50 mg, kh hydro (Air Liquide) c sc vo mi
mi (nc), sau dng pipet a dung dch mui trng phn ng vi lu lng 60 ml/pht v qu
tm ln b mt cht mang, tip theo cht mang trnh c tin hnh nhit 80oC, vi tc
c tm dung dch mui c sy kh. Qu trnh khuy trn c duy tr bng 400 vng/pht. xc
ny c lp li hai ln bo m ton b b mt nh s thay i nng cc cht trong hn hp phn
cht mang c ph ng u tin cht ca pha hot ng theo thi gian, mu c ly ra nh k. Lng
tnh; mu c ly ra cho mi ln phn tch l 0,1ml v
c pha long trong 2 ml dioxane sau s dng
- Sy kh: sau giai on th nht, cht mang
micro pipet ly 1 l v np vo my phn tch sc
c tm mui c n nh trong khng kh 2 gi
k kh (loi Varian 3800) c trang b h thng
trc khi a vo sy kh 110C trong thi gian 2
detector ion ha ngn la.
gi;
Thnh phn cht phn ng, sn phm to thnh
- Nung: giai on ny c thc hin 250C
c xc nh da vo kt qu phn tch nng ca
trong 2 gi trong khng kh nhm chuyn mui sang
chng trong mi trng phn ng v tnh theo cng
dng oxide tng ng;
thc sau:
- Kh: giai on ny c thc hin 300C
A %
A 100 (1)
trong thi gian 2 gi trong dng kh H2 nhm chuyn CAL HCAL COL HCOL
oxide sang Pd kim loi.
Trong :
2.3. Phng php nh gi c tnh ca sn phm
A: nng ca cht phn ng [CAL], sn phm
Cht mang FLG cng nh xc tc Pd/FLG tng
[HCAL], [COL], [HCOL] (mmol/lt).
hp c nh gi cc c trng bng mt s
phng php phn tch ha l hin i nhm hiu r chn lc i vi mi loi sn phm s c
hn v bn cht ca cht mang v s phn tn cng nh ngha theo cng thc sau:
nh kch thc ca ht nano Pd. Cht mang FLG
c phn tch quang ph Raman trn my SelX %
X 100 (2)
RENISHAW nhm xc nh c trng v mc HCAL COL HCOL
graphite ha (mc ny c tnh bng t s IG/ID,
vi IG v ID l cng pic ti nh G v nh D) v Trong :
c trng v s lp graphene. B mt ring c xc Selx: chn lc i vi mt loi sn phm to
nh bng phng php hp ph - gii hp ph ng thnh (%);
nhit nit trn my Tristar 3000 v x l s liu bng
l thuyt Brunauer-Emmett-Teller (BET). Hnh thi [X]: nng ca sn phm [HCAL], [COL],
b mt xc tc c chp nh bng knh hin vi in [HCOL] to thnh (mmol/lt).
t qut (SEM) trn my JEOL 6700-FEG, cui cng chuyn ha c xc nh theo cng thc
kch thc pha hot tnh xc tc c nghin cu sau:

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Tp ch Khoa hc v Cng ngh 116 (2017) 076-081

CALo CAL So snh gi tr ny vi gi tr c cng b bi Zhu


ConvCAL % 100 (3) v cc cng s (IG/ID = 1,9 - 6,7) [10] c th khng
CALo nh FLG c mc graphite ha cao. Kt qu o b
Trong : mt ring ca cht mang v xc tc bng phng
php hp ph nit c trnh by trn bng 2. T s
ConvCAL: chuyn ha CAL (%); liu thu c cho thy gi tr BET ca FLG rt nh so
[CAL]o: nng ca CAL ban u (mmol/lt); vi gi tr l thuyt i vi graphene n lp l 2630
m2/gam [17]. C nhiu nguyn nhn dn n gi tr
[CAL]: nng ca CAL trong mi trng phn BET thu c rt thp, trc ht l do quy trnh sn
ng (mmol/lt). xut mi ch to ra c FLG vi s lp kh ln, mt
nguyn nhn quan trng khc l trc khi tin hnh
3. Kt qu v tho lun
o b mt ring theo phng php hp ph - gii hp
3.1. c trng ca cht mang v xc tc Pd/FLG ph ng nhit nit, bung cha mu c ht to
chn khng nhm mc ch tch loi kh, hi m hoc
Trc ht cht mang c phn tch bng quang
dung mi trn b mt vt liu, khi cc tm FLG c
ph Raman, kt qu c trnh by trn hnh 2.
th kt dnh vi nhau, sau khi ngng ht chn
khng, nhiu tm FLG vn tn ti dng kt dnh vi
nhau nh vo lc ht Van der Waals. Nguyn nhn
va nu c chng minh bng thc nghim bi
Samulski v cng s [18]. Trong bng 2 cng cho
thy khi a pha hot tnh ln b mt ca FLG th cc
gi tr BET ca xc tc thu c tng ln gn 3,5
ln, iu ny c th do cc ht nano Pd c hnh
thnh trn b mt ca cht mang (nh kt qu c
trnh by trn hnh 4) t hn ch c s kt dnh
Hnh 2. Quang ph Raman ca FLG (cm-1).
ca cc tm FLG.
Bng 2. B mt ring BET xc nh bng phng
php hp ph - gii hp ph ng nhit nit.

