US008066969B2

(12) Ulllted States Patent (10) Patent N0.: US 8,066,969 B2

Cheon et a]. (45) Date of Patent: Nov. 29, 2011

(54) PREPARATION METHOD OF MAGNETIC C01 G 51/02 (2006.01)

AND METAL OXIDE NANOPARTICLES C01G 53/04 (2006-01)
(75) Inventors: Jin_W00 Cheon’ SeOu1(KR); (52) US. Cl. ............. .. 4.23/592.1;'423/593.1; 423/5941,
_ 423/594.5, 423/595, 423/594.14, 423/604,
i‘mgéwmilzlggs Seoul (KR), Jae-HY“ 423/605; 423/607; 423/622; 423/632; 423/633;
ee’ eou 423/594.19; 977/773; 977/775; 977/776
(73) Assignee: Industry-Academic Cooperation (58) Field of Classi?cation Search ..... .. 423/592.1*643;
Foundation, Yonsei University, Seoul 502/300i355; 977/773, 775*777
(KR) See application ?le for complete search history.
(*) Notice: Subject to any disclaimer, the term of this (56) References Cited
patent is extended or adjusted under 35
U_S_C_ 154(1)) by 757 days_ US. PATENT DOCUMENTS
(21) APPL No‘: 10/598,480 6,572,673 B2 * 6/2003 Lee et a1. ...................... .. 75/362
(22) PCT Filed: Nov. 26, 2004 (Commued)
(86) PCT N0.: PCT/KR2004/003088 FOREIGN PATENT DOCUMENTS
§ 371 (c)(l), EP 0977212 7/1999
(2), Date: Jlll. 6, (Continued)
(87) PCT Pub. N0.: WO2006/052042 OTHER PUBLICATIONS
PCT Pub. Date: May 18, 2006 l 1 th f l f l
_ _ _ Masa aeta . “Syn esis Routes 0r Large V0 umes 0 Nanopartic es”,
(65) Pm" Pubhcatlon Data Annu. Rev. Mater. Res. 2004. 34:41-81.*
US 2008/0003159 A1 Jan. 3 2008
’ Continued
(30) Foreign Application Priority Data ( )
Primary Examiner * Stanley Silverman
Nov. 10, 2004 (KR) ...................... .. 10-2004-0091240 Assistant Examiner i AmhOny J Zimmer
(51) Int- Cl- (74) Attorney, Agent, or Firm * Holme Roberts & OWen
C01B 13/14 (2006.01) LLP
C01B 13/00 (2006.01)
C01C 1/00 (2006.01) (57) ABSTRACT
(‘01D 1/02 (200601) This invention relates, in general, to a method of producing
C01G 49/00 (200601) magnetic oxide nanoparticles or metal oxide nanoparticles
C01G 51/04 (200601) and, more part1cularly,'to a method of producing magnetic or
C01G 37/14 (200601) metal oxide nanoparticles, Which comprises (1) addmg a
C01G 9/02 (200601) magnetic or metal precursor to a surfactant or a solvent con
C01G 11/02 (2006.01)
taming. the surfactant
.
to produce a mixed solution, (2) heatmg
.
the mixed solution to 50-6001 C to decompose the magnetic
C01G 13/02 (2006.01) . .
or metal precursor by heatmg so as to form the magnetic or
C01G 3/02 (2006.01) - - - -
C01 G 5/00 2006 01 metal oxide nanoparticles, and (3) separating the magnetic or
( ' ) metal oxide nano P articles. Since the method is achieved
C01 G 7/00 (200601) through a simple process Without using an oxidizing agent or
C01 G 45/02 (200601) a reducing agent, it is possible to simply mass-produce uni
C01 G 4 7/00 (2006-01) form magnetic or metal oxide nanoparticles having desired
g 39 sizes compared to the conventional method.
C01G 49/02 (2006.01) 27 Claims, 19 Drawing Sheets

