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  • Polymorphism Control in Nanocrystalline Binary Metal Oxides

    Transféré par

    Shantanu Sood
    97 vues124 pages
    Polymorphic phase transformations are common to all nanocrystalline binary metal oxides. The polymorphic nature of such metal oxides makes available a large number of phases with differing crystal structures, each stable under certain conditions of temperature, pressure, and/or particle size. These different crystal structures translate to unique physical and chemical properties for each structural class of polymorphs. Thus predicting when polymorphic phase transitions are likely to occur becomes important to the synthesis of stable functional materials with desired properties. Theoretical calculations using a heuristic approach have resulted in an accurate estimation of the critical particle size predicting metastable to stable phase transitions. This formula is applied to different case studies: for anatase to rutile titania; γ-Alumina to α-Alumina; and tetragonal to monoclinic zirconia. The theoretical values calculated have been seen to be very close to the experimental results from the literature. Manifestation of the effect of phase transitions in nanostructured metal oxides was provided in the study of metastable to stable phase transitions in WO3. Nanowires of tungsten trioxide have been synthesized in-situ inside an electron microscope. Such structure of tungsten iv trioxide result due to a metastable to stable phase transformation, from the cubic to the monoclinic phase. The transformation is massive and complete. The structures formed are unique one-dimensional nanowires. Such a method can be scaled inside any equipment equipped with an electron gun, for example lithography systems either using STEM or E-beam lithography. Another study on nanowire formation in binary metal oxides involved the synthesis of stable orthorhombic MoO3 by means of blend electrospinning. Both a traditional single jet electrospinning set up and a novel high-throughput process to get high aspect ratio nanowires. The latter is a jet-controlled and flow controlled electrospinning. The mechanism of the formation of nanowires of both tungsten trioxide and molybdenum trioxide are discussed in relation to the polymorphic nature of the oxides.

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    Polymorphic phase transformations are common to all nanocrystalline binary metal oxides. The polymorphic nature of such metal oxides makes available a large number of phases with differing crystal structures, each stable under certain conditions of temperature, pressure, and/or particle size. These different crystal structures translate to unique physical and chemical properties for each structural class of polymorphs. Thus predicting when polymorphic phase transitions are likely to occur becomes important to the synthesis of stable functional materials with desired properties. Theoretical calculations using a heuristic approach have resulted in an accurate estimation of the critical particle size predicting metastable to stable phase transitions. This formula is applied to different case studies: for anatase to rutile titania; γ-Alumina to α-Alumina; and tetragonal to monoclinic zirconia. The theoretical values calculated have been seen to be very close to the experimental results from the literature. Manifestation of the effect of phase transitions in nanostructured metal oxides was provided in the study of metastable to stable phase transitions in WO3. Nanowires of tungsten trioxide have been synthesized in-situ inside an electron microscope. Such structure of tungsten iv trioxide result due to a metastable to stable phase transformation, from the cubic to the monoclinic phase. The transformation is massive and complete. The structures formed are unique one-dimensional nanowires. Such a method can be scaled inside any equipment equipped with an electron gun, for example lithography systems either using STEM or E-beam lithography. Another study on nanowire formation in binary metal oxides involved the synthesis of stable orthorhombic MoO3 by means of blend electrospinning. Both a traditional single jet electrospinning set up and a novel high-throughput process to get high aspect ratio nanowires. The latter is a jet-controlled and flow controlled electrospinning. The mechanism of the formation of nanowires of both tungsten trioxide and molybdenum trioxide are discussed in relation to the polymorphic nature of the oxides.

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    97 vues124 pages

    Polymorphism Control in Nanocrystalline Binary Metal Oxides

    Transféré par

    Shantanu Sood
    Polymorphic phase transformations are common to all nanocrystalline binary metal oxides. The polymorphic nature of such metal oxides makes available a large number of phases with differing crystal structures, each stable under certain conditions of temperature, pressure, and/or particle size. These different crystal structures translate to unique physical and chemical properties for each structural class of polymorphs. Thus predicting when polymorphic phase transitions are likely to occur becomes important to the synthesis of stable functional materials with desired properties. Theoretical calculations using a heuristic approach have resulted in an accurate estimation of the critical particle size predicting metastable to stable phase transitions. This formula is applied to different case studies: for anatase to rutile titania; γ-Alumina to α-Alumina; and tetragonal to monoclinic zirconia. The theoretical values calculated have been seen to be very close to the experimental results from the literature. Manifestation of the effect of phase transitions in nanostructured metal oxides was provided in the study of metastable to stable phase transitions in WO3. Nanowires of tungsten trioxide have been synthesized in-situ inside an electron microscope. Such structure of tungsten iv trioxide result due to a metastable to stable phase transformation, from the cubic to the monoclinic phase. The transformation is massive and complete. The structures formed are unique one-dimensional nanowires. Such a method can be scaled inside any equipment equipped with an electron gun, for example lithography systems either using STEM or E-beam lithography. Another study on nanowire formation in binary metal oxides involved the synthesis of stable orthorhombic MoO3 by means of blend electrospinning. Both a traditional single jet electrospinning set up and a novel high-throughput process to get high aspect ratio nanowires. The latter is a jet-controlled and flow controlled electrospinning. The mechanism of the formation of nanowires of both tungsten trioxide and molybdenum trioxide are discussed in relation to the polymorphic nature of the oxides.

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    Polymorphism Control in Nanostructured Metal Oxides

    A Dissertation Presented
    by
    Shantanu Sood
    to
    The Graduate School
    in Partial Fulfillment of the
    Requirements
    for the Degree of
    Doctor of Philosophy
    in
    Materials Science and Engineering
    Stony Brook Uniersity
    August 20!
    (include this copyright page only if you are selecting copyright through ProQuest, which is
    optional)
    !o"yright by
    Shantanu Sood
    20!
    Stony "roo# $ni%ersity
    The Graduate School
    Shantanu Sood
    #e$ the dissertation committee for the aboe candidate for the
    Doctor of Philoso"hy degree$ hereby recommend
    acce"tance of this dissertation%
    Prof& Pelagia '& (ouma ) Dissertation Ad%isor
    Professor* Materials Science and Engineering
    Dr& Dilip (ersappe + Chairperson of Defense
    Professor* Materials Science and Engineering
    Dr& Milutin Stanace%ic
    Associate Professor* Electrical Engineering
    Dr& Ming,hao -iu
    Assistant Materials Scientist* "roo#ha%en National -a.oratory
    This dissertation is acce"ted by the Graduate School
    !harles Taber
    Dean of the Graduate School
    2
    Abstract of the Dissertation
    Polymorphism control in nanostructured metal oxides
    by
    Shantanu Sood
    Doctor of Philosophy
    in
    Materials Science and Engineering
    Stony Brook Uniersity
    20!
    Polymor"hic "hase transformations are common to all nanocrystalline binary metal
    o&ides% The "olymor"hic nature of such metal o&ides makes aailable a large number of "hases
    'ith differing crystal structures$ each stable under certain conditions of tem"erature$ "ressure$
    and(or "article si)e% These different crystal structures translate to unique "hysical and chemical
    "ro"erties for each structural class of "olymor"hs% Thus "redicting 'hen "olymor"hic "hase
    transitions are likely to occur becomes im"ortant to the synthesis of stable functional materials
    'ith desired "ro"erties% Theoretical calculations using a heuristic a""roach hae resulted in an
    accurate estimation of the critical "article si)e "redicting metastable to stable "hase transitions%
    This formula is a""lied to different case studies* for anatase to rutile titania+ ,-Alumina to .-
    Alumina+ and tetragonal to monoclinic )irconia% The theoretical alues calculated hae been seen
    to be ery close to the e&"erimental results from the literature%
    /anifestation of the effect of "hase transitions in nanostructured metal o&ides 'as
    "roided in the study of metastable to stable "hase transitions in #01% 2ano'ires of tungsten
    trio&ide hae been synthesi)ed in-situ inside an electron microsco"e% Such structure of tungsten
    3
    trio&ide result due to a metastable to stable "hase transformation$ from the cubic to the
    monoclinic "hase% The transformation is massie and com"lete% The structures formed are unique
    one-dimensional nano'ires% Such a method can be scaled inside any equi"ment equi""ed 'ith an
    electron gun$ for e&am"le lithogra"hy systems either using ST3/ or 3-beam lithogra"hy%
    Another study on nano'ire formation in binary metal o&ides inoled the synthesis of
    stable orthorhombic /o0
    1
    by means of blend electros"inning% Both a traditional single 4et
    electros"inning set u" and a noel high-through"ut "rocess to get high as"ect ratio nano'ires%
    The latter is a 4et-controlled and flo' controlled electros"inning%
    The mechanism of the formation of nano'ires of both tungsten trio&ide and molybdenum
    trio&ide are discussed in relation to the "olymor"hic nature of the o&ides%

    4
    Dedicated to
    /y highly motiating and su""ortie family%
    And
    3s"ecially to my mother$ Dr% /adhoolika Sood%
    5
    /a.le of Contents
    List of Tables..........................................................................................................................ix
    Preface...................................................................................................................................xi
    Acknowledgments.................................................................................................................xiii
    Vita.......................................................................................................................................xv
    Publications (Journal and Proceedings)...............................................................................xvi
    Chapter 1 !ntroduction.......................................................................................................2
    && Polymorphs of 0O1...............................................................................................................3
    &2& Polymorphs of MoO1.............................................................................................................4
    &1& Polymorphs of other .inary metal oxides..............................................................................5
    &!& Metasta.ility in nanocrystalline .inary metal oxides...........................................................6
    &2& Phase /ransformations due to nanoscale particle si,e........................................................10
    &3& Polymorphic nano4ires of 0O1 and MoO1.........................................................................12
    &5& Applications of nanocrystalline .inary metal oxides...........................................................14
    &6& Polymorphic nano4ires as sensing materials......................................................................22
    &7& Statement of the pro.lem.....................................................................................................24
    References............................................................................................................................................................25
    Chapter " #$perimental %etails........................................................................................35
    2&& Synthesis Methods...............................................................................................................35
    2&&& Sol+(el synthesis..............................................................................................................35
    2&&2& Electrospinning................................................................................................................35
    2&&1& 8igh throughput electrospinning.....................................................................................37
    2&2& Characteri,ation Methods...................................................................................................39
    2&2&& 9+ray diffraction..............................................................................................................39
    2&2&2& :aman Spectroscopy........................................................................................................39
    2&2&1& /ransmission electron microscopy...................................................................................40
    2&2&!& 8igh resolution /ransmission electron microscopy.........................................................40
    2&2&2& Scanning Electron Microscopy........................................................................................40
    References............................................................................................................................................................41
    Chapter & 'euristic model of pol(morphic transitions......................................................42
    1&&& /heory..............................................................................................................................43
    6
    1&&2& Entropic contri.ution......................................................................................................44
    1&&1& Surface ;ree Energy........................................................................................................45
    1&&!& Surface Stress...................................................................................................................46
    1&&2& ;ree Energy due to particle shape...................................................................................46
    1&&3& Critical particle si,e.........................................................................................................47
    1&2& Case Studies.........................................................................................................................48
    References............................................................................................................................................................48
    Chapter ) Tungsten Trio$ide nanowire in*situ T#+ s(nthesis..........................................53
    !&& Precursor phase...................................................................................................................53
    !&2& 'n+situ nano4ire synthesis...................................................................................................56
    !&1& /hermodynamics of nano4ire formation............................................................................61
    References............................................................................................................................................................65
    Chapter , +ol(bdenum Trio$ide nanowires b( electrospinning........................................67
    2&& MoO1 Electrospun nano4ire formation..............................................................................67
    2&2& Single <et..............................................................................................................................69
    2&1& Multi+=et...............................................................................................................................72
    2&1&& Case study on P>P and CA fi.ers....................................................................................73
    2&1&2& Process Parameters..........................................................................................................75
    2&1&1& Nanofi.er Synthesis.........................................................................................................77
    References............................................................................................................................................................80
    Chapter - %iscussion and future work..............................................................................84
    3&& Polymorphic transitions and critical particle si,e...............................................................84
    3&2& Phase transitions and 0O1 nano4ire synthesis...................................................................89
    3&1& Polytypism in nano4ires......................................................................................................92
    3&!& ;uture 4or#.........................................................................................................................95
    References............................................................................................................................................................99
    Appendi$ A Comparison between bulk and nano phases................................................105
    Appendi$ . Cr(stalline /tructures..................................................................................107
    Appendi$ C !nternal pressure calculations.....................................................................108
    Appendi$ % 0ree energ( due to particle shape calculations............................................109
    Appendi$ # Per mole con1ersion of surface energ(2tension and surface stress terms.....110
    Appendi$ 0 +echanism behind the 'igh throughput electrospinning............................114
    7
    -ist of ;igure
    ;igure ? Traditional electros"inning set u"%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%15
    ;igure 2? @aA /odified flo' controlled and 4et controlled high through"ut electros"inning set u"% @.A
    Source disk$ the metallic "late 'here one terminal of the high oltage source attaches is isible$ 56
    equidistant 7mm diameter holes drilled in to the inner base of the disk 'ith one hole "lugged for attaching
    the oltage terminal+ @cA Schematic of the setu"$ dimensions and other details are labeled%%%%%%%%%%%%%%%%%%%%%%%16
    ;igure 1? The source disk is a critical com"onent of the set u"+ @aA Schematic sho'ing the side ie' of
    the source disk% @.A Schemtic sho'ing the bottom ie' of the source disk% @cA The bottom ie' of the
    source disk% @dA The to" ie' of the source disk%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%18
    0igure )3 (a) Low magnification SEM image of sol-gel synthesied nanoparticles of tungsten trio!ide
    annealed at "#$%, (b) shows the higher magnification SEM image with uniformly distri&uted particle
    sie' (c) Shows the Raman spectra of the nanoparticles, the &ands o&ser(ed are mar)ed' (d) Shows the
    *R+ of the nanoparticles'%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 87
    ;igure 2 ? @-eftA T3/ microgra"h of the cubic nano"articles of Tungsten trio&ide$ @:ightA SAD "attern$
    brighter rings can be inde&ed to 97::;+ 977:;+ 957:; "lanes of the cubic "hase%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%85
    0igure -3 (Left) ,EM of nanowires grown on a Silicon -itride support film, (4ight) ,EM of nanowires
    grown on form(ar support film on a %opper mesh grid'%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%86
    0igure 53 (Left) ,ypical Electron diffraction pattern ta)en from a region with high concentration of
    nanowires' (4ight) Schematic of crystal structure of the monoclinic phase, with the preferred growth
    direction, the distortions ha(e &een e!aggerated to ser(e the purpose of illustration'%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%88
    ;igure 6? @-eftA <ighly aligned nano'ires$ sho'ing the =::7> gro'th direction along the long a&is+
    @:ightA !orres"onding diffraction "attern%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%8?
    0igure 63 .igh resolution ,EM of the structure of the nanowires/ (!nset) S0+ pattern from indi(idual
    nanowire'%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 8@
    ;igure 0? Gra"h "lotting the free energy for cubic and monoclinic "hase due to "article si)e$ and oerlay
    is the difference in the free energies for cubic nano"articles and monoclinic nano'ires as a function of the
    as"ect ratio of the nano'ires kee"ing the radius of nano'ires constant at the obsered alues 5:nm%%%%%%?:
    ;igure @aA S3/ microgra"h of metal o&ide enca"sulated electros"un nanofibers% @.A /olybdenum
    trio&ide enca"sulated inside ele&tros"un fibers$ @'nsetA 3DS "attern of the enca"sulated "articles%%%%%%%%%%%??
    ;igure 2* @aA S3/ microgra"h of heat treated nanofibers at 8::!+ @.A S3/ microgra"h of high as"ect
    ratio nano'ires%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% ??
    0igure 1&3 (a) -anowire growth after heat treatment at 1#$% and (inset) its corresponding S0+ pattern/
    (b) -anowire growth after heat treatment at #$$% and (inset) its corresponding S0+ pattern/ (c)
    .R,EM image of the nanowire and (inset) its corresponding S0+ pattern'%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%?@
    ;igure !? @aA <RT3/ of <igh-through"ut P7 electros"un fibers+ @.A S3/ of T23 "rocessed P7
    electros"un fibers%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% @:
    ;igure 2? @aA S3/ of <igh-through"ut P5 electros"un fibers+ @.A S3/ of T23 "rocessed P5
    electros"un fibers%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% @7
    ;igure 3 2anofiber diameter and "roduction rates "lotted as a function of oltage and concentration% % %@5
    ;igure 5? @a+dA S3/ microgra"hs for different oltages and concentration for PAP fibers%%%%%%%%%%%%%%%%%%%%@1
    ;igure 6? 3lectron microsco"y com"arison bet'een the nanofibers synthesi)ed by traditional needle
    setu" 9a B c; and those synthesi)ed by high throug"ut set u" 9. B d;%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%@8
    8
    ;igure 7* @aA !rystal structure of orthorhombic /o01 along 'ith )one a&is as marked% @.A B-Ray
    diffraction of /o01 orthorhombic nano'ires synthesi)ed by both traditional and high through"ut
    nano'ires$ the "lanes marked are from C!PDS D:8-:8:E%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%@8
    ;igure 20? Schematic describing the gro'th of monoclinic tungsten trio&ide nano'ires from
    nano"articles of cubic "hase in a ste"'ise fashion% Ste" 7 sho's the starting nano"articles 'hich hae a
    radius of bet'een 1: to 6:nm% As an electron beam is sho'n onto these nano"articles the "articles start to
    gro' into nano'ires as sho'n in ste" 5% As the nano"articles get consumed they start to coagulate and
    gro' into nano'ires% Ste" 1 sho's ho' these nano"articles gro' from "referred direction to form
    randomly oriented nano'ires before being totally consumed and forming highly aligned nano'ires of
    tungsten trio&ide as sho'n in ste" 6% The 'hole "rocess may take a fe' micro seconds to com"lete once
    the nano"articles receie the required amount of energy%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%E1
    ;igure 2* FFT images of the nano'ires+ 9Feft; Usually obsered nano'ire+ 9right; "eriodic nano'ire
    structure%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% E6
    ;igure 22* Analysis of electron diffractions of differently oriented nano'ires$ "ossibly sho'ing the
    reason for the streaking "resent in the diffraction "atterns%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%E@
    0igure "&3 Rotating source dis) design'%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%G:
    Figure 56* 9a; Structure 7* Rutile-ty"e Tetragonal+ 9b;Structure 5* Peroskite-ty"e+ 9c;Structure 1*
    !orundum-ty"e Rhombohedral+ 9d;Structure 6* !a!l5-ty"e 0rthorhombic+ 9e; Structure8* Rh501%%%%%%%%%G8
    ;igure 22? A liquid dro"let 'ith radius HrI$ a hy"othetical cylindrical dro"let 'ith radius HrI and height
    HhI%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% G?
    ;igure 23 @aA Dro"let formation at the surface of the metallic disk+ @.A As the dro"let gro's aboe the
    critical si)e$ it forms into a conical 4et+ @cA This 4et gets solidified as nanofibers at the cylindrical collector%
    %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% GE
    ;igure 25? /ulti"le 4et formation on the disk surface%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%GE
    ;igure 26? The electric field distribution$ 9a; bet'een the outer collector cylinder and source disk+ 9b; on
    the surface of the source disk%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% GG
    ;igure 27? Geometric inter"retation of the electros"inning "rocess$ 9Jnset; sho'ing the double fiber
    formation in the 4et oerla" region%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%7::
    ;igure 10? Plot of theoretical yield 9g(h; s number of holes and loss of yield due to K oerla" s number
    of holes%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% 7:7
    9
    -ist of /a.les
    /a.le * /etastable "hases of /etal 0&ides%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%@
    /a.le 2? !om"arison bet'een bulk and nano "hase at ambient tem"erature and "ressure%%%%%%%%%%%%%%%%%%%%%%%%77
    /a.le 1? Standard entro"y of formation a fe' Polymor"hs%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%6:
    /a.le !* Alumina$ titania$ )irconia critical "article si)e calculations%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%66
    /a.le 2
    * !ontributions from the three main factors influencing the nano'ire gro'th%
    %%%%%%%%%%%%%%%%%%%%%%%%%%%%%8E
    /a.le 3* Data accumulated from the literature$ and the free energy calculations%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%8E
    /a.le 5? Preious attem"ts to increase "roduction rates of electros"un fibers%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%?E
    /a.le 6? !om"arison bet'een traditional needle electros"inning and high through"ut electros"inning for
    PAP%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% @:
    /a.le 7* /odels for "hase transformation behaior de"endence on "article si)e%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%E:
    /a.le 0? !om"arison bet'een bulk and nano for same "hase and different conditions for tem"erature
    and "ressure%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% G1
    10
    Preface
    The 'ork done here focuses on understanding and controlling "hase transitions in
    nanostructured binary metal o&ides$ 'ith em"hasis on the synthesis of nano'ires of the stable
    "hases of molybdenum trio&ide and tungsten trio&ide$ res"ectiely%
    !ha"ter 7 introduces the conce"t of o&ide "olymor"hism and discusses bulk "hase
    "olymor"hs of arious metal o&ides like$ #0
    1
    $ /o0
    1
    $ Ti0
    5
    $ Sn0
    5
    $ !r0
    5
    $ Lr0
    5
    $ Jn
    5
    0
    1
    $ Fe
    5
    0
    1
    $ and
    Al
    5
    0
    1
    % Further the nanocrystalline "hases of these metal o&ides hae been tabulated% The
    "olymor"hs that result from "hase transformations at the nanoscale are also discussed% Parts of
    this 'ork hae been "ublished in -anomaterials and Energy 2 95;$ 7 95:71;%
    !ha"ter 5 focuses on the e&"erimental details and both synthesis techniques and
    characteri)ation techniques used for tungsten trio&ide and molybdenum trio&ide nanomaterials%
    !ha"ter 1 discusses a heuristic a""roach used to arrie u"on the critical "article si)e for
    the "hase transformation bet'een a metastable and stable "hase of a metal o&ide% !ase studies
    hae also been used to ascertain the accuracy of the e&"ression% This 'ork has a""eared in
    "ublication$ 2ournal of 0merican %eramic Society 7395;$ 178 95:71;%
    !ha"ter 6 discusses the in-situ synthesis of #0
    1
    based on a "olymor"hic "hase reaction%
    The formation of nano'ires by such a non-inasie route by the irradiation by an electron beam
    has im"ortant consequences for deelo"ment of a non-chemical route for nano'ire synthesis%
    The im"artation of energy using an electron beam can "otential be achieed by any electron
    beam based system%
    11
    !ha"ter 8 adds to the earlier 'ork done on the synthesis of single crystal nano'ires of
    /o01 by ada"ting a multi4et system% Such a system has been designed to achiee high
    through"ut synthesis of nanfibers% Jt is a 4et-controlled and flo'-controlled system% Part of this
    'ork has a""eared in "ublications$ 2ournal of -anoenegineering and -anomanufacturing$ !97;$
    1G95:76; and MRS eproceeding$ 327$ 5:76%
    !ha"ter ? discusses the im"ortant consequences of the 'orks described in this thesis% The
    im"ortance of a""lication of critical "article si)e "henomenon$ in-situ nano'ire synthesis of
    #0
    1
    and unique as"ects of the high through"ut /o0
    1
    nanofiber synthesis are discussed% The
    future research directions as eoled from this 'ork are also outlined
    12
    Ac#no4ledgments
    J 'ould like to e&tend the foremost gratitude to my adisor$ Dr% P% Gouma% She has been a
    source of great su""ort all throughout my stay at the uniersity% She has been a there through all
    the u"s and do'ns and it is only due to her encouragement that J hae been able to achiee
    anything% She is a kno'ledgeable mentor and the most "atient adisor% <er constructie
    criticisms hae allo'ed me to gro' to be a ca"able researcher% A short "aragra"h cannot be
    enough for the gratitude J hae for her$ it has been a "leasure to 'ork under her guidance for
    more than three years%
    J 'ould like to thank the su""ort of the de"artment$ es"ecially$ Dr% Cim Muin$ Deborah
    /ichien)i$ !handrani Roy and Shauntae Smith% Additionally$ J 'ould like to thank our graduate
    coordinator$ Dr% Dili" Gersa""e for being there to ans'er all my graduation related queries and
    for all the hel" he has rendered during my stay%
    Brookhaen 2ational Faboratory has been a source of intellectual "ro'ess during my
    doctorate% J 'ould like to thank /r% Nim Nisslinger for "atiently training me on the T3/$ Dr%
    3ric Stach for letting me use all the facilities in the electron microsco"y grou" and for guiding at
    im"ortant 4unctures in the "ro4ect%
    J 'ould like to ackno'ledge 2ational Science foundation 92SF D/R D77:?7?E and 2SF
    JJS D7517@?7;$ for the financial su""ort "roided to'ards the research%
    J hae s"ent most of my time in the lab$ therefore the su""ort and enironment "roided
    to me due to my lab mates has been the most im"ortant contributor to'ards my successful
    com"letion% J 'ould like to thank$ Dr% Cusang Fee$ Gagan Codhani$ Dr% Outaka 2omura for
    teaching me in lab% 0ther lab members$ Prasad Sundaram$ Narishma Ti4ori'ala$ Guokuo Lheng$
    13
    Fei Fi$ Cing Lhang$ Ruiyao !ui$ Ciahao huang$ Fynne Fiao$ Selda To"cu hae all contributed to
    making my e&"erience in lab a "leasant one%
    And finally J 'ould like to thank the most im"ortant "eo"le in my life$ my family$ 'ho J
    kno' 'ould al'ays be there no matter 'hat% /y father$ mother$ brother and both sisters and
    brother-in-la'%

