Detection of the onset of nanocrystallization by calorimetric and magnetic measurements

De ec ion o he onse o nanoc ys alliza ion by calo ime ic and magne ic measu emen s J. S. Blázquez, V. F anco, C. F. Conde, A. Conde, and S. Ro h Ci a ion: Jou nal o Applied Physics 97, 044308 (2005); doi: 10.1063/1.1849826 View online: h p://dx.doi.o g/10.1063/1.1849826 View Table o Con en s: h p://sci a ion.aip.o g/con en /aip/jou nal/jap/97/4? e =pd co Published by he AIP Publishing A icles you may be in e es ed in Magne ic pe meabili y o Si- ich (FeCoNi)-based nanoc ys alline alloy: The mal s abili y in a wide empe a u e ange J. Appl. Phys. 113, 17A310 (2013); 10.1063/1.4794718 Magne ic ield d i ing cus om assembly in (FeCo) nanoc ys als Appl. Phys. Le . 89, 033508 (2006); 10.1063/1.2222254 S uc u al, magne ic, and magne os ic ion beha io s du ing he nanoc ys alliza ion o he amo phous Ni 5 Fe 68.5 Si 13.5 B 9 Nb 3 Cu 1 alloy J. Appl. Phys. 99, 08F104 (2006); 10.1063/1.2162810 The momagne ic de ec ion o ec ys alliza ion in FeCoNbBCu nanoc ys alline alloys Appl. Phys. Le . 79, 2898 (2001); 10.1063/1.1413957 E ec s o Co addi ion on magne ic p ope ies and nanoc ys alliza ion in amo phous Fe 84 Z 3.5 Nb 3.5 B 8 Cu 1 alloy J. Appl. Phys. 86, 6301 (1999); 10.1063/1.371690 [This a icle is copy igh ed as indica ed in he a icle. Reuse o AIP con en is subjec o he e ms a : h p://sci a ion.aip.o g/ e mscondi ions. Downloaded o ] IP: 150.214.182.116 On: F i, 22 Jan 2016 15:34:58 De ec ion o he onse o nanoc ys alliza ion by calo ime ic and magne ic measu emen s J. S. Blázquez Depa amen o de Física de la Ma e ia Condensada, Ins i u o de Ciencia de Ma e iales de Se illa–Consejo Supe io de In es igaciones Cien i ícas (ICMSE-CSIC), Uni e sidad de Se illa, P.O. Box 1065, 41080 Se illa, Spain and Leibniz Ins i u e o Solid S a e and Ma e ials Resea ch D esden (IFW-D esden), Ins i u e o Me allic Ma e ials, Helmhol zs asse 20, 01069 D esden, Ge many V. F anco, C. F. Conde, and A. Condea兲 Depa amen o de Física de la Ma e ia Condensada, Ins i u o de Ciencia de Ma e iales de Se illa–Consejo Supe io de In es igaciones Cien i ícas (ICMSE-CSIC), Uni e sidad de Se illa, P.O. Box 1065, 41080 Se illa, Spain S. Ro h Leibniz Ins i u e o Solid S a e and Ma e ials Resea ch D esden (IFW-D esden), Ins i u e o Me allic Ma e ials, Helmhol zs asse 20, 01069 D esden, Ge many 共Recei ed 13 July 2004; accep ed 22 No embe 2004; published online 24 Janua y 2005兲 I is gene ally accep ed ha measu emen s o he magne ic p ope ies a e mo e sensi i e han measu emen s o he en halpy changes in he de ec ion o he onse o c ys alliza ion o e omagne ic phases eme ging om a pa amagne ic amo phous alloy. In his wo k, i is shown ha he o ma ion o a e y ine nanoc ys alline mic os uc u e can make his assump ion inco ec . Unde some ci cums ances, he nanoc ys alliza ion onse empe a u e ob ained om magne ic echniques is highe han he one ob ained om en halpy changes. The phenomenon is explained in e ms o he supe pa amagne ic beha io o he uncoupled nanoc ys als a he e y ea ly s ages o nanoc ys alliza ion. © 2005 Ame ican Ins i u e o Physics.