Mu th nghim Gi tr BET (m2/gam)


FLG 8,4
Pd/FLG 28,8

nh chp bng knh hin vi in t qut xc tc


Pd/FLG c trnh by trn hnh 3. Quan st hnh
Hnh 3. nh SEM ca xc tc Pd/FLG. thi bn ngoi ca xc tc bng nh chp SEM trn
hnh 3 cho thy FLG c nhiu tm vi kch thc
khc nhau v phn ln cc tm c kch thc ln hn
micromet, mt cc tm kh dy c.
Kch thc nano ca pha hot tnh xc tc c
nghin cu t nh chp bng knh hin vi in t
truyn qua (hnh 4). Quan st nh chp cho thy pha
hot tnh c phn b kh ng u trn b mt
ca cht mang. Ngoi mt vi v tr c pha hot tnh
vi kch thc ln (hn 20 nm), phn ch yu l cc
ht c kch thc khong 10-16 nm khi quan st nh
chp TEM vi phn gii cao (hnh 4 B). Ngoi ra
cng tm thy cc ht vi kch thc nh hn, t 2-5
Hnh 4. nh TEM ca xc tc Pd/FLG. nm.

Quan st pic ti nh 2D ( s sng 2723 cm-1) 3.2. Hydro ha chn lc cinnamaldehyde


cho thy hnh dng ca pic ny ging vi kt qu Qu trnh hydro ha c thc hin vi cc iu
c cng b bi Mustafa v cc cng s [16], nh kin nh nu trn. Thnh phn cc cu t trong
vy bc u c th xem vt liu s dng nghin mi trng phn ng c tnh ton theo cng thc
cu ny l graphene a lp. Tnh ton t s cng 1, kt qu c trnh by trn hnh 5.
pic ti nh G v nh D thu c gi tr IG/ID = 5,7.

