Mechanochemical Synthesis Reaction Setup Powder mixing High-energy ball-milling for several hours Ball-to-powder ratio (20:1) Vial (250 ml) and balls (d = 10-20 mm) WC, stainless steel, zirconia 250 rotations per minute Controlled atmosphere Mechanochemical Synthesis Particles repeatedly subjected to deformation, cold welding, and fracture, homogenization on an atomic scale On impact, high energy concentrated in a small spot, stress 200 MPa, duration of microseconds Fragmentation, atomically clean surface exposed Balance between fragmentation and coalescence Grain size ~10 nm Amorphization, product nucleation and crystallization 2 Mechanochemical Synthesis ■^ Phase Transitions (to denser structures) Oxide Before V,Á3 After V,Á3 Ge02 quartz 40.3 rutile 27.6 Ti02 anatase 34.1 rutile 31.2 Zr02 baddaleyite 35.2 fluorite 32.8 V = volume per formula unit ■^ Mechanical Alloying Ni + Nb ---------------► Nb40Ni60 amorphous Mechanochemical Synthesis ■^ Preparation of mixed oxides Al203(corundum) + Si02 (xerogel) ________> mullite A1203 + La203 _________► LaA103 120 min A1203 + Mn203 -------------► LaMn03 room temp., 180 min SnO + B203 + P205 + Li20 —► (Li20)2(Sn2BP06)4 in dry N2 anodic material for lithium batteries ■^ Preparation of chalcogenides Fe (powder 4 |im) + S (50 [im) -----------► FeS in Argon ZnCl2 + Na2S --------► ZnS + 2NaCl CdCl2 + Na2S --------► CdS + 2 NaCl 4 Mechanochemical Synthesis ■^ Preparation of carbides, borides, nitrides, suicides Nb + C (graphite) ---------► NbC (Fe impurities from abrasion) Nb + C + Cu + Fe -------► NbC/Cu/Fe cermet Ti + N2 ---------► TiN 60 h Ti + C ---------► TiC 35 h Ti + 2 B______► TiB2 15 h Ti02 + 2 Mg + C -------► TiC + 2MgO (MgO removed by HCl) W03 + 3 Mg + C —► a-W + 3 MgO + C explosive a-W + 3 MgO + C -----► WC 50 h (4-20 nm, MgO removed by HCl) Mechanochemical Synthesis ■^Reactive milling Na2C03 + Se02 -------► Na2Se03 + C02 2In + 3 urea.H202 + Sn02 —► ln203 + Sn02 + 3 H20 + 3 urea heating to 473 K for 4h to remove organics and calcination at 573-673 K in oxygen gives ITO FeCl2 + 2 CpNa —► 2 NaCl + Cp2Fe 6 Polymer Pyrolysis Preparation of: powders, monoliths, fibers, films, impregnation (PIP) Example: SiC fibers © polymer synthesis Li 400 °C, Ar Me2SiCl2 ---------► [Me2Si]6 ------------► [-SiMe2-]n soluble preceramic polymer Na Me2SiCl2 + MePhSiCl2 -----► [-SiMe2-SiMePh-]n © melt spinning or drawing from solution gives continuous polymer fiber © curing in 02, heat to 400 - 500 °C, thermoset, crosslinking to prevent melting © pyrolysis at 1000 -1500 °C to polyxtalline ß-SiC fiber 7 Polymer Pyrolysis Cl-CH2-SiCl3 Cij£i-CHŕ C 1. My, Ethar Z UAIH* í I H H C Hj. ĽH^ [H -£, ■ C h 21, - -l^i-CHjlz- [$ -CH,] H$i-CHah-H H H CH;, (SiCH4)n II s H,C H H—Si H**VaS/i h7 CH H CH, "X,,. / CH, \ H^/St-CH2 í ti CH,-----c; H H Z" ?% CH, H H H H \ / Si—H H V CH7 \ "Ní "f VH r ii H ^a/'W CH, m H:V1100K,NH3 ---------------► A1N powder Thermolysis of Organometallic Coordination Polymers (Me3Sn)nM(CN)6 n = 3,4; M = Fe, Co, Ru thermolysis in Ar or H2 gives intermetallics FeSn2, CoSn2, Ru3Sn7 thermolysis in air gives oxides Fe203/Sn02, Co2Sn04, Ru02 9 Thermolysis of Organometallic Coordination Polymers (Me3Sn)nM(CN)6 n = 3,4; M = Fe, Co, Ru thermolysis in Ar or H2 gives intermetal FeSn2, CoSn2, Ru3Sn7 thermolysis in air gives oxides Fe203/Sn02, Co2Sn04, Ru02 Prussian Blue structure An idealised structure tíl Prussian Blue wüh