关DOI: 10.1063/1.1849826兴 I. INTRODUCTION A widesp ead echnique o ob ain nanoc ys alline alloys is he con olled pa ial c ys alliza ion o a p ecu so amo - phous alloy wi h a sui able composi ion. The op imiza ion o he ma e ial p ope ies equi es an accu a e de e mina ion o he onse empe a u e o nanoc ys alliza ion, TX. This pa am- e e , which depends on he hea ing a e due o he he mally ac i a ed cha ac e o he de i i ica ion p ocess, can be di- ec ly measu ed om en halpy changes. Howe e , indi ec measu emen s, like changes in he elec ical esis i i y o in he magne ic p ope ies due o he o ma ion o a new phase, a e claimed o be mo e sensi i e han calo ime ic measu e- men s o he de ec ion o he eme ging c ys als.1This a ib- u ed highe sensi i i y is in ag eemen wi h he ac ha he onse empe a u e ex ac ed om magne ic echniques 共TX mag兲 is usually lowe han he one ob ained om di e en ial scan- ning calo ime y 共TX DSC兲.1Magne iza ion measu emen s a e especially use ul when TXis abo e he Cu ie empe a u e TC o he amo phous phase. In his case, a ze o signal is ob- ained p e ious o he onse o c ys alliza ion and he signal inc eases as he c ys alline olume ac ion Xinc eases, al- lowing de ailed kine ic s udies o he ans o ma ion.2 In his pape we epo expe imen al esul s indica ing ha , unde some ci cums ances, he assump ion TX mag艋TX DSC is no longe ue. Fo his pu pose, Fe-based nanoc ys alline alloys ha e been s udied. Thei cha ac e is ic mic os uc u e consis s o andomly dispe sed c ys alli es 共⬃10 nm兲o a e omagne ic phase 共 ␣ -Fe- ype兲embedded in a esidual amo phous ma ix, also e omagne ic bu wi h a lowe TC.3 This mic os uc u e acili a es he a e aging o he magne o- c ys alline aniso opy due o he exchange coupling o he nanoc ys als ia he e omagne ic amo phous ma ix. The educed alue o he o e all aniso opy is esponsible o he ou s anding so magne ic p ope ies exhibi ed by hese alloys.4The di e ence in he nanoc ys alliza ion onse em- pe a u es ob ained om he calo ime ic and magne ic ech- niques will be analyzed aking in o accoun he possibili y o a supe pa amagne ic beha io o he eme ging monodomain nanopa icles embedded in he pa amagne ic amo phous ma ix. II. EXPERIMENT Samples o Fe60Co18Nb6B15Cu1,Fe 60Co18Nb6B16 共Hi pe m- ype alloys兲, and Fe74Si16Nb3B6Cu1共Fineme - ype兲 we e s udied. They will be deno ed in he ollowing as Cu-HT, HT, and FM, espec i ely. Ribbons 5–10 mm wide and 10–20 ␮ m hick we e p oduced by mel spinning. TX DSC was measu ed by di e en ial scanning calo ime y 共DSC兲in a Pe kin–Elme DSC7 calo ime e ; TX mag was measu ed by he momagne ic g a ime y 共TMG兲in a Pe kin–Elme TGA7 he mobalance using a small magne 共maximum ield ⬃20 mT兲. Bo h measu emen s we e pe o med a hea ing a es o 10 K/min. A ib a ing-sample magno eme e 共VSM兲 was used o s udy quan i a i ely he dependence o he mag- ne ic signal wi h he applied magne ic ield B=0.002, 0.02, and 0.2 T, using a hea ing a e o 5 K/min. a兲Au ho o whom co espondence should be add essed; FAX: ⫹34-95/461- 2097; elec onic mail: [email p o ec ed] JOURNAL OF APPLIED PHYSICS 97, 044308 共2005兲 0021-8979/2005/97共4兲/044308/4/$22.50 © 2005 Ame ican Ins i u e o Physics97, 044308-1 [This a icle is copy igh ed as indica ed in he a icle. Reuse o AIP con en is subjec o he e ms a : h p://sci a ion.aip.o g/ e mscondi ions. Downloaded o ] IP: 150.214.182.116 On: F i, 22 Jan 2016 15:34:58 III. RESULTS The mic os uc u e o he Cu-HT and HT alloys is simi- la . Bo h de elop a nanoc ys alline ␣ -Fe,Co phase and p esen he same c ys alline olume ac ion a he end o he nanoc ys alliza ion p ocess 共X⬃0.65兲.5Howe e , he addi- ion o 1 a . % o Cu in he