Synthesis Mechanism of Nano Ba TO, Particles at Low Temperature by Molten Salt Method? use Hv Le, Hu Soox Suns", Danes Hux Yeo! Guo Hun Fla” and Sass Naive? ‘Advatwd Materials Conveigence Division, Kives Institute nf Corumie Fngincering & Technolog Seoul IS 80, Republic of Koren rea Fite of Mierias Science 331 Chamgncnders, Chanywon, Gyeow jpariment of Materials Scenes axl Engineering. Korea Univerily, Sect! 136-701, Repuinc of Korea 77, Wigitabo 10-g11, Geumeheon-a, 41-831, Republic of Kovea *Coeresponingsuthor: Fux: 482 232820700, Een: hsbin@kicen rok oaNrRopwen1oN Ba¥iO.,a representative fermeleciric material. 18 used in various eloctromics industries, Recemmly in onder to create a thinner dielectric layer hased in rhe mend of making slectonie ‘components tke MLCC more light weight nd smaller in size, ‘muiny stdies to applynato BaTiO. patiles are being vondacted Although broad studios on sintering and diclecteie propertics tre in demand with tbe expansion of nano diclectsic particle application, the synthesis and contrl of the ano particles is nat yet convenient, so there are no suflicient reports availahve ‘Monufuctoring, methods of BaTiO, powder, incleting hyn ‘thermal synthesis’, oxalate method ang soll phase method fare mainly used in the industry. Various methods 10 muse svathesize BaTiO. particles of 150 na, have been eomaier ialized. However. there is no cleur synthesis method for dispersed BaTiOy particles below approimately 20 nu, as well a6 no suificient research results repuried.In particule, fescurch on nano purticl synthesis using the olin salt miethonl” thet synthesizes nano BaTIO. particles through the meastaze abscrptfon of water under the low termperanate ol round 1S0%C aad atmospheric pressure is lacking. ‘Therefore, in his stay, the treads hesed on the synthesis time at low temperature using the molien salt meihead were ‘evaluated and thenano HiuTiO. of aprimary parce size below 2 nm und reproducibility was synthesized, Also. atvechanistn hat allows the syntuess of nano BaTiO, particles atlow tempe= ature where salt does not melt and prusiices nati patcles is Lobe presented, The vatiation in nao BaliO: shape according to the synthesis time way observed through both the electron microscopy and analysis of the electron miceoseumny after ‘utiing a cross section using FAB. This makes the shape and ‘composition of the «ait and reno BaliO, directly observable. Based on these results, the synthesis process of uano BeTIO., will be explained, ‘The base matecial used were RaCO. (09 %, Dassung € & MCo. Ltd. Keven), TiO; (09°%,N & A Materials Co. Ine., USA). KOH (85-100, Dagjung C& MCo. Led, Korea) and KCI (98 %, Dusiung C & M Co, Lid. Korea), The synthesis retiod of nano BaTiO, was the molten salt melt reported bey Park eal The nil raters used were the aforementiomect ‘Pesca 4 5" Insert Syiposan wn Application of Chena sad Anaiyiem TeshnOabis W NovkarTadavics Re ACY SUL Daaleon KG4126 Tes etal pase material powder 10 mix BaCOs und THO at the mole faction of 1] and for the molten salt, KOH-KCL was mixed fat the mole fraction of 1:), Then, the mixed stating materials dnd molten salt was mixed at the mole frscuon of 1-25 and placedin a crucible where the tempecanme was ised 10 150°C dt the rate of 10 °Chnia, The ervcible temperature was main tained at 150°C Toe 1, 5 and LO und then cooled to synthesize nano BATIOs, The svutliesied BaTiO; powder was cleaned with distilled water more than 3 times, Phuse analysis wa conducted tsing XID and the particle shape was observed nsing FF SEM (SM. 6700F, Jeol, Japan). order co observe the nano ByTiO, synthesis mechanism. the