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KHO ST NH HNG CA NNG TIN CHT LN KCH THC V T TNH HT NANO OXIDE ST T Fe3O4
Trn Yn Mi1, Dng Hiu u1 v L Vn Nhn2

ABSTRACT
In this work, the nanoparticle size of Fe3O4 is independent on changing the concentration(s) of FeCl2 and FeCl3, and the equivalent coefficient of reaction. The average particle size is ranging from 18nm to 22nm. The product exhibit superparamagnetic property at room temperature and the saturation magnetization of the products are in the range from 47,8 (emu/g) to 62 (emu/g). Keywords: iron oxide nanoparticles Fe3O4, superparamagnetic, applications in biomedicine Title: Investigating the effect of concentration of material chemicals on the size and the magnetization of nanoparticles Fe3O4

TM TT
Mc ch ca chng ti l kho st nh hng nng tin cht vo kch thc v tnh cht t ca cc ht nano oxide st t Fe3O4 bng phng php ng kt ta. Chng ti nhn thy rng kch thc tinh th v t tnh ca cc ht gn nh khng ph thuc vo s thay i h s ng lng, v nng cc mui st ban u. Sn phm c tnh cht siu thun t ngay c nhit phng, t bo ha khong t 47,8 (emu/g) n 62 (emu/g) v lc khng t gn nh bng khng. Kch thc ht c s phn b hp, vi gi tr trong khong 18nm n 22nm. T kha: nano oxide st t, h s ng lng, c ht, siu thun t, nng tin cht

1 GII THIU TNG QUAN Cng ngh nano ang tng ngy lm thay i cuc sng ca chng ta. Nhng thit b ch to bng cng ngh nano c cc c tnh siu vit nh kch thc nh, bn cao v c nhiu tnh cht hon ton mi so vi cc thit b c ch to trn nn tng cng ngh thng thng. Nano oxt st t Fe3O4 cng nm trong xu hng pht trin ca cng ngh nano, v vi khch thc nh (c nanomet), vt liu ny th hin tnh cht vt l hon ton khc so vi khi trng thi thng thng, l tnh siu thun t [4]. Theo tnh cht ny, lc khng t ca h ht nano oxt st t Fe3O4 rt nh (gn bng khng) v t bo ha cao so vi cu trc ca mt vt liu khi, nn chng rt nhy vi s thay i ca t trng bn ngoi [4, 9]. Chng hn, theo kt qu nghin cu ca nhm Nguyn Hong Hi [6] th t bo ha cc i o c l 74 (emu/g) khi kch thc ht t 10nm n 30nm v lc khng t bng khng. Theo nghin cu ca Hironori Iida [2] lc khng t ca h ht tin v khng tng ng vi t bo ha cc i m h ht
1 2

Khoa Khoa hc T Nhin, Trng i hc Cn Th Khoa S Phm, Trng i hc Cn Th

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t c l 88,6 (emu/g). Trong khi , nu ta xt cu trc Fe3O4 dng khi th lc khng t vo khong 90 (emu/g) [7]. Trn c s cc c tnh u vit ca cc ht nano oxide st t, chng c ng dng rng ri trong mt s lnh vc ca y sinh hc [8]. Theo nhiu nghin cu trc, nano oxide st t c th c ch to theo hai cch: Th nht (topdown) l vt liu khi c nghin n kch thc nano; Th hai (bottomup) l s hnh thnh cc ht nano t cc nguyn t. Trong , nguyn tc th hai ang c s dng rng ri hn so vi nguyn tc th nht v hiu sut cao, d thc hin v d iu khin kch thc ht to thnh. Trong , phng php tiu biu ca nguyn tc ny l phng php ng kt ta [1- 4, 6, 7, 9, 10 v 12]. Trong qu trnh nghin cu ti liu lin quan n vic tng hp cc ht nano oxide st t Fe3O4 bng phng php ng kt ta, chng ti cha thy kho st nh hng ca nng tin cht v h s ng lng ln kch thc tinh th v t tnh ca sn phm. Do , mc tiu ca vic nghin cu ny l ch to v kho st nh hng ca cc nng tin cht ln kch thc tinh th v t tnh ca cc ht nano oxide st t Fe3O4 to thnh bng phng php ng kt ta. 2 THC NGHIM Cc loi nguyn liu c dng l FeCl3.6H2O (Merck) c tinh khit 99%, FeCl2.4H2O (Merck) c tinh khit 98% v NaOH c tinh khit 96%, to ht st t theo phng trnh phn ng ng kt ta rt gn c dng: Fe2+ + 2Fe3+ + 8OH- Fe3O4+ 4H2O K hoch thc nghim nh sau: (1) Cc mu A, B v C c kho st di kho st nh hng ca h s ng lng R. (2) Cc mu A, D, E v F c kho st di nh hng ca nng cc mui st. T l mol c chn l 1 / 2 / 16 (h s ng lng bng 2):
Bng 1: Phn b nng mol ca tin cht trong cc mu o

