Upload
others
View
16
Download
0
Embed Size (px)
Citation preview
Research ArticleMicrowave-Assisted Hydrothermal Synthesis andAnnealing of DyF3 Nanoparticles
E M Alakshin1 A V Klochkov1 E I Kondratyeva1 S L Korableva1 A G Kiiamov1
D S Nuzhina1 A A Stanislavovas1 M S Tagirov12 M Yu Zakharov1 and S Kodjikian3
1Kazan Federal University Kremlevskaya 18 420008 Kazan Russia2Institute of Perspective Research TAS L Bulachnaya 36a 420111 Kazan Russia3University Grenoble Alpes CNRS Institut NEEL 38000 Grenoble France
Correspondence should be addressed to E M Alakshin alakshingmailcom
Received 14 June 2016 Revised 14 October 2016 Accepted 24 October 2016
Academic Editor Paulo Cesar Morais
Copyright copy 2016 E M Alakshin et alThis is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited
The series of DyF3 nanosized samples was synthesized by the colloidal chemistry method The microwave-assisted hydrothermaltreatment was used for the first time for the modification of DyF3 nanoparticles Transmission electron microscopy images showthat the DyF3 nanoparticles have average particle size of about 16ndash18 nm and the size distribution becomes narrower during themicrowave irradiation The X-ray diffraction analysis shows the narrowing of the diffraction peaks versus microwave treatmenttime The experimental data demonstrates restructuring of the nanoparticles and their crystal structure becomes closer to theideal DyF3 regular structure during the microwave irradiation of colloidal solutionThe defect-annealing model of the microwave-assisted hydrothermal modification process is suggested
1 Introduction
Several dozen research papers dedicated to LnF3 nanosizedsamples synthesis have been published in recent years Nowa-days the lanthanide fluoride nanoparticles attract scientificinterest because of their possible applications in many areassuch as lasers biolabels and optical amplifiers [1ndash12] Theautoclave hydrothermal treatment is often used for struc-ture and size modification of the lanthanide nanoparticlesThe microwave-assisted synthesis of PrF3 nanoparticles wassuggested by Ma et al [13] and modified at Kazan FederalUniversity (Kazan Russia) The PrF3 nanoparticles size andstructure dependence on the microwave-assisted hydrother-mal treatment time were obtained by the high-resolutiontransmission electron microscopy (TEM) nuclear magneticresonance (NMR) and electron paramagnetic resonance [14ndash21]
The other trifluoride compound of great interest is DyF3Recent research showed that DyF3 powders could signifi-cantly improve the properties of Nd-Fe-B magnets [22ndash25]In addition DyF3 is an important component of oxyfluorideglasses [26]On the other hand there is a ferromagnetic phase
transition in a single crystal at 119879119888 = 255K [27] Investigationof Curie temperature dependence versus the size of DyF3nanoparticles is a fundamental problem There are only fewreports about DyF3 nanoparticles synthesis [28ndash30] and thesize modification was achieved by the autoclave technique
The aim of the present work is a synthesis and modifi-cation of DyF3 nanoparticles using the microwave-assistedhydrothermal treatment method
2 Materials and Methods
Sodium fluoride NaF (999) and dysprosium oxide Dy2O3(9999) were obtained from Sigma-Aldrich The nanosizedDyF3 samples 1ndash3 were synthesized by similar method as forPrF3 nanoparticles synthesis [14 15] In a typical synthesis62 g of powdered dysprosium oxide Dy2O3 was dissolved in400mL of 10 nitric acid HNO3 aqueous solution to form atransparent solution
Dy2O3 (s) + 6HNO3 (aq)
997888rarr 2Dy (NO3)3 (aq) + 3H2O (l)(1)
Hindawi Publishing CorporationJournal of NanomaterialsVolume 2016 Article ID 7148307 5 pageshttpdxdoiorg10115520167148307
2 Journal of Nanomaterials
100nm
(a)
dc = 1695 plusmn 069nm
100 20 30 40 50 60
Diameter (nm)
0
20
40
60
80
100
DyF3 sample 1
Num
ber o
f par
ticle
s(b)
dc = 1691 plusmn 072nm
15
20
25
30
10
5
0100 20 30 40 50 60
Diameter (nm)
DyF3 sample 2
Num
ber o
f par
ticle
s
(c)
dc = 1815 plusmn 033nm
10
10
15
15
00
5
5
20
20
25
25
30
30
45 5535
35
40 50 60
Diameter (nm)
DyF3 sample 3
Num
ber o
f par
ticle
s
(d)
Figure 1 (a) TEM image of DyF3nanoparticles with corresponding electron diffraction pattern in the insert (sample 3) (b)ndash(d) The size
distribution diagrams for all samples Solid line is the log-normal distribution fitting and 119889119888 is the center
Then after filtering 475 g of sodium fluoride NaF (F Dy =3 1) was added into the abovementioned solution under vio-lent stirring A white colloidal precipitate of DyF3 appearedimmediately
Dy (NO3)3 (aq) + 3NaF (s)
997888rarr DyF3(s) + 3NaNO3 (aq)
(2)
The pH of the suspension was adjusted by 25 ammoniaaqueous solution (about 40ndash50) Deionized water was filledinto the suspension to make the volume up to 750mLAfter stirring for about 20min the suspension was finallytransferred into a 1 L round flask (synthesis of sample 1has been stopped at this stage) Part of the solution wasplaced into themicrowave oven (650W 245GHz) for furtherhydrothermal treatment (sample 2)The suspension was putinto the microwave oven at 70 of the maximum powerfor 30 minutes The resulting product was collected by
centrifugation (Janetski K24 12000 RPM) and washed usingthe deionized water for several times
Finally the solutionwas dried out on the flat surface in airat room temperature Sample 3 was prepared by the samemethod and treated by the microwave irradiation for 420minutes
TEM images of nanosized sampleswere obtained by usingPhilips CM300 operated at 300 kV (Neel Institute GrenobleFrance) Powder X-ray diffraction was done by Bruker D8Advance X-ray diffractometer with use of copper Ka (120572 =15418 A) radiation and continuous scan (scan speed 0005degrees per second in the range of diffraction angles 20ndash60degrees)
3 Results and Discussion
Figure 1 shows the TEM image with the correspondingelectron diffraction pattern in the insert (sample 3) and size
Journal of Nanomaterials 3
042165
151
059
DyF3 sample 1
20 30 40 50 60
Am
plitu
de (a
u)
2120579 (deg)
(a)
035094
042
089
DyF3 sample 2
20 30 40 50 60
Am
plitu
de (a
u)
2120579 (deg)
(b)
022 035 028
043
DyF3 sample 3
20 30 40 50 60
Am
plitu
de (a
u)
2120579 (deg)
(c)
011
020101111
210
20 30 40 50 60
121
201211
221112
131301
230311022
122212
212 321400 141
220 002
DyF3 simulated XRD pattern
Am
plitu
de (a
u)
2120579 (deg)
(d)
Figure 2 (a)ndash(c) Experimental XRD patterns of synthesized DyF3 nanosized samples 1ndash3 (d) simulated XRD patterns in PowderCellsoftware
distribution diagrams for all samples The sharp diffractionrings show the crystal particles presence (rings radii 036 nm032 nm and 020 nm) All diagrams were fitted by thelog-normal distribution The synthesized nanoparticles haveaverage size of about 16ndash18 nm (sample 1 169 nm sample2 169 nm sample 3 182 nm)There is no significant DyF3nanoparticles size dependence on the microwave-assistedhydrothermal treatment time unlike the case of PrF3 sample[20] Clearly the size distribution becomes narrower duringthe microwave irradiation In the case of the microwave-assisted synthesis of PrF3 nanoparticles the restructuring ofparticles was observed earlier by NMR [20] It was interestingto see the crystal structure changes in the process of DyF3nanosized samples treatment