    14
    >ita
    Shantanu Sood
    3orn4 Canuary 7@$ 7GEG$ Rhotak$ Jndia%
    3ducation*
    "&E& 9Culy 5::? P /ay 5:7:;$ /etallurgical 3ngineering$ Pun4ab 3ngineering !ollege Uniersity of
    Technology$ !handigarh$ Jndia%
    M&S& 9Canuary 5:77 P /ay 5:71;$ State Uniersity of 2e' Oork$ Stony Brook$ 2O$ USA%
    3&"erience*
    :esearch Assistant 90ctober 5:77 P "resent;$ De"artment of materials science and engineering$ State
    Uniersity of 2e' Oork$ Stony Brook$ 2O$ USA%
    /eaching Assistant 9Se"tember 5:75 P /ay 5:71;$ De"artment of materials science and engineering$
    State Uniersity of 2e' Oork$ Stony Brook$ 2O$ USA%
    15
    Pu.lications @<ournal and ProceedingsA
    7% P% Gouma$ S% Sood 95:71;% MRS 5nline Proc' Li&' 211%
    5% S% Sood$ P% Gouma 95:71;% 2' 0m' %eram' Soc', 73 Q5R$ 187P186%
    1% S% Sood$ P%Gouma$ -anomaterials and Energy$ 292/35;$ 7-7895:71;%
    6% S% Sood$ S% Diya$ P%Gouma$ 2ournal of nanoengineering and nanomanufacturing !$ 7P?$
    95:76;%
    8% S% Sood$ G% Lheng$ P% Gouma 95:76;% MRS 5nline Proc' Li&' 327%
    Chapter & 'ntroduction
    16
    Although$ "olymor"hism 'as discoered by Nla"roth in 7@GE Q7R$ 'hen he sho'ed that the
    chemical com"osition of minerals calcite and aragonite is same$ !a!01$ fe' gae any
    im"ortance to it at the time% Jt 'as the result of the 'ork of a young chemist and amateur
    mineralogist$ 3ilhardt /itscherlich Q5R in 7E5:s$ that "olymor"hism 'as uniersally acce"ted%
    /itscherlich "ublished "a"ers on arsenates Q1R$ "hos"hates Q1R and sulfur Q6R$ /itscherlichSs Tla'
    of isomor"hismT is sim"ly stated* Substances that crystalli)e in isomor"hous forms 9i%e%$ hae
    identical crystalline forms and form mi&ed crystals; hae similar chemical com"ositions% Bulk
    state o&ide "olymor"hism has been 'idely studied% Jn modern times 'ith the adent of
    nanoscience$ "olymor"hism has made aailable a s"ectrum of materials 'hich 'ere hitherto not
    aailable to science% S"ecifically nanocrystalline metal o&ides are of increasing interest Q8$ ?R
    and it 'as sho'n that certain metal o&ides deiate significantly from their bulk state "hase
    transformation "ro"erties 'hen they are sub4ect to similar conditions at the nanoscale% Follo'ing
    'e discuss certain binary metal o&ides 'hich crystalli)e in metastable forms as they are sub4ect
    to differing conditions of "ressure and tem"erature Q@R% These metastable states become aailable
    at ambient conditions due to the nanometer si)e of the "articles or grains% Table S7 in A""endi&
    A tabulates the bulk "hase transitions in the binary o&ides%
    Polymor"hic nanocrystalline metal o&ides hae been "roen time and again to hae better
    "ro"erties than there bulk counter"arts% 2anocrystalline !r0
    5
    a half metallic ferromagnetic QER
    o&ide has seen a""lications in magnetoelectronics Q8R and there magnetotrans"ort "ro"erties hae
    been inestigated Q8R% 0rthorhombic "hase of Sn0
    5
    is ery im"ortant in terms of gas sensing
    a""lications QGR% 2anocrystalline Tungsten trio&ide$ is another im"ortant sensor material and its
    sensing "ro"erties hae been 'ell studied Q7:R% /echanism for sensing behaior of metal o&ides
    17
    can be described by the surface "henomenon$ 'hen there are surface acancies on o&ide surface$
    the o&idising gas can get adsorbed$ and for e&am"le 20B gas is adsorbed at the monoclinic
    #01 surface$ on the contrary 'hen there is an access of electrons on the surface a reducing gas
    can get adsorbed% Polymor"hism can also be an im"ortant "henomenon 'hen considering
    electrochemical reactions in fuel cells$ different "olymor"hs of a metal o&ide can hae different
    ion conductiity$ for e&am"le$ in the case of .-Bi501$ U-Bi501$ ,-Bi501$ V-Bi501 the ion
    conductiities 'ere found to be 1B7:-6$ 5B7:-1$ 8B7:-1$ 7 res"ectiely Q77R% Polymor"hism is
    also im"ortant in "hotocatalytic behaior% Tungsten Trio&ide is a metal o&ide that e&ihibits
    "hotocatalytic behaior% Titania is by far the most 'idely used "hotocatalytic material$ but due to
    its 'ide bandga" it has some limitations$ 'hereas tungsten trio&ide 'hich has much smaller
    bandga" of bet'een 5%6 to 5%EeA Q75R and has better "hotocatalytic "ro"erties% Polymor"hism
    also "lays an im"ortant role in electrochemical cells and batteries% The lattice of orthorhombic
    molybdenum trio&ide due to its layered structure is "articularly suitable for FiW insertion reaction
    Q71R% Authors of ref% Q7?R re"orted Fithium ca"acity u" to 7%8 Fi(/o and discharge ca"acity oer
    1:: mAh gX7% The lattice of <e&agonal molybdenum trio&ide consists of a three-dimensional
    array of corner-sharing /o0? octahedrons and has a more o"en structure 'hich not only "ermits
    the ready intercalation of some monoalent cations including 2aW$ NW and 2<6W$ but also
    allo's them to be readily mobile in the tunnels Q78R% Authors of ref% Q76R re"orted lithium
    ca"acity of u" to 5%5 Fi(/o and discharge ca"acity oer 6:: mAh gX7$ 'hich is clearly much
    better than the orthorhombic molybdenum trio&ide%
    7%7%Polymor"hs of #0
    1
    #0
    1
    has numerous "olymor"hs 'ith different structures$ all originating as distortions of the
    ideal symmetry 'hich is cubic$ based on the re"etition of #0
    ?
    regular octahedral% The structure
    18
    of #0
    1
    is close to the Re0
    1
    structure% For bulk state$ "hase transformations in #0
    1
    take the
    follo'ing route Q7@$ 7ER$ the monoclinic Y-#0
    1
    9'ith s"ace grou" Pc; 'ith lattice constants$ a Z
    8%5@@ [$ b Z 8%788 [$ c Z @%??1 [$ transforms to triclinic V-#0
    1
    9P6; at 51:N$ 'hich then
    transforms to monoclinic ,-#0
    1
    9P7
    6
    8n; 'ith lattice contants$ a Z @%5G@ [$ b Z @%81G [$ c Z
    @%?EE [ at 1::N% The room tem"erature monoclinic "hase is the stable form of #0
    1
    under
    normal conditions and transforms to orthorhombic U-#0
    1
    9Pnma; 'ith lattice constants a Z
    @%1E6[$ b Z @%875 [$ c Z 1%E6? [ at ?51N% U-#0
    1
    tranforms to tetragonal .-#0
    1
    9P18ncc; at
    G::N 'hich is the high tem"erature "hase%
    7%5%Polymor"hs of /o0
    1
    /o0
    1
    e&hibits seeral "olymor"hs* the .-"hase 9s"ace grou" Pbmn; that is stable under
    ambient conditions+ the U-"hase 9P57(c;$ a metastable "olymor"h+ /o0
    1
    -JJ 9P57(m; a metastable
    high-"ressure "hase+ and the he&agonal "hase$ h-/o0
    1
    % Both bulk .- and U-/o0
    1
    hae
    /o0
    ?
    octahedra a the basic structural unit and their structure is formed by the linkage of
    distorted /o0
    ?
    octahedra Q7GR% .-/o0
    1
    crystalli)es 'ith lattice constants a Z 71%E88 [$ b Z
    1%?G? [ and c Z 1%G?1 [ 9S"ace Grou" Pbnm;% U-/o0
    1
    is similar to #0
    1
    and is related to the
    three-dimensional Re0
    1
    structure$ 'hich consists of corner-connected octahedra net'ork% Jt
    crystalli)es 'ith lattice constants a Z @%755 [$ b Z 8%1?? [$ and c Z 8%8?? [ 9s"ace grou" P57(c;%
    Phase transition bet'een "olymor"hs in the bulk state has been obsered to be much different
    than at the nanoscale% /c!arron 97GE?; Q5:R first obsered the U-"hase to .-"hase transformation
    in the bulk state and concluded that /o0
    1
    transforms from amor"hous to U-"hase at 881N and
    then to .-"hase aboe ?@1N% Similar results 'ere later confirmed by Leng 97GGE; Q57R and it 'as
    concluded that the U-"hase to the .-"hase reaction is both e&othermic and "hotochromic$ 'ith a
    19
    yello'-colored U-/o0
    1
    conerting to the 'hite-colored . "hase aboe ?6EN at moderate heating
    rates%
    7%1%Polymor"hs of other binary metal o&ides
    /iO
    2
    naturally occurs as crystalline "hases Q55$ 51R* rutile tetragonal 9a Z 6%8G1@ [$ c Z
    5%G8E@ [; 9P65(mnm;$ anatase tetragonal 9a Z 1%@E68 [$ c Z G%8761 [; 9J65(amd; and brookite
    orthorhombic 9Pcab; 9a Z 8%688E [$ b Z G%7E7G [$ c Z 8%765G [;% Rutile is thermodynamically
    stable at room tem"erature$ and anatase is kinetically stable and transforms to rutile at higher
    tem"eratures Q56R%
    SnO
    2
    crystalli)es in the rutile-ty"e tetragonal structure at ambient conditions and it
    transforms to !a!l
    5
    -ty"e$ then to 9-Pb0
    5
    Pty"e$ and finally a "yrite 9modified fluorite;-ty"e
    structure under high-"ressure Q58R% Rutile-ty"e tetragonal "hase and !a!l
    5
    -ty"e orthorhombic
    "hase are the t'o most common and im"ortant "olymor"hs of Sn0
    5
    % 0ther high "ressure
    "olymor"hs e&ist 9the reader is directed to follo'ing references; Q5?$ 5@R%
    CrO
    2
    is one of the sim"lest kno'n half-metals$ a metastable chromium o&ide and can easily
    decom"ose to chromia 9!r
    5
    0
    1
    ;$ it crystalli)es into the rutile structure Q5ER 9S"ace grou"
    P65(mnm$ LZ5; at ambient conditions$ a structure commonly found in many metal dio&ides
    9/0
    5
    + /ZTi$ !r$ /n$ Sn$ Ge$ Pb$ etc%;% The synthesis of nanocrystalline !r0
    5
    is difficult since$
    as it is a metastable state$ most attem"ts hae resulted in transformation into the more stable
    !r
    5
    0
    1
    o&ide of chromium% Jn atmos"heric "ressure !r0
    5
    decom"oses to !r
    5
    0
    1
    at as lo' as 6@1N
    Q5GR%
    CrO
    2
    can ado"t three different crystalline structures$ that is$ cubic$ tetragonal$ and
    monoclinic "olymor"hs% The monoclinic "hase$ stable at room tem"erature$ is transformed to
    20
    tetragonal at 7661N$ and then to cubic at 5?61N Q1:R% These t'o high-tem"erature "hases are
    unstable in bulk forms at ambient tem"erature 9although many dialent and trialent cationic
    s"ecies such as /g
    5W
    $ !a
    5W
    $ and O
    1W
    hae been incor"orated into )irconia to "re"are cubic and
    tetragonal )irconia that is stable at room tem"erature;%
    'n
    2
    O
    1
    crystalli)es in cubic bi&byite-ty"e structure 9cubic-Jn
    5
    0
    1
    $ s"ace grou" Ja1; Q17R under
    ambient conditions% !orundum-ty"e indium9JJJ; o&ide 9he&agonal-Jn
    5
    0
    1
    $ s"ace grou" R c; is 33
    kno'n to be the high-"ressure modification of Jn
    5
    0
    1
    Q15$ 11R%
    ;e
    2
    O
    1
    e&ists in a stable . "hase and has three metastable "hases ,$ U$ Y-Fe
    5
    0
    1
    % At high
    tem"eratures Fe
    5
    0
    1
    conerts to amor"hous "hase% And melts at 7E1E N% U "hase 'ith lattice
    constant$ a Z G%6:6 [$ is thermally unstable and conert to . "hase 'ith lattice constants$ a Z
    8%:18 [$ c Z 71%@6E [$ aboe @@1N Q16R% Jnformation on the U$ Y "hases is scarce% The , \ .
    transformation in bulk occurs at around G11N Q18R%
    Al
    2
    O
    1
    e&ists is arious "olymor"hic forms$ .$ ,$ V$ ]$ ^-Al
    5
    0
    1
    Q1?$ 1@$ 1ER .-Al
    5
    0
    1
    $
    corundum$ 'ith lattice constants$ a Z 6%@8E [$ c Z 75%GG5 [$ and ,-Al
    5
    0
    1
    'ith lattice constants$ a
    Z @%G66 [ are the more im"ortant "olymor"hs% At high "ressures of 7::GPa corundum changes
    to Rh
    5
    0
    1
    9JJ;-ty"e orthorhombic structure Q1GR%
    7%6%/etastability in nanocrystalline binary metal o&ides
    Bet'een the stable state and unstable state of a material system there can be many
    metastable states$ i%e% relatie stable states that succeed each other in ste"'ise decreasing free
    energy% This is kno'n as 0st'ald-ste" rule or _the la' of successie reactions` Q6:R% The
    occurrence of metastability is based on the structural transformations inoled% /tructure is the
    fundamental propert( of pol(morphs$ thus to hae a clearer understanding as to 'hy certain
    21
    materials result in ariable structural configurations at arying tem"eratures and ho' e&actly the
    "hases do transform% Table J lists the o&ide "olymor"hs that hae been synthesi)ed at the
    nanoscale$ along 'ith the synthesis techniques$ "rocessing conditions$ and relatie "article si)e
    of the transforming material%
    Table 14 Metasta&le phases of Metal 5!ides

    PhaseDPhase
    transition
    Conditions of
    P and /
    Particle Si,e Synthesis /echniEues 4eference
    Ti0
    5
    Rutile Aboe 7751N Belo' 77nm SolXgel method :16; < :17;
    Anatase RT 77 to 18nm SolXgel method :16; < :17;
    Brookite -- <igher than 18nm SolXgel method :16; < :17;
    !r0
    5
    .-"hase
    ?51N 18 to E:nm
    !hemical method inoling
    metal9!r6W;-"olymer
    com"osite "recursor$ no
    o&idation to !r501 obsered
    u"til @@1N
    3iswas and Ram
    (7$$1), :1";
    --
    2anodots+
    2ano'ires
    3"ita&ial chromium dio&ide
    by Selectie-Area gro'th
    technique
    =ou and *iao,
    :11;
    -- 7:: nm to 5 >m
    3lectron-beam lithogra"hy
    and Reactie ion etching
    *iao et al', :1#;
    Sn0
    5
    !a!l5-ty"e
    "hase
    -- 1:-6:nm dia
    Thermal ea"oration of Sn0
    "o'der
    =hou et al':1?;
    -- 8:nm
    3a"oration(!ondensation
    Techniques
    0r&iol et al':1@;
    E6EN Grain si)e 5:nm
    /echanical milling of tin
    mono&ide "o'ders
    Lamelas:1A;

    PhaseDPhase
    transition
    Conditions of
    P and /
    Particle Si,e Synthesis /echniEues 4eference
    Lr0
    5
    Tetragonal
    Phase
    7661N 7:nm --
    Bar(ie and
    Boss:1C;
    ?::N-7:@1N 1%7nm 2onhydrolytic solXgel
    method
    2oo et al':#$;
    22
    /onoclinic
    Phase
    Aboe 75@1N G%8nm to 5:nm
    Fiquid Thermal S"ray
    synthesis
    %hras)a et al'
    :#6;
    /o0
    1
    .-/o0
    1
    Aboe @51N ?:nm Jon-beam de"osition :#7;, :#";, :#1;
    @@1N
    7:-8:nm dia%
    2ano'ires$ length
    7-5am
    3lectros"inning
    Bouma et al'
    :##;
    U-/o0
    1
    Belo' @51N 2ano"articles Sol-gel method
    0' D' Prasad,
    :#?;,:#1;
    h- /o0
    1
    RT As"ect ratio of ?:
    Fo'-Tem"erature !hemical
    method
    :#@;,:#A;
    Phase change
    to U-/o01
    aboe @::N
    7D structures of
    5:: nm dia b
    length of E:: nm
    !hemical "reci"itation
    technique
    %hitham&araraE
    and 3ose,:#C;
    661N to
    ?@11N
    8:nm diameter b
    7am length
    #et !hemical route +hage et al',:?$;
    #0
    1
    h-#01
    8@1N to @51N 8:-7::nm
    Thermal annealing of
    ammonium tungsten bron)e
    :?6;
    ?::N 1:-8:nm thick Soft !hemical route
    3alasi et al'
    :?7, ?";/:?1;
    ,-#01 ?@1N 2ano"articles Sol-gel method :?#;
    Y-#01 RT 5:nm dia Flame S"ray Pyrolysis
    Bouma et al'
    :??;
    U-#0
    1
    ?6EN to @@1N
    E:nm dia
    2ano'ires
    3lectros"inning :?1;,:?@;
    .-#0
    1
    u"to ?6EN 2ano'ires 3lectros"inning :?1;,:?@;

    PhaseDPhase
    transition
    Conditions of
    P and /
    Particle Si,e Synthesis /echniEues 4eference
    !r
    5
    0
    1
    !orundum
    "hase
    7:@1N 2anobelts and
    2anorods
    <eat Treatment under
    3thanol Aa"or Flo'
    .an et al' :?A;
    23
    7:-1::N
    Single and
    "olycrystalline
    nanorods$ diameter
    8-Gnm$ length 7:-
    78nm
    /icro'ae "lasma 'ith
    chromium
    he&acarbonyl "recursor
    +' Follath et al'
    :?C;
    --
    <igh
    Tem"erature
    and Pressure
    7:nm aerage grain
    diameter
    Gas-condensation method
    3alachandran et
    al' :@$;
    Fe
    5
    0
    1
    .-"hase Aboe ?@1N Aboe 1:nm
    Three-com"onent /icro-
    emulsion Technique
    P 0yyu& et al'
    :@6;
    ,- Fe
    5
    0
    1
    -- 8nm to 1:nm
    Three-com"onent /icro-
    emulsion Technique
    P 0yyu& et al'
    :@6;
    8?1N - ?@1N 8nm to 58nm
    Thermal treatment fo ,-
    Fe00< and Fe106 "recursors
    Gen et al' :@7;
    Bi
    5
    0
    1
    V-Bi
    5
    0
    1
    Stable at
    ambeint
    conditions
    ?8nm
    3lectrode"osition directly
    from an alkaline Bi9JJJ;
    tartrate solution
    :@";
    ?51N 8:nm 2ano'ires Thermal 3nhanced Process Hung et al':@1;
    U- Bi501
    -- 8:-7::nm Flame S"ray Pyrolysis
    Madler and
    Pratsinis:@#;
    6@1N - ?51N @nm dia 2ano'ires
    0&idatie /etal Aa"or
    Trans"ort De"osition
    Technique
    Gang et al':@?;
    ?51N 8:nm Dia !itrate gel method
    0nil)umar et al'
    :@@;
    Jn
    5
    0
    1
    !orundum
    "hase
    ?@1N Aerage Dia 75nm Sol-gel method :@A;
    @8:N Dia E:nm
    Dehydration of the Jn00<
    nanofibers
    Gu et al':@C;
    E@1N 1:-8:nm Solothermal method :A$;
    PhaseDPhase Conditions of Particle Si,e Synthesis /echniEues 4eference
    24
    transition P and /
    Al
    5
    0
    1
    ,-Al501
    Ambient
    !onditions
    S"ecific surface
    area of alumina is
    larger than 758
    m
    5
    (g$ or "article
    si)e less than about
    71 nm
    --
    Mchale et al'
    :A6;
    6@1N 1%5nm% 2onaqueous Sol-Gel route :A7;
    7%8%Phase Transformations due to nanoscale "article si)e
    /etastability is key in "hase reactions inoling nanocrystals% Polymor"hic "hases often
    e&ist in metastable states for long "eriods of time$ 'hich makes these states ery useful in
    functional a""lications like gas sensing$ catalysis etc% At the nanoscale surface "ro"erties of
    "olymor"hic materials differ and in most cases are a""reciably enhanced% For e&am"le the
    catalytic "ro"erties of nanoscale !o0 are im"roed com"ared to the bulk state at lo'
    tem"eratures