(1)

Mu A Mu B Mu C Mu D Mu E Mu F

FeCl2 (M) FeCl3 (M) NaOH (M) T l mol Fe2+/Fe3+/OH- H s ng lng R 0,2 0,4 3,2 1 / 2 / 16 2 0,2 0,4 4,8 1 / 2 / 24 3 0,2 0,4 6,4 1 / 2 / 32 4 0,1 1,2 1,6 1 / 2 / 16 2 0,05 0,1 0,8 1 / 2 / 16 2 0,025 0,05 0,4 1 / 2 / 16 2

th nghim t kt qu mong mun, cc dung dch cha mui st 2 v mui st 3 c chun b sn nng thch hp, sau chng c ha ln vo nhau bng my khuy t khong mt pht. Tip tc dung dch NaOH c cho nhanh vo hn hp trn ( cho phn ng xy ra) v khuy u trong 5 pht vi tc khuy 200 vng/pht trong iu kin nhit phng v mi trng khng kh, hn hp c y kn trong qu trnh khuy. Sn phm dng huyn ph c tch ra
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v ra trong nc ct nhiu ln v pH c th bng giy qu bo m NaOH khng cn trong mu. Tip theo lc ly sn phm bng giy lc ri em sy 45oC trong 24 gi. Cui cng thu c cht rn Fe3O4 mu en, cht rn ny c nghin nh v phn tch. 3 CC PHNG PHP PHN TCH KT QU o ph nhiu x tia X ca cc mu bng Nhiu x k tia X D5005 ca hng Bruker (c) ti trung tm Khoa hc Vt liu, H Ni vi bc sng tia X ly t bc x K ca ng (1,54 ). p dng cng thc Scherrer tnh kch thc tinh th Fe3O4 [11]. Hnh dng mu c chp bng knh hin vi in t qut (SEM - JMS 5410 ca hng JOE Nht Bn) ti phng th nghim Trung tm Khoa hc Vt liu, H Ni. o thng k c ht trn nh SEM thng qua thc chun trn nh SEM. T tnh ca mu c xc nh thng qua ng cong t tr ca cc mu, ng cong ny c o bng T k mu rung (Vibrating Sample Magnetometer- VSM) ti trung tm Khoa hc Vt liu, H Ni. 4 KT QU V THO LUN 4.1 nh hng ca h s ng lng Hnh 1 l ph nhiu x tia X ca ba mu A, B v C vi h s ng lng tng ng l 2, 3 v 4. So snh hnh ny vi ph chun [7] cho thy rng cc mu thun khit v pha Fe3O4. trnh nh hng ca ph nn nhiu x, nh ph ti gc 2 630 c chn xc nh c ht, dng cng thc Scherrer, ta thu c kt qu nh trn bng 2. Kt qu cho thy h s ng lng thay i khng lm thay i kch thc tinh th mt cch ng k, cc gi tr kch thc tinh th gn nh bng nhau v bng 18nm. Vy, vic thay i h s ng lng khng nh hng nhiu n cu trc tinh th oxide st t Fe3O4.

Hnh 1: Ph nhiu x tia X ca ba mu A, B v C vi h s ng lng tng ng 2, 3 v 4

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Bng 2: Kch thc tinh th c tnh t ph nhiu x tia X ca cc mu A, B v C

Tn mu dc (nm) R

Mu A 18 2

Mu B 18 3

Mu C 17 4

Xem xt nh SEM ca ba mu A, B v C, sau dng thc mu o thng k kch thc ht to thnh (Hnh 2).