Crystal structure ofDyF3 nanoparticleswas characterizedby X-ray diffraction (XRD) Experimental XRD patterns ofthree DyF3 nanosized samples are shown in Figure 2 Diffrac-tion peaks could be indexed from the simulated patterncalculated by PowderCell [31] software (space group Pnma(No 62) lattice constants a = 06460 nm b = 06906 nmand c = 04376 nm [32]) Obviously sample 1 (Figure 2(a))has wide peaks and after 30 minutes of the microwave-assisted hydrothermal treatment the peaks becomes narrower(Figure 2(b)) After 7 hours of treatment the XRD patternbecame even narrower (Figure 2(c)) High and sharp peaksindicate high crystallinity of nanoparticles for sample 3
The analysis of obtained experimental data suggests thefollowing hypothetical picture of the microwave-assistedhydrothermal modification process Sample 1 has manydefects of crystal structure because of the explosive characterof the colloidal reaction Further microwave treatment of thecolloidal solution leads to local heating of DyF3 particlesSome bigger particles crack into smaller onesmaking the sizedistribution narrower but the local restructuring continues
further The restructuring leads to decrease in the number ofcrystal structure defects
The obtained results of restructuring process are differentfrom that of PrF3 nanoparticles where the weak size depen-dence [20] and absolutely no difference in XRD patternswere observed One of the possible reasons for differenceof the microwave-assisted hydrothermal treatmentrsquos resultsbetween DyF3 and PrF3 nanoparticles may be the differentsymmetry (DyF3 ndash orthorhombic 11986316
2ℎ-Pnma PrF3 ndash hexag-
onal 11986236V-P63cm) Another reason could be the difference of
lattice energies for lanthanide ions Pr and Dy [33]The type of crystal structure defects is also different
In the case of PrF3 nanoparticlesmdashpoint defects for DyF3nanoparticlesmdashthe defects are more severe Annealing of thedefects of the crystal structure of DyF3 nanoparticles leadsto significant (2ndash5 times) narrowing of XRD peaks Usuallythe width of XRD peaks is related to the nanoparticles sizeandmicrostrainsThere are variousmethods of X-ray analysissuch as Scherrer [34] Williamson-Hall [35] and Warren-Averbach [36] methods The average nanoparticles size wascalculated using Debye-Scherrerrsquos formula
119863 =119870120582
120573ℎ119896119897 cos 120579 (3)
For synthesized DyF3 nanoparticles the estimation gives toohigh values (ex for sample 3 55 nm) which supports thedefect nature of XRD peaks linewidth
The analysis of XRD pattern byWilliamson-Hall methodalso gives too high values for the average size of nanoparticlesand attempts to estimate lattice distortions do not give reliableresults Warren-Averbach analysis is suitable for resolvedXRD peaks and in our case is not applicable
4 Journal of Nanomaterials
4 Conclusions
In summary the series ofDyF3 nanoparticleswas successfullysynthesized by the microwave-assisted colloidal hydrother-mal method for the first time The nanoparticles were char-acterized by TEM and XRD The average size of particles isabout 16ndash18 nm and the size distribution becomes narrowerafter the microwave treatment It was observed that themicrowave irradiation treatment strongly affects the widthof XRD peaks They become narrower with the microwavetreatment The defect-annealing model of the microwave-assisted hydrothermal modification process is suggested
Competing Interests
The authors declare that they have no competing interests
Acknowledgments
The work was performed according to the Russian Gov-ernment Program of Competitive Growth of Kazan FederalUniversity E M Alakshin has been financially supported bythe Russian Foundation for Basic Research (Project no 16-32-60155 mol a dk)
References
[1] F Vetrone and J A Capobianco ldquoLanthanide-doped fluo-ride nanoparticles luminescence upconversion and biologicalapplicationsrdquo International Journal of Nanotechnology vol 5no 9ndash12 pp 1306ndash1339 2008
[2] B M Tissue ldquoSynthesis and luminescence of lanthanide ions innanoscale insulating hostsrdquo Chemistry of Materials vol 10 no10 pp 2837ndash2845 1998
[3] Z G Chen H L Chen H Hu et al ldquoVersatile synthe-sis strategy for carboxylic acid-functionalized upconvertingnanophosphors as biological labelsrdquo Journal of the AmericanChemical Society vol 130 no 10 pp 3023ndash3029 2008
[4] D K Chatterjee A J Rufaihah and Y Zhang ldquoUpconver-sion fluorescence imaging of cells and small animals usinglanthanide doped nanocrystalsrdquo Biomaterials vol 29 no 7 pp937ndash943 2008
[5] P R Diamente M Raudsepp and F C J M van Veggel ldquoDis-persible Tm3+-doped nanoparticles that exhibit strong 14 120583mphotoluminescencerdquoAdvanced Functional Materials vol 17 no3 pp 363ndash368 2007
[6] S Sivakumar P R Diamente and F C J M van Veggel ldquoSilica-coated Ln3+-doped LaF3 nanoparticles as robust down-andupconverting biolabelsrdquo Chemistry-A European Journal vol 12no 22 pp 5878ndash5884 2006
[7] X Teng Y Zhu W Wei et al ldquoLanthanide-doped NaxScF3+xnanocrystals crystal structure evolution and multicolor tun-ingrdquo Journal of the American Chemical Society vol 134 no 20pp 8340ndash8343 2012
[8] V Mahalingam F Vetrone R Naccache A Speghiniand and JA Capobianco ldquoColloidal Tm3+Yb3+-doped LiYF4 nanocrys-tals multiple luminescence spanning the UV toNIR regions vialow-energy excitationrdquo Advanced Materials vol 21 no 40 pp4025ndash4028 2009
[9] S Sarkar C Hazra and V Mahalingam ldquoBright lumi-nescence from colloidal Ln3+-doped Ca072Y028F228 (Ln=EuTmYb) nanocrystals via both high and low energy radiationsrdquoChemistrymdashA European Journal vol 18 no 23 pp 7050ndash70542012
[10] S Sarkar B Meesaragandla C Hazra and V MahalingamldquoSub-5 nm Ln3+-doped BaLuF5 nanocrystals a platform torealize upconversion via interparticle energy transfer (IPET)rdquoAdvanced Materials vol 25 no 6 pp 856ndash860 2013
[11] H Dong S-R Du X-Y Zheng et al ldquoLanthanide nanopar-ticles from design toward bioimaging and therapyrdquo ChemicalReviews vol 115 no 19 pp 10725ndash10815 2015
[12] P Rahman and M Green ldquoThe synthesis of rare earth fluoridebased nanoparticlesrdquoNanoscale vol 1 no 2 pp 214ndash224 2009
[13] LMaW-X Chen Y-F Zheng J Zhao andZ Xu ldquoMicrowave-assisted hydrothermal synthesis and characterizations of PrF3hollownanoparticlesrdquoMaterials Letters vol 61 no 13 pp 2765ndash2768 2007
[14] M S Tagirov E M Alakshin R R Gazizulin et al ldquoSpinkinetics of 3He in contact with synthesized PrF3 nanoparticlesrdquoJournal of Low Temperature Physics vol 162 no 5-6 pp 645ndash652 2011
[15] EMAlakshin BMGabidullin andA TGubaidullin ldquoDevel-opment of various methods for PrF3 nanoparticles synthesisrdquohttpsarxivorgabs11040208
[16] EM Alakshin A S Aleksandrov A V Egorov A V KlochkovS L Korableva and M S Tagirov ldquoNuclear pseudoquadrupoleresonance of 141Pr inVanVleck paramagnet PrF3rdquo JETPLettersvol 94 no 3 pp 240ndash242 2011