sal! powder was tut using PUB when the sall was not cleanetl and the cross section was observed using an electron microscope. Fig. | shows the FF-SEM images of the base powder materials BaCOs and TiO, as well a5 the synthesized namo RaMiO., The pusticle size of BuC0,, 1 shown in Hip. (2), 500 nm and the pasticle siee of THO; was approximately 10 fam, as shown in Fig. 1(b). When using 30. in the o#cer of a Few unutredl nn, the dissolution rats of the salt is Tow and previous experiments found that sufficient syathesis did not dbecue As arestlt, mosdertouse base materils of a maxirnun Sspecitie surface aren, commercial TiO: nan particles were tise, as shown in the figure’. However, it was fou hat the paxticles were severely agglomerated. Fig. (e) shows the nano ‘BaTiO, synthesized using the TIO, nano particles 36 the hase ‘matesinl. The particle size was observed ro be approximately below 21) nm amd were vdserved to be agglomerated as wel However the pimaty particles could he relatively easy ident lied through observation, which are tioughLto be the eau of it ugelomeration caused by the sai cleaning process Met, SEM image stesare carter a sa is results auxoeding to the ynbesstime. In Fig. Ya, the peaks of the unreacted terials BuCO, andTiO; were observed forthe case of} hsynthesis at $C aid it could be seen that the BaTiO) peak is not deve oped, This is though to be w result of tbe heating duration Fig. 2is the XRD phase ana Asien J. Chan Inert (8) ° 2 8 9 30 © 70 BD uk, 0) 3 ay diction pier of powder: ue stn a (30°C whet ee 1 TH Sy tons rand it being too short Vor sufficient dissolution ofthe base material owadcr inthe salt asthe syathesix inne was shor. tnLig. b>, ‘whica the synibesis malatenanee time was inereased to SOUS. the peak of the ungeacted BaCO was almost worexistent nd the'TiOs pouk was reduced. The developmeat of the synthesized atid peak was observed. However, the BsTiOs peak also tot mewsared in a distinet forty of intensity bot rather tuppeared as an unstable paitern. Thissignifies poor crystallinity of the synthesized nano BaTiOs", Finally, iis observed in Fig. 2(¢) with « synthesis time of (( i tata stable BaliOs phuse was formed, but in the 20 fo region, weak peaks for the unreacted BaCO, and TiO, were observed. This odservation fs thous] (© he thc unreacted rounder of the base material powder duc 10 the local non-uniformity in the moisture absorption amotmi, even though the ebsorption of moisture in the ai by the st causes syuttests at low Lensperatures, Fig, 3 shows she salt powder surface observed using E- SEM accoiding tothe synthesis time with te salt not cleaned Tn Fig. 3a), which shows the | h synthesis time at 150 lage amp of salt ith a smooth surface and sm agglomeration tof Ki nm oner particles can be observed together irom the XD phase analysis cesalts of Fig. 2, it can be deterwined ‘thatthe sana! nanto parce ore unreacted TiO: and as no S00) ‘nm order BuCO; particles were observed it wuy thought that the BaCO. is capully being dissolyed iat te sak. For the cave of te Sh synitacis ime shoven in Fig, 3). sre was a anion Formation of small particles that seem tobe Ba'FiOs nuclei on the sul surface. This phenomenon is predicted to he Ue form tia of nuclei ia the extraction process ofa new phase with tne supersaturation ofthe bae maveriul within the Lud salt The Salt powder aller 10 hof synthesis a showaln Fig. He) Ws found thatthe nuclei Jormed on the salt surface grew to larger sized particles, However, these particles formed on the salt surface 1 not of separated and inJeperacat particles, but ucts attached! to. lange sat particle, Ik was predicted that