M*-CaW-*MJ linkages in 3-D Whim U = Crr M - Ni 4na&nsJ is a faromignit, Tc = 90K Whin M= tf. M" ■ Mn material i5 a tcr-Tiüg"*!. Tc = 1Í5K ttlwn M= Cf, M- - V ntfenal ii a fHrimtywi. TL = 31SK Microwave-Assisted Synthesis Microwave radiation = electromagnetic radiation Microwaves: A, = 1 mm to Im, v = 0.3 to 300 GHz Microwave ovens 2.45 GHz, X = 12.24 cm power up to 1 kW, pulses, magnetron, microwaveguide, microwave cavity All kitchen microwave ovens and all microwave reactors for chemical synthesis operate at a frequency of 2.45 GHz to avoid interference with telecommunication and cellular phone frequencies. 12 Microwave-Assisted Synthesis The energy of the microwave photon in this frequency region too low to break chemical bonds (0.0016 eV) lower than the energy of Brownian motion Microwaves cannot induce chemical reactions Microwave-enhanced chemistry is based on the heating of materials by "microwave dielectric heating" effects = the ability of a material (solvent or reagent) to absorb microwave energy and convert it into heat 13 Microwave-Assisted Synthesis Interaction of materials with microwaves: /^reflectors: metals, alloys (ô skin depth, large E gradients, discharges) /^transmitters: quartz, zircon, glasses, ceramics (no TM), Teflon /^absorbers: amorphous carbon, graphite, powdered metals, metal oxides, sulfides, halides, water 14 Microwave-Assisted Synthesis Dielectric heating electric dipole reorientation in the applied alternating field the dipoles or ions aligning in the applied electric field applied field oscillates, the dipole or ion field attempts to realign itself with the alternating electric field energy is lost in the form of heat through molecular friction and dielectric loss if the dipole does not have enough time to realign, or reorients too quickly with the applied field, no heating occurs 15 Microwave-Assisted Synthesis Resistive heating polarization current, a reorientation phase lag Joule heating ionic current, ionic conduction, ions drift in the applied field Electronic transport metal powders, semimetallic and semiconducting materials Rotational excitation: weak bonds (interlayer bonds in graphite and other layer materials Eddy currents: metal powders, alternating magnetic fields Microwave absorption = f (frequency, temperature) Thermal runaway = increased dielectric loss at higher T 16 Microwave-Assisted Synthesis Dielectric heating: electric dipóle reorientation in the applied alternating field, the dipoles or ions aligning in the applied electric field, applied field oscillates, the dipóle or ion field attempts to realign itself with the alternating electric field and, in the process, energy is lost in the form of heat through molecular friction and dielectric loss, if the dipóle does not have enough time to realign, or reorients too quickly with the applied field, no heating occurs. Resistive heating: polarization current, a reorientation phase lag Joule heating: ionic current, ionic conduction, ions drift in the applied field Electronic transport: metal powders, semimetallic and semiconducting materials Rotational excitation: weak bonds (interlayer bonds in graphite and other layer materials Eddy currents: metal powders, alternating magnetic fields Microwave absorption = f (frequency, temperature) Thermal runaway = increased dielectric loss at higher T 17 Dielectric heating The applied field potential E of