[17] EMAlakshinD S Blokhin AM Sabitova et al ldquoExperimen-tal proof of the existence of water clusters in fullerene-like PrF3nanoparticlesrdquo JETP Letters vol 96 no 3 pp 181ndash183 2012
[18] EMAlakshin R RGazizulin AV Klochkov et al ldquoSize effectin the (PrF3 nanoparticles-
3He) systemrdquo JETP Letters vol 97no 10 pp 579ndash582 2013
[19] M S Pudovkin S L Korableva A O Krasheninnicova etal ldquoToxicity of laser irradiated photoactive fluoride PrF3nanoparticles toward bacteriardquo Journal of Physics ConferenceSeries vol 560 no 1 Article ID 012011 2014
[20] E M Alakshin R R Gazizulin A V Klochkov et al ldquoAnneal-ing of PrF3 nanoparticles by microwave irradiationrdquoOptics andSpectroscopy vol 116 no 5 pp 721ndash723 2014
[21] AM Gazizulina EM Alakshin E I Baibekov et al ldquoElectronparamagnetic resonance of Gd3+ ions in powders of LaF
3Gd3+
nanocrystalsrdquo JETP Letters vol 99 no 3 pp 149ndash152 2014[22] S-E Park T-H Kim S-R Lee S Namkung and T-S Jang
ldquoEffect of sintering conditions on the magnetic andmicrostruc-tural properties of Nd-Fe-B sintered magnets doped with DyF
3
powdersrdquo Journal of Applied Physics vol 111 no 7 Article ID07A707 2012
[23] X J Cao L Chen S Guo et al ldquoCoercivity enhancementof sintered Nd-Fe-B magnets by efficiently diffusing DyF3based on electrophoretic depositionrdquo Journal of Alloys andCompounds vol 631 pp 315ndash320 2015
[24] S Sawatzki I Dirba L Schultz and O Gutfleisch ldquoElectricaland magnetic properties of hot-deformed Nd-Fe-B magnetswith different DyF3 additionsrdquo Journal of Applied Physics vol114 no 13 Article ID 133902 2013
[25] R Sueptitz S SawatzkiMMooreMUhlemannOGutfleischand A Gebert ldquoEffect of DyF
3on the corrosion behavior
of hot-pressed NdndashFendashB permanent magnetsrdquo Materials andCorrosion vol 66 no 2 pp 152ndash157 2015
Journal of Nanomaterials 5
[26] Z Duan J Zhang and L Hu ldquoSpectroscopic properties andJudd-Ofelt theory analysis of Dy3+ doped oxyfluoride silicateglassrdquo Journal of Applied Physics vol 101 no 4 Article ID043110 2007
[27] A V Savinkov S L Korableva A A Rodionov et al ldquoMagneticproperties of Dy3+ ions and crystal field characterization inYF3Dy3+ and DyF3 single crystalsrdquo Journal of Physics Con-densed Matter vol 20 no 48 Article ID 485220 2008
[28] X Ye J Chen M Engel et al ldquoCompetition of shape andinteraction patchiness for self-assembling nanoplatesrdquo NatureChemistry vol 5 no 6 pp 466ndash473 2013
[29] S Bhowmik T Gorai and U Maitra ldquoA room temperaturetemplated synthesis of lanthanide trifluoride nanoparticles andtheir unusual self-assemblyrdquo Journal of Materials Chemistry Cvol 2 no 9 pp 1597ndash1600 2014
[30] C Li J Yang P Yang H Lian and J Lin ldquoHydrothermalsynthesis of lanthanide fluorides LnF3 (Ln = La to Lu) nano-microcrystals with multiform structures and morphologiesrdquoChemistry of Materials vol 20 no 13 pp 4317ndash4326 2008
[31] W Kraus and G Nolze ldquoPOWDER CELLmdasha program forthe representation and manipulation of crystal structures andcalculation of the resulting X-ray powder patternsrdquo Journal ofApplied Crystallography vol 29 no 3 pp 301ndash303 1996
[32] DyF3 crystal structure SpringerMaterials (electronic resource)httpmaterialsspringercomispcrystallographicdocssd1300541
[33] C Dong M Raudsepp and F Van Veggel ldquoKinetically deter-mined crystal structures of undoped and La3+-doped LnF3rdquoJournal of Physical Chemistry C vol 113 no 1 pp 472ndash478 2009
[34] P Scherrer ldquoBestimmung der Grosse und der inneren Strukturvon Kolloidteilchen mittels Rontgenstrahlenrdquo Nachrichten vonder Gesellschaft derWissenschaften zuGottingen vol 26 pp 98ndash100 1918
[35] G K Williamson and W H Hall ldquoX-ray line broadening fromfiled aluminium and wolframrdquo Acta Metallurgica vol 1 no 1pp 22ndash31 1953
[36] B E Warren and B L Averbach ldquoThe separation of cold-work distortion and particle size broadening in X-ray patternsrdquoJournal of Applied Physics vol 23 no 4 p 497 1952
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
2 Journal of Nanomaterials
100nm
(a)
dc = 1695 plusmn 069nm
100 20 30 40 50 60
Diameter (nm)
0
20
40
60
80
100
DyF3 sample 1
Num
ber o
f par
ticle
s(b)
dc = 1691 plusmn 072nm
15
20
25
30
10
5
0100 20 30 40 50 60
Diameter (nm)
DyF3 sample 2
Num
ber o
f par
ticle
s
(c)
dc = 1815 plusmn 033nm
10
10
15
15
00
5
5
20
20
25
25
30
30
45 5535
35
40 50 60
Diameter (nm)
DyF3 sample 3
Num
ber o
f par
ticle
s
(d)
Figure 1 (a) TEM image of DyF3nanoparticles with corresponding electron diffraction pattern in the insert (sample 3) (b)ndash(d) The size
distribution diagrams for all samples Solid line is the log-normal distribution fitting and 119889119888 is the center
Then after filtering 475 g of sodium fluoride NaF (F Dy =3 1) was added into the abovementioned solution under vio-lent stirring A white colloidal precipitate of DyF3 appearedimmediately
Dy (NO3)3 (aq) + 3NaF (s)
997888rarr DyF3(s) + 3NaNO3 (aq)
(2)
The pH of the suspension was adjusted by 25 ammoniaaqueous solution (about 40ndash50) Deionized water was filledinto the suspension to make the volume up to 750mLAfter stirring for about 20min the suspension was finallytransferred into a 1 L round flask (synthesis of sample 1has been stopped at this stage) Part of the solution wasplaced into themicrowave oven (650W 245GHz) for furtherhydrothermal treatment (sample 2)The suspension was putinto the microwave oven at 70 of the maximum powerfor 30 minutes The resulting product was collected by
centrifugation (Janetski K24 12000 RPM) and washed usingthe deionized water for several times
Finally the solutionwas dried out on the flat surface in airat room temperature Sample 3 was prepared by the samemethod and treated by the microwave irradiation for 420minutes
TEM images of nanosized sampleswere obtained by usingPhilips CM300 operated at 300 kV (Neel Institute GrenobleFrance) Powder X-ray diffraction was done by Bruker D8Advance X-ray diffractometer with use of copper Ka (120572 =15418 A) radiation and continuous scan (scan speed 0005degrees per second in the range of diffraction angles 20ndash60degrees)
3 Results and Discussion
Figure 1 shows the TEM image with the correspondingelectron diffraction pattern in the insert (sample 3) and size
Journal of Nanomaterials 3
042165
151
059
DyF3 sample 1
20 30 40 50 60
Am
plitu
de (a
u)
2120579 (deg)
(a)
035094
042
089
DyF3 sample 2
20 30 40 50 60
Am
plitu
de (a
u)
2120579 (deg)
(b)
022 035 028
043
DyF3 sample 3
20 30 40 50 60
Am
plitu
de (a
u)
2120579 (deg)
(c)
011
020101111
210
20 30 40 50 60
121
201211
221112
131301
230311022
122212
212 321400 141
220 002
DyF3 simulated XRD pattern
Am
plitu
de (a
u)
2120579 (deg)
(d)
Figure 2 (a)ndash(c) Experimental XRD patterns of synthesized DyF3 nanosized samples 1ndash3 (d) simulated XRD patterns in PowderCellsoftware