    QE1R% Thus it is im"ortant to study indiidual metal o&ides and come u" 'ith the
    nanoscale characteristics of each$ such characteristics can find e&tensie uses in "hotocatalysis$
    gas sensing$ electrochemical$ electrochromic deices to name a fe'%
    Such differing "hase transformations due to nano si)e are not 4ust seen in "olymor"hic
    metal o&ides$ but in general in all metal o&ides$ "olymor"hic or not$ for e&am"le the Room
    tem"erature bulk "hase of !u conerts to cubic !u
    5
    0 by o&idation at ery high tem"eratures of
    greater than 75::N QE6R$ if the tem"eratures are still increased the monoclinic !u0 forms%
    !ontrary it 'as obsered QE8R that !u
    5
    0 nano"hase starts to form aboe 851N$ and !u0 starts to
    form beyond ?51N$ the "article si)e at 851N and ?51N 'ere 7? and 1:nm res"ectiely% Jt is
    obsered that cubic !u
    5
    0 is more stable at the nanodimentions also QE?$ E@R than the monoclinic
    !u0 due to the increase ionic nature caused by reduction in the "article si)e% !u
    5
    0 nanocrystals
    25
    at lo'er than bulk tem"eratures hae been "re"ared by ion irradiation QEER$ s"uttering QEGR$
    reduction route QG:R$ etc%
    Thus$ e&"erimental obserations confirm that for nanocrystalline metal o&ides "hase
    transformation occurs ia different mechanism at the nano scale$ such as reersal in "hase
    stability at small "article si)e is obsered in some systems$ melting tem"eratures are generally
    lo'er in nano"articles$ transition tem"eratures to high tem"erature "hases are often lo'er$ 'hile
    transition "ressures to high "ressure "hases can be higher or lo'er% 0ne of the reasons that
    nano"articles sho' such differing "ro"erties is because of the significantly higher surface areas
    at nano scale 'hich makes the contribution from surface energies much more significant QG7R%
    Thermodynamic as"ects of the "hase transformations at nanoscale hae been elaborated in the
    ne&t sections% Table 5 gies a com"arison bet'een bulk and nano "hase at ambient tem"erature
    and "ressure% Similarly table in a""endi& A gies com"arison bet'een bulk and nano for same
    "hase and different conditions for tem"erature and "ressure%
    Table "3 %omparison &etween &ul) and nano phase at am&ient temperature and pressure
    Metal
    Oxide at
    am.ient
    conditio
    ns
    "ul# phase Nano Phase
    4ef
    Phase
    Conditions
    of
    temperatur
    e and
    pressure
    Phase
    Critical
    particle
    si,e
    /emperatu
    re
    Sn0
    5
    Rutile-ty"e
    tetragonal "hase
    RT and 7
    atm
    !a!l
    5
    -ty"e
    orthorhombic
    "hase
    Belo'
    8:nm
    RT and 7
    atm
    C7, C",
    1@, 1A
    Jn
    5
    0
    1
    !ubic bi&byite-
    ty"e structure
    RT and 7
    atm
    !ubic bi&byite-
    ty"e structure W
    !orundum-ty"e
    he&agonal
    structure
    Belo'
    E:nm
    RT and 7
    atm
    @A, @C,
    A$
    26
    Al
    5
    0
    1
    !orundum ty"e
    trigonal .-"hase
    RT and 7
    atm
    !ubic , "hase Belo'
    7@nm and
    belo'
    6@1N
    RT and 7
    atm
    C1, A6,
    A7
    Ti0
    5
    Rutile RT and 7
    atm
    Anatase Belo'
    77nm
    RT and 7
    atm
    16, 17
    /o0
    1
    0rthorhombic .
    "hase
    RT and 7
    atm
    0rthorhombic .
    "hase W
    <e&agonal
    /o01
    Belo'
    5::nm
    and 661
    to ?@1N
    RT and 7
    atm
    #C, ?$
    #0
    1
    Triclinic V-"hase RT and 7
    atm
    /onoclinic Y
    "hase
    2anosi)e RT and 7
    atm
    C#, ??,
    C?
    Lr0
    5
    /onoclinic "hase RT and 7
    atm
    Tetragonal
    "hase
    Belo'
    7Enm
    RT and 7
    atm
    1C, #$,
    #6
    7%?% Polymor"hic nano'ires of #0
    1
    and /o0
    1
    All the discussion u" till no' has concentrated on "olymor"hism in s"herical nano"articles$
    though nano"articles are im"ortant for engineering a""lication but the high as"ect ratio of the
    nano'ires "roide an een larger surface area% This enhances the "ro"erties of the material
    thereby increasing the range of a""lications% 2ano'ires of semiconducting materials are
    nanostructures 'ith high-as"ect ratio$ enormous surface area$ and controlled crystallogra"hic
    orientation that make them ideal for a""lications in sensing in a breath diagnostic tool QG@R$
    catalysis$ and nano-electronics deices QGE$ GGR% Such nanostructures hae been 'idely
    considered in the literature since the early re"ort of single crystal silicon by a a"or-liquid solid
    technique Q7::R and single crystal semiconducting nano'ires hae been synthesi)ed by "ulsed-
    laser ablation Q7:5R% /onocrystalline nano'ires of metal o&ides 9#0
    1
    $ /o0
    1
    $ !u0 etc; hae
    been "roduced through arious routes$ from thermal o&idation of a metal mesh$ to tem"late-
    assisted blend electros"ining$ to colloidal synthesis of o&ides Q7:7-7:8R$ as tabulated in table 7%?
    belo'%
    Table 1-4 Results from earlier research in our group'
    27
    Synthesis method Possi.le analyte sensed 4ef
    /o0
    1
    nano'ires 3lectros"inning Ammonia 6$1, 6$#
    #0
    1
    nano'ires 3lectros"inning 2itrogen Dio&ide CA
    !u0 nano'ires Tem"late assisted gro'th -- 6$"
    1D !u0 nanogrids 3lectros"inning and
    thermal o&idation
    3thanol 616
    <e&agonal #0
    1
    !hemical synthesis Ammonia 6"7
    Ti0
    5
    nano"lates Thermal o&idation !arbon /ono&ide 61$
    Single crystal nano'ires are of higher alue than "olycrystalline(multigranular
    nano'ires% Although this is only true 'hen single crystal nano'ires hae a s"ecific "lane
    e&"osed$ and the "ro"erties like gas sensitiity are enhanced Q7:8R% Jn that case the
    "olycrystalline nano'ires hae a disadantage$ because the "lanes are randomly oriented% But
    reerse maybe true 'hen gas sensitiity is not de"endent on s"ecifically oriented e&"osed "lane
    Q765R% For e&am"le$ in the case of "olycrystalline nano'ires of Jn
    5
    0
    1
    Q765R$ it 'as seen that
    "orosity due to ery small grain si)e increased the sensitiity to 3thanol$ as com"ared to single
    crystal nano'ires$ this can be the case in non-s"ecific materials% For highly s"ecific materials$
    like single crystals of monoclinic #0
    1
    Q761R the sensitiity is highly de"endent on the s"ecific
    "lanes being e&"osed and the absence of defects%
    #0
    1
    nano'ires$ in "articular$ hae also been synthesi)ed from gro'th directly from
    tungsten substrate Q7:?R or by thermal heating of a tungsten "late Q7:@R% 2on-aqueous
    "re"aration of crystalline tungsten o&ide nano'ires has been carried out using a tungsten
    iso"ro"o&ide "recursor in ben)yl alcohol Q7:@R% 2eertheless$ there has been no direct
    obseration of #0
    1
    nano'ire gro'th in-situ and solely from solid o&ide "recursors until no'$
    and thus the nature of the s"ontaneous transition of o&ide nanocrystals to nano'ires under the
    influence of an electron beam is being addressed here%
    28
    /o0
    1
    nano'ires$ in "articular hae also been synthesi)ed by other researchers% Pure
    orthorhombic structured nano'ire arrays of molybdenum trio&ide 'as synthesi)ed by Lhou et al%
    Q7:ER$ these 'ere gro'n on a silicon substrate% Due to the instability of trio&ide form of
    molybdenum o&ides$ many 'orks hae managed to synthesi)e molybdenum dio&ide in
    con4unction 'ith molybdenum trio&ide% Such structures hae been reie'ed e&tensiely by /ai
    et al% Q7:GR and the readers are directed to the source for more information%
    7%@% A""lications of nanocrystalline binary metal o&ides
    As has been elaborated aboe nanocrystalline metal o&ides hae "ro"erties much different
    from bulk metal o&ides% For e&am"le$ orthorhombic "hase of Sn0
    5
    is ery im"ortant in terms of
    gas sensing a""lications Q77:R% This high tem"erature and high "ressure bulk "hase has been
    re"orted at nano scale as single "hase Q77:$ 777R and as coe&istence of orthorhombic Sn0
    5
    and
    rutile-ty"e Sn0
    5
    "hase nano'ire Q775R% 2anocrystalline #0
    1
    $ is another im"ortant sensor
    material and its sensing "ro"erties hae been 'ell studied Q771R%
    Sensing behaior of nanocrystalline metal o&ides has been outlined by Gouma 95::?;
    Q776R$ gas selectiity can be achieed by achieing a s"ecific crystallogra"hic "hase of a "ure
    metal o&ide% Surface interactions on metal o&ides are "rimarily due to gas adsor"tion$ hydrogen
    e&traction$ or o&ygen addition% Due to structural differences the orientation of the surface atoms
    of metal o&ides differ 'hich intern causes differing catalytic behaiors for eery indiidual "hase
    of different metal o&ides% /echanism for sensing behaior of metal o&ides can be described by
    the surface "henomenon$ 'hen there are surface acancies on o&ide surface$ the o&idi)ing gas
    can get adsorbed$ and e%g% 20
    B
    gas is adsorbed at the monoclinic #0
    1
    surface$ on the contrary
    'hen there is an access of electrons on the surface a reducing gas can get adsorbed% /ost of the
    aboe mentioned metal o&ides sho' sensitiity or selectiity to different gases% The monoclinic
    29
    "hase of /o0
    1
    for e&am"le$ is selectie to o&idi)ing gas like iso"rene 'hereas the orthorhombic
    "hase of /o0
    1
    is selectie and sensitie to amines like 2<
    1
    Q778$ 77?R% Similarly$ the monoclinic
    "hase of #0
    1
    is selectie to o&idi)ing gases like 20
    5
    and 0
    1
    $ 'hereas the orthorhombic "hase is
    selectie to'ards reducing gases Q77@$ 77E$ 77GR%
    Catalysis hel"s the reaction go faster$ or 'hich alters the rate of a chemical reaction%
    <eterogeneous catalysis$ homogeneous catalysis$ biocatalysis$ electrocatalysis$ organocatalysis
    are all forms of catalysis% Jn the conte&t of "olymor"hism$ electrocatalysis 'hich is the basis for
    solid o&ide fuel cell Q75:R technology is im"ortant% 2anoscale si)e has additional benefits for
    fuel cell technology$ meso"ore si)e distribution and nanocrystalline channel 'alls may lead to
    im"roements in fuel mass trans"ort$ o&ide ion mobility$ electronic conductiity$ and charge
    transfer% For e&am"le Lirconia 9Lr0
    5
    ; is an effectie fuel cell material$ /amak et al% Q757R
    synthesi)ed meso"orous yttrium stabili)ed )irconia by soft chemistry route 'ith cubic
    mor"hology and obsered it to be more thermally stable 9u" to 7:@1N;$ haing more uniform
    intergranular "ore si)e and enlarged tri"le-"oint boundary9TPB;% Similar to )irconia$ arious
    "olymor"hs of Bismuth o&ide 9Bi
    5
    0
    1
    ; hae also seen a""lications in Solid o&ide fuel cells
    9S0F!s; because of its ionic conducting nature$ i%e% o&ygen atoms readily moe through it%
    !once"tually S0F!s are an o&ygen ion conducting electrolyte through 'hich the o&ide ions
    migrate from the enironment electrode 9cathode; side to the fuel electrode 9anode; side reacting
    'ith the fuel 9<
    5
    $ !0$ etc%; thereby generating electrical oltage% Bismuth o&ide 'as used as one
    of the layers in a bilayer ceria(bismuth o&ide assembly 'hich hel"ed enhance the o"en-circuit
    "otential 90!P; Q755R%
    Photocatalysis is the increase in the rate of a "hotoreaction occurs in the "resence of a
    catalyst% Photogenerated catalysis is 'hen the "hotocatalytic actiity 9P!A; de"ends on the
    30
    ability of the catalyst to create electronPhole "airs$ 'hich generate free radicals like hydro&yl
    grou" 'hich are able to undergo secondary reactions% Ability of titania for 'ater catalysis 'as
    the discoery by Fu4ushima and <onda 97G?G; that led to its early com"rehension in the 7G?:s
    Q751R% Titania has t'o "rimary "hases$ rutile and anatase$ both haing different band ga"s% Rutile
    e&hibiting a lo'er band ga" 91%: eA; in com"arison to anatase 91%5 eA; 'hich can cause it to be
    e&cited by irradiation at longer 'aelengths 'hereas anatase generally e&hibits su"erior
    "hotocatalytic actiity to rutile as a result of a significantly higher surface area and thus higher
    leels of adsorbed radicals Q756$ 758R% This 'as elaborated more e&tensiely in a recent reie'
    Q75?R% Jn recent times the nanometer si)e has enhanced some "ro"erties related to this
    "henomenon and the so called second generation "hotocatalyst hae been deelo"ed% As stated
    earlier$ anatase can be achieed at lo'er tem"eratures 9?@1N; for nanoscale si)e$ this is essential
    because of the fact that it sho's better "hotocatalytic behaior$ nanoscale si)e hel"s in increasing
    the "hotocatalytic behaior by increasing the number of "ores and enhancing solid-solid
    interactions% Jt has been seen that 'hen nano-titania is calcined to higher tem"erature 9aboe
    8@1N; the "hotocatalytic actiity is decreased Q75@R% This de"endence of "hotocatalytic actiity
    on titania "olymor"h 'as established 'hen !a""elletti et al% Q75ER found that for nanocrystalline
    sam"les of anatase-brookite com"osite and rutile$ the former had better "hotocatalytic actiity at
    G6K at G: min reaction time as against E:K at G: min reaction time for rutile% They also
    concluded that the mi&ed "hases of anatase-brookite or anatase-rutile sho'ed better
    "hotocatalytic actiity%
    31
    7%E% Polymor"hic nano'ires as sensing materials
    2ano'ires nanostructures are solid$ one dimensional materials 'ith diameters in the 7:-E:
    nm range$ and are metallic or semiconducting in nature$ made from metals or metal o&ides most
    often% #ires made from molecular entities and diameter less than 8nm are often called /olecular
    2ano'ires$ and these are different from 2ano'ires% !arbon nanotube research and nano'ires
    research are often "arallel% Though carbon nanotube materials are different$ the sensing
    mechanisms and underlying behaior are usually ery similar% 2ano'ire hae large surface area
    to olume ratio "romising high sensitiity and the si)e of the nanostructures is similar to the si)e
    of s"ecies being sensed$ thus nano'ires make good candidate transducers for "roducing the
    signals that are then read and recorded by conentional instruments% Since they 'ere discoered$
    silicone nano'ires hae "rimarily been inestigated for sensing a""lications in biological
    systems Q75GR% Biomedical research 'ould greatly benefit from the adent of nano'ires as
    sensors and they hae been ie'ed as one of most "romising areas Q71:R% Techniques for
    generating arious ty"es of im"ortant nano'ires$ nanorods$ nanobelts$ and nanotubes$ synthetic
    strategies$ design of sensing deices$ and sensing mechanism has been reie'ed Q717R%
    2ano'ire nanostructure sensors of metal o&ides hae enhanced "ro"erties as o""osed to
    nano"article nanostructures$ this is "articularly true for sensing sensitiity% For e&am"le$
    sensitiity of nano'ire structures of orthorhombic "hase of /o0
    1
    to 7:: ""m ammonia gas 'as
    5:%8 in com"arison to nano"articles 'here the sensitiity 'as ?%E for same concentration Q715$
    711R% Similarly in the case of #0
    1
    the sensor sensitiity analysis to'ards 20
    5
    sho'ed that the
    sensitiity im"roed significantly 'hen nano'ires 'ere used as o""osed to nano"articles Q716R%
    Single crystals are of "articular im"ortance for sensing of analytes$ as com"ared to the
    multigranular crystals% Jnstabilities may form at the grain .oundaries$ 'hich cause lo'ering of
    sensitiity to'ards gaseous analytes% Ra et al% Q718R studied such an affect for Ln0 nano'ires%
    They obsered much slo'er recoery and res"onse times and additionally the sensing res"onse
    'as much more unstable for multigranular nano'ires as com"ared to single crystal Ln0
    nano'ires% Therefore the single crystal character of 'ell-defined nano'ires is highly desirable
    for their use in sensing a""lications% Stoichiometry also "lays an im"ortant role in defining the
    sensing "ro"erties of nano'ires% The difference bet'een a non-stoichiometric and stoichiometric
    nano'ire may cause it to change sensing behaior significantly% Gali et al% Q71?R studied such
    behaior for Jn
    5
    0
    1
    nano'ires$ and found that lo'er the stoichiometry of the nano'ires higher
    'as res"onse to the o&idi)ing gas$ 'hereas 'hen the stoichiometric behaior increased it led to a
    more significant res"onse to reducing gas% Therefore$ a single crystal nano'ire of desired and
    kno'n stoichiometry 'ould be an ideal candidate for sensing lo' concentrations of s"ecific
    analytes% Exposed surfaces of the single crystals of nano'ires is another factor that influences
    the sensitiity behaior of the crystals% Jn many instances the "resence of higher surface o&ygen
    on certain "lanes "romote adsor"tion of the analytes at the surface% For e&am"le$ Naneti et al%
    Q71@R studied the gas-sensing behaior of Ln0 as it aries due to differently e&"osed crystalline
    "lanes% Jt 'as obsered that the 9:::7; "lane had double sensitiity to'ards 3thanol as com"ared
    to the 97:7:; "lane%
    Jn "reious 'ork done in our grou"$ the most common routes of synthesis of nano'ires has
    been either traditional needle electros"inning Q71ER or o&idatie synthesis Q71GR% These methods
    are effectie and "roduce clean mor"hology nano'ires$ though the inasie a""roach and slo'
    "roduction rates deter there industrial ado"tion% Jn this 'ork the a""roach to nano'ire
    "roduction has been to'ards high rate and(or instant gro'th 'hile maintaining mor"hological
    quality%
    7%G% Statement of the "roblem
    Polymor"hic reactions in binary metal o&ides are abundant% Due to the numerous number of
    crystalline configurations aailable$ the range of "olymor"hs of any binary metal o&ide offers a
    ariety of materials 'ith constant com"osition but distinct "ro"erties suitable to an array of
    engineering a""lications%
    /ost of these aailable "olymor"hs occur in high tem"erature and high "ressure range in the
    bulk form% Although due to the inherent energies inoled 'hen the "article si)e is lo'ered to
    sufficiently lo' alues$ many of the high "ressure and high tem"erature "olymor"hs could be
    aailable at ambient conditions at the nanoscale% This fact makes it im"eratie to study the
    "article si)e effect in the control of "olymor"hic reactions and the determination of "hase
    stability fields for nanostructured o&ides%
    2anostructures of metal o&ides occur in many different sha"es% S"herical nano"articles are
    the most common structures% 2ano'ire structures hae higher surface area and therefore are of
    greater use in engineering a""lications% This thesis also e&"loits "hase 9meta; stability for the
    synthesis of one-dimensional nanostructures%
    References
    7% /% <% Nla"roth% Bergmannische C%$ 5G697@GE;%
    5% 3% /itscherlich% Abhl% Akad%$ Berlin$ 6197E51;%
    1% 3%/itscherlich% Ann% !him% Phy% 7G$ 18:97E55;%
    6% 3%/itscherlich% Ann% !him% Phys%$ 56$ 5?697E51;%
    8% /arion 3% Franke$ Tobias C% No"lin$ and Ulrich Simon% Small 597;$ "ages 1?95::?;%
    ?% Ricardo <% R% !astro and Beibei #ang% C% Am% !eram% Soc%$ G691;$ 5:77$ G7E95:77;%
    @% A% 3% <enrich and P% A% !o&% The Surface Science of /etal 0&ides% 9!ambridge Uniersity
    Press$ !ambridge 7GG6; Aol% BJA$ "% 6?6 "$ JSB2 :P857P661EG-B%
    E% S% Bis'as and S% Ram% !hem% Phys% 1:?97-1;$ 7?195::6;%
    G% Cordi Arbiol$ 3lisabetta !omini$ Guido Faglia$ Giorgio Sbereglieri$ Coan Ramon /orante%
    Cournal of !rystal Gro'th 17:97;$ 58195::E;
    7:% Geng #ang$ Miang #ang$ #u Fu$ and Cinghong Fi% C% Phy% !hem% B$ 77:961;$ ""
    55:5G95::?;%
    77% 2% Randrianantoandro$ A% /% /ercier$ /% <erieu and C% /% Greneche% /ater% Fett% Aol%
    6@91;$ 78:95::7;%
    75% D # Bullett% C% Phys% !* Solid State Phys% 7?$ 57G@97GE1;%
    71% S%<% Fee$ /%C% Seong$ !%3% Tracy$ A% /ascarenhas$ C%R% Pitts$ S%N% Deb% Solid State Jonics
    76@$ 75G95::5;%
    76% Cimei Song$ Biong #ang$ Biaomin 2i$ <uagui Lheng$ Lude Lhang$ /ingrong Ci$ Tao Shen$
    Bing'ei #ang% /aterials Research Bulletin% 6:97:;$ 7@8795::8;%
    78% C% Guo$ P% Laali4 and /%S% #hittingham% C% Solid State !hem% 77@$ 15197GG8;%
    7?% 2% Numagai$ 2% Numagai and N% Tanno% 3lectrochim% Acta 15$ 785797GE@;%
    7@% 3%!a))anelli$ !%A inegoni$ G%/ariotto$ A%N u)min$ and C%Puransc% C% Solid State !hem% 761$
    5697GGG;%
    7E% 0% Berger$ #%C% Fischer and A% /ele% C% /ater% Sci* /ater% in 3lectr% 78$ 6?195::6;%
    7G% F% Nihlborg% Arki Nemi% 57$ 18@97G?1;%
    5:% 3% /% /c!arron% C% !<3/% S0!% !<3/% !0//U2% 6$ 11?97GE?;%
    57% <%!% Leng% C% !ryst% Gro'th 7E?$ 1G197GGE;%
    55% <% !heng$ C% /a$ L% Lhao$ and F% Mi% !hem% /ater% @$ ??197GG?; %
    51% Cing Sun and Fian Gao% C% Am% !eram% Soc% E89G;$ 51E595::5;%
    56% ! Suresh$ A Bi4u$ P /ukundan$ N%G%N #arrier% Polyhedron 7@97E;$ 171797GGE;%
    58% Shieh S% R%$ Nubo A%$ Duffy T% S%$ Praka"enka A% B% and Shen G% Phys% Re% B @1$
    :767:895::?;%
    5?% 0no S%$ Funakoshi N%$ 2o)a'a A% and Nikega'a$ T% C% A""l% Phys% G@$ :@185195::8;%
    5@% F% Gracia$ A% Beltrdn$ and C% Andres% C% Phys% !hem% B 777951;$ ?6@G95::@;
    5E% B% R% /addo&$ !% S% Ooo$ Dee"a Nasinathan$ #% 3% Pickett$ and R% T% Scalettar% Phys% Re% B
    @1$ 76677795::?;
    5G% /% Rabe$ C% Drefen$ D% Dahmen$ C% Pommer$ <% Stahl$ U% Rgdiger$ G% Ggntherodt$ S% Sen)
    and D% <esse% C% /agn% b /agn% /at% 577$ 17695:::;%
    1:% /% Ruehle% Ad% /ater% G$ 7G897GG@;%
    17% A% 3% SoloSea% Refractories and Jndustrial !eramics 5E9@-E;$ 1E:97GE@;
    15% R%D%Shannon% Solid State !ommun% 6$ ?5G97G??;%
    11% !%T% Pre'itt$ R%D% Shannon$ D%B% Rogers and A%#% Sleight% Jnorg% !hem% E$ 7GE897G?G;%
    16% R% /% !ornell$ U% Sch'ertmann% #iley-A!<$ ed% 5$ 9#einheim$ Germany$ 5::1;$ JSB2*
    G@E-1-85@-?:?66-1%
    18% 0)den 0)demir and Subir N% Baner4ee% Geo"hysics research letters 7791;$ 7?797GE1;%
    1?% Cung-Fu Fin$ 0lga Degtyarea$ !harles T% Pre'itt$ Pr)emysla' Dera$ 2agayoshi Sata$
    3ugene Gregoryan)$ <o-k'ang /ao and Russell C% <emley% 2ature /aterials 1$ 1EG95::6;%
    1@% Narl #efers and !hanakya /isra% Alcoa Technical Pa"er 7G$ Reised Alcoa Fab%$ 7GE@%
    1E% Takayuki Tsukada$ <ideo Sega'a$ Atsuo Oasumori and Niyoshi 0kada% C% /ater% !hem% G$
    86G97GGG;%
    1G% 2% Funamori and R% Ceanlo)% Science 5@E$ 77:G97GG@;%
    6:% 0st'ald$ #% Leitschrift fgr Physikalische !hemie 55$ 5EG97EG@;%
    67% <eng)hong Lhang and Cillian F% Banfield% C% Phys% !hem% B$ 7:6978;$ 16E795:::;
    65% Bisheng Oe$ Cian Sha$ Lhengkuan Ciao$ Fide Lhang%2anostructured /aterials E9@;$
    G7G97GG@;
    61% S% Bis'as and S% Ram% !hem% Phys%1:?97-1;$ 7?195::6;
    66% Biao4ing Lou and Gang Biao% A""lied Physics Fetters$ Aolume G7977;$ 77187595::@;
    68% M% Lhang$ O% Fi$ A% A% 2urmikko$ G% B% /iao$ G% Biao$ and A% Gu"ta% C% A""l% Phys% G?$
    @85@95::6;
    6?% O%B% !hen$ F%C% !am"bell$ #%F% Lhou% Cournal of !rystal Gro'th% 5@:91-6;$ 8:895::6;
    6@% Cordi Arbiol$ 3lisabetta !omini$ Guido Faglia$ Giorgio Sbereglieri$ Coan Ramon /orante%
    Cournal of !rystal Gro'th 17:97;$ 58195::E;
    6E% C% Famelas% Cournal of A""lied Physics G?977;$ ?7G895::6;
    6G% R% !% Garie$ /% F% Goss% C% /ater% Sc% 57$ 758197GE?;
    8:% Cin Coo$ Taekyung Ou$ Ooung #oon Nim$ <yun /in Park$ Fan&in #u$ Cin L% Lhang$ and
    Taegh'an <yeon% C% Am% !hem% Soc% 758$ ?88195::1;
    87% Tomas !hraska$ Ale&ander <% Ning and !hristo"her !% Berndt% /aterials Science and
    3ngineering A5E?$ 7?G95:::;
    85% A%N% Prasad$ P%J% Gouma$ D% C% Nubinksi$ C%<% Aisser$ R%3% Soltis$ and P%C% Schmit)% Thin
    Solid Films 61?$ 6?95::1;
    81% A% N% Prasad and P% Gouma% C% /at% Sci% 1E$ 616@95::1;
    86% A% N% Prasad$ D% Nubinski$ and P% J% Gouma% Sensors b Actuators B G$ 5895::1;
    88% P% Gouma$ N% Nalyanasundaram$ and A% Bisho"% Cournal of /aterials Research$ 2ano'ires
    and 2anotubes s"ecial issue 57977;$ 5G:695::?;
    8?% Arun N% Prasad% Phd thesis$ Stony brook uniersity$ 5::8
    8@% !%A% Ramana$ A%A% Atuchin$ J%B% Troitskaia$ S%A% Gromilo$ A%G% Nostrosky$ G%B% Sau"e%
    Solid State !ommunications 76G$ ?95::G;
    8E% !% A% Ramana$ J% B% Troitskaia$ A% A% Atuchin$ /% Ramos$ and D% Ferrer% C% Aac% Sci% Technol%
    A 5E$ @5?95:7:;
    8G% Angamuthura4 !hithambarara4 and Arumugam !handra Bose% Beilstein C% 2anotechnol% 5$
    8E895:77;
    ?:% Dhage S% R%$ <assan /% S% and Oang 0%B% /ater% !hem% Phys% 776$ 87795::G;
    ?7% J%/% S)ilagyi F%S% #ang$ P%J% Gouma$ !% Bala)si$ C% /adaras)$ and G% Pokol% /aterials
    Research Bulletin$ 6691;$ 8:895::G;
    ?5% !% Bala)si$ F% #ang% 3%0% Layim$ J%/% S)ilagyi$ J%/iklos$ N% Sedlackoa$ C% Pfeifer A%F%
    Toth$ and P%J% Gouma% C% 3ur% !eram% Soc% 5E98;$ G7195::E;
    ?1% !% Bala)si$ N% Nalyanasundaram$ 3%0% Layim$ C% Pfeifer$ A$F% Toth and P%J% Gouma% Acta
    /etallurgica Sloaca 71$ 7E?95::@;%
    ?6% G%A% #ang$ O%A% Ci$ B%R% <uang$ B%M% Oang$ P%J% Gouma$ and /% Dudley% C% Phys% !hem% B
    77:96@;$ 51@@@95::?;
    ?8% P%J Gouma and N% Nalyanasundaram% A""l% Phys% Fett% G1$ 5667:595::E;
    ??% F% #ang$ A% Teleki$ S% 3% Pratsinis$ and P% J% Gouma% !hem% /ater% 5:$ 6@G695::E;
    ?@% N%/% Sa'icka$ A%N% Prasad and P%J% Gouma% Sensor Fetters 1$ 1795::8;
    ?E% Miang <an$ Fi4un #u$ Aaron Stein$ Oimei Lhu$ Cames /ise'ich$ and Cohn #arren% Ange'%
    !hem% Jnt% 3d% 68$ ?88695::?;
    ?G% D% Aollath$ D%A% S)ab$ C%0% #illis% /aterials Fetters 5G$ 5@797GG?;
    @:% U% Balachandran$ R% #% Siegel$ O% B% Fiao$ T% R% Aske'% 2anostructured /aterials 898;$
    8:897GG8;
    @7% P Ayyub$ / /ultani$ / Parma$ Ar Palkar and R Ai4ayaraghaan% C% Phys% !* Solid State
    Phys% 57$ 555G97GEE;
    @5% Fu Su Oen$ #ei !hien !hen$ Canne /in Oang$ and !hen Tsung <ong% 2ano Fetters 591;$
    56895::5;
    @1% 3ric # Bohannan$ !hristo"her ! Caynes$ /ark G Shumsky$ Culie N Barton and Cay
    A S'it)er% Solid State Jonics 71797-5;$ Cune G@95:::;
    @6% !% !% <uang$ J% !% Feu$ and N% L% Fung% 3lectrochemical and Solid-State Fetters E96;$
    A5:695::8;
    @8% Fut) /adler and Sotiris 3% Pratsinis% C% Am% !eram% Soc% E89@;$ 7@7195::5;
    @?% Oongfu Miu$ Dongfang Fiu$ Cinhu Oang$ and Shihe Oang% Ad% /ater% 7E$ 5?:695::?;
    @@% Anilkumar$ Renu Pasricha and A% Rai% !eramics Jnternational 17$ EEG95::8;
    @E% Ale&ander Gurlo$ 2icolae Barsan$ Udo #eimar$ /aria Janoskaya$ Antonietta Taurino$ and
    Pietro Siciliano% !hem% /ater% 78951;$ 61@@95::1;
    @G% Dabin Ou$ Shu-<ong yu$ Shuyuan Lhang$ Cian Luo$ Debao #ang$ and Oitai Mian% Ad%
    Funct% /ater% 719?;$ 6G@95::1;
    E:% Ciaqiang Bu$ Ou"ing !hen$ Cianian Shen% /aterials Fetters% ?59E-G;$ 71?195::E;
    E7% C% /% /c<ale$ A% Aurou&$ A% C% Perrotta and A% 2arotsky% Science 5@@9815@;$ @EE97GGE;
    E5% Shu&ue Lhou$ /arkus Antonietti$ and /arkus 2iederberger% Small 198;$ @?195::@;
    E1% Ale&andra 2arotsky !hengcheng /a$ Nristina Filoa and 2ancy Birkner% Science 11:$
    7GG95:7:;%
    E6% A%0 /usa$ T Akomolafe and /%C !arter% Solar 3nergy /aterials and Solar !ells 87$ 91-6;$
    1:897GGE;%
    E8% Sheng <an$ <ong-Oing !hen$ Ouh-Bin !hu and <an !% Shih% Cournal of Aacuum Science b
    Technology B 519?;$ 588@95::8;
    E?% B% Balamurugan$ B% R% /ehta$ S% /% Shia"rasad% A""lied Physics Fetters @G97G;$
    17?@95::7;%
    E@% A% R% Palkar$ Pushan Ayyub$ Soma !hatto"adhyay$ and /anu /ultani% Phys% Re% B 8198;$
    57?@97GG?;%
    EE% B% Balamurugan$ B% R% /ehta$ D% N% Aasthi$ Fouran Singh$ Akhilesh N% Arora$ /%
    Ra4alakshmi$ G% Raghaan$ A% N% Tyagi and S% /% Shia"rasad% Cournal of A""lied Physics
    G59?;$ 11:695::5;%
    EG% Tane4a P%$ !handra R%$ Baner4ee R% and Ayyub P% Scri"ta /ater%$ 66$ 7G7895::7;%
    G:% Biao4ing Lou and Gang Biao% A""lied Physics Fetters$ Aolume G7977;$ 77187595::@;%
    G7% C% /% Blakely% Jntroduction to the Pro"erties of !rystal Surfaces% 9Pergamon Press$ 0&ford$
    7st edn%$ 7G@1;%
    G5% L% R% Dai$ C% F% Gole$ C% D% Stout$ and L% F% #ang% C% Phys% !hem% B 7:?$ 75@695::5;%
    G1% N% Suito$ 2% Na'ai$ O% /asuda% /aterials Research Bulletin 7:9@;$ ?@@97G@8;
    G6% C% /% /c<ale$ A% 2arotsky$ A% C% Perrotta% C% Phys% !hem% B 7:796;$ ?:197GG@;%
    G8% A% G% Sou)a Filho$ P% T% !% Freire$ 0% Pilla$ A% P% Ayala$ C% /endes Filho$ F% 3% A% /elo$ A% 2%
    Freire$ and A%Femos% Physics Reie' B ?59?;$ 1?GG95:::;%
    G?% Arai /%$ <ayashi S%$ Oamamoto N% and Nim S% S% Solid State !ommun% @89@;$ ?7197GG:;%
    G@% P% Gouma$ S% Sood 95:71; 1-sensor Array for <and <eld Breath Diagnostic Tool% MRS
    5nline Proc' Li&' 7811%
    GE% P% Gouma 95::G;% -anomaterials for %hemical Sensors and 3iotechnology 9Pan Stanford
    Pu&lishing%
    GG% F% #ang$ P% Gouma 95:75;% Integrated Microanalytical Systems$ cha"ter 8 9eds% /% A%
    !ar"enter et al%;$ 7?@-7EE%
    7::% R%S% #agner$ #%!% 3llis 97G?6;% Aa"or-liquid-solid mechanism of single crystal gro'th%
    0ppl' Phys' Lett' 6$ EG%
    7:7% G% F% Frey$ Rothschild$ C% Sloan$ Rosentseig$ R% Po"oit) Biro and R% Tenne 95::7;%
    Jnestigations of nonstoichiometric tungsten trio&ide nano"articles% 2' Solid State %hem' 7?5$
    1::%
    7:5% O%F% Lhang$ O%<% Lhang$ 2% #ang$ D%P% Ou$ !%S% Fee$ J% Bello$ S%T% Fee 97GGE;% Silicon
    nano'ires "re"ared by laser ablation at high tem"eratures% 0ppl' Phys' Lett' @5$ 7E18%
    7:1% N% Sa'icka$ /% Naradge$ P% J% Gouma 95::6;% 0&idation synthesi)ed !u0 nano'ires for
    gas sensing a""lications% Microsc' Microanal% 7:$ 1?:-1?7%
    7:6% P% Gouma$ N% Nalyanasundaram$ A% Bisho" 95::?;% 3lectros"un Single !rystal /o01
    2ano'ires for Bio-!hem sensing "robes 2' Mat' Res' 57977;$ 5G:6-5G7:%
    7:8% Patent granted US(Patent 2o @$GE7$578 issued on :@(7G(5:77$ entitled _3lectros"un
    Single !rystal /o01 2ano'ires for Bio-!hem Sensing Probes`
    7:?% Fusheng Bu$ Ste"hen D% Tse$ Cafar F% Al-Sharab and Bernard <% Near 95::?;% Flame
    synthesis of aligned tungsten o&ide nano'ires% 0ppl' Phys' Lett' EE$ 561778%
    7:@% G%O% !hen$ A% Stolo4an$ D%!% !o&$ !% Giusca$ S%R%P% Sila 95::?;% Gro'th of tungsten
    o&ide nano'ires using sim"le thermal heating% Emerging ,echnologies - -anoelectronics,
    J333 !onference$ 1@?%
    7:E% Cun Lhou$ 2ing-Sheng Bu$ Shao-Lhi Deng$ Cun !hen$ Cun-!ong She and Lhong-Fin
    #ang% 0d(' Mat' 78 957;$ 7E18 95::1;%
    7:G% Fiqiang /ai$ Fan Oang$ Ounlong Lhao$ Bu Bu$ Fin Bu$ Bin <u$ Oan)hu Fuo$ <angyu
    Fiu% /aterials today 769@-E;$ 16? 95:77;
    77:% Cordi Arbiol$ 3lisabetta !omini$ Guido Faglia$ Giorgio Sbereglieri$ Coan
    Ramon /orante% Cournal of !rystal Gro'th 17:97;$ 58195::E;
    777% O%B% !hen$ F%C% !am"bell$ #%F% Lhou% Cournal of !rystal Gro'th% 5@:91-6;$ 8:895::6;%
    775% L% R% Dai$ C% F% Gole$ C% D% Stout$ and L% F% #ang% C% Phys% !hem% B 7:?$ 75@695::5;%
    771% Geng #ang$ Miang #ang$ #u Fu$ and Cinghong Fi% C% Phy% !hem% B$ 77:961;$ ""
    55:5G95::?;%
    776% /% #ilson% C% Am% !eram% Soc% E797:;$ 588E97GGE;%
    778% Arun N% Prasad% Phd thesis$ Stony brook uniersity$ 5::8%
    77?% P% Gouma% Re% Ad% /ater% Sci% 8$ 75195::1;%
    77@% P%J% Gouma$ A% N% Prasad$ and N%N% Jyer% 2anotechnology 7@$ S6E95::?;%
    77E% /% Bendahan$ C% Guerin$ R% Boulmani$ N% Aguir% Sensors and Actuators B* !hemical% Aol
    75697;$ 5695::@;%
    77G% N%/% Sa'icka$ A%N% Prasad and P%J% Gouma% Sensor Fetters 1$ 1795::8;
    75:% Shinichi Nomaba$ 2aoaki Numagai$ Neiko Nato and <itoshi Oashiro% Solid State Jonics
    718$ 7G195:::;%
    757% /arc /amak$ 2eil !oombs$ and Geoffrey 0)in% C% Am% !hem% Soc% 75591@;$
    EG1595:::;%
    755% !% Delmas$ <% !ognac-Auradou$ C% /% !occiantelli$ /% /enetrier and C% P% Doumerc%
    Solid State Jonics ?G$ 58@97GG6;%
    751% A% Fu4ishima$ N% <onda and S% Nikuchi% Nogyo Nagaku Lasshi @5$ 7:E97G?G;%
    756% Amy F% Finsebigler$ Guangquan% Fu$ Cohn T% Oates% !hem% Re% G891;$ @1897GG8;%
    758% Pa) O$ <eller A% C% /ater% Res% 75$ 5@8G97GG@;%
    75?% Dorian A% <% <anaor$ !harles !% Sorrell% C% /ater% Sci% 6?$ E8895:77;%
    75@% Oao-<suan Tseng$ !hien-Sheng Nuo$ !hia-<ung <uang$ Ouan-Oao Fi$ Po-#en !hou$
    !hia-Fiang !heng and /ing-Sho' #ong% 2anotechnology 7@$ 56G:95::?;%
    75E% G% !a""elletti$ !%F% Bianchi$ S% Ardi))one% A""lied !atalysis B* 3nironmental% Aol
    @E91P6;$ 7G195::E;%
    75G% !ui$ O%$ M% #ei$ <% Park$ and !% /% Fieber% 5::7% Science% 5G1* 75EG%
    71:% <ood$ F%$ C%R% <eath$ /%3% Phel"s$ B% Fin% 5::6% Science% 1:?* ?6:P?61%
    717% <uang$ B%C% and O%-N% !hoi% 5::@% Sensors and Actuators B* !hemical% 755 95;* ?8G-?@7%
    715% Nrithika Nalyanasundaram$ Phd Thesis$ Stony Brook Uniersity$ 5::@%
    711% P% Gouma$ N% Nalyanasundaram$ and A% Bisho"% Cournal of /aterials Research$
    2ano'ires and 2anotubes s"ecial issue$ 57977;$ ""% 5G:6-5G7:$ 5::?%
    716% N%/% Sa'icka$ A%N% Prasad and P%J% Gouma$ Sensor Fetters 91;$ ""% 7-8$ 5::8%
    718% <-# Ra$ R Nhan$ C T Nim$ B R Nang and O < Jm% 2anotechnology$ 57 :E88:5 95:7:;
    71?% Pradee" Gali$ Go"al Sa"kota$ A C Syllaios$ !hris Fittler and U Phili"ose% 2anotechnology
    56$ 558@:6 95:71;
    71@% Ousuf A% Naneti$ Lheng4ie Lhang$ Ceffrey Oue$ Muadir /% D% Lakaria$ !huyang !hen$
    Buchuan Ciang and Aibing Ou% Phys% !hem% !hem% Phys%$ 5:76$ 7?$ 776@7
    71E% P% Gouma$ A% Bisho" and N%N% Jyer$ TSingle !rystal /etal 0&ide 2ano'ires as Bio-
