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    Lecture Notes II Defect Chemistry

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    rafel
    This document discusses defect chemistry in ceramic materials. It defines defects as any deviation from the perfect crystal structure and categorizes defects as atomic, electronic, or macroscopic. It describes common atomic point defects in oxides like oxygen and cation vacancies and interstitial ions. Defects are denoted using notation that indicates their type, position, and relative charge. Intrinsic defects like Frenkel and Schottky defects form to maintain stoichiometry. Extrinsic defects form via reactions with the surrounding atmosphere or substitution. Defect concentrations depend on factors like oxygen pressure and temperature and can be modeled using concepts like Brouwer plots and the law of mass action. Calculations of defect concentrations consider deviation from stoichiometry and site

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    Lecture Notes II Defect Chemistry

    Uploaded by

    rafel
    20 views40 pages
    This document discusses defect chemistry in ceramic materials. It defines defects as any deviation from the perfect crystal structure and categorizes defects as atomic, electronic, or macroscopic. It describes common atomic point defects in oxides like oxygen and cation vacancies and interstitial ions. Defects are denoted using notation that indicates their type, position, and relative charge. Intrinsic defects like Frenkel and Schottky defects form to maintain stoichiometry. Extrinsic defects form via reactions with the surrounding atmosphere or substitution. Defect concentrations depend on factors like oxygen pressure and temperature and can be modeled using concepts like Brouwer plots and the law of mass action. Calculations of defect concentrations consider deviation from stoichiometry and site

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    This document discusses defect chemistry in ceramic materials. It defines defects as any deviation from the perfect crystal structure and categorizes defects as atomic, electronic, or macroscopic. It describes common atomic point defects in oxides like oxygen and cation vacancies and interstitial ions. Defects are denoted using notation that indicates their type, position, and relative charge. Intrinsic defects like Frenkel and Schottky defects form to maintain stoichiometry. Extrinsic defects form via reactions with the surrounding atmosphere or substitution. Defect concentrations depend on factors like oxygen pressure and temperature and can be modeled using concepts like Brouwer plots and the law of mass action. Calculations of defect concentrations consider deviation from stoichiometry and site

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    20 views40 pages

    Lecture Notes II Defect Chemistry

    Uploaded by

    rafel
    This document discusses defect chemistry in ceramic materials. It defines defects as any deviation from the perfect crystal structure and categorizes defects as atomic, electronic, or macroscopic. It describes common atomic point defects in oxides like oxygen and cation vacancies and interstitial ions. Defects are denoted using notation that indicates their type, position, and relative charge. Intrinsic defects like Frenkel and Schottky defects form to maintain stoichiometry. Extrinsic defects form via reactions with the surrounding atmosphere or substitution. Defect concentrations depend on factors like oxygen pressure and temperature and can be modeled using concepts like Brouwer plots and the law of mass action. Calculations of defect concentrations consider deviation from stoichiometry and site

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    of 40

    Lecture Notes II

    Defect Chemistry

    Ole Toft Sørensen


    (Risoe National Laboratory)
    Ceramic Materials Consultant
    Email:otsdk@yahoo.dk

    1
    Electroceramics

    • Electrical properties determined by defects

    • Knowledge of defect chemistry necessary to


    understand Electroceramics!

    2
    What is a defect?

    Fundamental definition:
    Any deviation from the perfect crystal is a defect!

    - Macroscopic defects (porosities, cracks)

    - Atomic defects

    - Electronic defects

    3
    Atomic (point) defects in Oxides!

    Missing ions:
    - oxygen ions,
    oxygen vacancies
    - cations,
    cation vacancies
    Substituted ions
    Interstitiel ions 4
    Electronic defects in oxides

    •Atomic (point) defects


    – type, properties depend on position !

    •Electronic defects
    – type, properties depend on energy levels
    available for the electrons

    • electrons
    • positive holes
    5
    Defect notations
    subscript
    (Symbol for type)position

    VO = vacancy on oxygen position


    VM = vacancy on metal position, VFe

    Oi = interstitial oxygen ion


    Mi = interstitial cation

    YZr = Y-ion on Zr-ion position


    6
    Charges of defects
    Relative charge
    Charge relative to the charge normally
    present in the position of the defect

    Examples:
    ZrZr – relative charge = zero, FeO:
    but Fe2+ vacancy – rel. ch. = ?
    YZr - relative charge = -1
    -2 of course!
    ZrY ? Rel. ch.+1
    7
    Charges of oxygen vacancies
    Formation of oxygen vacancies:
    Oxygen atoms are removed from the crystal

    Oxygen ions – how many electron in outer orbital ? 8


    Oxygen atoms – how many electrons in outer orbital ? 6
    Oxygen vacancy – how many electrons left ? 2
    Rel. Charge ? Zero!
    But these electrons can easily migrate to neighbouring ions
    forming vacancies with one or zero electrons present.