distribution diagrams for all samples The sharp diffractionrings show the crystal particles presence (rings radii 036 nm032 nm and 020 nm) All diagrams were fitted by thelog-normal distribution The synthesized nanoparticles haveaverage size of about 16ndash18 nm (sample 1 169 nm sample2 169 nm sample 3 182 nm)There is no significant DyF3nanoparticles size dependence on the microwave-assistedhydrothermal treatment time unlike the case of PrF3 sample[20] Clearly the size distribution becomes narrower duringthe microwave irradiation In the case of the microwave-assisted synthesis of PrF3 nanoparticles the restructuring ofparticles was observed earlier by NMR [20] It was interestingto see the crystal structure changes in the process of DyF3nanosized samples treatment
Crystal structure ofDyF3 nanoparticleswas characterizedby X-ray diffraction (XRD) Experimental XRD patterns ofthree DyF3 nanosized samples are shown in Figure 2 Diffrac-tion peaks could be indexed from the simulated patterncalculated by PowderCell [31] software (space group Pnma(No 62) lattice constants a = 06460 nm b = 06906 nmand c = 04376 nm [32]) Obviously sample 1 (Figure 2(a))has wide peaks and after 30 minutes of the microwave-assisted hydrothermal treatment the peaks becomes narrower(Figure 2(b)) After 7 hours of treatment the XRD patternbecame even narrower (Figure 2(c)) High and sharp peaksindicate high crystallinity of nanoparticles for sample 3
The analysis of obtained experimental data suggests thefollowing hypothetical picture of the microwave-assistedhydrothermal modification process Sample 1 has manydefects of crystal structure because of the explosive characterof the colloidal reaction Further microwave treatment of thecolloidal solution leads to local heating of DyF3 particlesSome bigger particles crack into smaller onesmaking the sizedistribution narrower but the local restructuring continues
further The restructuring leads to decrease in the number ofcrystal structure defects
The obtained results of restructuring process are differentfrom that of PrF3 nanoparticles where the weak size depen-dence [20] and absolutely no difference in XRD patternswere observed One of the possible reasons for differenceof the microwave-assisted hydrothermal treatmentrsquos resultsbetween DyF3 and PrF3 nanoparticles may be the differentsymmetry (DyF3 ndash orthorhombic 11986316
2ℎ-Pnma PrF3 ndash hexag-
onal 11986236V-P63cm) Another reason could be the difference of
lattice energies for lanthanide ions Pr and Dy [33]The type of crystal structure defects is also different
In the case of PrF3 nanoparticlesmdashpoint defects for DyF3nanoparticlesmdashthe defects are more severe Annealing of thedefects of the crystal structure of DyF3 nanoparticles leadsto significant (2ndash5 times) narrowing of XRD peaks Usuallythe width of XRD peaks is related to the nanoparticles sizeandmicrostrainsThere are variousmethods of X-ray analysissuch as Scherrer [34] Williamson-Hall [35] and Warren-Averbach [36] methods The average nanoparticles size wascalculated using Debye-Scherrerrsquos formula
119863 =119870120582
120573ℎ119896119897 cos 120579 (3)
For synthesized DyF3 nanoparticles the estimation gives toohigh values (ex for sample 3 55 nm) which supports thedefect nature of XRD peaks linewidth
The analysis of XRD pattern byWilliamson-Hall methodalso gives too high values for the average size of nanoparticlesand attempts to estimate lattice distortions do not give reliableresults Warren-Averbach analysis is suitable for resolvedXRD peaks and in our case is not applicable
4 Journal of Nanomaterials
4 Conclusions
In summary the series ofDyF3 nanoparticleswas successfullysynthesized by the microwave-assisted colloidal hydrother-mal method for the first time The nanoparticles were char-acterized by TEM and XRD The average size of particles isabout 16ndash18 nm and the size distribution becomes narrowerafter the microwave treatment It was observed that themicrowave irradiation treatment strongly affects the widthof XRD peaks They become narrower with the microwavetreatment The defect-annealing model of the microwave-assisted hydrothermal modification process is suggested
Competing Interests
The authors declare that they have no competing interests
Acknowledgments
The work was performed according to the Russian Gov-ernment Program of Competitive Growth of Kazan FederalUniversity E M Alakshin has been financially supported bythe Russian Foundation for Basic Research (Project no 16-32-60155 mol a dk)
References
[1] F Vetrone and J A Capobianco ldquoLanthanide-doped fluo-ride nanoparticles luminescence upconversion and biologicalapplicationsrdquo International Journal of Nanotechnology vol 5no 9ndash12 pp 1306ndash1339 2008
[2] B M Tissue ldquoSynthesis and luminescence of lanthanide ions innanoscale insulating hostsrdquo Chemistry of Materials vol 10 no10 pp 2837ndash2845 1998
[3] Z G Chen H L Chen H Hu et al ldquoVersatile synthe-sis strategy for carboxylic acid-functionalized upconvertingnanophosphors as biological labelsrdquo Journal of the AmericanChemical Society vol 130 no 10 pp 3023ndash3029 2008
[4] D K Chatterjee A J Rufaihah and Y Zhang ldquoUpconver-sion fluorescence imaging of cells and small animals usinglanthanide doped nanocrystalsrdquo Biomaterials vol 29 no 7 pp937ndash943 2008
[5] P R Diamente M Raudsepp and F C J M van Veggel ldquoDis-persible Tm3+-doped nanoparticles that exhibit strong 14 120583mphotoluminescencerdquoAdvanced Functional Materials vol 17 no3 pp 363ndash368 2007
[6] S Sivakumar P R Diamente and F C J M van Veggel ldquoSilica-coated Ln3+-doped LaF3 nanoparticles as robust down-andupconverting biolabelsrdquo Chemistry-A European Journal vol 12no 22 pp 5878ndash5884 2006
[7] X Teng Y Zhu W Wei et al ldquoLanthanide-doped NaxScF3+xnanocrystals crystal structure evolution and multicolor tun-ingrdquo Journal of the American Chemical Society vol 134 no 20pp 8340ndash8343 2012
[8] V Mahalingam F Vetrone R Naccache A Speghiniand and JA Capobianco ldquoColloidal Tm3+Yb3+-doped LiYF4 nanocrys-tals multiple luminescence spanning the UV toNIR regions vialow-energy excitationrdquo Advanced Materials vol 21 no 40 pp4025ndash4028 2009
[9] S Sarkar C Hazra and V Mahalingam ldquoBright lumi-nescence from colloidal Ln3+-doped Ca072Y028F228 (Ln=EuTmYb) nanocrystals via both high and low energy radiationsrdquoChemistrymdashA European Journal vol 18 no 23 pp 7050ndash70542012
[10] S Sarkar B Meesaragandla C Hazra and V MahalingamldquoSub-5 nm Ln3+-doped BaLuF5 nanocrystals a platform torealize upconversion via interparticle energy transfer (IPET)rdquoAdvanced Materials vol 25 no 6 pp 856ndash860 2013
[11] H Dong S-R Du X-Y Zheng et al ldquoLanthanide nanopar-ticles from design toward bioimaging and therapyrdquo ChemicalReviews vol 115 no 19 pp 10725ndash10815 2015
[12] P Rahman and M Green ldquoThe synthesis of rare earth fluoridebased nanoparticlesrdquoNanoscale vol 1 no 2 pp 214ndash224 2009
[13] LMaW-X Chen Y-F Zheng J Zhao andZ Xu ldquoMicrowave-assisted hydrothermal synthesis and characterizations of PrF3hollownanoparticlesrdquoMaterials Letters vol 61 no 13 pp 2765ndash2768 2007
[14] M S Tagirov E M Alakshin R R Gazizulin et al ldquoSpinkinetics of 3He in contact with synthesized PrF3 nanoparticlesrdquoJournal of Low Temperature Physics vol 162 no 5-6 pp 645ndash652 2011
