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Physics & Chem Materials

by: Cathrine Kreiger II

Physics & Chem Materials EMS 289C

Cathrine Kreiger II
GPA 3.7


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Class Notes
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This 30 page Class Notes was uploaded by Cathrine Kreiger II on Tuesday September 8, 2015. The Class Notes belongs to EMS 289C at University of California - Davis taught by Staff in Fall. Since its upload, it has received 42 views. For similar materials see /class/187530/ems-289c-university-of-california-davis in Engineering Materials Science at University of California - Davis.


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Date Created: 09/08/15
G 3 M2 STRUCTURES one 39DIGn gt COORDINATION NUMBER STRUCTURE Ii 6 6 Fluorite 8 4 Rutile 6 3 9 9 Quartz Cristobalite 4 2 Tridymite Cadmium Iodide and other layer 6 3 56 99 Carbon dioxide 2 Pyrite 1S3Fe Harcasite Note 82 groups lt3 3 07 9 e on 04 c 9I I E g sz STRUCTURE TYPES 9 5 395 Sio2 Tio2 Zro2 MgCI2 Geo2 Ge02ow T Hfo2 MnCI2 E3er Sio2 high P Ceo2 FeCI2 Sno2 Pro2 00012 9 9 Pbo2 LJo2 NiCI2 5 Npo2 ZnCI2 Puo2 CdCl2 AmO2 MgBr2 CaF2 MnBr2 Q SrF FeBr2 6 amp BaF2 CoBr2 0ch2 NiBr2 ZnBr2 Mnl2 9 9 Col2 5 5 Nil2 an2 Tis2 ZrS 9 9 Isolated SrS 6 amp Molecules Tas2 7 CO2 Pts2 HgC2 MOS2 ws2 9 Fluorite 9 qua G39s9 p to hue pro 0 on Ffuorite depicted as an alternation of full and empty cubes 4 GIID ID 6 Oil1 390 ltl I Zirconia ZI39O2 H4 5 l Three distinct polymorphs uMonoclinic stable at STP ITetragonal stable 1443 to 2643 K nCubic fluorite stable above 2643 K to melting l However syntheses of fine grained powder yields the tetragonal or cubic form I Phase stability reversal in small particles seen in other oxides is titania alumina see discussion of nano later in course ll quot0 quot390 6 GilD in 9 Zirconia a b 0 Schematic representation of the three polymorphs of ZrO2 a cubic Fm3m b tetragonal P42lnmc c monoclinic P21lc R Hannink et al J Am Ceram 800 83 3 46187 2000 ca 4 Defect fluorite we 9 Crystal structure of defect uorite Fm3m cm 5 9 an 9 00 a a W Gd3 e e 39 VGZ 3 p ens 4 x M4 Ln3 05 oxygen vacancy lao I High oxide ion conductivity which goes through a maximum with increasing doping I D Structural evidence for short range order in cubic solid solutions at Low T long range ordered phases sluggish to form an 4 d q 6 Local ordering of vacancies in Ctype rare earth bixbyite structure YZO3 YO15 cm cm ID 6 FirD 10 q 5 0 Scanning calorimetry curve for Y203 Figure Explrimant New203 powdar 350 CYCLE 1 COOLING Cmclbh W 35 pl Akmasphem H6 5515 1210312004 Procedure 20240u 2o 20 Zone 1 Mass mg 11076 39 I l l I I l HaaIFlowluV Simph umpemunl c Exo 1 In 252 Peak a 4 Onset Paint 23El3 C linthnlpyluv slmg 4415 Onset P Sinhzzu c 400 Exolhermlc effect Enthalpy luVslmg 443 Exntharmhc affect m 2050 60 1 20 l 60 240 300 360 420 KO 540 600 660 720 39780 340 900 Timals I T l Ga 4 a Z YOLS 30 Prf 4 20 0560 5P 399 CF En nlpy of Mmg kImal N u D O 3 9 oacp q no Gal390 p 3 o 8 g o 4 F a 39lt 9 C202 Y015 Ii 1500 1250 7 a Disordered i 1000 7 U 5 7507 E 5007 250 7 0 i i i ij i I I 10 20 30 40 50 60 70 80 90 26 1500 1250 7 b Ordered i 1000 7 U 5 7507 E 5007 250 7 0 lLll 1 II II In 10 20 30 40 50 60 70 80 90 26 Xray diffraction patterns of a Disordered Zro43Yo57O196 cYSZ phase b Ordered Y4Zr3012 5phase AH ordered disordered is 04 i 14 kJmol 0 short range order rules q I Pyrochlore one 5 Ordered structure derived from fluorite Cation and vacancy a ordering and distortion from cubic cm 5 Pyrochlore and zirconolite related to waste forms for U and Pu tRadiation resistance varies with composition I D 0ur work addresses 395 IE Energetics of formation from oxides AHf If oEnergetics of disordering Correlation between AHf and critical temperature for 69 399 h radiation amorphization 4 on 0 ca c 4 Comparison of uorite F m3m and pyrochlore Fd3m cm 4 cm Ii 6 3 C C 0 w 0 NO NDgt NW 9 cm 9 O Acation GdY Bcation ZrTi o Anion 0 ED After Wilde and Catlow 1998 3 0 4 Applications of fluorite related structures Gilt Ionic conductivity solid oxide fuel cells SOFC oxygen sensors gas separation membranes mainly YSZ Catalysis transport of both oxide ions and electrons in CeOZbased materialseg 3way exhaust catalysts Nuclear fuels U02 UOZPuOZ UOZZrOZ plus lanthanides and actinides Thermal barrier coatings YSZ Nuclear waste disposal pyrochlores radiation resistance Gate dielectrics on Si HfOZbased systems I D I D h quot0 h riir J 3 r0 0 lil ii 1 ille 6 lt1 iJ ll an it Ii Rutile 0 04 4 l O N q 4 668 cm 2 2 F r x 13 3E b 339 r Xx 51 in a Iquot quotc a c 5 ih q 9 w ck rm x xi 5 Q a J a ED Ga 2 in 9 If 5 as 5 E 0a a I 6T 4 399 a Aplications of one 4 a Paint Photovoltaics one 9 These applications mainly rely on optical properties and bandgap The Ti4 Ti3 defect equilibrium is important 1 4 one 4 CD LAY39ERED sz STRUCTURES CdC2 PbClz LAY39ERED sz STRUCTURES Polymorphs ocquartz Bquartz Critobalite Tridymite Glass fused Coesite Stishovite a Low temperature form spaced groups reflect chirality handedness Silica Polymorphs Space group P3221 P3121a P6222 P6422 Fd3m P63mmcC P1 C2C P42mmm Molar volume cm3lmol at 298 K 2267 2578 2653 2727 2064 1401 Structural features 6rings 6rings 6rings 6rings Distribution of ring size but 6rings predominant 4 and 8 rings Octahedral Si rutile structure Enthalpy relative to or quartz 0 03 28 32 70 29 519 b High temperature form related by nonquenchable displacive transition 0 D88 high temperature form low temperature forms related by displacive transitions are very complex Ga 4 High Tridymite Gus 4 cans 9 4 5a 4 Ideal hexagonal array of 6membered rings in high tridymite 3 c 4 Impurities in Tridymite Structure cm 4 cm c Ii q 4 4 An impurity atom like cesium might sit inside the a ring of six tetrahedra Another impurity like aluminum might substitute for a silicon 3 ozQuartz at 298 111 projection High cristoabaliite W2 High trijdy mite Coesite 4 and 8 rings Cadmium chloride CdCl2 Cadmium iodide Cc 2


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