    !hem Sensing ProbesT$ Rare /etal /aterials 3ngineering$ 18$ ""% 5G8-5GE$ 5::?%
    71G% N% Sa'icka$ /% Naradge and P% J% Gouma$ T0&idation synthesi)ed !u0 nano'ires for gas
    sensing a""licationsS$ /icrosc% /icroanal% 7: 9Su""l 5;$ ""% 1?:-1?7$ 5::6
    76:% P% J% Gouma and /% C% /ills$ _Anatase to Rutile Transformation in Titania Po'ders`% C%
    Am% !eram% Soc%$ E6 Q1R$ ?7G-?5595::7;%
    767% C% Fee and P%J% Gouma$ TTailored 1D !u0 2anogrid FormationT$ C% 2anomaterials$
    5:77 95:77;$ Article JD E?1?17%
    765% Cun Fiu$ Lai"ing Guo$ Nai&ing Lhu$ #en4un #ang$ !haofeng Lhang and Biaolong !hen%
    C% /ater% !hem%$ 5:77$ 57$ 77675
    761% P%J Gouma and N% Nalyanasundaram% A""l% Phys% Fett% G1$ 5667:5$ 5::E%
    Chapter 2& Experimental Details
    5%7% Synthesis /ethods
    5%7%7% Sol-Gel synthesis
    Jn a ty"ical colloidal sol-gel "rocess the "recursor material 9either an inorganic salt or
    metal alko&ide solution; is chemically "rocessed to form hydrous metal o&ides or hydro&ides
    9hydrolysate;% !olloidal dis"ersions 9sols; of the hydrolysate are "re"ared by "e"ti)ation 9the
    "rocess res"onsible for the formation of stable dis"ersion of colloidal "articles in 'ater;$ a gel is
    formed by dehydration or "< control$ and the resulting body calcined to form the stable o&ide
    "roduct% A unique as"ect of sol-gel "rocessing is the ability to "roceed from molecular "recursor
    to final ceramic "roduct$ enabling intimate control oer all stages of "rocessing and the synthesis
    of _tailor-made` materials%
    Both #0
    1
    and /o0
    1
    colloidal "articles 'ere "roduced using sol-gel synthesis% Tungsten
    Jso"ro&ide 98K '( in Jso"ro"anol$ Alfa Aesar; 'as used hydroly)ed 'ith deioni)ed 'ater to
    synthesi)e the sol% The mi&ture 'as ultrasonicated and aged for 56 hours$ u"on 'hich 'hite
    "reci"itates 'ere obsered$ indicating the com"letion of hydrolysis% The synthesi)ed
    nano"articles 'ere subsequently dried in air and the finally the "o'der 'as heat-treated at 18:!
    in a tube furnace for E hours% Sol-gel synthesis 'as carried out on the "recursor /olybdenum
    Jso"ro"o&ide 98K '( in Jso"ro"anol$ Alfa Aersar;% Precursor 'as hydroly)ed using deioni)ed
    'ater to get :%7m/ solution% This solution 'as allo'ed to age for 56 hours%
    5%7%5% 3lectros"inning
    3lectros"un nanofiber mats "ossess high surface area and ariable "orosity Q7R% The
    traditional 4et-electros"inning "rocess requires a "olymer solution 'hich is loaded onto a
    syringe$ a flo' meter to control the flo' rate of the solution$ a needle 'ith a diameter in the
    millimeter range$ a collector "late 'hich is grounded and a high oltage "o'er su""ly% Jn the
    traditional set u"$ a dro"let forms at the ti" from the source$ 'hich is the syringe and needle$ and
    there is a buildu" of electrostatic charge at the surface of the dro"let 'hich induces the formation
    of a 4et% 3en though the single 4et technique makes a aluable research tool to e&"eriment on
    getting the best "recursors and "rocess "arameters for nanofiber mat formation of the desired
    configuration$ it has largely "roduced small amounts of nanomaterials that hae satisfied the
    engineering curiosity$ rather than offering a "rocessing route for nanofiber manufacturing%
    0igure 13 ,raditional electrospinning set up
    /o01 nanofibers 'ere synthesi)ed using this method% The sol-gel synthesi)ed /o01
    colloidal "articles 'ere mi&ed 'ith :%7 molar PAP solutions in ratios of 7*6 and 7*8% The
    enca"sulation ma&imi)ed at 7*8 ratio% The solution 'as electros"un 97ENA oltage+ :%1:hm(min
    flo' rate+ 7:cm collector to needle distance; to get metal o&ide enca"sulated nanofibers%
    /olybdenum trio&ide nano'ires 'ere then formed after the nanofibers 'ere heat treated in a
    tube furnace% Jt 'as obsered that electros"un nano'ires al'ays gre' into the orthorhombic .-
    /o01 structure no matter the heat treatment tem"erature%
    5%7%1% <igh through"ut electros"inning
    The 4et-controlled and flo'-controlled set u" used in this study is sho'n in Figure 7% An
    analogous flo' control mechanism is em"loyed to that of the traditional set u" to feed the
    "recursor solution% /ost solutions that could be s"un in the traditional single 4et set u" can be
    s"un in this scaled u" arrangement% For greater fle&ibility$ all the "arameters that are ariables in
    the case of traditional needle electros"inning 9T23;$ such as flo' rate$ 'orking distance$ oltage
    and material concentration can also be aried in this modified set u"%
    Figure 59a-c; describes the dimension of the scalable set u" used here% Jn our attem"t to
    hae multi"le dro"lets form at the surface$ a metallic source disk 9Figure 7:9b;; of height ? mm
    and$ outer diameter 7: cm 'as used% The de"th of the source disk 'as 5mm$ 'hile the inner
    diameter G: mm% Fluid solutions 'ere "um"ed into the hollo' source disk 'ith the hel" of a
    "rogrammable syringe "um" 9Nd scientific;% The flo' rate 'as ke"t at 7: to 75 times higher than
    the traditional needle electros"inning 9T23;% Testing to "roe the design conce"t 'as carried out
    using 51 equidistant holes drilled at the inner base of the disk% The 'orking distance 'as ke"t at
    78cm$ 'hich 'as the difference bet'een the outer collector cylinder and the source disk% The
    'hole set-u" 'as made out of aluminum% The charge distribution 'as such that the ma&imum
    charge accumulation occurred at the ring at the leel of the holes% Jn order to achiee the required
    leel of electrostatic charging at the dro"let surface$ the source disk bottom 'as machined to a
    minimum thickness for bottom surface% The "roblem of refilling the disc 'as oercome Q5R by
    using a re"lenishing source to constantly fill the disc%
    0igure "3 (a) Modified flow controlled and Eet controlled high throughput electrospinning set up'
    (b) Source dis), the metallic plate where one terminal of the high (oltage source attaches is
    (isi&le, 71 eJuidistant 6mm diameter holes drilled in to the inner &ase of the dis) with one hole
    plugged for attaching the (oltage terminal/ (c) Schematic of the setup, dimensions and other
    details are la&eled'
    To synthesi)e the nanofibers of /o0
    1
    using this set u" certain modifications had to be
    done to the source disk% The holes in the disk 'ere reduced in diameter to i mm and "laced at an
    angle of 68 degrees and by "lacing them at the inside edge of the disk in addition to the reduction
    of the hole diameter to "roides the ca"illary action that hel"s enca"sulate the sol inside the
    "olymer 'as achieed% !a"illary action generated by the needle in traditional needle
    electros"inning technique is an essential com"onent to get enca"sulation of /o0
    1
    sol-gel inside
    the PAP "olymer%
    0igure &3 ,he source dis) is a critical component of the set up/ (a) Schematic showing the side (iew of
    the source dis)' (b) Schemtic showing the &ottom (iew of the source dis)' (c) ,he &ottom (iew of the
    source dis)' (d) ,he top (iew of the source dis)'
    5%5% !haracteri)ation /ethods
    5%5%7% B-ray diffraction
    B-Ray Diffraction 'as carried on Rigaku Ultima JJJ B-Ray Diffractometer 'as used to
    characteri)e the films de"osited on sensor substrates and to confirm the "hases "resent in the
    stabili)ed sensors% Rigaku Ultima JJJ "erforms a kind of a non-destructie analysis of materials$
    ty"ically in "o'der or thin film form% The diffractometer o"erates at oltage and current alues
    of 6:kA and 1:mA% B-ray 'aelength is of !u N radiation 'hich is 7%867E6 [% The d alues are
    then com"ared 'ith standard C!PDS "o'der diffraction data for the material under test and
    "ossible "hases are identified%
    5%5%5% Raman S"ectrosco"y
    Raman studies 'ere "erformed on a #itec Al"ha combination near field o"tical and
    raman microsco"e% Jn combination 'ith B-ray diffraction Raman data 'as used to ascertain the
    "hase of the material% Jt 'as also used to eliminate the "ossibility of #-! and #-0< bond
    "resence in the colloidal solution%
    5%5%1% Transmission electron microsco"y
    Transmission electron microsco"e$ in a C30F 76:: Soft-bio 'as carried to determine the
    "hase and to obsere the grains of ceramic nano"articles synthesi)ed by sol-gel method%
    Additionally$ nano'ires 'ere obsered under the microsco"e and the as"ect ratio 'as
    ascertained%
    The C30F 76:: T3/ has a FaB? cathode electron source% Jt o"erates at a oltage of
    75:NeA and has a resolution of 5nm% Jt is es"ecially suited for soft and bio materials% The
    electron diffraction ca"abilities of the microsco"e 'as e&tensiely used to determine the crystal
    structures of the materials%
    5%5%6% <igh resolution Transmission electron microsco"y
    <igh resolution transmission electron microsco"y 'as carried on the C30F 57::F at
    Brookhaen national lab% The nano'ire "hase for both tungsten trio&ide and molybdenum
    trio&ide 'as ascertained using this% The C30F 57::F o"erates at 5::NeA and has a resolution of
    5 angstrom% This makes it es"ecially suited for determining the lattice structure of nano'ires%
    Additionally$ it is also 'ell suited to obsere the defects in the crystals of ceramic nano"articles%
    5%5%8% Scanning 3lectron /icrosco"y
    S3/ imaging 'as "erformed on Schottky Field 3mission Scanning 3lectron /icrosco"e
    9S3/; 9F30 Gemini 788:; and analytical high resolution S3/ 9C30F @?::F;% S3/ analysis
    has been used e&tensiely throughout the research% The nano"article si)e distribution analysis is
    carried out using S3/% Traditional and high through"ut electros"inning nanofiber formation and
    diameter si)e obserations are also carried out using S3/%
    References
    7% A%/% A)ad and P%J% Gouma% 3ncyclo"edia of 2anoscience and 2anotechnology$ <%S%
    2al'a 93ditor;$ American Scientific Publishers$ 76$ 1:7-15G95:77;%
    5% S% A% Theron$ A% F% Oarin$ 3% Lussman$ 3% Nroll% Polymer$ 6?$ 5EEG95::8;%
    Chapter 1& 8euristic model of polymorphic transitions
    As described in the "reious section$ binary metal o&ides go through a "olymor"hic
    transition 'hen they are heat treated at high tem"eratures% Polymor"hic transformation
    tem"eratures in nanocrystalline binary metal o&ides are obsered to be lo'er than bulk%
    3&am"les include ,-Fe501 to .-Fe501Q7$5R$ monoclinic to orthorhombic transformation in
    /o01Q1R$ anatase to rutile transformation in TitaniaQ6R$ , to . Alumina transformationQ8$?R%
    /any models e&ist 'hich deelo" our understanding of the mechanism of melting tem"erature
    lo'ering due to reduction in "article si)eQ@R$ cohesie energy based models to "redict
    thermodynamic "ro"erties of metallic nano"articlesQE$GR% But only a fe' attem"ts hae been
    made to study the thermodynamics of solid-solid "hase transformations of nanocrystalline binary
    metal o&ides$ theoretical alues for anatase to rutile transformation tem"erature Q7:R 'ere
    calculated to be bet'een ?:: and E::N at a critical "article si)e of 76nm% Gouma et al% 97GGG;
    Q77R obsered rutile gro'th at as lo' as ?@1N and 'ith a critical "article si)e of Enm$ 'hich 'as
    in agreement 'ith the earlier theoretical "redictions% Jn this communication for the first time$ an
    attem"t is made to "roide a generali)ed formula$ accounting for entro"ic$ si)e$ and other effects
    that control the onset of "olymor"hic "hase reactions in nanocrystalline o&ide systems%
    Jt is generally true that the relatie stability of any t'o "olymor"hs de"ends on their free
    energies+ the most stable "olymor"h has a minimum Gibbs free energy% Surface effects$ 'hich
    'ere ignored due to the small surface to olume ratio in bulk hae to be taken into consideration
    since the surface to olume ratio of nanocrystals is fairly large$ and the surface can affect the
    HbulkI "ro"erties of nanocrystals Q76R% Jnternal "ressure due to e&cessie number of dangling
    bonds has seen to cause discre"ancy in theoretical and e&"erimental "article si)e alues Q75R%
    0ther affects like sha"e factor Q71R also contribute to the general stability and thus hae to be
    considered 'hen deelo"ing theoretical background to "redict critical "article si)e alues% Thus$
    in our a""roach 'e hae taken into account the combined effect of all the factors to "redict the
    "article si)e quantitatiely for an obsered "olymor"hic transition%
    1%7%7% Theory
    Jf the nano"articles are kinetically stable the gibbs free energy is gien by$
    G Z < P T%S W 9" W "I;%A W ,%A W other terms 91%7;
    T and " are tem"erature and "ressure res"ectiely$ "I is an e&cess internal "ressure
    associated 'ith strain at the surface+ A is the surface area+ , is the surface
    energy(enthal"y(tension% /etastable states that differ from their bulk equilibrium "hases can
    stabili)e as "article si)e HrI is reduced to the nanoscale dimensions% Ciang and yang95::E;Q78R
    take the e&am"le of nanocarbon "hase transition to illustrate the solid-solid "hase transitions%
    #autelet et al% Q7ER hae demonstrated the im"ortance of "article sha"e 'hen considering solid-
    liquid "hase transformation% Banfield and Lhang97GGE;Q7:R illustrated the im"ortance of surface
    stress and 'ere able to successfully "redict the critical "article si)e in the case of titania%
    Follo'ing 'e demonstrate ho' these factors contribute in "redicting the critical "article si)e
    belo' 'hich the behaior of metal o&ides so noticeably changes%
    For the conce"tuali)ation of the thermodynamics inoled for nanocrystalline metal
    o&ides$ 'e need to find an e&"ression for the gibbs free energy of "hase transformation$
    jG
    U\.
    9T$r;$ from a U "hase to . "hase% From 3quation 91%7;+
    jG
    U\.
    9T$r; Z j
    k
    <
    U\.
    9T$r; P T%j
    k
    S
    U\.
    9T$r; W j9P%A;
    U\.
    9T$r; W j9A%,;
    U\.
    9T$r; W other factors 91%5;
    For bulk$ the gibbs free energy of "hase transformation is the difference bet'een the
    standard free energy of formation of indiidual "hasesQ51R$
    jG
    U\.
    9T$r; Z j
    k
    G
    f
    .
    9T; - j
    k
    G
    f
    U
    9T;
    91;
    Although$ additional factors contribute to the gibbs free energy of "hase transformation
    for nanocrystals%
    1%7%5% 3ntro"ic contribution
    Jn the case of solid-solid "hase transformation$ for the ease of calculations$ the entro"ic
    difference may be ignored$ also due to the nano si)e there is a lo'ering of the transformation
    tem"erature$ thus the term$ T%j
    k
    S
    U\.
    9T$r;$ is too small to affect the "article si)e calculations%
    Table 6 gies entro"y of formation of some "oymor"hs under standard conditions of "ressure
    and tem"erature$
    Table &3 Standard entropy of formation a few Polymorphs
    Metal Oxide Polymorph Standard Entropy of ;ormation
    Al501 Al"ha 8:%G8 C(N(molQ7?R
    Gamma 85%1: C(N(molQ7?R
    Delta 8:%?5 C(N(molQ7?R
    Fe501 Al"ha E@%6 C(N(molQ7?R
    Gamma G1 C(N(molQ7@R
    Ti05 Anatase 6G%G C(N(molQ7?R
    Rutile 8:%5G5 N(molQ7?R
    Although for many materials data for standard free energy of formation is aailable in
    s"ecific tem"erature range Q7?R$ and for them the alues can be "lugged into the follo'ing
    equation and free energy at s"ecific transformation tem"erature can be directly found$
    G9T; Z A W B%T W !%T%lnT W D%T
    5
    W 3%T
    1
    W F(T 91%6;
    But for most binary metal o&ides such data may not be aailable$ in those cases the
    a""ro&imation$ j
    k
    G
    U\.
    9T$r; Z j
    k
    <
    U\.
    9T$r;$ is useful% 3nthal"y data can be found by DS!(TGA
    analysis of a "ure binary metal o&ide%
    1%7%1% Surface Free 3nergy
    The surface to olume ratio is ery high in case of nanocrystals and this causes surface
    free energy$ jG
    s
    U\.
    9r;$ to constitute a large "art of the total free energy of the substance for
    nanocrystalsQ7:$51R% Thus an additional term is necessary in equation 91%5;%
    jG
    s
    U\.
    9r; Z A
    m
    .
    %,
    .
    - A
    m
    U
    %,
    U
    91%8;
    #here A
    m
    .
    and A
    m
    U
    are the molar surface areas and ,
    .
    and ,
    U
    are the surface energies%
    Further$ the molar surface area can be e&"ressed in terms of molar olume and "article si)e$
    A
    m
    Z A
    m
    (r 91%?;
    jG
    s
    U\.
    9r; Z 9A
    m
    U
    %,
    U
    P A
    m
    .
    %,
    .
    ;(r 91%@;
    Thus$ equation 91%8; can be 'ritten as$
    jG
    s
    U\.
    9T$r; Z 9A
    m
    U
    %,
    U
    P A
    m
    .
    %,
    .
    ;(r 91%E;
    1%7%6% Surface Stress
    Jt has been obsered that there e&ists a "ressure contribution due to the e&istence of
    surface stress and due to the curature of nano"articles Q15R% 3hrman97GGG;Q75R obsered in the
    case of silica that the obsered theoretical "redictions of "article si)e 'ere not in agreement 'ith
    the obsered e&"erimental results and attributed this discre"ancy u"on the internal "ressure
    effects% Similar internal "ressure effects 'ere also obsered in another study Q11R done on
    anatase titania% The authors had to a""ly additional "ressure to nanocrystalline anatase to
    com"ensate for the internal "ressure due to the nanosi)e%
    This e&cess "ressure can be quantified into the Gibbs free energy of "hase
    transformationQ7:R$
    jG
    s
    U\.
    9r; Z P
    in
    U
    %A
    m
    U
    P 1%P
    in
    .
    %A
    m
    .
    91%G;
    Jnternal "ressure can be e&"ressed in term of f
    s
    $ 'hich is the surface stress due to the
    e&cess internal "ressureQ76$56R$
    P
    in
    Z 5% f
    s
    (r 91%7:;
    3quation 91%7:; can be re'ritten as$
    jG
    P
    U\.
    9r; Z 95%f
    s
    U
    %A
    m
    U
    P 5%f
    s
    .
    %A
    m
    .
    ;(r 91%77;
    1%7%8% Free 3nergy due to "article sha"e
    The sha"e of nano"articles induces another constraint to "hase transformation%
    2ano"articles can be 2ano'ires$ 2anorods$ thin films etc% The aboe theory holds good for
    s"herical nano"articles% #autelet et al%Q7E$7G$5:R describe ho' sha"e affects the melting
    tem"erature of nano"articles$ and the follo'ing analysis has been ada"ted from ref% 7E$7G$5:
    'hich hae been modified for solid-solid "hase transformations% A geometric factor HgI could
    account for sha"e of a "article% There has been ery little theoretical 'ork on "redicting such a
    factor for solid-solid transformations% Sha"e of a "article can alter the theoretical alues for
    "article si)e% Free energy of such a "article de"ends on geometrical factor in the follo'ing 'ay$
    jG
    G
    U\.
    9r; Z g% 9,
    .
    - ,
    U
    ; (2
    7(1
    Z -.%lj
    k
    <
    f
    .
    9T; -j
    k
    <
    f
    U
    9T;m (5%r 91%75;
    Aalues of . 'ere calculated by the authors of ref% 7G for small "articles of inorganic materials$
    they found . to be "ositie and in the range of :%6 to 1%1nm% Such calculations are not aailable
    in literature for binary metal o&ides%
    1%7%?% !ritical "article si)e
    From the aboe mentioned discussion it can be inferred that$
    jG
    U\.
    9T$r; Z j
    k
    G
    U\.
    9r; W jG
    s
    U\.
    9r; W jG
    P
    U\.
    9r; W jG
    G
    U\.
    9r;
    91%71;
    #e kno' that at "hase transformation tem"erature there is an equilibrium bet'een t'o "hase
    thus$ jG
    U\.
    9T$r;nr
    c
    U\.
    9T;nZ:% Thus sim"ly substituting equations 1%E$ 1%77$ 1%75 in equation 1%71
    and rearranging 'e get the alue for the critical "article si)e%
    r
    c
    U\.
    9T;Z l9A
    m
    .
    %,
    .
    P A
    m
    U
    %,
    U
    W 5%f
    s
    U
    %A
    m
    U
    -5%f
    s
    .
    %A
    m
    .
    ;m(9j
    k
    <
    f
    .
    9T; - j
    k
    <
    f
    U
    9T;; P .(5 91%76;
    Aboe equation can be 'ritten in terms of density H^I of "hase . or U$ by substituting$ A
    m
    Z /(^$
    'here / is the molar mass$
    r
    c
    U\.
    9T;Z l/%9,
    .
    (^
    .
    P ,
    U
    (^
    U
    W 5%f
    s
    U
    (^
    U
    -5%f
    s
    .
    (^
    .
    ;m (9j
    k
    <
    f
    .
    9T; - j
    k
    <
    f
    U
    9T;; P .(5 91%78;
    1%5% !ase Studies
    Jn table 8 'e summari)e the "rediction of the critical "article si)e$ using equation 1%78 and
    the a""ro&imation of surface stress$ belo' 'hich a metastable "hase is "redicted to remain
    stable% The alue matches 'ell 'ith the e&"erimental results%
    Table )4 0lumina, titania, irconia critical particle sie calculations
    ,-Alumina to
    .-Alumina
    Phase
    Re
    f
    Anatase to
    Rutile Titania
    Phase
    Re
    f
    Tetragonal to
    /onoclinic Lirconia
    Phase
    Re
    f
    j
    k
    <
    f
    ,
    9T; -
    j
    k
    <
    f
    .
    9T; Z
    55%7@ kC(mole 5E 5%?7 kC(mole 5G
    7:o7 kC(mole
    11
    ?%6 C(m
    5
    8%?E g(cc
    5%7 C(m
    5
    ?%:Gg(cc
    Theoretical
    !ritical Particle
    si)e
    Bet'een
    6%:Enm b
    5%?Enm
    Bet'een
    G%:Gnm b
    @%87nm
    Bet'een 5E%1nm b
    5@%7nm
    3&"erimental
    !ritical Particle
    si)e
    1%5nm at
    6@1N
    1: 7:nm 5G
    1:nm
    15
    References
    7 Fu Su Oen$ #ei !hien !hen$ Canne /in Oang$ and !hen Tsung <ong% _!rystallite si)e
    ariation of nanosi)ed Fe501 "o'ders during , to . "hase transformation`$ 2ano Fetters$
    5Q1R$ 568-58595::5;%
    5 0)den 0)demir and Subir N% Baner4ee$ _<igh tem"erature stability of maghemite9,-
    Fe501;`% Geo"hysics research letters$ 77Q1R$ 7?7-7?697GE1;%
    1 Arun N% Prasad% Phd thesis$ Stony brook uniersity$ 5::8%
    6 P% J% Gouma and /% C% /ills$ _Anatase to Rutile Transformation in Titania Po'ders`% C%
    Am% !eram% Soc%$ E6 Q1R$ ?7G-?5595::7;%
    8 Shu&ue Lhou$ /arkus Antonietti$ and /arkus 2iederberger$ _Fo'-Tem"erature
    Synthesis of ,-Alumina 2anocrystals from Aluminum Acetylacetonate in 2onaqueous
    /edia`% Small 1Q8R$ @?195::@;%
    ? C% /% /c<ale$ A% 2arotsky$ A% C% Perrotta$ _3ffects of increased surface area and
    chemisorbed <50 on the relatie stability of nanocrystalline ,-Al501 and .-Al501`% C%
    Phys% !hem% B$ 7:7Q6R$ ?:1P?7197GG@;%
    @ !ouchman$ P%R%+ Cesser$ #%A$ _Thermodynamics theory of si)e de"endence of melting
    tem"erature in metals`% 2ature 5?G$ 6E797G@@;%
    E # < Mi$ / P #ang$ / Lhou and # O <u$ _Surface-area-difference model for
    thermodynamic "ro"erties of metallic nanocrystals`% C% Phys% D* A""l% Phys% 1E$
    765G95::8;%
    G #%<% Mi$ /%P% #ang and G%O% Bu$ _The "article si)e de"endence of cohesie energy of
    metallic nano"articles`% !hemical Physics Fetters 1@5$ ?1595::1;%
    7: <eng)hong Lhang and Cillian F% Banfield$ _Thermodynamic analysis of "hase stability of
    nanocrystalline titania`% C% /ater% !hem% 6$ 5:@197GGE;%
    77 P%J%Gouma$ P%N% Dutta and /%C%/ills$ _Structural Stability of Titania Thin Films`%
    2anostructured materials 77QER$ 751797GGG;%
    75 Sheryl <% 3hrman$ _3ffect of "article si)e on rate of coalescence of silica nano"articles`%
    Cournal of !olloid and Jnterface Science 571Q7R$ 58E97GGG;%
    71 /% #autelet$ _3ffects of si)e$ sha"e and enironment on the "hase diagrams of small
    structures`%2anotechnology 1 97GG5; 65-61%
    76 C% /% Blakely$ Introduction to the properties of crystal surfaces$ Pergamon Press$ 0&ford$
    7
    st
    edn%$ 7G@1%
    78 Ciang$ M% Oang$ !% !$ _Si)e effect on the "hase stability of nanostructures`% !urrent
    2anoscience 6Q5R$ 7@G95::E;%
    7? /% #% !hase$ C% F% !urnutt$ A% T% <u$ <% Pro"het$ A% 2% Syerud$ and F% !% #alker%
    CA2AF Thermochemical Tables$ 7G@6 9Su""l%;%
    7@ Cura4 /a4)lan$ Nlaus-Dieter Greel$ Ale&andra 2arotsky$ _Thermodynamics of Fe
    o&ides* Part JJ% 3nthal"ies of formation and relatie stability of goethite 9.-Fe00<;$
    le"idocrocite 9,-Fe00<;$ and maghemite 9,-Fe501;`% American /ineralogist$ EEQ8-?R$
    E88-E8G
    7E R Aallee$ / #autelet$ C P Dauchot and / <ecq$ _Si)e and segregation effects on the
    "hase diagrams of nano"articles of binary systems`% 2anotechnology 75$ ?E95::7;%
    7G /ichel #autelet$ _3stimation of the ariation of the melting tem"erature 'ith the si)e of
    small "articles$ on the basis of a surface-"honon instability model`% C% Phys% D* A""l%
    Phys% 56 161%
    5: /ichel #autelet and Aram S% Shirinyan$ _Thermodynamics* 2ano s% macro`% Pure A""l%
    !hem%$ Aol% E7$ 2o% 7:$ ""% 7G57P7G1:$ 5::G%
    57 ! Suresh$ A Bi4u$ P /ukundan$ N%G%N #arrier$ _Anatase to rutile transformation in sol-
    gel titania by modification of "recursor`% 7@Q7ER$ 171797GGE;%
    55 /% R% Ranade$A% 2arotsky$ <% L% Lhang$ C% F% Banfield$ S% <% 3lder$ A% Laban$ P% <%
    Borse$ S% N% Nulkarni$ G% S% Doran$ and <% C% #hitfield$ _3nergetics of nanocrystalline
    Ti05`% P2AS$ GG$ ?6@?95::5;%
    51 <ill$ T%F% ,hermodynamics of small systems% 9Ben4amin$ #%A% 2e' Oork$ 2O$
    7G?1(7G?6; Aol% J$JJ%
    56 R% !% !ammarata and N% Sierad)ki$ _Surface and Jnterface stresses`% Annu% Re% /ater%
    Sci%$ 56$ 57897GG6;%
    58 Blonski$ S+ Garofalini$ S$ <$ _/olecular dynamics simulations of .-alumina and ,-
    alumina surfaces`% Surface science$ 5G8Q7-5R$ 5?1-5@697GG1;%
    5? T% Ookoka'a and 0% C% Nle""a$ _A !alorimetric Study of the Transformation of Some
    /etastable /odifications of Alumina to .-Alumina`% C% Phys% !hem% ?EQ77R$ 156?97G?6;%
    5@ /% R% Ranade$ A% 2arotsky$ <% L% Lhang$ C% F% Banpeld$ S% <% 3lder$ A% Laban$ P% <%
    Borse$ S% N% Nulkarni$ G% S% Doran$ and <% C% #hitpeld$ _3nergetics of 2anocrystalline
    Ti05$` P2AS$ GG$ ?6@? 95::5;%
    5E S% Lhou$ /% Antonietti$ and /% 2iederberger$ _Fo'-Tem"erature Synthesis of c-Alumina
    2anocrystals From Aluminum Acetylacetonate in 2onaqueous /edia$` Small$ 1 Q8R @?1
    95::@;
    5G <% Lhang and C% F% Banpeld$ _Thermodynamic Analysis of Phase Stability of
    2anocrystalline Titania$` C% /ater% !hem%$ E$ 5:@1 97GGE;%
    1: R% !% Garie$ _The 0ccurrence of /etastable Tetragonal Lirconia as a !rystallite Si)e
    3ect$` C% Phys% !hem%$ ?G$ 751EP67 97G?8;
    17 T% Ookoka'a and 0% C% Nle""a$ _A !alorimetric Study of the Transformation of Some
    /etastable /odipcations of Alumina to a-Alumina$` C% Phys% !hem%$ ?E Q77R 156?
    97G?6;%
    15 Lhao D%S%$ Lhao /% and Ciang M$ _Si)e and tem"erature de"endence of nanodiamon-
    nanogra"hite transition related 'ith surface stress`% Diam% Relat% /ater% 77$ 51695::5;
    11 Aarghese S'amy$ Ale&ei Nu)netso$ Feonid S% Dubroinsky$ Rachel A% !aruso$ Dmitry
    G% Shchukin$ and Barry !% /uddle$ _Finite-si)e and "ressure effects on the Raman
    s"ectrum of nanocrystalline anatase Ti05`% Phys% Re% B$ @7$ 7E61:595::8;%
    Chapter !& /ungsten /rioxide nano4ire in+situ /EM synthesis
    Jn this section 'e describe the gro'th of highly aligned nano'ires of the monoclinic
    "olymor"h transformed from metastable "olymor"hs under the influence of an electron beam%
    The mor"hological transformation is a ra"id manifestation of a self-catalytic massie-ty"e "hase
    reaction occurring in acuum% The reaction a""ears to be self-cataly)ed due to the instability of
    the metastable "hase nano"articles under the influence of the beam% Jt is sho'n that the
    nano"articles due to the electron energy of the beam become 'ire-like gro'ing into highly
    aligned "eriodic crystalline structures% This finding has im"ortant im"lications for achieing
    scalable and controlled nano'ire synthesis%
    6%7% Precursor "hase
    The #0
    1
    nano"articles 'ere synthesi)ed using a sol-gel route% Tungsten Jso"ro"o&ide 98K
    '( in Jso"ro"anol$ Alfa Aesar; 'as used in equal quantities 'ith$ ethanol and acetic acid 9to
    control "<; to synthesi)e the sol% The mi&ture 'as ultrasonicated and aged for 56 hours$ u"on
    'hich 'hite "reci"itates 'ere obsered$ indicating the com"letion of hydrolysis% The synthesi)ed
    nano"articles 'ere subsequently dried in air and this resulted in a bro'nish "o'der% Finally the
    "o'der 'as heat-treated at 18:! in a tube furnace for E hours resulting in a yello'ish "o'der%
    This resulted is the formation of a metastable ma4ority cubic "hase 'hich has been obsered
    earlier using similar synthesis technique Q@R%
    The images in Figure 6 9a; and 9b; sho' a uniform distribution of nano"articles of radii 1:-
    6:nm% !rystalline si)e calculated from BRD using Scherrer equation gies a alue of roughly
    1E%8nm% Figure 6 9c; sho's the Raman s"ectra of the annealed nano"articles% The #-0-#
    stretching mode that is the characteristic of the #0
    ?
    octahedra can be obsered at @G5cm
    -7
    $
    although 'ith a slight shift% The "eaks bet'een @6:cm
    -7
    and GE:cm
    -7
    "oint to the "resence of
    distorted octahedral Q7R% The broad band obsered in the s"ectra bet'een starting about 78: to
    6:: can be ascribed to the cubic "hass Q8R% Similarly a broad instead of shar"er "eaks bet'een
    ?::cm
    -7
    and E8:cm
    -7
    can also be ascribed to the cubic "hase Q8R% Peaks Q?R sho'n bet'een
    56:cm
    -7
    and 5@:cm
    -7
    in addition to one at 156cm
    -7
    $ these "eaks are not sufficient to distinguish a
    "articular "hase of #0
    1
    from the other$ although these are indicatie of all stable #0
    1
    "hase%
    Therefore BRD 'as used$ Figure 6 9c; sho's the BRD of the nano"articles annealed at 18:q!%
    All the "eaks of the cubic "hase$ C!PDS card D67-:G:8$ can be identified$ 'hich is the ma4or
    "hase% Although many "eaks of monoclinic "hase 9C!PDS card D61-7:18; can also be identified%
    This "oints to distortions in the crystal$ 'hich can also be confirmed by the SAD "attern sho'n
    in figure 89Right; 'here 'e can obsere the "resence of other dimmer rings in addition to the
    rings corres"onding to the 97::;+ 977:;+ 957:; "lanes of the metastable cubic "hase of tungsten
    trio&ide% The nano"articles of cubic tungsten trio&ide are sho'n in figure 89Feft;$ 'ere
    characteri)ed under a C30F C3/-76:: analytical T3/%
    0igure )3 (a) Low magnification SEM image of sol-gel synthesied nanoparticles of tungsten
    trio!ide annealed at "#$%, (b) shows the higher magnification SEM image with uniformly
    distri&uted particle sie' (c) Shows the Raman spectra of the nanoparticles, the &ands
    o&ser(ed are mar)ed' (d) Shows the *R+ of the nanoparticles'
    0igure , 3 (Left) ,EM micrograph of the cu&ic nanoparticles of ,ungsten trio!ide, (4ight)
    S0+ pattern, &righter rings can &e inde!ed to (6$$)/ (66$)/ (76$) planes of the cu&ic phase'
    6%5% Jn-situ nano'ire synthesis
    The "re"ared nano"articles 'ere dro" coated onto a T3/ grid consisting of a Formar
    su""orting film 95:: /esh !o""er grids 'ith su""ort films$ T3D P3FFA Jnc%;% Formar is a
    family of "olymers formed from "olyinyl alcohol and formaldehyde as co"olymers 'ith
    "olyinyl acetate Q5R$ they are non-reactie class of com"ounds Q1R and additionally hae a
    2FPA @:6 reactiity rating of :% A 75:kA soft(bio materials analytical transmission electron
    microsco"e 9C30F C3/-76::; 'as used to gro' the nano'ires in-situ% The formar film 'as
    intact after the gro'th and 3DS analysis 9A""endi& G; sho'ed no carbon on the nano'ires 9ery
    small atomic "ercentages 9small "eak; is obsered$ 'hich can be attributed to the "resence of
    su""orting film in the icinity$ similarly the co""er "eak is due to the co""er mesh of the T3/
    grid;% To com"letely rule out the "ossibility of the transformation being affected by the "resence
    of carbon on the su""ort film$ the nano'ire gro'th 'as carried on a grid containing Silicon
    2itride as su""ort film$ the nano'ires gre' similar to the formar su""ort film%
    A 75:keA electron beam 'as used for the nano'ire gro'th% The beam 'as s"read initially
    'hile obsering the nano"articles and it 'as then slo'ly conerged on the sam"le$ the cubic
    "hase of the nano"articles instantaneously gre' into highly aligned nano'ires 9Figure ?; due to
    the energy im"arted by the electron beam% #hereas the stable monoclinic "hase did not
    transform$ this is consistent 'ith obseration of certain nano"articles not transforming% Such
    energy can be calculated% The C30F C3/76:: T3/ uses a FaB
    ?
    filament as the electron source
    'hich gies a current density of 76A(cm
    5
    on the s"ecimen 'hen using a :%Emrad illuminating
    a"erture Q6R% This current density can be conerted to energy density using the "o'er formula of
    current times oltage$ 'hich gies a alue of 7?E: 4oules(cm
    5
    for 7 second at 75:kA accelerating
    oltage% For 8:::B magnification$ a focused electron beam of 75:kA 'ould "roide @?keA of
    energy at the surface of an aerage 6:nm grain si)e nano"article for about half a microsecond to
    instantly transform it to a monoclinic "hase nano'ire% Figure ? 9Feft; and 9Right; images sho's
    the S3/ of nano'ires gro'n on Silicon 2itride su""ort film and T3/ of nano'ires gro'n on
    the Formar su""ort film%
    2ano'ires gro'n on Silicone 2itride su""ort films 2ano'ires gro'n on Formar su""ort films

