Chapter 5

Structural Imperfections

1
屏東科技大學材料工程系
實際的晶體並非完美的晶體結構，而都含有各種晶格
缺陷。離子型晶體的特徵是為了保持局部的電中性，
所以點缺陷總是成對地出現，代表性的點缺陷為
Frenkel defect 與 Schottky defect

一個間隙型離
子與一個空位 一對陰陽離子
形成 空位形成

2
In the previous two chapters we have considered structures of ideal crystals and also
structures of some noncrystalline glasses. There are many properties that are
markedly dependent on small deviations from ideal structures, and we can best
approach these structure-sensitive properties on the basis of departures from the ideal
structures.
If we consider a perfect crystal as one with a completely ordered structure having its
atoms at rest (except for zero-point oscillation at the absolute zero temperature) and
with the electrons distributed in the lowest-energy states, there are several types of
deviations or imperfections which may occur. The first is increased amplitude of
vibration of the atoms about their equilibrium rest positions as the temperature is
increased. Imperfections also occur in the electronic energy levels: electrons may be
excited into higher energy levels, leaving vacant positions in the normally filled
electronic energy-level bands, called electron holes.

3
Finally there are a number of atomic defects, including substitution of a wrong atom
or a foreign atom for a normal one, interstitial atoms, vacant atom sites, and line
imperfections called dislocations. Finally we might also consider the crystal surfaces
or boundaries between crystals as imperfections.

dislocations

boundaries

4
4.1 Notation used for Atomic Defects
Several types of structural imperfections are believed to occur in ceramic materials.
One departure from ideality involves the motion of an atom from a normal site to an
interstitial position, as illustrated in Fig. 4.1a. This type of disorder, which results in
equal concentrations of vacant lattice sites and interstitial atoms, is called Frenkel
disorder.

Fig. 4.1(a): Frenkel disorder. Ion leaving normal site forms interstitial ion and
5
leaves a vacancy.
4.1 Notation used for Atomic Defects
Another kind of disorder, which involves the simultaneous production of both cation
and anion vacancies, as illustrated in Fig. 4.1b, is referred to as Schottky disorder.

Fig. 4.1(b): Schottky disorder. Equal numbers of anion and cation vacancies
6
occur..
Ceramic systems are rarely if ever without impurities, and solute atoms may either
substitute for host atoms on normal lattice sites, as in substitutional solid solution, or
incorporate on normally unoccupied interstitial sites in the host lattice, as in
interstitial solid solution. These two arrangements are illustrated in Fig. 4.1 c and d.

Substitutional Interstitial solid solutions

Fig. 4.1(c) Substitutional & (d) Interstitial solid solutions.

7
8
In keeping track of the various defects which may exist simultaneously in a single
ceramic material, an essential requirement is an adequate system of notation for
describing point defects in ceramics. The Kroger Vink notation is most widely
used. In this notation, when we add or subtract elements from the crystal, we do
so by adding or subtracting electrically neutral atoms and thus avoid making
judgments and decisions about bond types; for application to ionic systems this
requires that we separately add or subtract electrons.
Consider the various conceivable defects and notations for the imaginary binary
compound MX.
1. Vacant Lattice Sites (Vacancies): When empty lattice sites occur, they are
indicated by the symbols VM and Vx for the M and X sites, respectively; in the
atomic notation, the subscript M indicates a missing M atom.
2. Interstitial Atoms: In addition to the normally occupied lattice sites of a crystal
structure, there are also interstitial sites. When atoms occupy these interstitial
positions , they are denoted by Mi and Xi.
3. Misplaced Atoms: It is also possible in some compounds for M atoms to be on
X sites (Mx); the subscript always indicates the position of each particular atom
in the lattice.

9
4. Associated Centers: In addition to single defects, it is also possible for one or
more lattice defects to associate with one another, that is, to cluster together.
These are indicated by breaketing the components of such a cluster; for
example, (VMVX) or (XiXM).

5. Solutes: These, if present, are coded as to lattice position in the same way as
native defects; LM and SX indicate a solute atom L on an M site and S on an X
site. Li indicate that the solute L is on an interstitial site.

6. Free Electrons, Electron Holes: In strongly ionic materials, electrons are

normally localized at a particular atom site in a way which can be described in
terms of the ion valence. However, as discussed in Chapter 2, this is not always
the case , and some fraction of the electrons denoted e΄, may not be localized at
a particular site; similiarly there may be missing electrons, denoted electron
holes h., which are not localized at a particular atom site.