Cu-HT alloy wi h espec o he HT alloy p o okes a s ong e inemen o he mic os uc u e h ough an enhancemen o he he e ogeneous nuclea ion due o he o ma ion o Cu clus e s be o e nanoc ys alliza ion.6 Consequen ly, he mean g ain sizes a e e y di e en : D ⬃5 nm o Cu-HT and ⬃20 nm o HT.7In he case o he FM alloy, he Cu-clus e ing phenomenon is also p esen , and he mean g ain size o he ␣ -Fe,Si phase a he end o nanoc- ys alliza ion is ⬃15 nm.2Al hough he Cu-clus e ing phe- nomenon occu s in bo h he FM and Cu-HT alloys, a la ge g ain size is ob ained in he case o FM.8A lowe Nb con en 共3 a . %兲wi h espec o ha o Cu-HT 共6 a . %兲and he p esence o Si in he ␣ -Fe c ys als could be he o igin o his la ge g ain g ow h in he FM alloys. In o de o calcula e he c ys alline olume ac ion, bo h calo ime ic and magne ic measu emen s can be used. In he i s case, he c ys alline olume ac ion Xcan be associa ed wi h he en halpy change 共X⬀⌬H兲, while o magne ic mea- su emen s i is connec ed o he magne iza ion 共X⬀M兲.In ac , he magne iza ion o he nanoc ys als depends on he empe a u e bu , in he case o iso he mal expe imen s o o small empe a u e anges 共p o ided ha he Cu ie empe a- u e o he phase is dis an enough兲, easonable esul s can be ob ained by conside ing a empe a u e-independen magne i- za ion o he phase. Unde hese condi ions i can be assumed ha he c ys alline ac ion is di ec ly p opo ional o he magne iza ion signal. Ne e heless, he ela ionship in ol - ing en halpy and c ys alline ac ion is also no exemp om c i icisms,9as i dis ega ds he con inuous composi ional change o he amo phous ma ix along he nanoc ys alliza- ion p ocess. The signal measu ed in a DSC un co esponds o he ime a ia ion o he en halpy o he sys em du ing he ans o ma ion, dH/d . Bo h echniques, TMG and DSC, allow a e y good con- ol o he hea ing a e. The e o e, a compa ison be ween TX ob ained a he same hea ing a e will gi e an idea o he sensi i i y o he echnique wi hou being a ec ed by he he mally ac i a ed cha ac e o he p ocess. Figu e 1 shows he no malized DSC plo s 共peak a ea=1兲o he h ee as-cas alloys, oge he wi h he no malized i s de i a i e o he TMG cu es 共a a ield o ⬃20 mT兲wi h espec o he em- pe a u e 共 he noise in hese cu es is due o he nume ical de i a i es兲. The onse o c ys alliza ion is de ec ed a a lowe empe a u e by TMG han by DSC. Howe e , whe eas he di e ence in TXbe ween bo h echniques is only o 3 K o he Cu-HT alloy, ha di e ence clea ly inc eases o he o he wo alloys, being ⬎10 K. To explain his e ec , he Cu-clus e ing p ocess be o e nanoc ys alliza ion in he alloys wi h Cu could be aken in o accoun . The o ma ion o his Cu- ich nonmagne ic phase implies ha an ex a amoun o en halpy change would be obse ed a a lowe empe a u e. This could make he onse empe a u es de ec ed om DSC and TMG close , as ound o he Cu-HT alloy. Howe e , i canno explain he di e - ence be ween he TX alues obse ed by DSC and TMG o he FM alloy, o which an e en highe densi y o Cu clus e s han o he Cu-HT alloy is expec ed.10 To in es iga e hese di e ences in he c ys alliza ion on- se de ec ed by DSC and TMG echniques o he s udied alloys, he applied magne ic ield in he TMG measu emen s was changed o es i s in luence on he obse ed alue o TX mag. Table I shows TX alues ob ained by DSC and by TMG using wo applied ields con olled by he posi ion o he magne a he he mobalance: he maximum achie