    0igure -3 (Left) ,EM of nanowires grown on a Silicon -itride support film, (4ight) ,EM of
    nanowires grown on form(ar support film on a %opper mesh grid'
    The
    high
    0igure 53 (Left) ,ypical Electron diffraction pattern ta)en from a region with high
    concentration of nanowires' (4ight) Schematic of crystal structure of the monoclinic phase,
    with the preferred growth direction, the distortions ha(e &een e!aggerated to ser(e the
    purpose of illustration'
    concentration of nano'ires causes a distinct diffraction "attern at high magnification$ the
    diffraction "attern can be made into a ring "attern by reducing the magnification and taking a
    larger sam"le area into focus$ figure @9left;% The rings corres"ond to lattice "lanes 9::5;$ 95::;$
    955:;$ 9575;$ 9717;$ 9::6;$ 9767;$ 9 15;$ in Figure @9left;$ of the monoclinic ,-#0 33
    1
    9C!PDS D61-
    7:18;% A Re0
    1
    ty"e corner sharing octahedral forms the basic building block of all "hases of
    tungsten trio&ide% The crystal lattice symmetry of monoclinic #0
    1
    is a distorted rhenium o&ide
    cubic configuration$ figure @9Right;%
    0igure 73 (Left) .ighly aligned nanowires, showing the K$$6L growth direction along the
    long a!is/ (4ight) %orresponding diffraction pattern'
    The nano'ires gro' in to highly aligned crystals$ figure E9Feft; along the =::7> direction$
    'ith the corres"onding SAD "attern is sho'n in figure E9Right;% The high resolution T3/ 'as
    carried out on C30F 57::F Field 3mission Forent) T3/% The microgra"h in figure @ along 'ith
    the SAD "attern in figure G9Jnset; gies a more detailed "icture of the crystal structure% The
    s"acing of :%1E1nm and :%11nm corres"ond to the 9::5; and 975:; "lanes of the monoclinic
    "hase of tungsten trio&ide 9C!PDS D61-7:18;% Gro'th direction of =::7> "er"endicular to the
    9::5; "lane is along the long a&is of the nano'ires%
    0igure 63 .igh resolution ,EM of the structure of the nanowires/ (!nset) S0+ pattern from
    indi(idual nanowire'
    6%1% Thermodynamics of nano'ire formation
    By e&"loring the theoretical mechanism 'hich goerns the metastable to stable "hase
    transitions
    in nanocrystalline materials QER 'e can further e&"lain the gro'th of stable "hase
    nano'ires% The thermodynamic data for a "suedocubic "hase 'as unaailable$ thus that of cubic
    is used%
    The free energy of a nano"articles system 9jG2S9T$r;; or a nano'ire system
    9jG2#9T$r;; de"ends on three factors$ surface free energy 9jGS9T$r;;$ surface stress
    9jGP9T$r;;$ and free energy due to "article sha"e 9jGG9T$r;;$ as discussed in "reiously
    "ublished 'ork by the authors QER%
    Thus$
    jG2S9T$r; Z jG
    k
    9T$r; W jGS9T$r; W jGP9T$r; W jGG9T$r;
    96%7;
    jG2S9T$r; Z Am%, W Pin%A W .%r
    k
    <f%9A(A;
    96%5;
    Table ,
    4 %ontri&utions from the three main factors influencing the nanowire growth'
    NanoparticleDNanosphere Nano4ireDNanocylinder
    jGS9T$r; 96%s%r5;%, 95%s%r5 W 5%s%r%h;%, QA""endi& !R
    jGP9T$r;
    95%fs(r;%
    96%s%r1(1; Q97(h W 7(s%r;%5%fsR%9s%r
    5
    %h;
    jGG9T$r;
    .%r
    k
    <f(5%r .%r
    k
    <f%95(h W 5(r; QA""endi& DR
    Therefore$ the free energy for the nano'ire 9
    jG
    2#
    9T$r;;
    and nano"articles
    9
    jG
    2S
    9T$r;;$
    systems can be gien by$
    jG
    2S
    9T$r; Z 96%s%r5;%, W
    95%f
    s
    (r;%
    96%s%r1(1; W .%rS
    k
    <f(5%r
    96%1;
    jG
    2#
    9T$r; Z 95%s%r5 W 5%s%r%h;%, W
    Q97(h W 7(s%r;%5%f
    s
    R%9s%r
    5
    %h; W
    .%r!
    k
    <f%95(h W 5(r; 96%6;
    Table -4 +ata accumulated from the literature, and the free energy calculations
    0bsered 2ano'ire radius 5:nm
    Predicted 2ano'ire length 8?:nm
    Aerage nano"article radius 6:nm
    ,monoclinic :%?58 C(m
    5
    QGR
    ,cubic 7%?@ C(m
    5
    for 9::7; "lanes QGR
    rS
    k
    <f 9cubic;
    - @@%5 NC(mole
    78