Mu A (R 2) Mu A (R=2)

100nm
(nm)

100nm Mu B (R=3)
(nm)

100nm Mu C (R=4) (nm) Hnh 2: nh SEM v th phn b kch thc ht ca ba mu A, B v C tng ng vi h s ng lng 2, 3 v 4. Kch thc ht trung bnh trong ba mu tng ng nhau v nm trong khong t 18nm n 22nm

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Hnh 2 cho thy c ht tng i ng u trong mi mu v kch thc ht trung bnh trong cc mu tng ng nhau, c gi tr trong khong 18nm n 22nm. Tin hnh kho st t tnh ca cc mu bng phng php VSM, ta c cc ng cong t tr nh hnh 3. Theo th, lc khng t ca c ba mu gn nh bng khng. T bo ha xp x bng nhau v bng 62emu/g. iu ny cho thy cc mu nano oxide st t A, B v C u mang tnh siu thun t, vi lc khng t gn nh bng khng v gi tr t bo ha cao, ph hp vi cc cng b trong nc v quc t [1-7, 10 v 12] Tm li, vic kho st kch thc v t tnh ca cc ht nano oxide st t theo nh hng ca h s ng lng R cho thy h s ng lng thay i khng nh hng n cu trc v t tnh ca sn phm. Cc ht c kch thc tinh th khong 18nm v kch thc ht khong t 18nm n 22 nm. Chng mang tnh siu thun t vi t bo ha c 62 emu/g v lc khng t gn nh bng khng.

Hnh 3: ng cong t tr ca cc mu A, B v C tng ng vi h s ng lng 2, 3 v 4. T bo ha xp x ca c ba mu vo khong 62 (emu/g)

4.2 nh hng ca nng cc tin cht Tng t trn, ph nhiu x tia X ca cc mu A, D, E v F c kho st. Cc mu c h s ng lng bng nhau (R=2), nhng nng tin cht khc nhau. C th, khi kho st s thay i nng tin cht theo FeCl2, th gi tr tng ng trong cc mu A, D, E v F l 0,2; 0,1; 0,05 v 0,025. Kt qu thu c trn cng mt th (hnh 5). So snh ph c c vi ph chun trong ti liu [7] th cc mu tinh khit v pha Fe3O4. Hnh 4 cho thy khi nng tin cht gim th rng ca nh nhiu x ti gc nhiu x 2 630 tng dn, dn n kch thc tinh th trong cc mu gim dn. C th, xt nh nhiu x ti 2 630 v quan tm n nhiu x nn, theo cng thc Scherrer ta c bng 3:

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Hnh 4: th tng hp ca cc mu A, D, E v F c xt trong iu kin h s ng lng khng i (R=2), nhng nng cc tin cht thay i. C th, nu xt theo nng ca Fe2+ th gi tr tng ng trong cc mu A, D, E v F ln lt l 0,2; 0,1; 0,05; 0,025

Bng 3: S liu t ph nhiu x tia X ca cc mu c tng hp khi nng tin cht thay i

Tn mu Fe2+ R dc (nm)

Mu A 0,2 2 18,07

Mu D 0,1 2 13,53

Mu E 0,05 2 12,03

Mu F 0,025 2 10,84

Theo bng trn, khi gim nng cc tin cht th rng ca nh nhiu x tng dn, cho thy kch thc tinh th Fe3O4 ang gim. l do khi gim nng cc cht tham gia phn ng th PH trong mi trng phn ng gim, t lm gim mt mm tinh th, nn tc to ht nano xy ra chm dn v kch thc tinh th cng gim theo. nh SEM ca mu A v F c kho st, sau tin hnh o thng k kch thc ht trong hai nh ny. Hnh 5 cho thy cc ht trong mi mu l tng i ng u v kch thc ht trung bnh trong mi mu tng ng nhau. Hai th thng k kch thc trong hnh 5 cho thy cc ht c kch thc ch yu trong khong t 18nm n 22nm. Mc d kch thc tinh th ca cc ht trong mu F l nh hn cc ht trong mu A (bng 3), nhng kch thc ht trong cc mu l nh nhau, l do khi kch thc tinh th ca cc ht cng nh th chng cng c xu hng kt dnh vi nhau gim nng lng b mt, lm kch thc ht trong mu F tng ng vi kch thc cc ht trong mu A.