able ield 共high兲and a ield which supplies a signal equal o 10% o he maximum signal 共low兲. I can be obse ed ha whe eas o he HT and FM alloys TX mag is almos independen o he ield, o he Cu-HT alloy, TX mag is highe o low- ield mea- su emen s han o high- ield ones. In he case o low- ield measu emen , TX mag is e en highe han ha obse ed om he DSC measu emen s. A quan i a i e s udy o he ield dependence o TX mag was done using a VSM. Figu e 2 shows M e sus empe a u e plo s o he Cu-HT and HT alloys ob ained o di e en FIG. 1. The momagne ic g a ime y 共TMG兲共dM/d 兲and di e en ial scan- ning calo ime y 共DSC兲共dH/d 兲plo s a a hea ing a e o 10 K/min. The TMG signal is ob ained as he de i a i e o he expe imen al M共T兲da a o an applied ield o ⬃0.02 T. TABLE I. Values o TXmeasu ed om DSC and TMG echniques a he same hea ing a e, 10 K/min. High ield co esponds o he posi ioning o he magne o ob ain he maximum signal a oom empe a u e 共⬃20 mT兲. Low ield is ob ained o a signal equal o 10% o ha maximum. Alloy Composi ion 共a . %兲TX DSC 共±1 K兲 TX mag 共±2 K兲 共high ield兲 TX mag 共±2 K兲 共low ield兲 Cu-HT Fe60Co18Nb6B15Cu1727 724 731 HT Fe60Co18Nb6B16 759 741 740 FM Fe74Si16Nb3B6Cu1784 771 769 044308-2 Blázquez e al. J. Appl. Phys. 97, 044308 共2005兲 [This a icle is copy igh ed as indica ed in he a icle. Reuse o AIP con en is subjec o he e ms a : h p://sci a ion.aip.o g/ e mscondi ions. Downloaded o ] IP: 150.214.182.116 On: F i, 22 Jan 2016 15:34:58 applied magne ic ields. Samples we e hea ed a ⬃5 K/min. Fo he highes ield 共B=0.2 T兲, e en he pa amagne ic ma- ix gi es a nonze o signal. Howe e , i is possible o dis in- guish a empe a u e a which he signal ises due o he onse o nanoc ys alliza ion. In he case o he alloy wi hou Cu, TX mag=730±1 K and is independen o he applied ield. On he o he hand, o he alloy wi h Cu, TX mag inc eases as he applied ield is dec eased: TX mag=707, 712, and 722±1 K o B=0.2, 0.02, and 0.002 T, espec i ely. A i s sigh , his inc ease could be ela ed o he sensi i i y o he measu ing equipmen . Howe e , his can be uled ou as he signal le el o a gi en ield alue is he same o bo h he Cu-HT and HT samples and he TXinc ease as he applied ield dec eases is only obse ed o he Cu-HT samples. IV. DISCUSSION An explana ion o his e ec may be ound in he di e - ences obse ed in he mic os uc u e o he s udied alloys. A he e y beginning o nanoc ys alliza ion, e y small c ys als a e o med, which can be conside ed isola ed and, he e o e, in a supe pa amagne ic s a e. The magne iza ion p oduced by a monodispe sed supe pa amagne ic sys em is desc ibed by M=N ␯ mL共mB/kBT兲,共1兲 whe e N ␯ is he nume ical densi y o pa icles, m he mag- ne ic momen o he indi idual pa icles, B he magne ic ield, T he empe a u e, kB he Bol zmann cons an , and L he Lange in unc ion. Se e al assump ions may be made o ha e a iew o he exis ing mic os uc u e a he e y ea ly s ages o nanoc ys- alliza ion. A i s app oxima ion would be o conside ins an- aneous nuclea ion egime, i.e., he numbe o nanoc ys als emains cons an du ing he nanoc ys alliza ion. A e his, i is easy o ob ain he alue o N ␯ o each alloy: 0.01 and 0.00016 nm−3 o he Cu-HT and HT alloys, espec i ely, which yields X⬃65% o a alue o Do 5 and 20 nm, espec i ely. The alue o mcan be ob ained as he numbe o a oms in he nanoc ys al imes i s a omic magne ic mo- men , which can be es ima ed as 2.2 ␮ B. The bcc uni cell con ains wo a oms in a olume equal o a3, whe e a =0.28625 nm is he la ice pa ame e ,10 he e o e, m共D兲= 2.2 ␮ B2 a3 ␲ D3 6.