Prodm?on of magnetic/maul oxide nmpnrdclu

olét
magnetic/metal oxide moplrmlzl
 US 8,066,969 B2
Page 2

US. PATENT DOCUMENTS Sanchez et al. “Designed Hybrid Organic -Inorganic Nanocompo sites
from Functional Nanobuilding Blocks”, Chem. Mater. 2001, 3061
6,984,369 B1 * 1/2006 Alivisatos et al. ....... .. 423/592.1
3083*
7,393,518 B2 * 7/2008 Chiang et al. ............... .. 423/608 Cushing et al. “Recent Advances in the Liquid-Phase Synthesis of
2004/0115124 A1 6/2004 Woo et al. Inorganic Nanoparticles”, Chem. Rev. 2004, 104, 3893-3946.*
2004/0253174 A1* 12/2004 Williams .................... .. 423/608 Sun et al. “Size-Controlled Synthesis of Magnetite Nanoparticles”,
2005/0191231 A1* 9/2005 Sun ............................. .. 423/632 Journal ofthe American Chermical Society 2002, 124, 8204-8205.*
2005/0214190 A1* 9/2005 Hyeon et al. ................ .. 423/299 International Search Report dated Aug. 8, 2005, for PCT Application
2006/0245998 A1* 11/2006 Kahn et al. ............... .. 423/592.1 No. PCT/KR2004/003088.
Written Opinion dated Aug. 8, 2005, for PCT Application No. PCT/
FOREIGN PATENT DOCUMENTS KR2004/003088.
EP 00977212 2/2000 P. Deb et al. “Characteristics of Fe203 nanoparticles prepared by heat
KR 10-2004-0029871 4/2004 treatment of a nonaqueous powder precipitate” J. of Nanoparticle
W0 W0 03/031323 4/2003 Research, 2002, 4:91-97, 2002, Kluwer Academic Publishers, The
W0 W0 03/053851 7/2003 Netherlands.
WO 2006/025627 3/2006 J. Rochenberger et al. “A New Nonhydrolytic Single-Precursor
Approach to Surfactant-Capped Nanocrystals of Transition Metal
Oxides” J. Am. Chem. Soc. 1999, 121, pp. 11595-11596, American
OTHER PUBLICATIONS Chemical Society.
Y. Jun et al. “Surfactant-Assisted Elimination of a High Energy Facet
O’Brien et al. “Synthesis of Monodisperse Nanoparticles of Barium as a Means of Controlling the Shapes of TiO2 Nanocrystals” J. Am.
Titanate: Toward a Generalized Strategy of Oxide Nanoparticle Syn Chem. Soc. 2003, 125, pp. 15981-15985, American Chemical Soci
thesis”, Journal ofthe American Chemical Society 2001, 123, 12085 ety.
12086.* Kurihara, L.K. et al. “Nanocrystalline Metallic Powders and Films
Rajamathi et al. “Oxide and chalcogenide nanoparticles from Produces by the Polyol Method” NanoStructured Materials, vol. 5,
No. 6, pp. 607-613, 1995, Elsevier Science Ltd., USA.
hydrothermal/solvothermal reactions”, Current Opinion in Solid
State and Materials Science 6 (2002) 337-345.* * cited by examiner
US. Patent Nov. 29, 2011 Sheet 1 0f 19 US 8,066,969 B2

FIG.1

‘ Production of magneticfmetal oxide nanoparticles

‘ I)
\a surfactant, solvent, [1/
magneticfmetal precurs M
\X J,’

Heating‘
' ,mlagneltitfmgtal oxide nanoparticlcs f
US. Patent Nov. 29, 2011 Sheet 2 0f 19 US 8,066,969 B2
US. Patent Nov. 29, 2011 Sheet 3 0f 19 US 8,066,969 B2

FIG.2b
US. Patent Nov. 29, 2011 Sheet 4 0f 19 US 8,066,969 B2

FIG.2c
US. Patent Nov. 29, 2011 Sheet 5 0f 19 US 8,066,969 B2

FIG.3a
US. Patent Nov. 29, 2011 Sheet 6 6f 19 US 8,066,969 B2
US. Patent Nov. 29, 2011 Sheet 7 0f 19 US 8,066,969 B2

FIGBC
US. Patent Nov. 29, 2011 Sheet 8 0f 19 US 8,066,969 B2

FICA

Msg)(atcgurnmeituofc 80

--L— MnFe20412nm
“'1- MnFe2O4 9nm
20.: ml" MHFBQOA Bnm
0 " 1 l r 1 I I I I ' I 1

0 10000 20000 30000 40000 50000

Intensity ofmagnctic ?eld [0e]

US. Patent Nov. 29, 2011 Sheet 9 0f 19 US 8,066,969 B2
US. Patent Nov. 29, 2011 Sheet 10 0f 19 US 8,066,969 B2

FIGJS
US. Patent Nov. 29, 2011 Sheet 11 0f 19 US 8,066,969 B2
US. Patent Nov. 29, 2011 Sheet 12 0f 19 US 8,066,969 B2
US. Patent Nov. 29, 2011 Sheet 13 0f 19 US 8,066,969 B2

FIG.9
US. Patent Nov. 29, 2011 Sheet 14 0f 19 US 8,066,969 B2

FIG.1O

TIOQ

2U 3U 40 50 60 7O 80

reference
JCPDS 21-1272

I 1 | 1 I \ I I | I |
20 3O 40 50 60 TO 80
US. Patent Nov. 29, 2011 Sheet 15 0f 19 US 8,066,969 B2

F1G.11
US. Patent Nov. 29, 2011 Sheet 16 6f 19 US 8,066,969 B2

FIG.12
US. Patent Nov. 29, 2011 Sheet 17 0f 19 US 8,066,969 B2

FIG .13
US. Patent Nov. 29, 2011 Sheet 18 0f 19 US 8,066,969 B2

FIG.14