[15] EMAlakshin BMGabidullin andA TGubaidullin ldquoDevel-opment of various methods for PrF3 nanoparticles synthesisrdquohttpsarxivorgabs11040208
[16] EM Alakshin A S Aleksandrov A V Egorov A V KlochkovS L Korableva and M S Tagirov ldquoNuclear pseudoquadrupoleresonance of 141Pr inVanVleck paramagnet PrF3rdquo JETPLettersvol 94 no 3 pp 240ndash242 2011
[17] EMAlakshinD S Blokhin AM Sabitova et al ldquoExperimen-tal proof of the existence of water clusters in fullerene-like PrF3nanoparticlesrdquo JETP Letters vol 96 no 3 pp 181ndash183 2012
[18] EMAlakshin R RGazizulin AV Klochkov et al ldquoSize effectin the (PrF3 nanoparticles-
3He) systemrdquo JETP Letters vol 97no 10 pp 579ndash582 2013
[19] M S Pudovkin S L Korableva A O Krasheninnicova etal ldquoToxicity of laser irradiated photoactive fluoride PrF3nanoparticles toward bacteriardquo Journal of Physics ConferenceSeries vol 560 no 1 Article ID 012011 2014
[20] E M Alakshin R R Gazizulin A V Klochkov et al ldquoAnneal-ing of PrF3 nanoparticles by microwave irradiationrdquoOptics andSpectroscopy vol 116 no 5 pp 721ndash723 2014
[21] AM Gazizulina EM Alakshin E I Baibekov et al ldquoElectronparamagnetic resonance of Gd3+ ions in powders of LaF
3Gd3+
nanocrystalsrdquo JETP Letters vol 99 no 3 pp 149ndash152 2014[22] S-E Park T-H Kim S-R Lee S Namkung and T-S Jang
ldquoEffect of sintering conditions on the magnetic andmicrostruc-tural properties of Nd-Fe-B sintered magnets doped with DyF
3
powdersrdquo Journal of Applied Physics vol 111 no 7 Article ID07A707 2012
[23] X J Cao L Chen S Guo et al ldquoCoercivity enhancementof sintered Nd-Fe-B magnets by efficiently diffusing DyF3based on electrophoretic depositionrdquo Journal of Alloys andCompounds vol 631 pp 315ndash320 2015
[24] S Sawatzki I Dirba L Schultz and O Gutfleisch ldquoElectricaland magnetic properties of hot-deformed Nd-Fe-B magnetswith different DyF3 additionsrdquo Journal of Applied Physics vol114 no 13 Article ID 133902 2013
[25] R Sueptitz S SawatzkiMMooreMUhlemannOGutfleischand A Gebert ldquoEffect of DyF
3on the corrosion behavior
of hot-pressed NdndashFendashB permanent magnetsrdquo Materials andCorrosion vol 66 no 2 pp 152ndash157 2015
Journal of Nanomaterials 5
[26] Z Duan J Zhang and L Hu ldquoSpectroscopic properties andJudd-Ofelt theory analysis of Dy3+ doped oxyfluoride silicateglassrdquo Journal of Applied Physics vol 101 no 4 Article ID043110 2007
[27] A V Savinkov S L Korableva A A Rodionov et al ldquoMagneticproperties of Dy3+ ions and crystal field characterization inYF3Dy3+ and DyF3 single crystalsrdquo Journal of Physics Con-densed Matter vol 20 no 48 Article ID 485220 2008
[28] X Ye J Chen M Engel et al ldquoCompetition of shape andinteraction patchiness for self-assembling nanoplatesrdquo NatureChemistry vol 5 no 6 pp 466ndash473 2013
[29] S Bhowmik T Gorai and U Maitra ldquoA room temperaturetemplated synthesis of lanthanide trifluoride nanoparticles andtheir unusual self-assemblyrdquo Journal of Materials Chemistry Cvol 2 no 9 pp 1597ndash1600 2014
[30] C Li J Yang P Yang H Lian and J Lin ldquoHydrothermalsynthesis of lanthanide fluorides LnF3 (Ln = La to Lu) nano-microcrystals with multiform structures and morphologiesrdquoChemistry of Materials vol 20 no 13 pp 4317ndash4326 2008
[31] W Kraus and G Nolze ldquoPOWDER CELLmdasha program forthe representation and manipulation of crystal structures andcalculation of the resulting X-ray powder patternsrdquo Journal ofApplied Crystallography vol 29 no 3 pp 301ndash303 1996
[32] DyF3 crystal structure SpringerMaterials (electronic resource)httpmaterialsspringercomispcrystallographicdocssd1300541
[33] C Dong M Raudsepp and F Van Veggel ldquoKinetically deter-mined crystal structures of undoped and La3+-doped LnF3rdquoJournal of Physical Chemistry C vol 113 no 1 pp 472ndash478 2009
[34] P Scherrer ldquoBestimmung der Grosse und der inneren Strukturvon Kolloidteilchen mittels Rontgenstrahlenrdquo Nachrichten vonder Gesellschaft derWissenschaften zuGottingen vol 26 pp 98ndash100 1918
[35] G K Williamson and W H Hall ldquoX-ray line broadening fromfiled aluminium and wolframrdquo Acta Metallurgica vol 1 no 1pp 22ndash31 1953
[36] B E Warren and B L Averbach ldquoThe separation of cold-work distortion and particle size broadening in X-ray patternsrdquoJournal of Applied Physics vol 23 no 4 p 497 1952
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
Journal of Nanomaterials 3
042165
151
059
DyF3 sample 1
20 30 40 50 60
Am
plitu
de (a
u)
2120579 (deg)
(a)
035094
042
089
DyF3 sample 2
20 30 40 50 60
Am
plitu
de (a
u)
2120579 (deg)
(b)
022 035 028
043
DyF3 sample 3
20 30 40 50 60
Am
plitu
de (a
u)
2120579 (deg)
(c)
011
020101111
210
20 30 40 50 60
121
201211
221112
131301
230311022
122212
212 321400 141
220 002
DyF3 simulated XRD pattern
Am
plitu
de (a
u)
2120579 (deg)
(d)
Figure 2 (a)ndash(c) Experimental XRD patterns of synthesized DyF3 nanosized samples 1ndash3 (d) simulated XRD patterns in PowderCellsoftware
distribution diagrams for all samples The sharp diffractionrings show the crystal particles presence (rings radii 036 nm032 nm and 020 nm) All diagrams were fitted by thelog-normal distribution The synthesized nanoparticles haveaverage size of about 16ndash18 nm (sample 1 169 nm sample2 169 nm sample 3 182 nm)There is no significant DyF3nanoparticles size dependence on the microwave-assistedhydrothermal treatment time unlike the case of PrF3 sample[20] Clearly the size distribution becomes narrower duringthe microwave irradiation In the case of the microwave-assisted synthesis of PrF3 nanoparticles the restructuring ofparticles was observed earlier by NMR [20] It was interestingto see the crystal structure changes in the process of DyF3nanosized samples treatment
Crystal structure ofDyF3 nanoparticleswas characterizedby X-ray diffraction (XRD) Experimental XRD patterns ofthree DyF3 nanosized samples are shown in Figure 2 Diffrac-tion peaks could be indexed from the simulated patterncalculated by PowderCell [31] software (space group Pnma(No 62) lattice constants a = 06460 nm b = 06906 nmand c = 04376 nm [32]) Obviously sample 1 (Figure 2(a))has wide peaks and after 30 minutes of the microwave-assisted hydrothermal treatment the peaks becomes narrower(Figure 2(b)) After 7 hours of treatment the XRD patternbecame even narrower (Figure 2(c)) High and sharp peaksindicate high crystallinity of nanoparticles for sample 3
The analysis of obtained experimental data suggests thefollowing hypothetical picture of the microwave-assistedhydrothermal modification process Sample 1 has manydefects of crystal structure because of the explosive characterof the colloidal reaction Further microwave treatment of thecolloidal solution leads to local heating of DyF3 particlesSome bigger particles crack into smaller onesmaking the sizedistribution narrower but the local restructuring continues
further The restructuring leads to decrease in the number ofcrystal structure defects