共2兲 A his poin , magne iza ion can be ob ained as a unc- ion o he g ain size using Eq. 共1兲, whe e N ␯ would cha ac- e ize he mic os uc u e o each pa icula case. The nex s ep will be o ela e he g ain size D o he empe a u e. This can be done using he known kine ic pa ame e s o hese alloys11,12 and he A ami equa ion. Al hough his equa ion is alid o iso he mal egimes, we a e only in e es ed in a e y small empe a u e ange, jus a e he onse o c ys alliza- ion. The e o e, kine ic pa ame e s will be used in he ol- lowing wi hou conside ing hei he mal dependence. The A ami equa ion es ablishes a ela ionship be ween he ac ion o he p ocess, X*, and he ime, , X*=1−exp关−共K 兲n兴,共3兲 whe e Kis he equency ac o and nis he A ami expo- nen . The A ami exponen is app oxima ely 1 and is inde- penden o he empe a u e a he ea ly s ages o nanoc ys alliza ion.12 K ollows an A henius- ype depen- dence wi h he empe a u e, K=K0exp共−Q/kBT兲,共4兲 whe e K0is a cons an and Qis an ac i a ion ene gy. F om he kine ic esul s, K0⬃1013 s−1 and Q⬃2.4 eV.12 In he aim o simpli ying he calcula ions and aking in o accoun ha we a e in e es ed in a e y small empe a u e ange, he he - mal dependence o Khas been neglec ed and a alue o ⬃0.0004 s−1 共a T=725 K兲has been used. X*=X/0.65 o bo h he s udied alloys, hus X*=1 a he end o he nanoc- ys alliza ion. F om =共T−TX兲/ ␤ , and aking in o accoun 共2兲and 共3兲, T=TX− ␤ Kln 冉 1− 1 0.65N ␯ ␲ 6D3 冊 ,共5兲 whe e TXis 710 K o he Cu-HT alloy and 730 K o he HT alloy, and ␤ =5 K/min, he same alue as used in he VSM expe imen s. Conside ing a sensi i i y o he VSM de ice o 0.1 memu, he de ec ion limi o he magne iza ion will be abou 0.1 mT in he case o he s udied samples 共sample mass ⬃8 mg, densi y ⬃7.8 g/cm3兲. Figu e 3 shows he e - ec o he applied ield on he de ec ed c ys alliza ion onse as is expec ed unde he assump ions indica ed abo e; ex- pe imen al alues om Fig. 2 a e also included. I can be seen ha he obse ed beha io is quali a i ely ep oduced. An impo an e ec o he applied magne ic ield is ound o FIG. 2. Magne iza ion M共T兲cu es o Fe60Co18Nb6B16−yCuy共y=0,1兲al- loys a a hea ing a e o ⬃5 K/min egis e ed in he ib a ing-sample mag- ne ome e 共VSM兲a he ea ly s ages o nanoc ys alliza ion using di e en applied ields. 044308-3 Blázquez e al. J. Appl. Phys. 97, 044308 共2005兲 [This a icle is copy igh ed as indica ed in he a icle. Reuse o AIP con en is subjec o he e ms a : h p://sci a ion.aip.o g/ e mscondi ions. Downloaded o ] IP: 150.214.182.116 On: F i, 22 Jan 2016 15:34:58 he Cu-HT sample 共wi h a much lowe g ain size han HT兲: he de ec ion limi o 0.2 T is o e come a a empe a u e 18 K lowe han o 0.002 T. Howe e , o he HT sample his di e ence is smalle han 2 K. In e ms o c ys alline olume ac ion, o he HT sample he de ec ion limi would be o e come o X⬍2% e en o he lowes applied ield 共0.002 T兲. Howe e , in he case o he Cu-HT alloy a B =0.002 T, he de ec ion limi would be o e come only o X⬎15%, which could explain why he appa en onse o c ys alliza ion is de ec ed in his case e en la e han using DSC 共Table I兲. Al hough s ong assump ions we e made o model he M signal, he ends obse ed expe imen ally a e desc ibed wi h a ai ly good quali a i e ag eemen . I mus be aken in o accoun ha he app oxima ions used abo e lose