    r!
    k
    <f 9monoclinic;
    -7G5%?8 NC(mole
    f
    s9monoclinic; 7%58 C(m
    5
    95%
    ,m;
    f
    s9cubic; 1%16 C(m
    5
    95%
    ,c;
    . 5nm Q7:R
    jGP9T$r; 92#;
    5%68 NC(mole
    jGS9T$r; 92#; 57E%@8 NC(mole
    jGG9T$r; 92#; -5: NC(mole
    jGP9T$r; 92S;
    5%8@ NC(mole
    jGS9T$r; 92S; 71E%?7 NC(mole
    jGG9T$r; 92S; -7%G1 NC(mole
    jG
    2S
    9T$r;
    71G%58 NC(mole
    jG
    2#
    9T$r;
    5:7%5 NC(mole
    Table @ tabulates all the alues substituted and the results for the free energy% Jt can be
    seen that the free energy alues for nano'ires is greater than for nano"articles% Thus for the
    transformation to occur an e&ternal source 'ith the energy equialent to the difference in the free
    energy of nano'ire and nano"article is necessary for the gro'th to occur% jG
    2#
    9T$r; -
    jG
    2S
    9T$r;%
    To ascertain the a""licability of this theory$ a lot of data "oints 'ere "lotted using
    /icrosoft 3&celt% The gra"h in figure 7: "lot difference in free energy 9jG
    2#
    9T$r; -
    jG
    2S
    9T$r;; s nano"article radius% Jn the eent that a single nano"article formed a single
    nano'ire s"ontaneously 9'ithout any e&ternal "erturbation;$ then a 1:-6:nm aerage "article
    si)e 'ould form a nano'ire 'ith radius bet'een E and 7:nm 'ith as"ect ratio 1:$ this ha""ens
    'hen jG
    2#
    9T$r; - jG
    2S
    9T$r; goes to )ero% Although this is not 'hat is obsered in our
    e&"eriments$ the reaction is not s"ontaneous 9e&ternal "erturbation is required; and the gro'th is
    due to coalesce and gro'th of nano"article therefore the aerage nano'ire radius obsered is
    5:nm 'ith lengths of u" to half a micron%
    Figure 10: (Lef) Free energy (in KJ/mole) vs nanopar!le ra"i#s $or "i%eren& ra"ii an" aspe!& rao
    nano'ires. (Right) Free energy (in KJ/mole) vs nanopar!le ra"i#s (eeping aspe!& rao !ons&an&.
    References
    7% G% F% Frey$ Rothschild$ C% Sloan$ Rosentseig$ R% Po"oit) Biro and R% Tenne 95::7;%
    Jnestigations of nonstoichiometric tungsten trio&ide nano"articles% 2' Solid State %hem'
    7?5$ 1::%
    5% 3% Daison$ #% !olquhoun 97GE8;% Ultrathin formar su""ort films for transmission
    electron microsco"y 2' Elect' Micros' ,ech% 2* 18-61%
    1% /% Stadermann$ S% 0% Nucheye$ C% Fe'icki$ and S% A% Fetts95:75;% Radiation tolerance
    of ultra-thin Formar films% 0ppl' Phys' Lett% 7:7$ :@7G:E%
    6% C% !% <% S"ence 97GE7;$ E!perimental .igh-resolution Electron Microscopy 90&ford
    Science Publications$ ""58:%
    8% F% Sangaletti$ F% 3% De"ero$ G% Sbereglieri$ B% Alieri$ 3% Bontem"i and S% Gro""elli
    97GGG;% Gro'th of #0
    1
    crystals from #-Ti-0 thin films% 2' %ryst' Bro' 7GE(7GG$ 756:%
    ?% 3% !a))anelli$ !% Ainegoni$ G% /ariotto$ A% Nu)min$ and C% Purans 97GGG;% Fo'-
    Tem"erature Polymor"hism in Tungsten Trio&ide Po'ders and Jts De"endence on
    /echanical Treatments% 2' Sol' St' %hem% 761$ 56D15%
    @% A%N% Sriastaa$ S%A% Agnihotry$ /% Dee"a 95::?;% SolPgel deried tungsten o&ide films
    'ith "seudocubic triclinic nanorods and nano"articles% Thin Solid Films 878 767GP7651%
    E% S% Sood$ P% Gouma 95:71;% Polymor"hic "hase transitions in nanocrystalline binary metal
    o&ides 2' 0m' %eram' Soc', G? Q5R$ 187P186%
    G% Peter /% 0lier$ Ste"hen !% Parker$ Russell G% 3gdell and Frances <% Cones 97GG?;%
    !om"uter simulation of the surface structures of #0
    1
    % 2' %hem' Soc', Haraday ,rans'
    G5975;$ 5:6G-5:8?%
    7:% /% #autelet 95:::;% 3stimation of the Aariation of the /elting Tem"erature 'ith the si)e
    of Small Particles$ on the Basis of a Surface-Phonon Jnstability model% 2' Phys' +4 0ppl'
    Phys% 56$ 161%
    Chapter 2& Moly.denum /rioxide nano4ires .y electrospinning
    8%7% /o0
    1
    3lectros"un nano'ire formation
    Single crystals of ceramic materials in one-dimensional nano'ire mor"hology by a single
    ste" non-catalytic "rocess has been inented and demonstrated by P% Gouma and her grou" Q7R%
    2anofiberous mats hae been "roduced by blend electros"inning 'hich is a bottom u" synthesis
    method Q5R% These com"osite nanofibrous mats are heat treated and after doing so "ure metal
    o&ide nano'ires are formed$ and there e&ist no organic residual material% !ontinuous single
    crystals of e&tremely high as"ect ratio 9nm diameter s mm; are "roduced in this 'ay%
    Such a high as"ect ratio gro'th needs to be analy)ed further$ and main issues need to be
    analy)ed 'ith regards to their mor"hology and structure% The reasons for the gro'th into single
    crystals and gro'th into high as"ect ratio structures$ both need to understood in de"th%
    /etastable to stable "olymor"hic reactions in metal o&ides hae been demonstrated earlier Q1-6R%
    Jn such reactions a critical "article si)e nuclei is initially formed and further the nanocrystalline
    aggregates gro' into "referentially oriented high as"ect ratio structures 'hile retaining
    mor"hology of the original aggregates Q6R%
    The "olymeric fiber 'all structure is im"ortant for determining the mor"hology of
    nanocrystalline aggregates in the sol-gel o&ide in electros"un com"osites 9ref Gouma et al%;% The
    sol-gel com"onent in the com"osite gro's undisturbed until it runs out of material forming into
    single crystal "olymor"hs% Relatie "hase stability of "olymor"hs determine the heat treatment
    conditions$ this is unique for each metal o&ides and yield stable "hase in single crystalline
    nano'ire structures% This 'as first sho'n in our grou" for #0
    1
    system% A PAP-#0
    1
    Q5GR
    com"osite 'as used to electros"un single crystal nano'ires of #0
    1
    $ these nano'ires 'ere
    different from the ones formed in earlier 'ork% Such a "rocess forms ery large as"ect ratio
    nano'ires$ the as"ect ratio is much larger than the earlier formed nano'ires although they hae
    larger diameters than before% This 'as the foundation of the later 'ork done on /o0
    1
    QER in our
    grou"$ and therefore to assess the uniersality of such a system the 'ork done here is also based
    on such a system% Jn such a system a com"osite system similar to PAP-#0
    1
    $ a PAP-/o0
    1
    system is electros"un to form enca"sulated nanofibers$ 'hich are then heat treated to form the
    nano'ires$ similar to ref 7C$ but much different from the 'ork described earlier%
    /o0
    1
    is kno'n for gro'ing in anisotro"ic mor"hologies% The 9orthorhombic "hase; consists
    of distorted edge-sharing octahedra% 0ctahedral layers share edges along the a-a&is Q7::R and
    corners along the c-a&is Q::7R% Along the b-a&is$ the layers are bound by Aan der #aals forces%
    Gro'th along the a-a&is is energetically faorable o'ing to the fact that only one /oP0 bond
    has to be created as o""osed to the c-direction$ in 'hich t'o such bonds 'ill hae to be formed%
    Aarious methods hae been used to crystalli)e different "olymor"hic forms of /o0
    1
    % /o0
    1
    nano"articles hae been synthesi)ed using sol-gel$ hydrolysis of /olybdenum iso"ro"o&ide
    leads to colloidal /o0
    1
    nano"articles 9Figure 6;$ u"on heat treatment these colloidal "articles
    crystalli)e in different "olymor"hic structures Q@$ GR$ metastable U-/o0
    1
    monoclinic structure
    bet'een 6::! to 68:! and stable .-/o0
    1
    orthorhombic bet'een 68:! and 878!%
    0rthorhombic /o0
    1
    'as synthesi)ed by ion beam de"osition Q8$ ?$ @R and as electros"un
    nano'ires QER for gas sensing a""lications% 2anostructured orthorhombic /o0
    1
    $ the stable
    "olymor"h of /o0
    1
    has also been synthesi)ed by Ding et al% Q7:R using thermal o&idation of
    /olybdenum and Fi et al% Q77R synthesi)ed /o0
    1
    nanostructures using an enironmentally
    friendly chemical route% The metastable "olymor"hs$ U-/o0
    1
    monoclinic and h-/o0
    1
    he&agonal
    structures are much more com"licated to synthesi)e as nanostructures% U-/o0
    1
    monoclinic
    nanosheets 'ere de"osited onto silicon substrate using atmos"heric micro"lasma QER% <e&agonal
    /o0
    1
    nanorods 'ere synthesi)ed at room tem"erature by "reci"itation of molybdenum o&ide
    from an ammonium "aramolybdate solution Q71$ 76$ 78$ 7?R$ they 'ere seen to be stable u"to
    @::N$ and transformed to .-/o0
    1
    aboe @::N%
    8%5%Single Cet
    #e synthesi)e ery high as"ect ratio nano'ires of .-/o0
    1
    orthorhombic structure% The
    mechanism of formation of nano'ires is e&"lained% Jt is seen that unlike sol-gel synthesis$
    electros"un nano'ires al'ays gro' in the stable orthorhombic mor"hology no matter the heat
    treatment conditions% Such nano'ires can be used for sensing a""lications% By arying the
    tem"erature of the films de"osited on the substrate different gases can be sensed Q7@R%
    Sol-gel synthesis 'as carried out on the "recursor /olybdenum Jso"ro"o&ide 98K '( in
    Jso"ro"anol$ Alfa Aersar;% Precursor 'as hydroly)ed using distilled 'ater to get :%7m/ solution%
    This solution 'as allo'ed to age for 56 hours% The sol-gel synthesi)ed colloidal "articles 'ere
    mi&ed 'ith :%7 molar PAP solutions in ratios of 7*6 and 7*8% The enca"sulation ma&imi)ed at 7*6
    ratio% The solution 'as electros"un 97ENA oltage+ :%1:hm(min flo' rate+ 7:cm collector to
    needle distance; to get metal o&ide enca"sulated nanofibers 9Figure 89a$ b;;% The aim is to
    minimi)e the amount of material in s"lat form and ma&imi)e the enca"sulation of metal o&ide
    inside the electros"un fibers%
    0igure 11 (a) SEM micrograph of metal o!ide encapsulated electrospun nanofi&ers' (b)
    Moly&denum trio!ide encapsulated inside ele!trospun fi&ers, (!nset) E+S pattern of the
    encapsulated particles'
    To get molybdenum trio&ide nano'ires$ the nanofibers 'ere heat treated in a tube
    furnace% The heat treatment 'as carried out at tem"eratures ranging from 65:! to 8::!% The
    yield of nano'ires 'as obsered 9Figure 8a;% Jt 'as found that the yield ma&imi)ed at 8::!%
    Although still not ideal$ the nano'ires 'ere ery high as"ect ratio 9Figure 8b; 'hich is useful for
    sensing a""lications%
    0igure 1"4 (a) SEM micrograph of heat treated nanofi&ers at #$$%/ (b) SEM micrograph of
    high aspect ratio nanowires
    a) b)
    a) b)
    The nano'ires gre' in high as"ect ratio structures after heat treatment% Preious DS!
    results Q7ER hae sho'n that /olybdenum trio&ide is monoclinic U-/o0
    1
    u"to tem"erature of
    6E8! and then transforms to its stable form orthorhombic .-/o0
    1
    % Although it 'as obsered
    that nano'ires al'ays gre' into the orthorhombic .-/o01 structure no matter the heat
    treatment tem"erature% At 68:!$ figure ?9a; the nano'ires 'ere orthorhombic 9C!PDSD :8-
    :8:E;$ similarly at 8::! 9Figure ?9b;;% Figure ?9c; sho's high resolution T3/ image sho'ing
    the lattice structure of the nano'ires$ the orthorhombic .-/o0
    1
    consists of distorted edge-
    sharing /o0
    ?
    octahedra$ 'hich share edges along the a-a&is Q7::R and corners along the c-a&is
    Q::7R% The measured d-s"acing for a-a&is 'as 1%G@[ and 1%@5[ for c-a&is$ 'hich is in agreement
    to the unit cell "arameters for the aboe crystals aZ1%G?1: [$ bZ71%E8? [$ and cZ1%?G?? [
    corres"onding to the standard C!PDS file :8-:8:E% Jt is kno'n that 9:7:; is the closed "acked
    "lane in the .-/o0
    1
    $ and the gro'th along Q::7R direction has been 'idely documented Q7G$ 5:R%
    0igure 1&3 (a) -anowire growth after heat treatment at 1#$% and (inset) its corresponding
    S0+ pattern/ (b) -anowire growth after heat treatment at #$$% and (inset) its corresponding
    S0+ pattern/ (c) .R,EM image of the nanowire and (inset) its corresponding S0+ pattern'
    8%1%/ulti-4et
    3en though the single 4et technique makes a aluable research tool to e&"eriment on getting
    the best "recursors and "rocess "arameters for nanofiber mat formation of the desired
    configuration$ it has largely "roduced small amounts of nanofibers that hae satisfied the
    engineering curiosity$ rather than offering a "rocessing route for nanofiber manufacturing% Thus
    focus has diersified into high through"ut techniques% Researchers hae "ro"osed arious
    techniques and mechanisms$ enlisted in Table E% Although none so far has seen a""ro"riate for
    easy ado"tion$ mainly due to shortcomings like$ requirement for high oltages in some cases
    Q57R$ requirement for s"ecific material iscosity in others Q5?R% Jt is our belief that an
    electros"inning mechanism closest to traditional electros"inning technique 'hile simultaneously
    increasing the yield to a""ro"riate leels$ in addition to being scalable is the requirement% Thus
    'e "ro"ose a scalable set u" 'ith an o"erating mechanism similar to the traditional set u" 'hich
    "roduces fibers of similar mor"hology% All the "rocess "arameters$ oltage$ 'orking distance$
    flo' rate$ material concentration$ ariable in traditional set u" are also ariable in the scaled u"
    set u"%
    Table 53 Pre(ious attempts to increase production rates of electrospun fi&ers
    Source Collector >oltage Production :ate 4eferences
    Flat disk !ylindrical 88NA for
    initiation+ 7?NA
    'orking
    U" to :%?E6gm(hour :76;
    Porous cylindrical
    tube
    #ire mesh
    ty"e
    5:kA 8gm(hour :77;
    /ulti"le needles Rotating
    solid cylinder
    5:kA U" to :%71Egm(hour :7";
    Graity("ressure
    drien nine 4et
    no))les
    Flat collector 7:kA across all
    nine no))les
    55%8 ml(9cm
    5
    min;
    to 55%8 l(9cm
    5
    min;
    "er 7 cm
    5
    of the
    s"inneret "late
    :71;
    !onical metal 'ire-
    coil
    Flat collector ?:kA U" to 5%@8g(h :7#;
    /agnetic field
    induced
    Flat collector U"to 1:kA 75-fold increase :7?;
    8 no))les 'ith holes
    on the surface and
    conductie fluid
    /oing flat
    'all
    7:-6:kA -- :7@;
    8%1%7% !ase study on PAP and !A fibers
    Polymeric solutions named$ P7$ and P5 'ere used for electros"inning% Solution P7 'as
    :%7m/ "olyinyl"yrrolidone 9PAP+ 9!
    G
    <
    G
    20;n; 'ith an aerage molecular 'eight of 7$1::$:::
    gm(mol 'ith ethanol as the solent% Solution P5 of 7:K cellulose acetate 9!
    ?
    <
    @
    0
    5
    90<;
    1
    -
    n900!!<
    1
    ;n;$ n Z :%1 ; haing a molecular molecular 'eight of 5G$::: gm(mol 'ith a solent
    solution containing acetone and acetic acid% The electros"un sam"les 'ere s"utter coated 'ith
    gold "articles to make them conductie% T3/ 'as "erformed using clam"ed T3/ grid made of
    co""er on C30F 76::F T3/$ a 75:kA soft(bio materials T3/%
    Polyinyl"yrrolidone and cellulose acetate fibers 'ere "rocessed by this noel "rocess%
    They are im"ortant carrier(substrate "olymer systems and are used as model materials in this
    study% Preious 'ork by the authors has e&tensiely researched the "ro"erties of as-s"un mats of
    these systems "rocessed by T23 Q5E$ 5GR% The e&"eriments carried out 'ith the high through"ut
    tool$ "roduced mats 'ith fiber diameter similar to those obtained in T23 haing similar
    "arameters like$ 'orking distance$ flo' rate$ solution concentration and oltage% Figure @9a;$
    E9a;$ sho' the high through"ut nanofibers in com"arison to the nanofibers s"un using T23$
    sho'n in Figure @9b;$ E9b;% /ost of the "rocess "arameters remained unchanged+ Table G enlist a
    com"arison bet'een the T23 and the modified set u" for sam"les P7and P5% Due to larger
    'orking distance and hole si)e the oltage is slightly higher in the case of the modified set u"$ as
    e&"lained in the ne&t section% The fiber mor"hology remained unchanged as can be seen from the
    S3/ and T3/ microgra"hs% Thus 'ith similar "rocess "arameters this scalable set u" can
    "roduce fibers com"arable to T23%
    Table 73 %omparison &etween traditional needle electrospinning and high throughput
    electrospinning for PFP
    P7 P5
    T23 Scaled u" set u" T23 Scaled u" set u"
    Production :%55? g(h 2&36 gDh :%556 gm(hour 2&52 gDh
    Flo' Rate :%:18-:%:68
    ml(min
    :%6-:%8 ml(min :%:18-:%:68
    ml(min
    :%6-:%8 ml(min
    Aoltage 5:kA 58kA 55kA 58kA
    !oncentration :%7m/ :%7m/ 7:K solent 7:K solent
    Source to
    collector
    distance
    7::mm 78:mm 7::mm 78:mm
    Ag% fiber
    diameter
    7::-1::nm 5::-18:nm :%?-7 micron :%E-7%8 micron
    0igure 1)3 (a) .R,EM of .igh-throughput P6 electrospun fi&ers/ (b) SEM of ,-E processed P6
    electrospun fi&ers
    0igure 1,3 (a) SEM of .igh-throughput P7 electrospun fi&ers/ (b) SEM of ,-E processed P7
    electrospun fi&ers
    8%1%5% Process Parameters
    Ascertaining the "rocess "arameter is essential to control the nanofiber mor"hology% To
    do so 'e use the "olymer Polyinyl"yrrolidone 9PAP; 'ith ethanol as the solent% The ceramic
    nanofibers are synthesi)ed using a com"osite of PAP and /o0
    1
    sol-gel% Thus using PAP as a
    reference system to deelo" these "arameters can gie a fair control oer the nanofiber synthesis%
    !a"illary action generated by the needle in traditional needle electros"inning technique is an
    essential com"onent to get enca"sulation of /o0
    1
    sol-gel inside the PAP "olymer%
    Figure G sho's the de"endence of oltage on the nanofiber diameter$ there seems to be a
    "arabolic de"endence$ 'ith fiber diameter smallest at 55k and 1:k$ although at lo'er
    concentration of :%:Em/ there 'as bead formation and at higher oltage of 1:k there 'as high
    distribution of nanofiber diameter as can be seen by larger error bars$ thus 56k 'as chosen for
    /o0
    1
    nanofiber synthesis% Figure G also sho's negligible de"endence of concentration as
    com"ared to oltage to'ards nanofiber diameter% The "roduction rate has a similar "arabolic
    de"endence to oltage and the error bars sho'n are due to the concentration ariation% 0n
    aerage the "roduction rate is 5%8gm(hr%
    Figure 7: 9a-d; sho's S3/ microgra"hs for nanofibers for different concentration and
    oltage$ as can be seen the diameter is more uniform for lo'er oltages as com"ared to higher
    oltages%
    @aA :%:Em/ b 55kA @.A :%75m/ b 55kA
    0igure 1- -anofi&er diameter and production
    rates plotted as a function of (oltage and
    concentration
    @cA :%7m/ b 56kA @dA :%7m/ b 5?kA
    0igure 153 (a*d) SEM micrographs for different (oltages and concentration for PFP fi&ers'
    8%1%1% 2anofiber Synthesis
    Jn this section 'e demonstrate an a""lication of this set u" for "roducing high yield of
    ceramic nanofibers% A com"osite material of "olymer and ceramic sol is electros"un to form high
    as"ect ratio nanofibers of single crystal /o0
    1
    similar to that accom"alished by Gouma et al%
    earlier Q17R% The source disk of the set u" 'as modified from the earlier set u" Q5?R$ the holes
    diameter 'as reduced to i mm as sho'n in figure 7: 9a-d;$ and the holes 'ere "laced at the
    bottom corners of the disk at an angle of 68 degrees% Figure 5 and 1 sho's the schematic of the
    set u" used% The source is constantly re"lenished using a syringe "um" 9Nd scientific; at a
    constant flo' rate% The 'orking distance although ariable$ is ke"t constant at 78cm for this
    study% <igh oltage is a""lied bet'een the source disk and collector cylinder to synthesi)e
    ceramic nanofibers%
    /o0
    1
    nanofiber synthesis is one of the a""lications that such a set u" can be used for% To
    synthesi)e the nanofibers of /o0
    1
    'e electros"in a com"osite material 'ith com"osition similar
    to ref' "6' This resulted in /o0
    1
    sol gel enca"sulated 9in PAP; nanofibers similar to ref' "6% The
    analysis u"til no' suggests the "rocess "arameters need to be modified for this set u" as
    com"ared to that used in ref "6% The oltage used 'as 56k$ 'ith 'orking distance being fi&ed at
    78cm and flo' rate of :%16ml(hour% The "olymer fibers 'ere burned off by heat treating the
    electros"un material at 8:: degree !elsius in a tube furnace for E hours%
    Figure 8 sho's com"arison bet'een the "ost heat treated nanofibers formed by the
    traditional needle set u" similar to earlier study Q17R and those formed by the set u" in this study%
    The figures 77 9a; and 9b; are the S3/ microgra"hs of the nanofiber formed% As can be seen the
    yield as a "ercent of total 'as less but as a quantitatie com"arison to the 'hole 'as ? to E-fold
    higher% This calculation 'as achieed by using the S3/ analysis and 'eight of nanofibers
    "roduced% The 'eight of material synthesi)ed after heat treatment 'as 75-fold higher% The
    gro'th of the single crystal of /o01 nanofibers seems to be as a concentric cylindrical layers of
    fibers forming on to" of each other and gro'ing as layered structures as is eident from figure 77
    9d;$ seen at the to" of the nanofiber%
    @aA /o0
    1
    nanofibers "roduced using
    traditional needle electros"inning
    @.A /o0
    1
    nanofibers "roduced using
    <igh- through"ut electros"inning
    @cA T3/ of /o0
    1
    nanofibers synthesi)ed
    using T23$ 9Jnset; sho's the selected
    area diffraction$ 'ith the "lanes
    labeled for =:7:> )one a&is%
    @dA T3/ of /o0
    1
    nanofibers synthesi)ed
    using high through"ut set u"$ 9Jnset;
    sho's the selected area diffraction$
    'ith the "lanes labeled for =::7> )one
    a&is%
    0igure 173 Electron microscopy comparison &etween the nanofi&ers synthesied &y traditional
    needle setup (a 8 c) and those synthesied &y high througput set up (b 8 d)'
    0igure 164 (a) %rystal structure of orthorhom&ic Mo5" along with one a!is as mar)ed' (b)
    *-Ray diffraction of Mo5" orthorhom&ic nanowires synthesied &y &oth traditional and high
    throughput nanowires, the planes mar)ed are from 2%P+S M$#-$#$A'
    Figure 77 9c; and 9d; sho' the T3/ microgra"hs of a single nanofiber of /o01
    synthesi)ed using traditional needle electros"inning and the high though"ut set u" in this study%
    Jn the inset is the SAD "atterns of each of the nanofibers 'hich sho' there single crystal
    mor"hology% Figure 779c P Jnset; can be inde&ed to the orthorhombic "hase of /o01 9C!PDS
    D:8-:8:E; 'hich is the stable "hase of /o01% The inde&ed "lanes hae been labeled for )one
    a&is =:7:> as sho'n in figure 759a;% Figure 779d P Jnset; is also inde&ed to the orthorhombic
    "hase of /o01 9C!PDS D:8-:8:E;$ the inde&ed "lanes are labeled for )one a&is =::7> as sho'n
    in figure 759a; 'hich is also the gro'th a&is and the long a&is of the nanofiber% Figure 75 9b;
    gies the BRD of the sam"le for both traditional needle and high through"ut setu"% As is eident
    from the shar" "eaks$ both the BRD are of the single "hase$ the orthorhombic one%
    Therefore$ it has been demonstrated that this high though"ut set u" can "roduce high
    yield high quality nanofibers 'ith controllable mor"hology% #e successfully "roduced single
    crystal /o01 nanofibers% The yield 'as much higher at ? to E folds and the mor"hology and
    crystallinity of the nanofibers 'as not com"romised% This could hae im"ortant im"lication for
    e&am"le for "roducing nanosensors for ammonia detection% #ith higher yield of controllable
    nanofibers of orthorhombic "hase of /o01$ the hindrance to slo' "rocessing of nanosensors
    could be oercome%
    References
    7% P% Gouma$ N% Nalyanasundaram$ and A% Bisho"$ T3lectros"un Single !rystal /o01
    2ano'ires for Bio-!hem sensing "robesT$ Cournal of /aterials Research$ 2ano'ires and
    2anotubes s"ecial issue$ 57977;$ ""% 5G:6-5G7:$ 5::?%
    5% N% Sa'icka and P% J% Gouma$ T3lectros"un com"osite nanofibers for functional
    a""licationsT$ C% 2ano"article Research$ E9?;$ ""% @?G-@E7$ 5::?%
    1% P% J% Gouma$ P% N% Dutta$ and /% C% /ills$ TStructural Stability of Titania Thin FilmsT$
    2anostructured /aterials$ 779E;$ ""% 7517-751@$ 7GGG%
    6% P% J% Gouma and /% C% /ills$ TAnatase to Rutile Transformation in Titania Po'dersT$ C%
    Am% !eram% Soc%$ E6 Q1R$ ""% ?7G-?55$ 5::7%
    8% TReactiely S"uttered /o01 films for ammonia sensingT$ A%N% Prasad$ P%J% Gouma$ D% C%
    Nubinksi$ C%<% Aisser$ R%3% Soltis$ and P%C% Schmit)% ,hin Solid Hilms$ 61?$ 2001$ ""% 6?-
    87$
    ?% _/o01 and #01 based thin film conduductimetric sensors for automotie a""lications`$
    A% N% Prasad and P% Gouma% 2' Mat' Sci% 1E$ 2001$ "" 616@ P 6185$
    @% T!om"arison of Sol-Gel and RF S"uttered /o01 Thin Film Gas Sensors for Selectie
    Ammonia DetectionT$ A% N% Prasad$ D% Nubinski$ and P% J% Gouma' Sensors < 0ctuators
    3 G$ 2001$ ""%58-1:$
    E% P% Gouma$ N% Nalyanasundaram$ and A% Bisho"$ T3lectros"un Single !rystal /o01
    2ano'ires for Bio-!hem sensing "robesT$ 2ournal of Materials Research, -anowires
    and -anotu&es special issue$ 57977;$ 2003$ ""% 5G:6-5G7:$
    G% _Study of gas s"ecificity in /o01(#01 Thin Film Sensors and their Arrays`$ Arun N%
    PrasadIs% Phd thesis$ Stony brook uniersity$ May 2002%
    7:% M%P% Ding$ <%B% <uang$ C%<% Duan$ C%F% Gong$ S%G% Oangu$ B%2% Lhao$ O%#% Du%
    _/olybdenum trio&ide nanostructures "re"ared by thermal o&idi)ation of molybdenum`%
    Cournal of !rystal Gro'th 5G6 95::?; 1:6P1:E
    77% Guicun Fi$ Fi Ciang$ Shu"ing Pang$ <ongrui Peng$ and Lhikun Lhang% _/olybdenum
    Trio&ide 2anostructures* The 3olution from <elical 2anosheets to !rosslike
    2anoflo'ers to 2anobelts`% C% Phys% !hem% B 5::?$ 77:$ 566@5-566@8%
    75% _/onoclinic U-/o01 nanosheets "roduced by atmos"heric micro"lasma* a""lication to
    lithium-ion batteries`% Daide /ariotti$ <enrik Findstrom$ Arumugam !handra Bose and
    Nostya 9Nen; 0striko% -anotechnology 2006 7G 6G81:5
    71% _Fo'-tem"erature synthesis of mor"hology controlled metastable he&agonal
    molybdenum trio&ide 9/o01;`$ !%A% Ramana$ A%A% Atuchin$ J%B% Troitskaia$ S%A%
    Gromilo$ A%G% Nostrosky$ G%B% Sau"e% Solid State %ommunications Aolume 76G$ Jssues
    7P5$ <anuary 2007$ Pages ?PG$
    76% _3lectron microsco"y characteri)ation of he&agonal molybdenum
    trio&ide 9/o01;nanorods`$ !% A% Ramana$ J% B% Troitskaia$ A% A% Atuchin$ /% Ramos$
    and D% Ferrer$ 2' Fac' Sci' ,echnol' 0 5E$ 200$ @5?
    78% _Jnestigation on structural$ thermal$ o"tical and sensing "ro"erties of meta-stable
    he&agonal /o01 nanocrystals of one dimensional structure`$ Angamuthura4
    !hithambarara4 and Arumugam !handra Bose% 3eilstein 2' -anotechnol% 5$ 20$ ""
    8E8P8G5$
    7?% _Fo' tem"erature fabrication of he&agon sha"ed h-/o01nanorods and its "hase
    transformation`$ Dhage$ S% R%+ <assan$ /% S%+ Oang$ 0%B% Mater' %hem' Phys' 776$ 2007$
    "" 877P876%
    7@% P% Gouma$ A% N% Prasad and /% Stanaceic$ TSelectie nanosensor deice for e&haled
    breath analysisT$ C% Breath Res%$ 8$ :1@77:$ 5:77%
    7E% Nrithika Nalyanasundaram$ Phd Thesis$ Stony brook uniersity$ 5::@%
    7G% _Aa"our "hase gro'th of orthorhombic molybdenum trio&ide crystals at normal "ressure
    of "urified air`$ <%!% Leng% Cournal of !rystal Gro'th 7E? 97GGE; 1G1-6:5
    5:% _Fo'-tem"erature synthesis of large-scale single-crystal molybdenum trio&ide 9/o01;
    nanobelts`$ Biao-Fin Fi$ Cun-Feng Fiu$ and Oa-Dong Fi% A""l% Phys% Fett% E7$ 6E15
    95::5;
    57% 2 / Tho""ey$ C R Bochinski$ F J !larke and R 3 Gorga% -anotechnology$ 55
    1681:7920A&
    55% 0% 0% Dosunmu$ G% G% !hase$ #% Nata"hinan$ D% <% Reneker% -anotechnology$ 77$
    775192003A%
    51% B% Ding$ 3% Nimura$ T% Sato$ S% Fu4ita$ S% Shiratori% Polymer$ 68$ 7EG89200!A%
    56% S% A% Theron$ A% F% Oarin$ 3% Lussman$ 3% Nroll% Polymer$ 6?$ 5EEG92002A%
    58% B% #ang$ <% 2iu$ T% Fin$ B% #ang% Polym' Eng' Sci%$ 6G$ 78E592007A%
    5?% A% F% Oarin$ 3% Lussman% Polymer$ 68$ 5G@@9200!A%
    5@% P% <eikkilv$ A% <arlin% Polymer Letters* 19@;$ 61@P668 92007A%
    5E% A%/% A)ad and P%J% Gouma% Encyclopedia of -anoscience and -anotechnology, .'S'
    -alwa (Editor), 0merican Scientific Pu&lishers* 76$ 1:7-15G920A%
    5G% N% Sa'icka and P% J% Gouma% 2' -anoparticle Research* E9?;$ @?G-@E792003A%
    1:% S% Sood$ S% Diya$ P%Gouma$ 2ournal of nanoengineering and nanomanufacturing !$ 7P?$
    95:76;%
    17% P% Gouma$ N% Nalyanasundaram$ and A% Bisho"% 2ournal of Materials Research,
    -anowires and -anotu&es special issue 2977;$ 5G:6-5G7:$ 5::?%
    Chapter 3& Discussion and future 4or#
    The strength of the internal bonds in the crystal structure corres"ond to there stability%
    Some crystals could hae ery stable bonds 'hereas others may only be held by Aan Der #aals
    forces% Solubility of crystals in a "articular solent is also an indication of its stability% The less
    the stability of the crystal stucture$ more the solubility% This is due to higher "olarity% This is the
    reason for the amor"hous materials being higher in solubility than the crystalline "hases% Such is
    also the reason for metastability arising in "olymor"hs of metal o&ides% This is because een if
    certain conformations of crystals maybe stable at one tem"erature$ heating the crystal could
    loosen the bonds$ as a result other crystal conformations may become o"timal% As discussed
    earlier in cha"ter 1$ due to nanoscale certain additional forms of energies that 'ere negligible in
    bulk "hase become significant% Jn terms of solubility$ this results in nanocrystalline materials
    being more soluble in a "articular solent than its bulk counter"art Q7R%
    ?%7%Polymor"hic transitions and critical "article si)e
    3&"erimental obserations confirm that for nanocrystalline metal o&ides "hase
    transformation occurs ia different mechanism at the nano scale$ such as reersal in "hase
    stability at small "article si)e is obsered in some systems$ melting tem"eratures are generally
    lo'er in nano"articles$ transition tem"eratures to high tem"erature "hases are often lo'er$ 'hile
    transition "ressures to high "ressure "hases can be higher or lo'er% 0ne of the reasons that
    nano"articles sho' such differing "ro"erties is because of the significantly higher surface areas
    at nano scale 'hich makes the contribution from surface energies much more significant Q5R%
    Thermodynamic as"ects of the "hase transformations at nanoscale hae been elaborated in
    cha"ter 1% Researchers hae time and again seen nano scale "olymor"hic transitions 'hich differ
    from bulk "hase$ some results about the same hae been elaborated ahead%
    Jn the case of Sn05 studies Q1$ 6R hae sho'n that the high "ressure orthorhombic Sn05
    "hase require "ressures of u"to 78 kbar at 7:@1N for its synthesis% But$ for nanometer "article
    si)e this high "ressure orthorhombic structured Sn0
    5
    has been obsered at ambient "ressures%
    Although$ Famelas Q8R 'ho synthesi)ed nanocrystalline tin dio&ide by mechanical milling of tin
    mono&ide "o'ders argued that the formation of orthorhombic "hase at nano scale is not a si)e
    drien behaior$ but the formation of the orthorhombic "hase