The obtained results of restructuring process are differentfrom that of PrF3 nanoparticles where the weak size depen-dence [20] and absolutely no difference in XRD patternswere observed One of the possible reasons for differenceof the microwave-assisted hydrothermal treatmentrsquos resultsbetween DyF3 and PrF3 nanoparticles may be the differentsymmetry (DyF3 ndash orthorhombic 11986316
2ℎ-Pnma PrF3 ndash hexag-
onal 11986236V-P63cm) Another reason could be the difference of
lattice energies for lanthanide ions Pr and Dy [33]The type of crystal structure defects is also different
In the case of PrF3 nanoparticlesmdashpoint defects for DyF3nanoparticlesmdashthe defects are more severe Annealing of thedefects of the crystal structure of DyF3 nanoparticles leadsto significant (2ndash5 times) narrowing of XRD peaks Usuallythe width of XRD peaks is related to the nanoparticles sizeandmicrostrainsThere are variousmethods of X-ray analysissuch as Scherrer [34] Williamson-Hall [35] and Warren-Averbach [36] methods The average nanoparticles size wascalculated using Debye-Scherrerrsquos formula
119863 =119870120582
120573ℎ119896119897 cos 120579 (3)
For synthesized DyF3 nanoparticles the estimation gives toohigh values (ex for sample 3 55 nm) which supports thedefect nature of XRD peaks linewidth
The analysis of XRD pattern byWilliamson-Hall methodalso gives too high values for the average size of nanoparticlesand attempts to estimate lattice distortions do not give reliableresults Warren-Averbach analysis is suitable for resolvedXRD peaks and in our case is not applicable
4 Journal of Nanomaterials
4 Conclusions
In summary the series ofDyF3 nanoparticleswas successfullysynthesized by the microwave-assisted colloidal hydrother-mal method for the first time The nanoparticles were char-acterized by TEM and XRD The average size of particles isabout 16ndash18 nm and the size distribution becomes narrowerafter the microwave treatment It was observed that themicrowave irradiation treatment strongly affects the widthof XRD peaks They become narrower with the microwavetreatment The defect-annealing model of the microwave-assisted hydrothermal modification process is suggested
Competing Interests
The authors declare that they have no competing interests
Acknowledgments
The work was performed according to the Russian Gov-ernment Program of Competitive Growth of Kazan FederalUniversity E M Alakshin has been financially supported bythe Russian Foundation for Basic Research (Project no 16-32-60155 mol a dk)
References
[1] F Vetrone and J A Capobianco ldquoLanthanide-doped fluo-ride nanoparticles luminescence upconversion and biologicalapplicationsrdquo International Journal of Nanotechnology vol 5no 9ndash12 pp 1306ndash1339 2008
[2] B M Tissue ldquoSynthesis and luminescence of lanthanide ions innanoscale insulating hostsrdquo Chemistry of Materials vol 10 no10 pp 2837ndash2845 1998
[3] Z G Chen H L Chen H Hu et al ldquoVersatile synthe-sis strategy for carboxylic acid-functionalized upconvertingnanophosphors as biological labelsrdquo Journal of the AmericanChemical Society vol 130 no 10 pp 3023ndash3029 2008
[4] D K Chatterjee A J Rufaihah and Y Zhang ldquoUpconver-sion fluorescence imaging of cells and small animals usinglanthanide doped nanocrystalsrdquo Biomaterials vol 29 no 7 pp937ndash943 2008
[5] P R Diamente M Raudsepp and F C J M van Veggel ldquoDis-persible Tm3+-doped nanoparticles that exhibit strong 14 120583mphotoluminescencerdquoAdvanced Functional Materials vol 17 no3 pp 363ndash368 2007
[6] S Sivakumar P R Diamente and F C J M van Veggel ldquoSilica-coated Ln3+-doped LaF3 nanoparticles as robust down-andupconverting biolabelsrdquo Chemistry-A European Journal vol 12no 22 pp 5878ndash5884 2006
[7] X Teng Y Zhu W Wei et al ldquoLanthanide-doped NaxScF3+xnanocrystals crystal structure evolution and multicolor tun-ingrdquo Journal of the American Chemical Society vol 134 no 20pp 8340ndash8343 2012
[8] V Mahalingam F Vetrone R Naccache A Speghiniand and JA Capobianco ldquoColloidal Tm3+Yb3+-doped LiYF4 nanocrys-tals multiple luminescence spanning the UV toNIR regions vialow-energy excitationrdquo Advanced Materials vol 21 no 40 pp4025ndash4028 2009
[9] S Sarkar C Hazra and V Mahalingam ldquoBright lumi-nescence from colloidal Ln3+-doped Ca072Y028F228 (Ln=EuTmYb) nanocrystals via both high and low energy radiationsrdquoChemistrymdashA European Journal vol 18 no 23 pp 7050ndash70542012
[10] S Sarkar B Meesaragandla C Hazra and V MahalingamldquoSub-5 nm Ln3+-doped BaLuF5 nanocrystals a platform torealize upconversion via interparticle energy transfer (IPET)rdquoAdvanced Materials vol 25 no 6 pp 856ndash860 2013
[11] H Dong S-R Du X-Y Zheng et al ldquoLanthanide nanopar-ticles from design toward bioimaging and therapyrdquo ChemicalReviews vol 115 no 19 pp 10725ndash10815 2015
[12] P Rahman and M Green ldquoThe synthesis of rare earth fluoridebased nanoparticlesrdquoNanoscale vol 1 no 2 pp 214ndash224 2009
[13] LMaW-X Chen Y-F Zheng J Zhao andZ Xu ldquoMicrowave-assisted hydrothermal synthesis and characterizations of PrF3hollownanoparticlesrdquoMaterials Letters vol 61 no 13 pp 2765ndash2768 2007
[14] M S Tagirov E M Alakshin R R Gazizulin et al ldquoSpinkinetics of 3He in contact with synthesized PrF3 nanoparticlesrdquoJournal of Low Temperature Physics vol 162 no 5-6 pp 645ndash652 2011
[15] EMAlakshin BMGabidullin andA TGubaidullin ldquoDevel-opment of various methods for PrF3 nanoparticles synthesisrdquohttpsarxivorgabs11040208
[16] EM Alakshin A S Aleksandrov A V Egorov A V KlochkovS L Korableva and M S Tagirov ldquoNuclear pseudoquadrupoleresonance of 141Pr inVanVleck paramagnet PrF3rdquo JETPLettersvol 94 no 3 pp 240ndash242 2011
[17] EMAlakshinD S Blokhin AM Sabitova et al ldquoExperimen-tal proof of the existence of water clusters in fullerene-like PrF3nanoparticlesrdquo JETP Letters vol 96 no 3 pp 181ndash183 2012
[18] EMAlakshin R RGazizulin AV Klochkov et al ldquoSize effectin the (PrF3 nanoparticles-
3He) systemrdquo JETP Letters vol 97no 10 pp 579ndash582 2013
[19] M S Pudovkin S L Korableva A O Krasheninnicova etal ldquoToxicity of laser irradiated photoactive fluoride PrF3nanoparticles toward bacteriardquo Journal of Physics ConferenceSeries vol 560 no 1 Article ID 012011 2014
[20] E M Alakshin R R Gazizulin A V Klochkov et al ldquoAnneal-ing of PrF3 nanoparticles by microwave irradiationrdquoOptics andSpectroscopy vol 116 no 5 pp 721ndash723 2014
[21] AM Gazizulina EM Alakshin E I Baibekov et al ldquoElectronparamagnetic resonance of Gd3+ ions in powders of LaF
3Gd3+
nanocrystalsrdquo JETP Letters vol 99 no 3 pp 149ndash152 2014[22] S-E Park T-H Kim S-R Lee S Namkung and T-S Jang
ldquoEffect of sintering conditions on the magnetic andmicrostruc-tural properties of Nd-Fe-B sintered magnets doped with DyF
3
powdersrdquo Journal of Applied Physics vol 111 no 7 Article ID07A707 2012
[23] X J Cao L Chen S Guo et al ldquoCoercivity enhancementof sintered Nd-Fe-B magnets by efficiently diffusing DyF3based on electrophoretic depositionrdquo Journal of Alloys andCompounds vol 631 pp 315ndash320 2015