hei alid- i y as he di e ence in empe a u e be ween he de ec ed on- se s becomes la ge : he iso he mal kine ic pa ame e s will be modi ied and, a a high c ys alline olume ac ion, supe - pa amagne ic pa icles will in e ac .13 These e ec s could ex- plain he o e es ima ed modeled alue o he c ys alliza ion onse o he Cu-HT alloy a 0.002 T wi h espec o he expe imen al alue. As he ange o empe a u es is ex- ended, he empe a u e dependence o Kshould be aken in o accoun . On he o he hand, as he c ys alline olume ac ion inc eases, he in e ac ion among he pa icles will modi y he magne ic esponse o he sys em om he simple Lange in unc ion used in his wo k. Ne e heless, he ob- se ed end is success ully desc ibed. V. CONCLUSIONS In conclusion, o a compa ison o calo ime ic and mag- ne ic echniques as ools o de ec ing he c ys alliza ion on- se , i has o be aken in o accoun ha he sensi i i y o he la e can be dependen , in some cases, on he applied mag- ne ic ield. The gene ally accep ed idea ha magne ic ech- niques ha e a highe sensi i i y han he calo ime ic ones is no necessa ily ue in p esence o a e y ine mic os uc u e, which can p oduce a supe pa amagne ic beha io . ACKNOWLEDGMENTS This wo k was suppo ed by he CICYT o he Spanish Go e nmen and EU FEDER 共P ojec MAT 2001-3175兲, and he PAI o he Regional Go e nmen o Andalucía. One o he au ho s 共J.S.B.兲acknowledges a esea ch con ac o ha egional go e nmen . 1W. Ho s e e , H. Sassik, R. G össinge , R. T ausmu h, G. Ve esy, and L. F. Kiss, Ma e . Sci. Eng., A 226–228,213共1997兲. 2C. F. Conde and A. Conde, Ma e . Le . 21, 409 共1994兲. 3M. E. McHen y, M. A. Willa d, and D. E. Laughlin, P og. Ma e . Sci. 44, 291 共1999兲. 4A. He nando, M. Vázquez, T. Kulik, and C. P ados, Phys. Re . B 51, 3581 共1995兲. 5J. S. Blázquez, V. F anco, C. F. Conde, and A. Conde, J. Magn. Magn. Ma e . 254–255, 460 共2003兲. 6Y. Zhang, J. S. Blázquez, A. Conde, P. J. Wa en, and A. Ce ezo, Ma e . Sci. Eng., A 353, 158 共2003兲. 7J. S. Blázquez, V. F anco, and A. Conde, J. Phys.: Condens. Ma e 14, 11717 共2002兲. 8J. S. Blázquez, J. M. Bo ego, C. F. Conde, A. Conde, and J. M. G eneche, J. Phys.: Condens. Ma e 15, 3957 共2003兲. 9J. M. Ba andia án, I. Telle ía, J. S. Ga i aonandia, and H. A. Da ies, J. Non-C ys . Solids 329,57共2003兲. 10M. Ohnuma, D. H. Ping, T. Abe, H. Onode a, K. Hono, and Y. Yoshizawa, J. Appl. Phys. 93, 9186 共2003兲. 11J. S. Blázquez, C. F. Conde, and A. Conde, J. Non-C ys . Solids 287,187 共2001兲. 12J. S. Blázquez, C. F. Conde, and A. Conde, Appl. Phys. A: Ma e . Sci. P ocess. 76, 571 共2003兲. 13V. F anco, L. F. Kiss, T. Kemény, I. Vincze, C. F. Conde, and A. Conde, Phys. Re . B 66, 224418 共2002兲. FIG. 3. Expe imen al TX mag ob ained by ib a ing-sample magno eme e 共VSM兲measu emen s 共solid symbols兲and esul s o he modelliza ion 共hol- low symbols兲o Fe60Co18Nb6B16−yCuy共y=0,1兲alloys as nonin e ac ing monodispe sed supe pa amagne ic pa icles 共nume ical densi ies N ␯ =0.01 and 0.00016 nm−3 and c ys alliza ion onse empe a u e TX=710 and 730 K o he alloys wi h and wi hou Cu, espec i ely兲. The expe imen al symbols a e joined by lines as a guide o he eye. 044308-4 Blázquez e al. J. Appl. Phys. 97, 044308 共2005兲 [This a icle is copy igh ed as indica ed in he a icle. Reuse o AIP con en is subjec o he e ms a : h p://sci a ion.aip.o g/ e mscondi ions. Downloaded o ] IP: 150.214.182.116 On: F i, 22 Jan 2016 15:34:58