    is faored by a nucleation barrier
    'hich is lo'er than

    that for cassiterite$ nanoscale tin mono&ide is o&idi)ed to form tin

    dio&ide at
    ambient "ressure% This finding 'as based on an earlier result Q?R 'here the authors reduced the
    "article si)e to as lo' as 5%8nm but orthorhombic "hase 'as not obsered%
    Titania is kno'n to transform from anatase "hase to rutile Q@$ ER "hase at 76@1N 'hen in
    bulk si)e$ ho'eer this transition occurs at tem"eratures as lo' as ?@1N for Enm nanocrystals of
    anatase QG$ 7:R% /ore recently$ the ne' "olymor"h of titanium dio&ide$ Ti0
    5
    9B;$ has been
    synthesi)ed as nano'ires Q77R by facile solothermal route% The mechanism of "hase
    transformation in o&ides changes 'ith decreasing "article si)e% 3&"eriments hae confirmed that
    this is true% /ost "hase transitions in binary metal o&ides differ for nanocrystals% Belo' 'e
    "resent eidence collected from the literature%
    The .-Fe
    5
    0
    1
    to ,-Fe
    5
    0
    1
    "hase transformation at nanoscale 'as studied by Oen et al% Q75R$ 'ho
    obsered a critical "article si)e of about 58nm aboe 'hich .- Fe
    5
    0
    1
    'as more stable and belo'
    'hich u" to 8nm ,- Fe
    5
    0
    1
    'as more stable% Further$ as the tem"erature increased from 8@1N to
    about @::N$ there 'as coarsening of grains and .- Fe
    5
    0
    1
    'as more stable% The decrease of
    surface enthal"y 'ith increasing metastability of the bulk "olymor"h leads to crossoers in
    enthal"y 9and also free energy; of "olymor"hs at the nanoscale% Thus$ ,- Fe
    5
    0
    1
    9maghemite;
    becomes stable 'ith res"ect to .- Fe
    5
    0
    1
    9hematite;%
    The monoclinic to tetragonal transformation in Lr0
    5
    'as also found to be si)e de"endent
    'hen Garie and Goss Q71R obsered si)e de"endence of "hase transformation tem"erature and
    found the reci"rocal crystallite si)e is a linear function of the transformation tem"erature%
    !oncluding that the 9unquenchable; high tem"erature tetragonal Lirconia "hase that is stable
    only aboe 7661N$ e&isted indefinitely at room tem"erature in nanocrystals of about 7:nm
    diameter%
    Jn nanocrystalline #0
    1
    . Y "hase transition Q76$ 78R occurs at much higher tem"eratures
    than the bulk% Both of these transition hae been "roen to be si)e drien$ Gouma et al% Q76R
    sho'ed ho' si)e effects caused the formation of Y-#0
    1
    at tem"eratures aboe room
    tem"erature% Arai et al% Q78R had first obsered the "resence of Y "hase at RT in #0
    1
    % Further$
    they also concluded that as the "article si)e decreases$ the ratio of Y-#0
    1
    increases%
    The cubic-Jn
    5
    0
    1
    to he&agonal-Jn
    5
    0
    1
    "hase transition under ambient conditions is su""osed to
    be faored 'hen a foreign atom / 9Fe
    1W
    $ Sn
    6W
    ; Q7?$ 7@R 'ith a smaller ionic radius than indium is
    inserted into the cubic indium o&ide net'ork in bulk conditions% The formation of he&agonal
    Jn
    5
    0
    1
    under ambient conditions 'ithout any do"ing is unusual% A study Q7ER demonstrated the
    de"endence of "hase transformation nano"article si)e of indium o&ide on "article si)e of Jn00<
    "recursor% The authors could ary the si)e of the indium o&ide nanocubes by sim"ly changing the
    amount of surfactant used% They obsered that the formation of small Jn00< nano"articles 'as
    an indis"ensable ste" to'ards the formation of indium o&ide nanocubes and obtained indium
    o&ide nanocubes 'ith aerage si)e of 7:nm%
    ,-Al
    5
    0
    1
    to .-Al
    5
    0
    1
    "hase transformations is also seen to be si)e de"endent% .- Al
    5
    0
    1
    corundum structure is the stable "hase in bulk but at the nano scale ,-Al
    5
    0
    1
    is more stable% This
    'as confirmed by 2arotsky and /c<ale Q7GR 'hen using high tem"erature o&ide melt
    calorimetry for nanocrystalline Al
    5
    0
    1
    $ it 'as obsered that ,-Al
    5
    0
    1
    9the "hase obsered for nano-
    si)ed "articles; is more stable in enthal"y than nano"hase .-Al
    5
    0
    1
    9corundum;$ others hae also
    synthesi)ed ,-Al
    5
    0
    1
    Q5:-55R and hae been able to obsere similar results%
    Such differing "hase transformations due to nano si)e are not 4ust seen in "olymor"hic metal
    o&ides$ but in general in all metal o&ides$ "olymor"hic or not$ for e&am"le the Room tem"erature
    bulk "hase of !u conerts to cubic !u
    5
    0 by o&idation at ery high tem"eratures of greater than
    75::N Q51R$ if the tem"eratures are still increased the monoclinic !u0 forms% !ontrary it 'as
    obsered Q56R that !u
    5
    0 nano"hase starts to form aboe 851N$ and !u0 starts to form beyond
    ?51N$ the "article si)e at 851N and ?51N 'ere 7? and 1:nm res"ectiely% Jt is obsered that
    cubic !u
    5
    0 is more stable at the nano dimensions also Q58$ 5?R than the monoclinic !u0 due to
    the increase ionic nature caused by reduction in the "article si)e% !u
    5
    0 nanocrystals at lo'er than
    bulk tem"eratures hae been "re"ared by ion irradiation Q5@R$ s"uttering Q5ER$ reduction route
    Q5GR$ etc%
    Therefore$ "olymor"hic transitions are much different at the nanoscale$ the higher
    inherent energies inoled lo'er the conditions of tem"erature and "ressure required for "hase
    transformation% Thus$ as can be seen the literature is filled 'ith such e&am"les of "olymor"hic
    transitions$ therefore the aim of this study 'as to establish theoretical background so that any
    metastable to stable "hase transitions could be "redicted before they are obsered%
    Table 64 Models for phase transformation &eha(ior dependence on particle sie
    -iterature models /arget Materials :esultant Euantity 4ef
    Surface-area-difference
    model
    /etallic nanocrystals /elting Tem"erature lo'ering+
    acancy formation energy
    "$
    !ohesie energy model /etallic nanocrystals !ohesie energy "6
    Thermodynamic analysis
    of "hase stability
    Titania s"ecific Particle si)e and tem"erature
    of transformation
    "7
    2one&tensie
    thermodynamics
    a""roach
    2ano"articles 9in
    general;
    Su"ersaturation ratio
    9Solubility;
    6
    Thermodynamics of
    catalytic kinetics
    2ano"article
    catalysts
    2ano"article si)e ""
    As can be seen in table 7:$ the literature doesnIt "roide any generali)ed model that
    could "redict the critical "article si)e for nanocrystalline binary metal o&idesI metastable to
    stable "hase transformations% Thus the heuristic a""roach deelo"ed in this 'ork$ has formulated
    a useful basis to "redict the critical nucleus si)e% Jt has been kno'n for quite a 'hile that there
    e&ists a "oint of infle&ion at 'hich the instability in the metastable system of a binary metal
    o&ide become too high for the material to remain in that state Q16R% By combining three im"ortant
    factors 9surface energy affects$ internal "ressure affects and "article sha"e affects;$ yields the
    most accurate formulation of this critical "article si)e for the metastable to stable "hase
    transformation% A mani"ulation of surface and interfacial energies become driing forces leading
    to "olymor"hic transitions% During the transformation "rocess$ binary metal o&ides reach a
    critical "article si)e at the nucleation stage at 'hich the internal "ressures and surface energies
    are sufficiently high that one "olymor"hic "hase begins to crystalli)e from another 'ith much
    smaller "erturbation in the form of e&ternal a""lied tem"erature%
    As described in the aboe sections$ t'o different 'ays can be deduced to take adantage
    of the model sho'n in cha"ter 1% Due to the im"ortant addition of the sha"e considerations$ the
    heuristic a""roach 'as modified to take into consideration the sha"e change in addition to the
    metastable to stable "hase transformation%
    r
    c
    U\.
    9T;Z l9A
    m
    .
    %,
    .
    P A
    m
    U
    %,
    U
    W 5%f
    s
    U
    %A
    m
    U
    -5%f
    s
    .
    %A
    m
    .
    ;m(9j
    k
    <
    f
    .
    9T; - j
    k
    <
    f
    U
    9T;; P .(5 9?%7;
    jG
    7
    9T$r; - jG
    5
    9T$r; Z 9A7 P A5;%, W
    95%f
    s
    (r;%
    9A7 P A5; W .%rS
    k
    <f(5%r
    9?%5;
    Thus such an a""roach can be used to either directly calculate the critical "article si)e$
    equation ?%7 or by deducing the free energies inoled such an a""roach can "redict the "hase
    transformation behaior$ equation ?%5 if certain e&"erimental conditions are kno'n%
    ?%5%Phase transitions and #0
    1
    nano'ire synthesis
    #0
    1
    e&ists in an array of stable and metastable "hases Q18R$ from triclinic 'hich is lo'
    symmetry to higher symmetrical structures like tetragonal "hase% This is mainly due to the
    electronic structure of #0
    1
    $ 'hich is a three dimensional net'ork of corner-sharing #0
    ?
    octahedra$ and ariable o&idation states% Synthesis of these "hases in nano'ire mor"hology is
    highly desirable Q1?R% The mechanism of massie Q1@R nucleation and gro'th aboe a critical
    "article si)e of metastable "hase has been "reiously established Q1ER% 3&"erimentally such
    transformations hae been obsered in titania by Gouma et al% Q1G$ 6:R as did the nano'ire
    formation obsered for the orthorhombic "hase of /o0
    1
    Q65R system%
    3arlier 'ork by our
    research grou" has also "roduced monocrystalline #01 nano'ires Q67R%
    Gu et al% Q61R
    synthesi)ed single crystal nano'ires of he&agonal #0
    1
    by a tem"late-less and direct
    hydrothermal method% Similarly Fu et al% Q66R synthesi)ed the nano'ires of monoclinic "hase of
    #0
    1
    by thermal ea"oration on a silicon substrate% This monoclinic "hase of tungsten trio&ide is
    the stable "hase and has been obsered to be highly sensitie and selectie to 2itric 0&ide Q68R%
    Thus high yield and through"ut synthesis of nano'ires of monoclinic "hase of #0
    1
    $ due to its
    higher surface area$ 'ould hel" im"roe u"on the sensitiity and selectiity%
    The most im"ortant contribution of this 'ork is the ability to synthesi)e the material in a
    single ste" onto any desired substrate% The unique "ro"erty of self-catalysis and synthesis under
    the electron beam irradiation of the "recursor is the key to gro'th of nano'ires% Such a synthesis
    lends su""ort of the earlier theoretical 'ork Q6?R% The monoclinic nano'ires are a result of the
    metastable 9cubic-#0
    1
    ; to stable 9monoclinic-#0
    1
    ; "hase transition%
    A cubic to monoclinic "hase transition has been "reiously obsered in nano"articles of
    Re01 'hich is an isostructural material to #01 Q6@R% A lo'ering of e&ternal "erturbation
    required 9"ressure in that case; 'as re"orted to be much lo'er than that required for the bulk
    Re01% There has been no direct obseration of cubic to monoclinic "hase transformation in
    tungsten trio&ide nanocrystals$ 'hich may be due to the high energies inoled in the
    transformation in the bulk "hase% Although a cubic to orthorhombic "hase transformation has
    been obsered Q6ER$ as both orthorhombic and monoclinic "hase of tungsten trio&ide are stable
    "olymor"hic structures%
    0igure "93 Schematic descri&ing the growth of monoclinic tungsten trio!ide nanowires from
    nanoparticles of cu&ic phase in a stepwise fashion' Step 6 shows the starting nanoparticles
    which ha(e a radius of &etween "$ to 1$nm' 0s an electron &eam is shown onto these
    nanoparticles the particles start to grow into nanowires as shown in step 7' 0s the nanoparticles
    get consumed they start to coagulate and grow into nanowires' Step " shows how these
    nanoparticles grow from preferred direction to form randomly oriented nanowires &efore &eing
    totally consumed and forming highly aligned nanowires of tungsten trio!ide as shown in step 1'
    ,he whole process may ta)e a few micro seconds to complete once the nanoparticles recei(e the
    reJuired amount of energy'
    Figure 5: sho's the schematic of the "ro"osed gro'th of the nano'ires% The nucleation
    and gro'th of the stable "hase can either occur randomly throughout the crystal by doing so at
    s"ecific defects or crystal edges or such a gro'th can occur in a diffusie manner like a front
    moing for'ard at a fast rate% Jn the gro'th of nano'ires in this study$ it a""ears that "hase
    change occurs ra"idly by a moing front that results in a massie Q1@R grain gro'th and radical
    sha"e change% The metastable "hase "articles on the "ath of the moing front are consumed and
    transformed$ as sho'n in figure 5:% As the nano'ire gro'th "roceeds the nano"articles coalesce
    and get consumed 'hich gies rise to ery long thin nano'ires%
    ?%1%Polyty"ism in nano'ires
    Polyty"es are essentially a "olymor"h$ although such indiidual "olymor"hs differ in crystal
    structures in one dimension only% Such "olyty"ic structures are ery common in geological
    settings Q8:R% A 'idely quoted e&am"le for "olyty"ism is Silicon !arbide Q6GR% Polyty"es are
    common in metal o&ides$ for e&am"le Jn
    5
    0
    1
    "olyty"es 9I5
    7
    1$ Ia
    3
    $ and R
    3
    ; hae been
    studied and there is a "ressure induced transition bet'een the three Q87R% As can be seen from
    Jn
    5
    0
    1
    "olyty"es e&am"le$ the "olyty"es essentially differ in the crystal structure$ indicated by
    different s"ace grou"s% The crystallogra"hic character is thus an im"ortant feature in the study of
    "olyty"es$ and "eriodicity is fundamental to it%
    Thus by controlling "olyty"ism 9crystal structure at atomic leel;$ 'e can adance
    successfully in using such materials in a""lications like single-electron memories Q?5R$ single-
    molecule sensors Q?1R and nano'ire lasers Q?6R% Semiconducting material can be made more
    controllable and highly efficient$ for e&am"le controlled "olyty"ic gro'th of 'urt)ite nano'ires
    'as studied by !aroff et al% Q?8R% #urt)ite "olyty"es 'ere obsered in another study Q??R% A
    ty"ical light and dark bands 'ere obsered in images taken using the transmission electron
    microsco"e$ similar to our nano'ires 9Figure E;% Jt 'as obsered from high resolution imagery
    that the bands 'ere "er"endicular to the gro'th direction$ 'hich is also similar to our
    obserations% There 'as streaking obsered in the electron diffraction "attern 'hich is ty"ical for
    stacking faults and t'inning as e&"lained earlier%
    The nano'ires "roduced in this 'ork are e&"ected to be "olyty"ic in character% The formed
    nano'ires are one-dimensional structures 'hich "otentially gro' as this front ra"idly gro's out
    of the cubic "hase into the "referred =::7> monoclinic direction in a non-"eriodic manner% The
    streaking ty"e diffraction "attern obsered$ figure E9Right; and figure G9Jnset; lend credibility to
    this argument Q85R% Jt is im"ortant to note that in electron microsco"y "eriodic re"eats of only a
    fe' units can be seen% A material is essentially described by t'o indicators$ com"osition and
    structure% /aterials haing different "eriodicities are e&"ected to hae different structures and
    should be dealt 'ith se"arately as indiidual "olyty"es%
    Jnitial FFT microgra"h analysis is sho'n in figure 57% The nano'ire in figure 57 9right; is
    "eriodic$ and the obsered FFT a""ears to sho' a dot "attern% #hereas the FFT "atterns in figure
    57 9left; sho' the usually obsered nano'ires$ 'here streaking is common% Thus initial
    obserations "oint to the fact that the non-"eriodicity in the lattice structure of the nano'ires is
    the reason for the streaking obsered%