79
Tp ch Khoa hc v Cng ngh 116 (2017) 076-081

T th trn hnh 5 cho thy thnh phn ca oxide (GO) [1] cho thy cc cht mang ny c cha
cht phn ng CAL gim tuyn tnh theo thi gian. lin kt - trong mng li tinh th ca chng, khi
i vi cc sn phm to thnh th hm lng ca cc electron lin kt ny s chuyn dch n cc
chng tng dn theo thi gian, trong sn phm tm xc tc kim loi (metal particles) nn mt
hydro ha vo ni i C=C to HCAL chim phn electron s tng ln, kt qu lm tng kh nng
ch yu, (trn 94%); sn phm hydro ha vo ni i hp ph nhm chc aldehyde ln b mt xc tc, do
C=O to sn phm COL c thnh phn rt thp (di lm tng kh nng hydro ha ln ni i C=O
0,5%); sn phm hydro ha hon ton c hai ni i to COL, ni cch khc l cc cht mang va nu
to sn phm HCOL c thnh phn vo khong lm gim kh nng hydro ha ln ni i C=C to
6%. HCAL. Khc vi kt qu cc nhm va nu, nhm
ca Zhu v cc cng s [10] tin hnh nghin cu
nh hng ca xc tc l Pd c phn tn trn cc
cht mang l carbon nano tm (CNS) vi mc
graphite ha khc nhau. Kt qu nghin cu ca
nhm ny cho thy, khi mc graphite ha tng, gi
tr IG/ID thay i t 1,9 n 6,7 th chn lc i vi
HCAL cng tng ln tng ng t 36,4% n 65,3%.
FLG s dng nghin cu ny c mc graphite
ha cao (IG/ID = 5,7), y c th l l do dn n
Hnh 5. Thay i nng cc cht trong mi trng chn lc cao i vi sn phm HCAL trong phn ng
phn ng theo thi gian. hydro ha CAL nghin cu ny.
Da vo kt qu phn tch, chn lc i vi Ngoi l do va nu trn th kch thc ht xc
mi loi sn phm theo chuyn ha c tnh theo tc cng c th l l do quan trng khc nh hng
cng thc 2. Hnh 6 trnh by s thay i chn lc ln chn lc nh kt qu c cng b ca nhm
i vi cc sn phm theo chuyn ha. T th nghin cu Fu v cc cng s [19]. C th nhm tc
c th thy chn lc ca cc loi sn phm thay gi ny nghin cu chn lc i vi HCAL trn
i rt t theo chuyn ha. xc tc ca 1,5%Pd-WN/SBA-15. Kt qu cho thy
khi a thm wolfram nitride (tungsten nitride) vo
xc tc th kch thc trung bnh ca ht nano Pd thu
c nm khong 16,8 nm (kch thc ca ht nano
Pd thu c nghin cu ny cng gn tng t vi
gi tr va nu nh c nhn thy trn hnh 4 B), vi
kch thc ny th c hai lin kt C=C v C=O trong
phn t CAL s b hp ph ln trn b mt pha hot
tnh, trong trng hp qu trnh hydro ha vo ni
i C=C s xy ra d dng hn nn sn phm thu
c c chn lc i vi HCAL cao hn, kt qu
Hnh 6. Thay i chn lc cc cht trong mi
ny c trong cng b ca Bond [3] v Fu [19].
trng phn ng theo chuyn ha ca CAL.
4. Kt lun
Nh vy, so vi cc kt qu cng b c
cp n trong bng 1 th kt qu thu c nghin nghin cu ny ht nano Pd c phn tn
cu ny c chn lc i vi HCAL rt cao, c ng u ln b mt cht mang FLG bng phng
bit khi so snh vi cc kt qu ca cc nhm s php tm t. B mt ring BET ca xc tc Pd/FLG
dng cht mang trn c s ca vt liu carbon [1,9- tng ln gn 3,5 ln so vi cht mang FLG ban u.
12]. Khi s dng xc tc thu c cho phn ng hydro
ha CAL thu c HCAL vi chn lc cao,
Nh phn tch phn m u, trong phn
trn 94%. Kt qu nghin cu ny cng cho thy
ng hydro ha CAL th chn lc ln ni i C=C
mc graphite ha ca cht mang lm t vt liu
hay C=O ph thuc vo nhiu yu t khc nhau.
carbon hay kch thc ca ht xc tc l nhng yu t
Trc ht kt qu cng b ca Liu [1] cho thy loi
c th lm tng chn lc ny.
dung mi c cha nguyn t oxy (tetrahydrofuran)
khng lm tng chn lc i vi HCAL m ngc Ti liu tham kho
li cn lm gim nh chn lc ny. Cc nghin
[1]. Feng Jiang, Jian Cai, Bing Liu, Yuebing Xu and
cu v nh hng ca cht mang, c bit l cc cht Xiaohao Liu, Particle Size Effects in the Selective
mang n t vt liu carbon nh Hydrogenation of Cinnamaldehyde over Supported
triphenylphosphorine (PPh3) [12], carbon nano ng Palladium Catalysts, RSC Advances, Vol.6, (2016)
(CNTs) [9,11], than hot tnh (AC) [1] hay graphene p.75541-75551.

