Beruflich Dokumente
Kultur Dokumente
Lecture 16-17
Magnetic Properties of
Ceramic Materials
Callister, Materials Science and Engineering- An Introduction.
Fe: [Ar]3d64s2
Important magnetic materials are Fe,Ni,Co,Gd,Ho (metallic) and
Fe3O4(Feo.Fe2O3)and all ferrites.
The most fundamental magnetic moment is the Bohr magneton, B which is of
magnitude 9.27 x10-24 Am2
Comparison of the Electron Configurations and
Unpaired Electrons for Various Ions
Ion Electron Number of Magnetic moment in
Configuration Unpaired Electrons Bohr magneton (B)
Mg2+ 2p6 0 0
Al3+ 2p6 0 0
O2- 2p6 0 0
Sc3+ 3p6 0 0
Ti4+ (Ti3+) 3p6(3d1) 0(1) 0(1)
V3+ (V5+) 3d2(3p6) 2(0) 2(0)
Cr3+ (Cr2+) 3d3(3d4) 3(4) 3(4)
Mn2+ (Mn3+)(Mn4+) 3d5(3d4)(3d3) 5(4)(3) 5(4)(3)
Fe2+ 3d6 4 4
Fe3+ 3d5 5 5
Co2+ (Co3+) 3d7(3d6) 3(4) 3(4)
Ni2+ 3d8 2 2
Cu2+ (Cu+) 3d9(3d10) 1(0) 1(0)
Types of Magnetism
Cooperative behavior
Ferromagnetism
Antiferromagnetism
Ferrimagnetism
Non-cooperative (statistical) behavior
Diamagnetism
Paramagnetism
Diamagnetism:
very weak , nonpermanent and persists only while an external field is being applied.
Induced magnetic moment is extremely small, and in a direction opposite to that of
the applied field.
Thus, r is less than unity (however, only very slightly), and the magnetic
susceptibility is negative.
Paramagnetism:
a permanent dipole moment by virtue of
incomplete cancellation of electron spin and/or
orbital magnetic moments.
the orientations of these atomic magnetic
moments are random, such that a piece of material
possesses no net macroscopic magnetization.
These atomic dipoles are free to rotate, and
paramagnetism results when they preferentially
align, by rotation, with an external field
Ferromagnetism:
• Certain metallic materials possess a permanent magnetic moment in the absence of
an external field,
• This mutual spin alignment exists over relatively large volume regions of the
crystal called domains
Bs =µoMs
Antiferromagnetism:
The alignment of the spin moments of neighboring atoms or ions in exactly
opposite directions is termed antiferromagnetism.
No net magnetic moment is associated with the O2- ions, since there is a total
cancellation of both spin and orbital moments.
However, the Ni2+ ions possess a net magnetic moment that is predominantly of
spin origin. These ions are arrayed in the crystal structure such that the moments of
adjacent ions are antiparallel.
Ferrimagnetism:
Antiparallel spin-coupling interactions, but not same magnitude. However, the net
1) If Jex is positive, Eex is a minimum when the spins are parallel (Cos = 1), leading to
ferromagnetism
2) If Jex is negative, Eex is a minimum when the spins are antiparallel (Cos = -1), leading to
antiferromagnetism.
Molecular . weight M s
nB
N B
• Where nB is the saturation magnetization per formula unit in Bohr magneton, Ms is
the saturation magnetization in emu/gm, N is the Avogadro’s number, 6.02×1023
and µB is the Bohr magneton, 0.927×10-20erg/Oe
Theoretical magnetic moment calculation
Calculation of magnetic moment in Bohr magneton (nB) and saturation magnetization, Ms
(emu/gm using above equation) of Ni0.75Zn0.25Fe2O4,, Ni0.55Zn0.45Fe2O4 mixed ferrites are:
• Ms (emu/gm) can be calculated using equation for the respective Ni-Zn ferrites are
When, Zn=0.25; or, n Molecular . weight M s
N B
B
234.33 M s
4
6.02 1023 0.927 10 20
Ms= 95 emu/gm
Magnetic Behavior of Spinel ferrites Composition
Ferrite Postulated ion Distribution Magnetic Magnetic Magnetic Moment Magntizati Lattice const.