10
7. Charged Defects: In insulators and semiconductors we usually think of the
respective species as ions; for example , sodium chloride is made up of Na+
and Cl- ions. If we conceive of removing a positively charged Na+ sodium ion
from the NaCl structure , we remove the sodium atom without one of its
electrons; as a result , the vacancy has associated with it an extra electron with
a negative charge which we write as e’, where the superscript refers to a unit
negative charge. If this excess electron is localized at the vacant site, as would
normally be the case in NaCl, we write V’Na . Similarly , if we conceive of
removing a negatively charged Cl- chlorine ion , we remove the chlorine atom
plus an associated electron , leaving a positive electron hole , which we write
h·, where the superscript refers to a unit positive charge . If this excess positive
charge is localized at the vacant site, as would normally be the case for NaCl,
we write V·Cl. In some materials less strongly ionic than NaCl these excess or
missing electrons, e' or h·, may not remain localized at the vacant site, the
separation being represented by the reactions

11
 ‘
VNa
Na+ Cl- Na+ Cl- Na+

.
VCl Cl- Na+ Cl- Cl-

Na+ Na+ Cl- Na+

Cl- Na+ Cl- Na+ Cl-

12
 With each of the other defect symbols - VM, VX, Mi , MX, (VMVX) - an effective
charge relative to the host lattice is also possible. Thus Zn‥
i would indicate a Zn
2+

ion at an interstitial site which is normally unoccupied and without an effective

change. Substituting a divalent Ca2+ ion for monovalent Na+ on a sodium site gives
a local electronic structure augmented by one extra positive charge and is
﹒
represented as CaNa.
Note that the superscripts + and – are used to indicate real charged ions, whereas
the superscripts
﹒ and ' indicate effective positive and negative charges with
respect to the hose lattice. Other possibilities arise from nonstoichiometry. In FeO,
for example, it is possible to have Fe3+ ions in addition to the normal Fe2+ ions. In
﹒
this case, Fe3+ ions are indicated as FeFe﹒

13
Kroger-Vink notation
A standard used for the description of defects in ionic materials is Kroger-Vink
notation, in which a defect is described by three parts.
The main body of the notation identifies whether the defect is a vacancy “V”, or an ion
such as “Mg”.
The subscript denotes the site that the defect occupies, either the normal atom sites of
the host lattice or an interstitial site “i”.
The superscript identifies the effective charge (or relative charge) of the defect relative
to the perfect crystal lattice. For this part of the notation, dots () represent positive
effective charges, dashes (΄) represent negative charge, and x’s are sometimes used
to show neutrality.

14
V”Mg: There is the absence of an Mg2+ ion in the perfect lattice.
…
Ali : is an interstitial aluminum ion. The subscript i denotes that the aluminum is
interstitial, and the superscript show that the normally unoccupied interstitial
site now has an excess +3 charge due to the Al3+ ion.

Some atoms can accept more than one valence state. This is especially common for the
transition metal ions. It is therefore possible to have several distinctly different
defects for a particular element on a given site with different “ionization” or
oxidation” states. Iron substituted for Fe2+ in MgO can be FeMgx (an Fe2+ ion) or

FeMg (if it is Fe3+). In FeO, where the iron oxidation state is predominantly 2+,

trivalent iron can also be described as a positive defect, FeFe.

15
 4.2 Formulation of Reaction Equations
As each type of defect and its concentration in a material can be described in terms
of associated energies of formation and other thermodynamic properties, it is possible
to treat all imperfections as chemical entities and treat them in a manner referred to as
defect chemistry. Defect interactions may be conceptualized in terms of mass-action
equilibria, thus enabling the representation of such interactions by means of defect
equations. The following rules must be observed:

1. Site Relation. The number of M sites in a compound MaXb must always be in

correct proportion to the number of X sites (1:1 in MgO,1:2 in UO2, etc.). In
maintaining this proportion, however, the total number of each type of site may
change.
2. Site Creation. Some defect changes such as introducing or eliminating a vacant
M site VM correspond to an increase or decrease in the number of lattice sites. It
is important that this be done in a way that does not change the site relation
described in rule 1. Defects indicating site creation are VM , VX , MM , MX , XM ,
﹒
XX , and so on. Nonsite-creating entities are e’ , h , Mi , Li , and so on.

16
3. Mass Balance. As in any chemical equation ,a mass balance must be maintained.
Here it is helpful to remember that the subscript in the defect symbol indicates the
site under consideration and is of no significance for the mass balance.

4 .Electrical Neutrality. The crystal must remain electrically neutral. Only neutral
atoms or molecules are exchanged with other phases outside the crystal under
consideration ; within the crystal neutral particles can yield two or more oppositely
charged defects. The condition of electrical neutrality requires that both sides of a
defect-reaction equation have the same total effective charge, not necessarily zero.