80
Tp ch Khoa hc v Cng ngh 116 (2017) 076-081

[2]. T. Szumeda, A. Drelinkiewicz, R. Kosydar, J. [11]. Bao-Hui Zhao, Jian-Gang Chen, Xuan Liu, Zhong-
Gurgul, Hydrogenation of cinnamaldehyde in the Wen Liu, Zhengping Hao, Jianliang Xiao, and Zhao-
presence of PdAu/C catalysts prepared by the reverse Tie Liu, Selective Hydrogenation of
water-in-oil microemulsion method, Applied Cinnamaldehyde over Pt and Pd Supported on
Catalysis A: General 487, (2014) p.1-15 Multiwalled Carbon Nanotubes in a CO2-Expanded
Alcoholic Medium, Ind. Eng. Chem.
[3]. G.C. Bond, Catalysis of Metals, Academic Press, Res.,Vol.51(34), (2012) p.11112-11121.
London, 1962.
[12]. Yuankui Zhang, Shijian Liao, Yun Xu, Daorong Yu,
[4]. Marjolein L. Toebes, T. Alexander Nijhuis, Jan Catalytic selective hydrogenation of cinnamaldehyde
Hjek, Johannes H. Bitter, A. Jos van Dillen,Dmitry to hydrocinnamaldehyde, Applied Catalysis A:
Yu. Murzin, Krijn P. de Jong, Support effects in General 192, (2000) p.247-251.
hydrogenation of cinnamaldehyde over carbon
nanober-supported platinum catalysts: Kinetic [13]. Masayuki Shirai, Tomonari Tanaka, Masahiko Arai,
modeling, Chemical Engineering Science, Vol.60, Selective hydrogenation of -, -unsaturated
(2005) p.5682-5695 aldehyde to unsaturated alcohol with supported
platinum catalysts at high pressures of hydrogen,
[5]. Arie J. Plomp, Heli Vuori, A. Outi I. Krause, Krijn P. Journal of Molecular Catalysis A: Chemical 168,
de Jong, Johannes H. Bitter, Particle size effects for (2001) p 99-103.
carbon nanober supported Pt and Ru catalysts for the
selective hydrogenation of cinnamaldehyde, Applied [14]. Jian Ru Gong, Graphene - Synthesis,
Catalysis A: General 351, (2008) p.9-15. characterization, properties and applications, Janeza
Trdine 9, 51000 Rijeka, Croatia, 2011.
[6]. Marjolein L. Toebes, Frans F. Prinsloo, A. Jos van
Dillen, Johannes H. Bitter, and Krijn P. de Jong, [15]. I. Janowska, F. Vigneron, D. Begin, O. Ersen, P.
Inuence of oxygen-containing surface groups on Bernhardt, T. Romero, M.J. Ledoux, C. Pham-Huu,
the activity and selectivity of carbon nanober- Mechanical thinning to make few-layer graphene
supported ruthenium catalysts in the hydrogenation of from pencil lead, Carbon, Vol.50, (2012) p.3092-
cinnamaldehyde, Journal of Catalysis, Vol.214, 3116.
(2013) p.78-87.
[16]. Mustafa Lotya, Yenny Hernandez, Paul J.
[7]. A. Hammoudeh, S. Mahmoud, Selective King, Ronan J. Smith, Valeria Nicolosi, Lisa S.
hydrogenation of cinnamaldehyde over Pd/SiO2 Karlsson, Fiona M. Blighe, Sukanta De,
catalysts: selectivity promotion by alloyed Sn, ZhimingWang, I. T. McGovern, Georg S.
Journal of Molecular Catalysis A: Chemical 203, Duesberg and Jonathan N. Coleman, Liquid phase
(2003) p.231-239. production of graphene by exfoliation of graphite in
surfactant/water solutions, J. Am. Chem.
[8]. P. Gallezot, D. Richard, Selective Hydrogenation of Soc, Vol.131, (2009) p.3611-3620.
,-Unsaturated Aldehydes, Catal. Rev.-Sci. Eng.,
Vol.40, (1998) p.81-126. [17]. H.S.S. Ramakrishna Matte, K. S. Subrahmanyam and
C. N. R. Rao, Synthetic Aspects and Selected
[9]. Jieshan Qiu, Hongzhe Zhang, Xiuna Wang, Hongmei Properties of Graphene, Nanomater. Nanotechnol,
Han, Changhai Liang and Can Li, selective Vol. 1, (2011) p.3-13.
hydrogenation of cinnamaldehyde over carbon
nanotube supported Pd-Ru catalyst, React. Kinet. [18]. Yongchao Si and Edward T. Samulski, Exfoliated
Catal. Lett., Vol. 88, No. 2, (2006) p.269-275. Graphene Separated by Platinum Nanoparticles,
Chem. Mater, Vol.20, (2008) p.6792-6797.
[10]. Qing Han, Yunfei Liu, Dong Wang, Fulong Yuan,
Xiaoyu Niu and Yujun Zhu, Effect of carbon [19]. Dong Wang, Yujun Zhu, Chungui Tian, Lei Wang,
nanosheets with different graphitization degrees as a Wei Zhou, Yongli Dong, Haijing Yan, and Honggang
support of noble metals on selective hydrogenation of Fu, Synergistic Effect of Tungsten Nitride and
cinnamaldehyde, RSC Advances, Vol.6, (2016) Palladium for the Selective Hydrogenation of
p.98356-98364. Cinnamaldehyde at the C=C bond, ChemCatChem,
Vol.8, (2016) p.1718-1726.

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