when the salt is cleaned, euch pastiels would separate. shown in Li. 16), Alo, based on the ergstl strctare change of Fig. 2and the salt sunfuce shape change of Fig. 3, il was estimated that the synuliesis of navio BuT3O, of low temperatures requires synuhiesis time of 10.Vil 26.Ne, 13.2014 2. SEM ngs, of application Mele at met with eat ne Fig. 4 is a disgram proposed according fo the synthesis time based om the above results, For the established molten sall method, synthesis has w be conducted ar remmperatares sahove 4€0)°C where salt mets, However in thik studs, synthe sisozeuired al 150°C: This was Gus tothe absorption of ucis- (ure in the air by the salt caring the mixing process between the saan hase materials. The absorbed moisture by the sal, ‘as shown in Fig. 4(a), also formed a thin oxalate coating layer tn the salt surface, ‘The basis for this conclision was thal the salt was not sulficienty dissolved overall based on the panicle state being mainisined te a ceruiin degree. Also, when the {emperatare isinereased inthis state, BuCO, Which dissolves better wih salt, can be dissolved hy the oxalate Layee ax showa, inFig. tbl. THO. which slso has alow sohnbility can gradually dissolve fo react within the salt, 1s shown in Fig, (0) to res inthe synthesisof nano B40, atthe dissolved oxalate coating layer ofthe salt surface. ) co, ‘ an eee "* + esto, ‘ithe ie: (a) Th B19.) 1h ‘To verify ihe presented diagram, [18 was used wo first cut the cross section of the salt and thon the sal particle suriuce using FE-SEM. Thisis shown in Fig, S. The inside of thoeross Syahcsis Mechanism of Nano BatiO, Panis at Low Tempastore by Molien Slt Metbidl 4127 Hy. SEM imogss of aB-prpace oeaseat Uf oye sal section eu sall was uniform and the image was in agreemect ‘with the prediction of Fig. 4 that nano particles ate not syithe= sired inside the salt. in addition, like the diagram presenta, uniform and sepamted nano BeTiO. particles below 20 n with nuclei formed are food only on the salt surface snd it was observed that layers of the particles were formed, This signes that syncs preoeeds with satin astate of no melting ‘overall at 150°C an the result of Figs, 2 and 3 confirms tne ‘overall mechanism of Fig. 4 ‘Conclusion Using the molten salt method, nano BaTiO, was gynthe. Sized at 150°C for over 10h with the synthesized paiticie size being lower than 20 nm, In order to identity the mechanism of nano BaTiO: synthesis at low temperatures, FIR was used to cout the craks section of the synthesized salt. Then, FE-SEM. ‘as ued 10 observe the salt surface, sevealing a layer of nano BaTiO, formed 20 nen below the salt surface. Based on the ‘observations, thisstucy proposed a mechanism of nano BaTiO. synthesis at temperatures below the meling point, This is due \e the formation ofa coating Tayer of dissolved KOH through theabsomption of moisture and ihe reaction of the base materials BaCO, and THO> atthe Hquid coating layer | IL Kish: Mizu una. Chait JA oe, AB |e 2D Hennings, :Roveeic and H.Shusisashe, J.B Conn Soy 107 LIM) 9.3, Wad, Yas, 1: Moshiag Sat Nan HL, Kakernet an Trururisd dp Poe, 42st Ty Ne. 9B) 8H CN 4, MI Bnscghi ML ssl Bhscygln aad Atos Ae Cor, Sie, 88,2514 23 5. Cid Yamgans, HCazoms HK ane M.S Kees, 3500 O40) 619, Pak DoH. terme, $6. Ne Mo Lim J-¥ Mad J-¥ Pa 1 Koyean Che, Sues $3,781 2009), 3. KMD, Gu ILS Shi, DIL Veo H5 hen, 25,3015 (23), 30, Feat eC Moa toson, BL, Garver, MOM. Leek and BE Rint dn Conte Sey 78, 2959 (1996) 8. GA Wilsison sa WH. Mall Auta Wot 10. BLE: Ware aud BAL AvebaC Apr, Pic 1 WA Waves, vg Mer Dns 8147 1999), 12. 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