5.Surface Sites. No special indication of surface sites is used. When an atom M is

displaced from the bulk of the crystal to its surface, the number of M sites increases.

17
 點缺陷的表示方法
為了表示離子型晶體的點缺陷種類，常常採用Kroger - Vink
符號表示法，如Aa這裡，A 表示離子或空位，下標a 為與其
對應的晶格點陣位置，上標b 表示由於引入缺陷而引起的化 b
合價偏移。

現在我們討論1價的陽離子M＋和1價的陰離子X-構成的化合
物MX。A對應於陽離子可寫成M，對應於陰離子可寫成X，
空位寫成V，對於A，用M 表示M+位置，用X表示X-位置，
間隙原子（離子）用i表示。用 · 表示化合價正偏差，用 ˊ 表
示化合價負偏差，x表示無化合價偏差。

18
在上述兩種情況下由一個Ca2+ 離子形成的空位數是不等的。
這種反應式的建立必須滿足下述條件：

1. 反應時要保持物質不滅定律。
2. 由分子式AaBb給出的定比化合物陽離子A 位置與陰離子B
位置的比例總是a : b 。
3. 空位數的增減引起位置數的增減，但間隙式離子、電子、
電洞對位置的形成沒有貢獻。
4. 保持電中性。

19
At this point we anticipate the next section, in which we discuss the solution of CaCl2 in
KCl to see how these rules apply.

Considering only atomic substitutions, a possible solution process is

We may further assume that the substitutions are fully ionized.

interstitials

20
4.3 Solid solutions
Of the many types of departure from an ideal crystal, the one easiest to visualize
is the inclusion of foreign atoms in the host crystal, as illustrated in Fig. 4.1 c and
d.

Substitutional Interstitial solid solutions

Fig. 4.1(c) Substitutional & (d) Interstitial solid solutions.

21
If a material crystallizes in the presence of foreign atoms, they may be almost
completely rejected by the crystal if they appreciably increase the energy of the
crystalline form. On the other hand, if building them into the host structure in an
ordered way leads to a large lowering of the system’s energy, a new crystalline form
develops.
Solid solutions are stable when the mixed crystal has lower free energy than the
alternative—building up two crystals of different composition or building up a new
structure in which the foreign atoms are put on ordered sites. As previously
discussed, the free energy is given by the relation

G = E + PV – TS --- (4.6)

Where E is largely determined by the structural energy and the entropy is a measure
of the randomness (probability) of the structure. If an atom added at random greatly
increases the structure energy, the solid solution is unstable and two crystal
structures result. On the other hand, if the addition of a foreign atom greatly lowers
the structure energy, the system tends to form an ordered new phase. If the energy is
not much changed, the entropy is increased by random additions so that the solid
solution has the lowest energy and is the stable configuration.
22
 For the MgO-NiO system, both end members
have the sodium chloride crystal structure,
and a complete series of solid solutions
occurs. The schematic free-energy-
composition diagram for 1500 C is 4.2b. The
lowest-free-energy phase for all compositions
at 1500  C is the solid solution rather than
any ordered structure or the liquid.

Fig. 4-2: (a) Phase diagram of MgO-NiO. (b) Schematic representation of free-energy- 23
composition diagram of MgO-NiO system for T < 2000  C
 For the MgO-Al2O3 system, the end members
have different crystal structures, and a third
possibility is the formation of an intermediate
compound. Experimentally it is found that for a
50:50 mixture of MgO and Al2O3, the spinel
phase has the lowest free energy and at 1750 C
in the intervals a-b and c-d two solid solutions of
fixed composition but variable amounts are in
equilibrium with each other (the compositions in
equilibrium have the same values of chemical
potential,  = (G/X)T,P, that is , an equal slope,
a common tangent, for the free-energy-
composition curves).

Fig. 4-3: (a) Phase diagram of the MgO-Al2O3 system. (b) Schematic representation of free-
24
energy-composition diagram of MgO-Al2O3 for T =1750 C.
Substitutional Solid Solution. Substitution of one ion for another is common in the
formation of ceramic crystals. The solid-solution phases shown in Figs. 4.2 and
4.3 represent this kind of substitution. For example, crystals of magnesium oxide
frequently contain appreciable amounts of NiO or FeO with a random distribution
of Ni2+ or Fe2+ ions replacing Mg2+ in the crystals so that the final composition of
the crystal can be read Mg1-xNixO, as shown in the phase diagram in Fig. 4.2. A
similar series of solid solutions exists in the system Al2O3-Cr2O3 (rubies are 0.5 to
2% Cr2O3 in Al2O3), ThO2-UO2, albite-anorthite, and many of the spinels.
However, in most systems only a limited number of foreign atoms can be added to
the substitutional solid solution; an excess above the solubility limit at a given
temperature results in the formation of a second phase.