    0igure "14 HH, images of the nanowires/ (Left) Nsually o&ser(ed nanowire/ (right) periodic
    nanowire structure'
    As defined earlier$ "olyty"es are essentially a "olymor"h 'hich differ in crystal structure in
    one dimension only$ eidence of the same has been obsered% Figure 55 sho's the com"arison
    bet'een the electron diffraction "atterns for differently oriented nano'ires% The streaking goes
    a'ay 'hen the nano'ires are oriented e&actly at a )one a&is% This may be due to the non-
    "eriodicity of the lattice s"acing in the ( direction as sho'n in the figure 55% Although the dot
    "attern is indeci"herable due to numerous dots in one direction% Jn contrast if the nano'ire is
    "erfectly "eriodic in both directions$ and is oriented at a )one a&is then the e&"ected diffraction
    "attern is obsered%
    A randomly oriented
    nano'ire
    2ano'ire oriented "erfectly
    on a )one a&is
    A "eriodic nano'ire on )one
    a&is =::7>
    ;igure 22* Analysis of electron diffractions of differently oriented nano'ires$ "ossibly sho'ing
    the reason for the streaking "resent in the diffraction "atterns%
    ?%6%Future 'ork
    The future 'ork should concentrate on follo'ing directions$
    7% Scanning Transmission 3lectron /icrosco"y route for nano'ire formation$ should be
    accom"lished%
    The electron beam has been seen to affect the materials being analy)ed% The beam affects
    the material in arious forms$ some of 'hich can be heating affect$ ioni)ation damage$
    electrostatic charging$ etc Q81R% Similar to electron beam lithogra"hy based systems$ this 'ork
    demonstrates another usefulness of the electron beam% Researchers hae used Scanning
    Transmission 3lectron /icrosco"e based systems to 'rite lithogra"hy "atterns Q86R% This is
    encouraging as such a system mirrors closely 'ith the obsered scenario in this 'ork% Such an
    ST3/ based method could be useful$ as the resist adhesion difficulties are obsolete% /oreoer
    such an a""roach 'as recently demonstrated Q88R for "roducing ultra-thin nano'ires of /oS
    5
    by
    an ST3/ based system% The 'ork also 'as a result of a "hase transition$ though from a
    semiconducting to a metallic "hase due to the energy im"arted from the beam% The nano'ires
    that are formed due to irradiation of the electron beam inside a T3/$ can also be formed by
    using a Scanning transmission electron microsco"e 9ST3/; route% A lithogra"hy system requires
    im"artation of energy by the beam on to a material under a resist thereby e&"osing it to form a
    "attern% Some of the im"ortant factors for the deelo"ment are$ feature si)e$ 'hich are of the
    order of 7: to 5:nm in our case and the "oint-s"read function 9PSF;% Additionally getting the
    resist right is one of the ma4or challenges in such a system$ therefore im"ortantly the absence of
    resist in our system is an adantage%
    5% !rystallogra"hic consideration for #0
    1
    nano'ires$ should be e&"lored%
    Jt is "ro"osed that 7D "late like "lanes oriented in non-"eriodic bands$ due to "olyty"ism$
    this causes multi"le s"ots on the diffraction "attern because of arying lattice "arameter on (
    direction 'hile the lattice "arameter remains constant in the u direction% There hae been arious
    obserations of "olyty"ism% Geological sciences are filled 'ith minerals that occur under
    differing conditions% Figure 51 9ada"ted from ref' 8?; sho's the crystal structure of one such
    mineral$ there is non-"eriodicity in the crystal structure although there is "eriodicity inside the
    crystal 'here lattice s"acing of 7E$ G and 86 angstrom can be obsered% Therefore such a mineral
    is "olyty"ic in character%
    0igure "&3 (0dapted from ref' #?) Electron microscope micrograph of a typical mineral
    specimen showing polytypism at the lattice structure le(el'
    0ur nano'ires are "olyty"ic too$ due to the non-"eriodicity% Although more
    crystallogra"hic analysis needs to be done in order to find the "eriodicity "resent inside the
    crystal% This 'ould be an im"ortant contribution in crystallogra"hy of #0
    1
    as such "olyty"es
    hae neer been obsered as "er our kno'ledge in #0
    1
    monoclinic "hase% Jnde&ing these
    "olyty"es could be a "ro4ect in itself%
    1% U"grading the high through"ut electros"inning set u"$
    The needleless$ multi4et electros"inning described in this 'ork hae clear adantages
    oer the other 'orks done in the field of high through"ut electros"inning% A ty"ical edge
    electros"inning Q8@R has adantage of "roducing higher yield due to high number of 4ets$ though
    the high initiating oltage required is a ma4or dra'back 'hen considering ease of ada"tation$
    additionally the iscosity of material being s"un also has to be taken into consideration% The ti"-
    less electros"inning Q8ER has the adantage of eliminating the difficulty of "olymer clogging
    though it is hard to estimate the "olymer 4et number and the 'orking oltage could be rather
    high% /ulti"le needle electros"inning Q8GR has the adantage of ease of scaling u" to increase
    "roduction rate% Though the 4et "aths are greatly affected by e&ternal field and columbic
    interactions$ and the "roduced nanofibers are non-uniform due to re"ulsie forces% 0ther source
    modifications such as ste""ed "yramid sha"ed s"inneret Q?:R and conical 'ire coil Q?7R hae
    their disadantages$ ranging from easily blocked 4et holes to instability of 4ets and high 'orking
    oltage%
    The setu" designed in this 'ork attem"ts to oercome most of these challenges and has the
    follo'ing adantages oer the aboe mentioned 'orks$
    Relatiely lo' 'orking oltage
    Due to the relatiely lo' 'orking oltage and no s"ecific initiating oltage requirements$ this
    set u" can be easily ada"ted to the traditional setu"% This is achieed due to the cleer "lacement
    of holes 'hich hel"s "roduce ca"illary action and the dro"lets are formed inde"endently of the
    oltage requirements in contrast to the edge electros"inning
    <igh "roduction rate and scalable technology
    The number of 4ets "roduced in this 'ork are controllable therefore e&"ected yields are
    achieed% By changing the dimension or addition of additional source disks the technology is
    easily scalable%
    All the "arameters can be indiidually aried
    Another im"ortant factor for ease of ada"tion and 'ider engineering sco"e of the technology
    is that all the "arameters that are aailable for modification in a traditional setu" can also be
    modified in this setu"% Aoltage$ flo' rate$ 'orking distance and material concentration can be
    indiidually modified%
    A range of materials can be electros"un
    Due to the addition of a flo' controller$ iscosity of the "olymer is not one of the
    consideration for the "rocess% This means that almost any material that could be electros"un on
    the traditional setu" can also be synthesi)ed on this setu"% This has clear adantages 'hen
    considering com"arisons 'ith edge and ti"less electros"inning%
    0igure ")3 Rotating source dis) design'
    The addition of a motor 'ould add another "arameter to the design and 'ould aid in the
    generation of e&tremely long fibers% !ou"led 'ith thin nanofibers$ the higher as"ect ratio
    achieed could be useful in arious "olymeric a""lications% Such a "roision has already been
    "roided in e&isting design% T'o im"ortant considerations for such a modification are$ one$
    maintaining constant contact bet'een rotating disk and electrical contact$ 'hich can be achieed
    by haing a cylindrical electrical contact 'hich is attached to the source disk% T'o$ ball bearing
    mechanism should be added to the source re"lenishing "i"e so that the disk maybe free to rotate
    'hile the source is constantly re"lenished%
    References
    7% Pierre Fetellier$ Alain /ayaffre and /ireille Turmine% 2' Phys'4 %ondens'
    Matter 7 61?55G 95::@;%
    5% C% /% Blakely% Jntroduction to the Pro"erties of !rystal Surfaces% 9Pergamon Press$
    0&ford$ 7st edn%$ 7G@1;%
    1% 0% Berger$ #%C% Fischer and A% /ele% C% /ater% Sci* /ater% in 3lectr% 78$ 6?195::6;%
    6% N% Suito$ 2% Na'ai$ O% /asuda% /aterials Research Bulletin 7:9@;$ ?@@97G@8;%
    8% C% Famelas% Cournal of A""lied Physics G?977;$ ?7G895::6;%
    ?% <% Deng$ F% C% Famelas$ and C% /% <ossenlo""% !hem% /ater% 78$ 565G95::1;%
    @% Nirk-0thmer 3ncyclo"edia of !hemical Technology$ 0nline edition$ 9#iley$ 2e' Oork$
    5:::; "% 75%
    E% Oali Fi and Takamasa Jshigaki% C% !ryst% Gro'th 565$ 87795::5;%
    G% /% R% Ranade$ A% 2arotsky$ <% L% Lhang$ C% F% Banfield$ S% <% 3lder$ A% Laban$ P% <%
    Borse$ S% N% Nulkarni$ G% S% Doran $ and <% C% #hitfield% 2ational Acad Sci% GG9Su""l 5;$
    ?6@?95::5;%
    7:% P% J% Gouma and /% C% /ills% C% Am% !eram% Soc% E691;$ ?7G95::7;%
    77% Geng #ang$ Miang #ang$ #u Fu$ and Cinghong Fi% C% Phy% !hem% B$ 77:961;$ ""
    55:5G95::?;%
    75% Fu Su Oen$ #ei !hien !hen$ Canne /in Oang$ and !hen Tsung <ong% 2ano Fetters 591;$
    56895::5;%
    71% R% !% Garie$ /% F% Goss% C% /ater% Sc% 57$ 758197GE?;%
    76% F% #ang$ A% Teleki$ S% 3% Pratsinis$ and P% J% Gouma% !hem% /ater% 5:$ 6@G695::E;
    78% Arai /%$ <ayashi S%$ Oamamoto N% and Nim S% S% Solid State !ommun% @89@;$
    ?7197GG:;%
    7?% Gurlo A%$ Janoskaya /%$ Barsan 2% and #eimar U% Jnorg% !hem% !ommun% ?$
    8?G95::1;%
    7@% Nim B%!%$ Nim C%O%$ !hang S%<% /ater% Res% Soc% Sym"% Proc% 8E7$ 5@95:::;%
    7E% !hang <oon Fee$ /insik Nim$ Taekhoon Nim$ Ansoon Nim$ Cungsun Paek$ Cu #ook
    Fee$ Sung-Oool !hoi$ Nyu'on Nim$ Cong-Bong Park$ and N'angyeol Fee% C% Am% !hem%
    Soc% 75E 95G;$ G15?95::?;%
    7G% C% /% /c<ale$ A% 2arotsky$ A% C% Perrotta% C% Phys% !hem% B 7:796;$ ?:197GG@;%
    5:% G% Paglia$ !% 3% Buckley$ A% F% Rohl$ R% D% <art$ N% #inter$ A% C% Studer$ B% A% <unter$ C%
    A% <anna% !hem% /ater% 7?$ 55:95::6;%
    57% A% J% /amchik$ S% A% Nalinin and A% A% Aertegel% !hem% /ater% 7:$ 186E97GGE;%
    55% B% F% Song$ P% Mu$ <% P% Oang$ B% <e and G% L% Miu% C% !ent% South Uni% Technol% 75$
    81?95::8;%
    51% A%0 /usa$ T Akomolafe and /%C !arter% Solar 3nergy /aterials and Solar !ells 87$ 91-
    6;$ 1:897GGE;%
    56% Sheng <an$ <ong-Oing !hen$ Ouh-Bin !hu and <an !% Shih% Cournal of Aacuum Science
    b Technology B 519?;$ 588@95::8;%
    58% B% Balamurugan$ B% R% /ehta$ S% /% Shia"rasad% A""lied Physics Fetters @G97G;$
    17?@95::7;%
    5?% A% R% Palkar$ Pushan Ayyub$ Soma !hatto"adhyay$ and /anu /ultani% Phys% Re% B
    8198;$ 57?@97GG?;%
    5@% B% Balamurugan$ B% R% /ehta$ D% N% Aasthi$ Fouran Singh$ Akhilesh N% Arora$ /%
    Ra4alakshmi$ G% Raghaan$ A% N% Tyagi and S% /% Shia"rasad% Cournal of A""lied
    Physics G59?;$ 11:695::5;%
    5E% Tane4a P%$ !handra R%$ Baner4ee R% and Ayyub P% Scri"ta /ater%$ 66$ 7G7895::7;%
    5G% #%L% #ang$ G%<% #ang$ B%S% #ang$ O%C% Lhan$ O%N% Fiu and !%F% Lheng% Ad% /ater% 76$
    ?@95::5;%
    1:% # < Mi$ / P #ang$ / Lhou and # O <u% C% Phys% D* A""l% Phys% 1E$ 765G95::8;%
    17% #%<% Mi$ /%P% #ang and G%O% Bu% !hemical Physics Fetters 1@5$ ?1595::1;%
    15% <eng)hong Lhang and Cillian F% Banfield% C% /ater% !hem% E$ 5:@197GGE;%
    11% Dmitry Ou% /ur)in% !hemical 3ngineering Science% ?6 98;$ 7:6?-7:85 95::G;
    16% P%J%Gouma$ P%N% Dutta and /%C%/ills$ _Structural Stability of Titania Thin Films`%
    2anostructured materials 77QER$ 751797GGG;%
    18% TPolymor"hism in nanocrystalline binary metal o&idesT$ S% Sood$ P%Gouma$
    2anomaterials and 3nergy$ 592/35;$ 7-7895:71;%
    1?% S% Barth$ F% <% Ramire)$ C% D% <olmes$ and A% R% Rodrigue)$ _Synthesis and a""lications
    of one-dimentional semiconductors`% Pro% /at% Sci% 889?;$ 8?1 95:7:;%
    1@% Anil A% Airkar$ Pomin Su$ Nuan-Long Fung% /assie Transformation in Bismuth -0&ide
    based !eramics 95::?;% /et /ater Trans A 1@A$ E58
    1E% S% Sood$ P% Gouma 95:71;% Polymor"hic "hase transitions in nanocrystalline binary metal
    o&ides C% Am% !eram% Soc%$ G? Q5R$ 187P186%
    1G% P%J% Gouma$ /%C% /ills 95::7;% Anatase to Rutile Transformation in Titania Po'ders C%
    Am% !eram% Soc% E691;$ ?7G%
    6:% P%J% Gouma$ P%N% Dutta$ and /%C% /ills 97GGG;% Structural Stability of Titania Thin Films
    2anostruct% /ater% 779E;$ 7517%
    67% N%/% Sa'icka$ A%N% Prasad$ P%J% Gouma 95::8;% /etal 0&ide 2ano'ires for Use in
    !hemical Sensing A""lications% Sensor Fetters 1$ 7-8%
    65% P% Gouma$ N% Nalyanasundaram$ A% Bisho" 95::?;% 3lectros"un Single !rystal /o01
    2ano'ires for Bio-!hem sensing "robes 2' Mat' Res' 57977;$ 5G:6-5G7:%
    61% Lhan4un Gu$ <uiqiao Fi$ Tianyou Lhai$ #ensheng Oang$ Oongyao Bia$ Oing /a$ Ciannian
    Oao$ _Farge-scale synthesis of single-crystal he&agonal tungsten trio&ide nano'ires and
    electrochemical lithium intercalation into the nanocrystals`$ Cournal of Solid State
    !hemistry 7E:97;$ 5::@$ GE-7:8%
    66% Dong Ou Fu$ Cian !hen$ <uan Cun !hen$ Fi Gong$ Shao Lhi Deng$ 2ing Sheng Bu$ and
    Ou Fong Fiu$ _Raman study of thermochromic "hase transition in tungsten trio&ide
    nano'ires`% A""l% Phys% Fett% G:$ :67G7G 95::@;%
    68% P%J Gouma and N% Nalyanasundaram$ TA Selectie 2anosensing Probe for 2itric 0&ideT$
    A""l% Phys% Fett% G1$ 5667:5 95::E;%
    6?% S% Sood$ P% Gouma$ TPolymor"hic "hase transitions in nanocrystalline binary metal
    o&idesT% C% Am% !eram% Soc% G? Q5R$ 187-18695:71;%
    6@% Nanishka Bis'as$ D A S /uthu$ A N Sood$ / B Nruger$ B !hen and ! 2 R Rao 95::@;%
    Pressure-induced "hase transitions in nanocrystalline Re01% C% Phys%* !ondens% /atter
    7G$ 61?576
    6E% !s% Bala)si$ /% Farkas-Cahnke$ J% Notsis$ F% Petras$ C% Pfeifer 95::7;% The obseration of
    cubic tungsten trio&ide at high tem"erature dehydration of tungstic acid hydrate% Solid
    State Jonics 767P765$ 677P67?%
    6G% S% 2akashima and <% <arima% Physica Status Solidi 9a;$ 7?5 97;$ 1GP?6 97GG@;%
    8:% Andrei A% Shiryae$ #illiam F% Griffin$ 3mil Stoyano$ <iroyuki Nagi% Gth Jnternational
    Nimberlite !onference 3&tended Abstract 2o% GJN!-A-:::@8$ 5::E%
    87% S% Lh% Nara)hano$ P% Raindran$ P% Aa4eeston$ A% Ulyashin$ T% G% Finstad$ and <%
    F4ellwg% Phy% Re% B @?$ :@875G 95::@;
    85% A Baronnet$ L! Nang 97GEG;% Phase Transitions* A /ultinational Cournal 9Taylor b
    Francis;%
    81% R%F% 3gerton$ P% Fi$ /% /alac 95::6;% Radiation damage in the T3/ and S3/% /icron
    18$ 1GGP6:G
    86% Aitor R% /anfrinato$ Fihua Lhang$ Dong Su$ <uigao Duan$ Richard G% <obbs$ 3ric A%
    Stach and Narl N% Berggren% 2ano Fett% 71$ 7888X788E 95:71;%
    88% Oung-!hang Fin$ Dumitru 0% Dumcenco$ Oing-Sheng <uang and Na)u Suenaga2ature
    2anotechnology G$ 1G7P1G? 95:76;%
    8?% Peter R% Buseck and Sumio Ji4ima% American /ineralogist% ?:$ @@7-@E6 97G@8;
    8@% 2% /% Tho""ey$ C% R% Bochinski$ F% J% !larke and R% 3% Gorga% _3dge electros"inning for
    high through"ut "roduction of quality nanofibers`$ 2anotechnology$ Aol% 55$ 1681:7$
    5:77
    8E% De)hi #u$ Biao"ing <uang$ Biting Fai$ Daoheng Sun$ and Fi'ei Fin% _<igh Through"ut
    Ti"-Fess 3lectros"inning ia a !ircular !ylindrical 3lectrode`$ 2anoscience and
    2anotechnology$Aol% 7:$ 7-?$ 5:7:
    8G% S%A% Theron$ A%F% Oarin$ 3% Lussman$ 3% Nroll% _/ulti"le 4ets in electros"inning*
    e&"eriment and modeling `Polymer$ Aol% 6?$ 5EEG-5EGG$ 5::8
    ?:% Guo4un Ciang$ Sai Lhang$ Biaohong Min$ _<igh through"ut of quality nanofibers ia one
    ste""ed "yramid- sha"ed s"inneret`$ /aterials Fetters$ Aol% 7:?$ 8?-8E$ 5:71
    ?7% Bin #ang$ <aitao 2iu$ Tong Fin$ Bungai #ang$ _2eedleless 3lectros"inning of
    2anofibers #ith a !onical #ire !oil `$ Polymer engineering and science$ Aol% 6G$ 78E5$
    5::G
    ?5% 2ilsson$ <% A%$ Thelander$ !%$ Froxberg$ F% 3%$ #agner$ C% B% b Samuelson$ F% A""l% Phys%
    Fett% EG$ 7?17:7 95::?;%
    ?1% Duan$ B%$ <uang$ O%$ Agaral$ R% b Fieber$ !% /% 2ature 657$ 567 P566 95::1;%
    ?6% #ang$ #% U%$ !hen$ !%$ Fin$ N% <%$ Fang$ O% b Fieber$ !% /% Proc% 2atl Acad% Sci% USA
    7:5$ 15:E P1575 95::8;%
    ?8% P% !aroff$ N% A% Dick$ C% Cohansson$ /% 3% /essing$ N% De""ert and F% Samuelson% 2ature
    2ano% 6$ 8: 95::G;%
    ??% Oang Ciang$ Biang-/in /eng$ Ci Fiu$ Lhi-Ro <ong$ un-Sing Fee and Shuit-tong Fee%
    Ad% /ater% 78$ 77G8 95::1;%
    A""endi& A% !om"arison bet'een bulk and nano "hases
    ,a&le 6$4 %omparison &etween &ul) and nano for same phase and different conditions for
    temperature and pressure
    Metal
    Oxide
    at
    am.ien
    t
    conditi
    ons
    "ul# phase Nano Phase 4ef
    Phase
    Conditions
    of
    temperature
    and pressure
    Phase
    Critical
    particle
    si,e
    /emperature
    !r0
    5
    . 7 atm b RT
    to 6@1N
    . 1:-E:nm ?51N 6, 7
    !r
    5
    0
    1
    !orund
    um
    Phase
    7 atm b RT
    to 6@1N
    !orundu
    m Phase
    2anorods U"to 7:@1N ", 1
    Fe
    5
    0
    1
    . W , G11N . W , 1:nm @71N #
    , @@1-G11N , 1:nm to
    8nm
    8?1-?@1N ?, @, A
    Bi
    5
    0
    1
    V G75-7:G@N V 8:-?8nm Belo' ?51N C, 6$, 66,
    6", 61
    y ?:1-G51N y @nm 6@1-?51N C, 6$, 67
    References
    7% Ou% Nu)netsoa$ C% S% de Almeidab$ F% Dubroinsky$ R% Ahu4ab$ S% N% N'onb$ J%
    Nantor$ A% Nantor$ and 2% Guignotc% C% of A""% Phy% GG98;$ 88195::7;%
    5% S% Bis'as and S% Ram% !hem% Phys% 1:?97-1;$ 7?195::6;%
    1% P%Pascal$ 2oueau traitea de chimie minearale 9/asson$ Paris$ 7G8G; Aol% 76$ "% 7@7%
    6% Miang <an$ Fi4un #u$ Aaron Stein$ Oimei Lhu$ Cames /ise'ich$ and Cohn #arren%
    Ange'% !hem% Jnt% 3d% 68$ ?88695::?;%
    8% Bisheng Oe$ Dongsheng Fin$ Lhengkuan Ciao and Fide Lhang% C% Phys% D* A""l% Phys% 17$
    5@1G97GGE;%
    ?% 2% Randrianantoandro$ A% /% /ercier$ /% <erieu and C% /% Greneche% /ater% Fett% Aol%
    6@91;$ 78:95::7;%
    @% P Ayyub$ / /ultani$ / Parma$ Ar Palkar and R Ai4ayaraghaan% C% Phys% !* Solid State
    Phys% 57$ 555G97GEE;%
    E% Fu Su Oen$ #ei !hien !hen$ Canne /in Oang$ and !hen Tsung <ong% 2ano Fetters 591;$
    56895::5;%
    G% <%A% <ar'ig$ Phd% Thesis$ State Uniersity Utrecht$ 7G@@%
    7:% P% Shuk$ <% D% #iemhzfer$ U% Guth$ #% Gz"el and /% Greenblatt% Solid State Jon%
    EG$ 7@G97GG?;%
    77% 3ric # Bohannan$ !hristo"her ! Caynes$ /ark G Shumsky$ Culie N Barton and Cay
    A S'it)er% Solid State Jonics 71797-5;$ Cune G@95:::;%
    75% Oongfu Miu$ Dongfang Fiu$ Cinhu Oang$ and Shihe Oang% Ad% /ater% 7E$ 5?:695::?;%
    71% !% !% <uang$ J% !% Feu$ and N% L% Fung% 3lectrochemical and Solid-State Fetters E96;$
    A5:695::8;%
    76% Anilkumar$ Renu Pasricha and A% Rai% !eramics Jnternational 17$ EEG95::8;%
    A""endi& B% !rystalline Structures
    Higure 7#4 (a) Structure 64 Rutile-type ,etragonal/ (&) Structure 74 Per(os)ite-type/ (c)Structure
    "4 %orundum-type Rhom&ohedral/ (d)Structure 14 %a%l7-type 5rthorhom&ic/ (e) Structure#4
    Rh75"
    A""endi& !% Jnternal "ressure calculations
    For the internal "ressure calculations for cylindrical surfaces$ the s"herical liquid dro"let
    should be re"laced 'ith a cylindrical surface%
    0igure "-3 0 liJuid droplet with radius OrP, a hypothetical cylindrical droplet with radius OrP and
    height OhP'
    Jnstead of a half s"here$ 'e hae a half cylinder as the dro"let$ thus$ modifying la"lace-
    young equation$
    rP
    in
    %A Z 9edge length;%9surface tension; 9!%7;
    rP
    in
    9s%r%h;(5 Z 9sr W h;%f
    s
    9!%5;
    rP
    in
    Z 97(h W 7(s%r;%5%f
    s
    9!%1;
    A""endi& D% Free energy due to "article sha"e calculations
    Due to lack of literature data on the alue of .$ 'e 'ill consider it similar for both cylindrical
    and s"herical "articles$ but the 7(r term 'hich stems from the Area(Aolume term is altered for
    considering the cylindrical sha"e of the nano'ires% Thus$ for cylindrical "article sha"e%

    jGG9T$r; Z .%r
    k
    <f%9A(A; Z .%r
    k
    <f%95(h W 5(r; 9D%7;
    A""endi& 3% Per mole conersion of surface energy(tension and
    surface stress terms%
    The olume of single unit cell of cubic tungsten trio&ide$ can be calculated using the lattice
    constants gien in the C!PDS file D67-:G:8$ 'hich comes out to be 8%75 B 7:
    -5G
    m
    1
    and
    monoclinc tungsten trio&ide$ can be calculated using the lattice constants gien in the C!PDS file
    D61-7:18$ 'hich comes out to be 5%77 B 7:
    -5E
    m
    1
    % Therefore number of molecules in an aerage
    s"herical "article of 6:nm radius and in an aerage cylindrical "article of 5:nm radius and
    8?:nm length can thus be calculated%
    A
    m
    Z /olar Aolume of nano'ires or nano"articles(mole
    A
    m
    Z /olar surface area of nano'ires or nano"articles(mole
    Nanoparticle calculations
    2umber of "articles in a gien olume of aerage nano"article
    Z Aolume of s"herical "article(olume of single unit cell{number
    of molecules "er unit cell
    Z 5%?E B 7:
    -55
    ( 8%75 B 7:
    -5G
    Z 8%51 B 7:
    ?

    2umber of moles in a olume of an aerage nano"article
    Z 8%51 B 7:
    ?
    ( ?%:51 B 7:
    51

    Z E%?E B 7:
    -7E
    moles
    A
    m
    92S; Z /olar olume of an aerage nano"article
    Z 5%?E B 7:
    -55
    ( E%?E B 7:
    -7E
    Z 1%:E B 7:
    -8
    m
    1
    (mole
    2umber of surface "articles in a gien surface area of aerage nano"article
    Z Surface area of a s"herical "article(surface area of one face of unit
    cell{number of molecules "er unit cell
    Z 5:%7 B 7:
    -78
    ( 71%E B 7:
    -5:
    Z 7%68? B 7:
    8
    2umber of moles in a surface area of an aerage nano"article
    Z 7%68? B 7:
    8
    ( ?%:51 B 7:
    51
    Z 5%65 B 7:
    -7G
    Am 92S; Z /olar surface area of an aerage nano"article
    Z
    5:%7 B 7:
    -78
    ( 5%65 B 7:
    -7G
    Z E%1 B 7:
    6
    m
    5
    (mole
    F(P@/*rA Z Pin%AmZ
    95%f
    s
    2P
    (r;%A
    m
    Z 9E%18 B 7:
    @
    C(m
    1
    ; % 91%:E B 7:
    -8
    m
    1
    (mole; Z 2&25 G<Dmole
    F(S@/*rA Z Am%, Z 9
    E%1 B 7:
    6
    m
    5
    (mole
    ;%97%?@ C(m5; Z 16&3 G<Dmole
    Nano4ire calculations
    2umber of "articles in a gien olume of aerage nano'ire
    Z Aolume of cylindrical "article(olume of single unit cell{number
    of molecules "er unit cell
    Z 1%11 B 7:
    ?

    2umber of moles in a olume of an aerage nano'ire
    Z 1%11 B 7:
    ?
    ( ?%:51 B 7:
    51

    Z 8%85 B 7:
    -7E
    moles
    A
    m
    92#; Z /olar olume of an aerage nano'ire
    Z 5%87 B 7:
    -57
    ( 8%85 B 7:
    -7E
    Z 6%86 B 7:
    -6
    m
    1
    (mole
    2umber of "articles in a gien surface area of aerage nano'ire
    Z Surface area of a cylindrical "article(surface area of one face of unit
    cell{number of molecules "er unit cell
    Z ?%5 B 7:
    -76
    ( 8%E B 7:
    -7G
    Z 7%:@ B 7:
    8
    2umber of moles in a surface area of an aerage nano'ire
    Z 7%:@ B 7:
    8
    ( ?%:51 B 7:
    51
    Z 7%@@ B 7:
    -7G
    Am 92#; Z /olar surface area of an aerage nano'ire
    Z
    ?%5 B 7:
    -76
    ( 7%@@ B 7:
    -7G
    Z 1%8 B 7:
    8
    m
    5
    (mole
    F(P@/*rA @N0A Z
    Q97(h W 7(s%r;%5%f
    s
    R%A
    m Z 9;
    % 96%86 B 7:
    -6
    m
    1
    (mole; Z 2&!2 G<Dmole
    F(S@/*rA @N0A Z Am%, Z 9
    1%8 B 7:
    8
    m
    5
    (mole
    ; % 9:%?58 C(m5; Z 26&52 G<Dmole
    A""endi& F% /echanism behind the <igh through"ut electros"inning
    The set u" described in section 5%7%1 aids in the "roduction of ery high yield of nanofibers%
    Jt is also im"ortant to note that such a design is easily scalable after addition of additional disks%
    Therefor the u""er limit as far as the yield is concerned is limitless% Although it is im"ortant to
    reali)e the mechanism behind the formation of the nanofibers% Jn this section 'e describe using
    electric field analysis$ geometric analysis the reasons for such im"roed yields and the
    e&"lanation for the "arameters used%
    0igure "5 (a) +roplet formation at the surface of the metallic dis)/ (b) 0s the droplet grows
    a&o(e the critical sie, it forms into a conical Eet/ (c) ,his Eet gets solidified as nanofi&ers at the
    cylindrical collector'
    0igure "73 Multiple Eet formation on the dis) surface'
    Figure 5?9a; sho's ho' the dro"let forms on the surface of the metallic source disk% As
    the dro"let reaches a critical si)e it is stretched into a conical 4et$ Figure 5?9b;$ similar to T23$
    this 4et solidifies onto the collector cylinder$ Figure 5?9c;% The flo' rate is oer an order of
    magnitude higher than the T23$ and in combination 'ith the multi4et "rocess$ figure 5@$
    significantly im"roes the "roduction rate% The main dra'back hindering the multi4et
    electros"inning "rocesses is the deterioration of local electric field at the needle ti" Q7$ 5R%
    0igure "63 ,he electric field distri&ution, (a) &etween the outer collector cylinder and source
    dis)/ (&) on the surface of the source dis)'
    3lectric field models 'ere generated to model the electric field distribution% A soft'are
    "ackage !0/S0F| /ulti"hysics 'as used for electrostatic field calculations% Figure 5E9a;
    illustrates the electric field distribution bet'een the outer collector cylinder and the source disk%
    Jt sho's that the side 'here the terminals 'ere connected had more intense field on the outer
    cylinder$ 'hich 4ustifies 'hy higher concentration fibers 'ere collected on this side% Jn future
    designs to obtain a more uniform fiber distribution$ the terminals 'ould be connected at four
    distinct locations around the outer cylinder to hae a more uniform distribution of oltage%
    Figure 5E9b; sho's the electric field distribution around the disk% Due to this uniformity in the
    distribution a disk like structure 'ith holes is a better alternatie to multi"le needles set u"%
    2umber of holes is a critical "arameter for the "rocess% Too many holes 'ould lead to
    oerla""ing of taylors cones forming double fibers 9Figure 5G9Jnset;; and too fe' 'ould lo'er
    the effectie yield increase% Thus o"timum number of holes need to be calculated%
    0igure &93 Beometric interpretation of the electrospinning process, (Inset) showing the dou&le
    fi&er formation in the Eet o(erlap region'
    !ircle A! in figure 5G re"resents the disk 'ith 56 equidistant holes$ the fluid 4et shoots
    out and then forms a conical 4et starting at "oint B$ an imaginary circle B! is dra'n$ . is the 4et
    angle$ 6:%@ degrees and because .
    o
    is an angle subtended by the arc at the circumference of the
    circle B!$ its alue is 5:%18 degrees% Because ! is the center of the collector dome$ the length of
    the segment subtended can be calculated% The "ercent of oerla" is the ratio of the total length
    coered by the 4ets and the actual circumference of the collector surface%
    0igure &13 Plot of theoretical yield (g8h) (s num&er of holes and loss of yield due to Q o(erlap
    (s num&er of holes'
    This is "lotted in figure 1:$ along 'ith the e&"ected theoretical yield for increasing
    number of holes$ the "lot of yield is "arabolic as there 'ill be an effectie loss of efficiency due
    to oerla""ing fibers% #ith 56 holes there is an acce"table 1:K oerla" and the yield is at the
    higher end of the gra"h% Unlike T23 there is no ca"illary action inoled in this set u"% The
    ca"illary action is re"laced 'ith the internal "ressure generated inside the disk 'hich hel"s to
    "ush the liquid out of the holes% Thus using taylors e&"ression Q1R for the critical oltage$
    A
    c
    5
    Z 96<
    5
    (F
    5
    ;%9:%77@{s{R{,;%l ln95R(F; P 7%8m
    9F%7;
    This e&"ression can be more sim"ly 'ritten as$
    A
    c
    Z 95%<(F;%}!%R
    9F%5;
    #here ! is a constant consisting of the surface tension and natural logarithmic terms%
    Thus the alue of F can be a""ro&imated as the diameter of the source disk$ and the radius$ R of
    the tube is 7mm in this set u"% Plugging in the electrode distance alues of 78:mm and 7::mm
    for our set u" and T23 res"ectiely$ 'e get the ratio of the oltages for our scaled u" set u" and
    T23$
    A
    c
    9Scaled set u"; ( A
    c
    9T23; Z 7%?8
    9F%1;
    #hich e&"lains the slight increase in the required oltage$ although this increase 'ould
    be true in an ideal system% 2ot all the holes s"un in our e&"eriments$ thus requiring a lesser
    increase in the critical oltage%
    References
    7 S% A% Theron$ A% F% Oarin$ 3% Lussman$ and 3% Nroll% Polymer 6?$ 5EEG-5EGG92002;%
    5 0%0%Dosunmu$ G%G% !hase$ '% Nata"hinan$ and D%<% Reneker% -anotechnology 7@$ 7751-
    775@92003;%
    1 G% J% Taylor$ Proc' Royal Soc' Lond% 5E:$ 1E1 973!;%

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