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Mu A (R 2) Mu A (Fe2+: 0,2)

100nm

(nm)

100nm Mu F (Fe2+: 0,025)

(nm)

Hnh 5: th phn b c ht ca hai mu A v F c nng mol Fe2+ tng ng l 0,2 v 0,025. Kch thc ht trung bnh trong hai mu tng ng nhau v nm trong khong 18nm n 24nm

Tip tc dng phng php VMS kho st t bo ha v lc khng t ca cc mu (hnh 6). Theo hnh, khi gim nng tin cht th t tnh ca sn phm to thnh cng gim theo. C th l t bo ha ca mu A, D, E v F ln lt l 59 emu/g; 52,3 emu/g; 52,1 emu/g v 47,8 emu/g. C th l do khi nng tin cht gim ngoi vic to ra pha ca Fe3O4, cn c mt s pha tp khng mong mun, nhng lng pha tp ny nh v khng pht hin c trn ph XRAY. D vy, lng pha tp ny cng lm gim t ca cc mu khi nng tin cht trong cc mu gim dn. Kt qu ny hon ton ph hp vi kt qu trong ti liu [3]. Vy, thng qua vic phn tch nh hng ca nng tin cht ln kch thc v t tnh ht to thnh, chng ti nhn thy rng khi gim nng tin cht th kch thc tinh th ca oxide st t cng gim theo, trong mu d dng xut hin cc pha tp, chnh chng lm t bo ha gim, nhng lc khng t vn hu nh bng khng, nn ht vn mang tnh siu thun t.

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Hnh 6: ng cong t tr ca cc mu A, D, E v F tng ng vi nng Fe2+ ln lt l 0,2; 0,1; 0,05; 0,025

5 KT LUN Tm li, chng ti dng phng php ng kt ta tng hp cc ht nano oxide st t Fe3O4 t cc tin cht FeCl2, FeCl3 v NaOH trong iu kin khng kh. Kt qu cho thy vic thay i h s ng lng khng lm nh hng n kch thc tinh th sn phm, nhng nu nng cc tin cht gim th kch thc tinh th v t bo ha ca mu cng gim theo. Vy, cc ht nano oxide st t chng ti thu c c kch thc ch yu t 18nm n 22nm, v c tnh cht siu thun t, vi lc khng t gn nh bng khng v t bo ha c gi tr t 47,8 (emu/g) n 62 (emu/g). c bit, kch thc ht trong cc mu c s phn b hp v hnh dng tng i ng u, c t cao, p ng c yu cu ng dng trong mt s lnh vc y sinh hc [8]. TI LIU THAM KHO
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[7] Nguyn Minh Hiu, 2008. Xy dng quy trnh nng sut cao ch to ht nano oxit st t c cc v bc khc nhau. Lun vn tt nghip h i hc chnh quy, HQGHN, trng i hc Khoa hc t nhin, khoa Vt l [8] Q A Pankhurst, J Connolly, S K Jones, J Dobson, 2003. Applications of magnetic nanoparticles in biomedicine. in: J.Phys. D: Appl. Phys. 36 (2003) R167 R181 [9] S P Gubin, Yu A Koksharov, G B Khomutov, G Yu Yurkov, 2005. Magnetic nanoparticles: preparation, structure and properties. in: Russian Chemical Reviews 74 (6) 489 520 (2005) [10] Tomohiro Iwasaki, Kazunori Kosaka, Tomoya Yabuuchi, Satoru Watano, Takeshi Yanagida, Tomoji Kawai, 2009. Novel mechanochemical process for synthesis of magnetite nanoparticles using coprecipitation method. in: Advanced Powder Technology 20 (2009) 521 528 [11] U. Schewertmann, R.M. Cornell , 2000. Iron Oxides in the Laboratory. in: WILEYVCH [12] Wanquan Jiang, H.C.Yang, S.Y.Yang, H.E.Horng, J.C,Hung, Y.C.Chen, Chin-Yih Hong, 2004. Preparation and properties of superparamagnetic nanoparticles with narrow size distribution and biocompatible. in: Jourhnal of Magnetism and Magnetic Material 283 (2004) 210 - 214

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