[24] S Sawatzki I Dirba L Schultz and O Gutfleisch ldquoElectricaland magnetic properties of hot-deformed Nd-Fe-B magnetswith different DyF3 additionsrdquo Journal of Applied Physics vol114 no 13 Article ID 133902 2013
[25] R Sueptitz S SawatzkiMMooreMUhlemannOGutfleischand A Gebert ldquoEffect of DyF
3on the corrosion behavior
of hot-pressed NdndashFendashB permanent magnetsrdquo Materials andCorrosion vol 66 no 2 pp 152ndash157 2015
Journal of Nanomaterials 5
[26] Z Duan J Zhang and L Hu ldquoSpectroscopic properties andJudd-Ofelt theory analysis of Dy3+ doped oxyfluoride silicateglassrdquo Journal of Applied Physics vol 101 no 4 Article ID043110 2007
[27] A V Savinkov S L Korableva A A Rodionov et al ldquoMagneticproperties of Dy3+ ions and crystal field characterization inYF3Dy3+ and DyF3 single crystalsrdquo Journal of Physics Con-densed Matter vol 20 no 48 Article ID 485220 2008
[28] X Ye J Chen M Engel et al ldquoCompetition of shape andinteraction patchiness for self-assembling nanoplatesrdquo NatureChemistry vol 5 no 6 pp 466ndash473 2013
[29] S Bhowmik T Gorai and U Maitra ldquoA room temperaturetemplated synthesis of lanthanide trifluoride nanoparticles andtheir unusual self-assemblyrdquo Journal of Materials Chemistry Cvol 2 no 9 pp 1597ndash1600 2014
[30] C Li J Yang P Yang H Lian and J Lin ldquoHydrothermalsynthesis of lanthanide fluorides LnF3 (Ln = La to Lu) nano-microcrystals with multiform structures and morphologiesrdquoChemistry of Materials vol 20 no 13 pp 4317ndash4326 2008
[31] W Kraus and G Nolze ldquoPOWDER CELLmdasha program forthe representation and manipulation of crystal structures andcalculation of the resulting X-ray powder patternsrdquo Journal ofApplied Crystallography vol 29 no 3 pp 301ndash303 1996
[32] DyF3 crystal structure SpringerMaterials (electronic resource)httpmaterialsspringercomispcrystallographicdocssd1300541
[33] C Dong M Raudsepp and F Van Veggel ldquoKinetically deter-mined crystal structures of undoped and La3+-doped LnF3rdquoJournal of Physical Chemistry C vol 113 no 1 pp 472ndash478 2009
[34] P Scherrer ldquoBestimmung der Grosse und der inneren Strukturvon Kolloidteilchen mittels Rontgenstrahlenrdquo Nachrichten vonder Gesellschaft derWissenschaften zuGottingen vol 26 pp 98ndash100 1918
[35] G K Williamson and W H Hall ldquoX-ray line broadening fromfiled aluminium and wolframrdquo Acta Metallurgica vol 1 no 1pp 22ndash31 1953
[36] B E Warren and B L Averbach ldquoThe separation of cold-work distortion and particle size broadening in X-ray patternsrdquoJournal of Applied Physics vol 23 no 4 p 497 1952
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
4 Journal of Nanomaterials
4 Conclusions
In summary the series ofDyF3 nanoparticleswas successfullysynthesized by the microwave-assisted colloidal hydrother-mal method for the first time The nanoparticles were char-acterized by TEM and XRD The average size of particles isabout 16ndash18 nm and the size distribution becomes narrowerafter the microwave treatment It was observed that themicrowave irradiation treatment strongly affects the widthof XRD peaks They become narrower with the microwavetreatment The defect-annealing model of the microwave-assisted hydrothermal modification process is suggested
Competing Interests
The authors declare that they have no competing interests
Acknowledgments
The work was performed according to the Russian Gov-ernment Program of Competitive Growth of Kazan FederalUniversity E M Alakshin has been financially supported bythe Russian Foundation for Basic Research (Project no 16-32-60155 mol a dk)
References
[1] F Vetrone and J A Capobianco ldquoLanthanide-doped fluo-ride nanoparticles luminescence upconversion and biologicalapplicationsrdquo International Journal of Nanotechnology vol 5no 9ndash12 pp 1306ndash1339 2008
[2] B M Tissue ldquoSynthesis and luminescence of lanthanide ions innanoscale insulating hostsrdquo Chemistry of Materials vol 10 no10 pp 2837ndash2845 1998
[3] Z G Chen H L Chen H Hu et al ldquoVersatile synthe-sis strategy for carboxylic acid-functionalized upconvertingnanophosphors as biological labelsrdquo Journal of the AmericanChemical Society vol 130 no 10 pp 3023ndash3029 2008
[4] D K Chatterjee A J Rufaihah and Y Zhang ldquoUpconver-sion fluorescence imaging of cells and small animals usinglanthanide doped nanocrystalsrdquo Biomaterials vol 29 no 7 pp937ndash943 2008
[5] P R Diamente M Raudsepp and F C J M van Veggel ldquoDis-persible Tm3+-doped nanoparticles that exhibit strong 14 120583mphotoluminescencerdquoAdvanced Functional Materials vol 17 no3 pp 363ndash368 2007
[6] S Sivakumar P R Diamente and F C J M van Veggel ldquoSilica-coated Ln3+-doped LaF3 nanoparticles as robust down-andupconverting biolabelsrdquo Chemistry-A European Journal vol 12no 22 pp 5878ndash5884 2006
[7] X Teng Y Zhu W Wei et al ldquoLanthanide-doped NaxScF3+xnanocrystals crystal structure evolution and multicolor tun-ingrdquo Journal of the American Chemical Society vol 134 no 20pp 8340ndash8343 2012
[8] V Mahalingam F Vetrone R Naccache A Speghiniand and JA Capobianco ldquoColloidal Tm3+Yb3+-doped LiYF4 nanocrys-tals multiple luminescence spanning the UV toNIR regions vialow-energy excitationrdquo Advanced Materials vol 21 no 40 pp4025ndash4028 2009
[9] S Sarkar C Hazra and V Mahalingam ldquoBright lumi-nescence from colloidal Ln3+-doped Ca072Y028F228 (Ln=EuTmYb) nanocrystals via both high and low energy radiationsrdquoChemistrymdashA European Journal vol 18 no 23 pp 7050ndash70542012
[10] S Sarkar B Meesaragandla C Hazra and V MahalingamldquoSub-5 nm Ln3+-doped BaLuF5 nanocrystals a platform torealize upconversion via interparticle energy transfer (IPET)rdquoAdvanced Materials vol 25 no 6 pp 856ndash860 2013
[11] H Dong S-R Du X-Y Zheng et al ldquoLanthanide nanopar-ticles from design toward bioimaging and therapyrdquo ChemicalReviews vol 115 no 19 pp 10725ndash10815 2015
[12] P Rahman and M Green ldquoThe synthesis of rare earth fluoridebased nanoparticlesrdquoNanoscale vol 1 no 2 pp 214ndash224 2009
[13] LMaW-X Chen Y-F Zheng J Zhao andZ Xu ldquoMicrowave-assisted hydrothermal synthesis and characterizations of PrF3hollownanoparticlesrdquoMaterials Letters vol 61 no 13 pp 2765ndash2768 2007
[14] M S Tagirov E M Alakshin R R Gazizulin et al ldquoSpinkinetics of 3He in contact with synthesized PrF3 nanoparticlesrdquoJournal of Low Temperature Physics vol 162 no 5-6 pp 645ndash652 2011
[15] EMAlakshin BMGabidullin andA TGubaidullin ldquoDevel-opment of various methods for PrF3 nanoparticles synthesisrdquohttpsarxivorgabs11040208
[16] EM Alakshin A S Aleksandrov A V Egorov A V KlochkovS L Korableva and M S Tagirov ldquoNuclear pseudoquadrupoleresonance of 141Pr inVanVleck paramagnet PrF3rdquo JETPLettersvol 94 no 3 pp 240ndash242 2011
[17] EMAlakshinD S Blokhin AM Sabitova et al ldquoExperimen-tal proof of the existence of water clusters in fullerene-like PrF3nanoparticlesrdquo JETP Letters vol 96 no 3 pp 181ndash183 2012
[18] EMAlakshin R RGazizulin AV Klochkov et al ldquoSize effectin the (PrF3 nanoparticles-