electromagnetic radiation E = Emax-00^) Emax = the amplitude of the potential (V) co = the angular frequency (rad s"1) t = the time (s) If the polarization lags behind the field by the phase (ô, radians) then the polarization (P, coulombs) varies as P = Pmax-COS^ " ô) Pmax is the maximum value of the polarization 18 Dielectric heating The current (I, A) varies as I = (dP/dt) = - co Pmax sin(coT - ô) The power (P, watts) given out as heat is the average value of (current x potential). P is zero if there is no lag (i.e. if ô = 0), otherwise ^=0-5PmaxEmax^-sin(0) 19 Dielectric Properties The ability of a substance to convert electromagnetic energy into heat at a given frequency and temperature Loss factor tanS tanS=s"/s' s" is the dielectric loss, indicative of the efficiency of radiation-to-heat conversion e' is the dielectric constant, the ability of molecules to be polarized by the electric field a high tanô value required for efficient absorption and for rapid heating solvents can be classified as microwave absorbing high (tanô > 0.5) medium (tanô = 0.1 - 0.5) low (tanô < 0.1) 20 Loss factors (tanô) of different solvents (2.45 GHz, 20 °C) Solvent tanô Solvent tanô ethylene glycol 1.350 DMF 0.161 ethanol 0.941 1,2-dichloroethane 0.127 DMSO 0.825 water 0.123 2-propanol 0.799 chlorobenzene 0.101 formic acid 0.722 chloroform 0.091 methanol 0.659 acetonitrile 0.062 nitrobenzene 0.589 ethyl acetate 0.059 1-butanol 0.571 acetone 0.054 2-butanol 0.447 tetrahydrofuran 0.047 1,2-dichlorobenzene 0.280 dichloromethane 0.042 NMP 0.275 toluene 0.040 acetic acid 0.174 hexane 0.020 Temperature Gradients MW °il bat*1 SOG ! 440 4M J l420 400 1 Ir/K • 400 350 1 |x>o 300 I 1 5? tí Microwave-Assisted Synthesis Examples of Microwave-assisted syntheses Si + C -----► ß-SiC AG°298 = - 64 kJ/mol silica crucible, 1 kW, 4-10 min, 900 °C, inert ambient (I2), conventional process requires 1400 °C metal + chalcogenide -----► ME evacuated quartz ampoules, 5-10 min, 900 W, melting, light emission PbSe, PbTe, ZnS, ZnSe, ZnTe, Ag2S Mo+ Si + graphite-----► MoSi2 high mp, oxidation and carbidation resistance, metallic conductivity, heating elements and high-T engine parts 23 Microwave-Assisted Synthesis Mixed oxides Y203 + BaO + CuO ____►YBa2Cu307x 200 W, 25 min BaO + WO3 -------► BaW03 500 W, 30 min Amorphous carbon is a secondary susceptor, does not react with reagents or products (carbothermal reduction) C burns and initiates decomposition of carbonates or nitrates BaC03 + Ti02 + C —► BaTi03 + C02 PbN03 + Ti02 + C —► PbTi03 + C02 NaH2P04.2H20 good MW susceptor, rotational excitation of water, dehydrates to NaP03, melts, 700 °C in 5 min Na2HP04.2H20, KH2P04 no MW heating NaH2P04.2H20 + Zr02 —►NaZr2(P04)3 NASICON superionic conductor, 8 min Microvawe-Active Elements, Natural Minerals, and Compounds (2.45 GHz, 1 kW) element/ mineral/compound time (min) of microvawe exposure T, K element/ mineral/compound time (min) of microvawe exposure T, K Al 6 850 Mn02 6 1560 C (amorphous, < 1 um) 1 1556 MO 6.25 1578 C (graphite, 200 mesh) 6 1053 v2o5 11 987 C (graphite, < 1 um) 1.75 1346 WO3 6 1543 Co 3 970 Ag2S 5.5 925 Fe 7 1041 Cu2S 7 1019 Mo 4 933 CuFeS2 (chalcopyrite) 1 1193 V 1 830 FeS2 (pyrite) 6.75 1292 w 6.25 963 MoS2 7 1379 Zn 3 854 PbS 1.25 1297 TiB2 7 1116 CuBr 11 995 Co203 3 1563 CuCl 13 892 CuO 6.25 1285 ZnBr2 7 847 Fe3C>4 (magnetite) 2.75 1531 ZnCl2 7 882 Microwave-Assisted Synthesis