    Thus VO with rel. charges of zero, +1 and +2 can be formed !


    8
    Relative charges of interstitial ions

    O2- ions,Oi ? -2

    Cl-1 – ions, Cli, rel. charge = -1

    Na+1 – ions, Nai , ? +1

    Zr4+ - ions, Zri, rel. charge = +4

    9
    Nomenclature: relative charges
    Relative charges are indicated
    by a superscript:
    • neutral - x
    • positive charges – black dots
    • negative charges - apostrophes

    Examples:
    Neutral: VOx
    Positive charges: VO•, VO••

    Negative charges: VFe″


    10
    Practise: Nomenclature

    11
    Answers to practise

    12
    Formation of defects
    Three typical areactions:

    - ”high” temperatures, INTRINSIC DEFECTS

    - reaction with surrounding atmosphere

    - substitution

    13
    Intrinsic defects
    Pair of defects:

    -Frenkel defect:
    cation vacancy and interstitial cation
    -Anti-Frenkel defect:
    oxygen vacancy and interstitial oxygen ion
    -Schottky defect:
    oxygen vacancy and cation vacancy
    MO: OOx + MMx = VO•• + VM″
    M2O3: 3OOx + 2MMx = 3VO•• + 2VM″′
    Stoichiomtry must be maintained ! 14
    Defects formed in an reaction
    Reduction
    with surronding atmosphere.
    MO2 = MO2-x+ x/2 O2

    OOx + 2MMx = VO•• + 2MM′ + 1/2O2

    Oxides with cations


    easily reduced!

    15
    Defects formed in a reaction with
    Oxidation
    a surrounding atmosphere - 2
    MO + y/2O2 = M1-yO

    Note – clusters !

    Cations easily oxidized!

    16
    Formation of interstitial
    oxygen ions- Oi
    High oxygen pressures !

    1/2 O2 + 2MMx = Oi″ + 2MM•

    Oxides where cations are easily oxidized – FeO

    17
    Defects formed by substitution!
    Substitution of cations !

    Lower valency: Higher valency:

    ZrO2 doped with CaO: Y2O3 doped with ZrO2:

    CaO(ZrO2) = CaZr″ + VO•• + OOx 2ZrO2(Y2O3) =


    Oxygen vacancies formed to 2ZrY• + Oi″ + 3OO
    maintain electrical neutrality !

    Same valency?
    18
    Practice
    Formation of Defects

    19
    Answers
    Practice – Formation of Defects

    20
    Dependence on oxygen
    pressure

    Can defects in a solid be considered as ions in a solution?

    Yes if these conditions are fulfilled:


    - random distribution of defects
    - no interactions
    - high mobility

    Law of mass action can be used. 21


    Rules which must be obeyed

    • ratio between cation and anion positions – Constant!

    • the total number of positions can be changed,


    but not the ratio!

    • neutrality must be maintained

    22
    Formation of oxygen
    vacancies

    23
    [VO]  log pO2
    1

    24
    Brouwer plots - VO

    25
    Practise:
    Brouwer plots oxygen vacancies

    26
    Answers to practice:
    Brouwer plots oxygen vacancies

    27
    [VM]  log pO2

    28
    5
    Brouwer plots - VM

    29
    Practice:
    Formation of cation vacancies

    30
    Answers to practice:
    Formation of cation vacancies

    31
    Brouwer plot for Oi

    32
    Brouwer plot:
    many defects
    Construction:
    - Log Conc. defect
    vs log(pO2)
    - 3 p(O2) regions;
    - one type of defect
    dominates in each
    region
    - sharp transition
    between regions,
    approximation

    33
    Calculation of defect
    concentrations

    • Deviation from the stoichiometric composition.

    • Fraction of defects

    • Number of defects per cm3

    34
    Deviation from stoichiometric
    composition

    35
    Site Fractions

    MO2-x

    Fe1-yO

    MO2+x

    36
    Number of defects per cm3

    37
    Practice
    Calculation of defect
    concentrations

    38
    Answers
    Calculaion of defect
    concentrations

    39
    Content

    40

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