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Solid State Reaction: General
     - Reaction between the solids
     Advantages
     1. Simple apparatus (ball milling,
                                                                             A+B
        rotatory evaporator)
     2. Inexpensive (cost-effective)
     Disadvantages
     1. Wide particle-size distribution
     2. Coarse particle size ( ≥1µm)
     3. Contamination during mixing
     4. High temperature is required for reaction
         especially when the particle size is large
                                                                             C+A+B
         or when the mixing is insufficient
     5. Compositional fluctuation due to
        the incomplete reaction
     6. Difficult to control the particle shape


Advanced Electronic Ceramics I (2004)




                                Rotatory evaporator




            http://www.buchi-analytical.com/file/2/ct_1120_ctDownload1.pdf
Advanced Electronic Ceramics I (2004)
Solid State Reaction
                    AO




                    BO2
    Starting powder        Incomplete reaction Proper reaction Strong bond
                                                               due to excessive
                                                               reaction
                                     ABO3
                                           A+
           AO     BO2               AO           BO2
                                                                  L ∝ t1/2
                                           B2+


                                            L
          Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984)
Advanced Electronic Ceramics I (2004)




                          Solid State Reaction: Particle size
                     (1) coarse particles

                                                            AO
                           AO
                                                                ABO3
                          BO2                              BO2


                                             L ∝ t1/2
                     (2) fine particles
                        AO
                                                           ABO3
                                  BO2




                                 For complete reaction, t1 = 4t2
          Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984)
Advanced Electronic Ceramics I (2004)
Solid State Reaction: Particle-size distribution

           At the presence of a coarse particle in a fine matrix particles
                      AO
                                                         ABO3

                              BO2                              BO2




                 Strong bond between particles can be occurred
                 when the reaction time increased in order to achieve
                 complete reaction




          Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984)
Advanced Electronic Ceramics I (2004)




                           Solid State Reaction: mixing
                       (1) good mixing                        AO         BO2
                               AO

                                                                  ABO3
                                BO2


                       (2) bad mixing

                                                              AO
                                                                  ABO3
                                                             BO2


          Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984)
Advanced Electronic Ceramics I (2004)
Solid State Reaction: other parameters

          1. Compaction or filling state
          - The reaction occurs and the contact points between two phase

          2. Temperature
          - the temperature dependence of diffusion coefficient
              D = Do exp (-E/RT)




          Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984)
Advanced Electronic Ceramics I (2004)




                                                Solid State Reaction: BaTiO3
                                                       Fig. In-situ X-ray diffraction
                                                       BL: γ-BaCO3, BH: β-BaCO3,
                                                       T: TiO2, B2T: Ba2TiO4,
                                                       BT: BaTiO3, BT3: BaTi3O7,
    BaCO3:
                                                       BT4: BaTi4O9,
     TiO2


                                                     B2T formation from ~800oC
                                                     BT formation from ~900oC
                                                     The completion of BT formation
                                                     : ~1200oC




                      Temperature (oC)
          Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984)
Advanced Electronic Ceramics I (2004)
Solid State Reaction: BaTiO3
                                                          Fig. In-situ X-ray diffraction
                                                          BL: γ-BaCO3, BH: β-BaCO3,
                                                          T: TiO2, B2T: Ba2TiO4,
                                                          BT: BaTiO3, BT3: BaTi3O7,
                                                          BT4: BaTi4O9,
    BaCO3:
     TiO2
                                                          Avg. size of BaTiO3: 1 µm
                                                          (A) avg. size of TiO2: 6.5 µm
                                                          (B) avg. size of TiO2: 2.0 µm
                                                          (C) avg. size of TiO2: 0.05 µm

                                                          In the case of fine powder,
                                                          - small B2T formation
                                                          - BT formation
                      Temperature (oC)
                                                            at low temperature

          Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984)
Advanced Electronic Ceramics I (2004)




                                                 Solid State Reaction: BaTiO3
                                                         Fig. In-situ X-ray diffraction
                                                         BL: γ-BaCO3, BH: β-BaCO3,
                                                         T: TiO2, B2T: Ba2TiO4,
                                                         BT: BaTiO3, BT3: BaTi3O7,
                                                         BT4: BaTi4O9,
    BaCO3:
     TiO2

                                                     The curves for the co-precipitated
                                                     BaTiO3 powder
                                                     - almost no intermediate reaction
                                                     - low temperature formation



                      Temperature (oC)

          Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984)
Advanced Electronic Ceramics I (2004)
Solid State Reaction: BaTiO3


                1. Reaction at the contact points
                In order to avoid the incomplete reaction,
                - smaller particle size
                - good mixing
                - narrow particle-size distribution
                - good compaction between particles

                2. Reaction at relatively high temperature
                - frequently results the milling the powder aggregates
                  for further process
                - involves the contamination during ball milling




          Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984)
Advanced Electronic Ceramics I (2004)

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Aem Lect2

  • 1. Solid State Reaction: General - Reaction between the solids Advantages 1. Simple apparatus (ball milling, A+B rotatory evaporator) 2. Inexpensive (cost-effective) Disadvantages 1. Wide particle-size distribution 2. Coarse particle size ( ≥1µm) 3. Contamination during mixing 4. High temperature is required for reaction especially when the particle size is large C+A+B or when the mixing is insufficient 5. Compositional fluctuation due to the incomplete reaction 6. Difficult to control the particle shape Advanced Electronic Ceramics I (2004) Rotatory evaporator http://www.buchi-analytical.com/file/2/ct_1120_ctDownload1.pdf Advanced Electronic Ceramics I (2004)
  • 2. Solid State Reaction AO BO2 Starting powder Incomplete reaction Proper reaction Strong bond due to excessive reaction ABO3 A+ AO BO2 AO BO2 L ∝ t1/2 B2+ L Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984) Advanced Electronic Ceramics I (2004) Solid State Reaction: Particle size (1) coarse particles AO AO ABO3 BO2 BO2 L ∝ t1/2 (2) fine particles AO ABO3 BO2 For complete reaction, t1 = 4t2 Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984) Advanced Electronic Ceramics I (2004)
  • 3. Solid State Reaction: Particle-size distribution At the presence of a coarse particle in a fine matrix particles AO ABO3 BO2 BO2 Strong bond between particles can be occurred when the reaction time increased in order to achieve complete reaction Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984) Advanced Electronic Ceramics I (2004) Solid State Reaction: mixing (1) good mixing AO BO2 AO ABO3 BO2 (2) bad mixing AO ABO3 BO2 Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984) Advanced Electronic Ceramics I (2004)
  • 4. Solid State Reaction: other parameters 1. Compaction or filling state - The reaction occurs and the contact points between two phase 2. Temperature - the temperature dependence of diffusion coefficient D = Do exp (-E/RT) Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984) Advanced Electronic Ceramics I (2004) Solid State Reaction: BaTiO3 Fig. In-situ X-ray diffraction BL: γ-BaCO3, BH: β-BaCO3, T: TiO2, B2T: Ba2TiO4, BT: BaTiO3, BT3: BaTi3O7, BaCO3: BT4: BaTi4O9, TiO2 B2T formation from ~800oC BT formation from ~900oC The completion of BT formation : ~1200oC Temperature (oC) Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984) Advanced Electronic Ceramics I (2004)
  • 5. Solid State Reaction: BaTiO3 Fig. In-situ X-ray diffraction BL: γ-BaCO3, BH: β-BaCO3, T: TiO2, B2T: Ba2TiO4, BT: BaTiO3, BT3: BaTi3O7, BT4: BaTi4O9, BaCO3: TiO2 Avg. size of BaTiO3: 1 µm (A) avg. size of TiO2: 6.5 µm (B) avg. size of TiO2: 2.0 µm (C) avg. size of TiO2: 0.05 µm In the case of fine powder, - small B2T formation - BT formation Temperature (oC) at low temperature Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984) Advanced Electronic Ceramics I (2004) Solid State Reaction: BaTiO3 Fig. In-situ X-ray diffraction BL: γ-BaCO3, BH: β-BaCO3, T: TiO2, B2T: Ba2TiO4, BT: BaTiO3, BT3: BaTi3O7, BT4: BaTi4O9, BaCO3: TiO2 The curves for the co-precipitated BaTiO3 powder - almost no intermediate reaction - low temperature formation Temperature (oC) Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984) Advanced Electronic Ceramics I (2004)
  • 6. Solid State Reaction: BaTiO3 1. Reaction at the contact points In order to avoid the incomplete reaction, - smaller particle size - good mixing - narrow particle-size distribution - good compaction between particles 2. Reaction at relatively high temperature - frequently results the milling the powder aggregates for further process - involves the contamination during ball milling Ceramic Processing: Powder Preparation and Forming, Ceramic Society of Japan (1984) Advanced Electronic Ceramics I (2004)