Moment (B) Moment (B) (B) per Molecule on (Å)
of of Octahedral MeFe2O4 emu/gm
Tetrahedral Ions at 0K
Ions
Tetrahedral Octahedral Theor Experi
Ions (A) Ions (B)
0.8Mn2++ 0.2Mn2+ +
MnFe2O4 4+1 1+9 5 4.6 112 8.50
0.2Fe3+ 1.8Fe3+
0.1Mg2+ 0.9Mg2+ +
MgFe2O4 0+4.5 0+5.5 1 1.1 31 8.36
0.9Fe3+ 1.1Fe3+
Li+0.5 +
Li0.5Fe2O4 Fe3+ 5 0+7.5 2.5 2.6 69 8.33
1.5Fe3+
Yafet-Kittel (Y-K) angles
The decrease of magnetization can be treated theoretically by
triangular arrangement of spins as proposed by Yafet and Kittel.
Yafet-Kittel (Y-K) angles are calculated by using the formula,
n B M B (x) cos YK M A ( x)
where Y-K is the canted angle (Y-K angle), MA and MB are the
magnetic moment of A and B sites. As the canting angle cos YK
increases, the value of magnetic moment on the B site (MB)
decreases, resulting in a decrease of overall magnetic moment
(nB) of the sample according to the above equation with
increasing Zn(x) or Cd(x) The canting angle starts to develop
sizeable value when x is greater than 0.4 due to weakening of JAB
exchange interaction.
Theoretical calculation of lattice constant of spinel ferrites:
a th
8
3 3
r
A
R O 3 rB R O
where Ro is the radius of the oxygen ion (1.32 Å) and rAand rB are the ionic radii of tetrahedral
(A-site) and octahedral (B-site), respectively. The values of rA and rB will depend critically on
the cation distribution of the system. In order to calculate rA and rB, the following cation distribution
is proposed for the composition Cu1-xZnxFe2O4:
where the brackets ( ) and [ ] indicate the A-site and B-site respectively. The cation
distribution is based on the following:
rA C AZn r Zn 2
CAFe'r(Fe3 )
rB
1
2
C BCu r (Cu 2 ) C BFe r ( Fe3 )
where r(Zn2+), r(Cu2+) and r(Fe3+) are ionic radii of Zn2+(0.83), Cu2+(0.76) and Fe3+(0.67)
respectively,
Using these formulae, the ionic radius of A-site (rA) and B-site (rB) were calculated and also
the calculated theoretical lattice parameter given in Table.
x Chemical A-site B-site (Å) (Å) ath (Å)
formulae
0.0 CuFe2O4 Fe 3
1
Cu
2
1
Fe13 O42 0.67 0.715 8.491
0.1 Cu0.9Zn0.1Fe
Zn 2
0 .1 Fe03.9 Cu 2
0.9
Fe13.1 O42 0.686 0.711 8.503
2O4
0.4 Cu0.6Zn0.4Fe
Zn 2
0. 4 Fe03.6 Cu 2
0.6
Fe13.4 O42
0.734 0.697 8.541
2O4
0.5 Cu0.5Zn0.5Fe
Zn 2
0. 5 Fe03.5 Cu 2
Fe13.5 O42
0.75 0.693 8.544
2O4
0.5
Soft Ferrites
Motors
Power conversion Large MR
Generators
electrical - mechanical Small HC
Electromagnets
Low losses = small Fe based materials, e.g.
conductivity Fe + » (0,7 - 5)% Si
Power adaption (Power) Transformers Fe + » (35 - 50)% Co
Transformer
Linear M - H curve
("Überträger")
Hard Ferrites
Loudspeaker Fe/Co/Ni/Al/Cu
Small generators »50/24/14/9/3
Permanent magnets Small motors Large HC (and MR) SmCo5
Sensors Sm2Co17
"NdFeB" (= Nd2Fe14B)
Video tape
Data storage analog
Audio tape Medium HC(and MR),
BaFe12O19 ,NiCo, CuNiFe,
hystereses loop as
Ferrite core memory CrO2
rectangular as possible
Drum Fe2O3
Magnetic ferrite or
garnets (AB2O4, or
Data storage digital A3B5O12), e.g.
with A = Yttrium (or
Bubble memory Special domain structure mixtures of rare earth),
and B = mixtures of Sc,
Ga, Al
Most common:
Y3Fe5O12,Gd3Fe5O12