3He) systemrdquo JETP Letters vol 97no 10 pp 579ndash582 2013
[19] M S Pudovkin S L Korableva A O Krasheninnicova etal ldquoToxicity of laser irradiated photoactive fluoride PrF3nanoparticles toward bacteriardquo Journal of Physics ConferenceSeries vol 560 no 1 Article ID 012011 2014
[20] E M Alakshin R R Gazizulin A V Klochkov et al ldquoAnneal-ing of PrF3 nanoparticles by microwave irradiationrdquoOptics andSpectroscopy vol 116 no 5 pp 721ndash723 2014
[21] AM Gazizulina EM Alakshin E I Baibekov et al ldquoElectronparamagnetic resonance of Gd3+ ions in powders of LaF
3Gd3+
nanocrystalsrdquo JETP Letters vol 99 no 3 pp 149ndash152 2014[22] S-E Park T-H Kim S-R Lee S Namkung and T-S Jang
ldquoEffect of sintering conditions on the magnetic andmicrostruc-tural properties of Nd-Fe-B sintered magnets doped with DyF
3
powdersrdquo Journal of Applied Physics vol 111 no 7 Article ID07A707 2012
[23] X J Cao L Chen S Guo et al ldquoCoercivity enhancementof sintered Nd-Fe-B magnets by efficiently diffusing DyF3based on electrophoretic depositionrdquo Journal of Alloys andCompounds vol 631 pp 315ndash320 2015
[24] S Sawatzki I Dirba L Schultz and O Gutfleisch ldquoElectricaland magnetic properties of hot-deformed Nd-Fe-B magnetswith different DyF3 additionsrdquo Journal of Applied Physics vol114 no 13 Article ID 133902 2013
[25] R Sueptitz S SawatzkiMMooreMUhlemannOGutfleischand A Gebert ldquoEffect of DyF
3on the corrosion behavior
of hot-pressed NdndashFendashB permanent magnetsrdquo Materials andCorrosion vol 66 no 2 pp 152ndash157 2015
Journal of Nanomaterials 5
[26] Z Duan J Zhang and L Hu ldquoSpectroscopic properties andJudd-Ofelt theory analysis of Dy3+ doped oxyfluoride silicateglassrdquo Journal of Applied Physics vol 101 no 4 Article ID043110 2007
[27] A V Savinkov S L Korableva A A Rodionov et al ldquoMagneticproperties of Dy3+ ions and crystal field characterization inYF3Dy3+ and DyF3 single crystalsrdquo Journal of Physics Con-densed Matter vol 20 no 48 Article ID 485220 2008
[28] X Ye J Chen M Engel et al ldquoCompetition of shape andinteraction patchiness for self-assembling nanoplatesrdquo NatureChemistry vol 5 no 6 pp 466ndash473 2013
[29] S Bhowmik T Gorai and U Maitra ldquoA room temperaturetemplated synthesis of lanthanide trifluoride nanoparticles andtheir unusual self-assemblyrdquo Journal of Materials Chemistry Cvol 2 no 9 pp 1597ndash1600 2014
[30] C Li J Yang P Yang H Lian and J Lin ldquoHydrothermalsynthesis of lanthanide fluorides LnF3 (Ln = La to Lu) nano-microcrystals with multiform structures and morphologiesrdquoChemistry of Materials vol 20 no 13 pp 4317ndash4326 2008
[31] W Kraus and G Nolze ldquoPOWDER CELLmdasha program forthe representation and manipulation of crystal structures andcalculation of the resulting X-ray powder patternsrdquo Journal ofApplied Crystallography vol 29 no 3 pp 301ndash303 1996
[32] DyF3 crystal structure SpringerMaterials (electronic resource)httpmaterialsspringercomispcrystallographicdocssd1300541
[33] C Dong M Raudsepp and F Van Veggel ldquoKinetically deter-mined crystal structures of undoped and La3+-doped LnF3rdquoJournal of Physical Chemistry C vol 113 no 1 pp 472ndash478 2009
[34] P Scherrer ldquoBestimmung der Grosse und der inneren Strukturvon Kolloidteilchen mittels Rontgenstrahlenrdquo Nachrichten vonder Gesellschaft derWissenschaften zuGottingen vol 26 pp 98ndash100 1918
[35] G K Williamson and W H Hall ldquoX-ray line broadening fromfiled aluminium and wolframrdquo Acta Metallurgica vol 1 no 1pp 22ndash31 1953
[36] B E Warren and B L Averbach ldquoThe separation of cold-work distortion and particle size broadening in X-ray patternsrdquoJournal of Applied Physics vol 23 no 4 p 497 1952
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
Journal of Nanomaterials 5
[26] Z Duan J Zhang and L Hu ldquoSpectroscopic properties andJudd-Ofelt theory analysis of Dy3+ doped oxyfluoride silicateglassrdquo Journal of Applied Physics vol 101 no 4 Article ID043110 2007
[27] A V Savinkov S L Korableva A A Rodionov et al ldquoMagneticproperties of Dy3+ ions and crystal field characterization inYF3Dy3+ and DyF3 single crystalsrdquo Journal of Physics Con-densed Matter vol 20 no 48 Article ID 485220 2008
[28] X Ye J Chen M Engel et al ldquoCompetition of shape andinteraction patchiness for self-assembling nanoplatesrdquo NatureChemistry vol 5 no 6 pp 466ndash473 2013
[29] S Bhowmik T Gorai and U Maitra ldquoA room temperaturetemplated synthesis of lanthanide trifluoride nanoparticles andtheir unusual self-assemblyrdquo Journal of Materials Chemistry Cvol 2 no 9 pp 1597ndash1600 2014
[30] C Li J Yang P Yang H Lian and J Lin ldquoHydrothermalsynthesis of lanthanide fluorides LnF3 (Ln = La to Lu) nano-microcrystals with multiform structures and morphologiesrdquoChemistry of Materials vol 20 no 13 pp 4317ndash4326 2008
[31] W Kraus and G Nolze ldquoPOWDER CELLmdasha program forthe representation and manipulation of crystal structures andcalculation of the resulting X-ray powder patternsrdquo Journal ofApplied Crystallography vol 29 no 3 pp 301ndash303 1996
[32] DyF3 crystal structure SpringerMaterials (electronic resource)httpmaterialsspringercomispcrystallographicdocssd1300541
[33] C Dong M Raudsepp and F Van Veggel ldquoKinetically deter-mined crystal structures of undoped and La3+-doped LnF3rdquoJournal of Physical Chemistry C vol 113 no 1 pp 472ndash478 2009
[34] P Scherrer ldquoBestimmung der Grosse und der inneren Strukturvon Kolloidteilchen mittels Rontgenstrahlenrdquo Nachrichten vonder Gesellschaft derWissenschaften zuGottingen vol 26 pp 98ndash100 1918
[35] G K Williamson and W H Hall ldquoX-ray line broadening fromfiled aluminium and wolframrdquo Acta Metallurgica vol 1 no 1pp 22ndash31 1953
[36] B E Warren and B L Averbach ldquoThe separation of cold-work distortion and particle size broadening in X-ray patternsrdquoJournal of Applied Physics vol 23 no 4 p 497 1952
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials
Submit your manuscripts athttpwwwhindawicom
ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CorrosionInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Polymer ScienceInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CeramicsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CompositesJournal of
NanoparticlesJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
International Journal of
Biomaterials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
NanoscienceJournal of
TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Journal of
NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
CrystallographyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CoatingsJournal of
Advances in
Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Smart Materials Research
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
MetallurgyJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
BioMed Research International
MaterialsJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Nano
materials
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal ofNanomaterials