25
There are several factors determining the extent of substitution that can take place
in solid solutions, and a number of rules expressing these factors have been
devised. These rules reflect variations in the free energy, which is made up of
several terms. Lowering of the free energy resulting from an increase in
entropy requires that there be at least a small solubility of foreign atoms in
any structure. Factors which allow extensive substitution are as follows.
1. Size factor. If the sizes of two ions differ by less than about 15% conditions
are favorable for the formation of substitutional solid solutions. If the relative
ion sizes differ by more than 15% substitution is generally limited and is
usually less than a fraction of 1%.
2. Valency factor. If the added ion has a valence different from that of the host
ion, substitution is limited. It can occur, as indicated below, but other
structural changes are also required to maintain overall electrical neutrality.
3. Chemical affinity. The greater the chemical reactivity of the two crystalline
materials, the more restricted is solid solubility, since a new phase is usually
more stable.
4. Structure type. For complete solid solubility the two end members must have
the same type of crystal structure. For TiO2 could obviously not form a
complete series of solid solutions with SiO2.
26
For example, additions of CaO to ZrO2 form a solid solution with the cubic
fluorite structure in which Ca2+ are substituted for Zr4+. Each time this is done,
an oxygen ion site is left vacant to maintain the cation-anion site relationship
of 1:2.

ZrO2
CaO Ca“Zr + Oo + Vo (4.7)

27
 BaSrTiO3
CuO Cu“ Ti + Oo + Vo (4.7)

Why Ti site is substituted by Cu?

dislocation

Ni electrode

Ni electrode BCTZ

BCTZ

BST + 0.6mol% CuO 28

Lattice constant, a (Å )

3.96725
62.48
3.96700
a 62.46
3.96675
Volume 62.44
3.96650
62.42
3.96625
62.40
3.96600
62.38
3.96575
62.36
3.96550 62.34
3.96525 62.32

3.96500 62.30

3.96475 62.28
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

CuO (mol%)

29
BST+ 0.9mol% CuO

30
Similarly, additions of La2O3 to CeO2 or ZrO2 and CdO with Bi2O3 give rise to
substantial numbers of vacant sites in the anion array. In contrast, additions of
MgCl2 to LiCl, Al2O3 to MgAl2O4 and Fe2O3 to FeO lead to vacant sites in the
cation array. Although in the systems just mentioned these effects are large, similar
effects occur in samples for which solid solution is extremely limited; for example,
CaCl2 dissolved in KCl. In this system the solid solubility is less than 1%

In refractory oxides with close-packed crystal structures, the temperature

dependence of the solubility is often large. Although the solubility of Al2O3 in MgO
is several percent at 2000 C, it decreases to only 0.01% at a temperature of 1300C.

At high temperatures the TS product dominates the free energy for solution;
but as the temperature is lowered, the large enthalpy term ( E + PV ) for the
formation of vacant lattice sites dominates (Eq. 4.6)

G = E + PV – TS --- (4.6)

31
The most direct evidence for the formation of vacancies is obtained by determining
the lattice constant for a structure in order to compare theoretical with measured
crystal density. Several examples follow.
A crystal with the composition Zr0.85Ca0.15O1.85 which crystallizes in the fluorite
structure has an X-ray pattern indicating that in a unit cell having an edge of 5.131Å ,
there are four cation sites and eight anion sites. If the cation sites are all filled, and
oxygen ion vacancies occur to give the proper site relationship, there are
4 X 0.15 X 40.08 /6 X 1023 g Ca
4 X 0.85 X 91.22 /6 X 1023 g Zr
8 X 1.85 / 2 X 16 / 6X1023 g O
In 135.1 A3 for a total of 5.48g/cm3.
This is in excellent agreement with the directly measured value of
5.477g/cm3

32
Figure 4.4a shows the change in density calculated from
the X-ray lattice parameter as compared with the directly
measured density; the upper curve is calculated for
another possible model in which the extra cation
occupies an interstitial position. The anion vacancy
structure (Eq.4.7) is found to be in accordance with these
calculations. However, for samples quenched from
1800℃, the data in Fig.4.4b show that the higher
temperature equilibrium corresponds to a different sort of
defect structure. When CaCl2 is added to KCl, the density
change is found to be in accordance with cation-vacancy
formation, as indicated in Eq.4.4 and Fig.4.5a. When
Al2O3 is added to MgO, the density change is also found
to be in accordance with cation-vacancy formation.
These data are shown in Fig. 4.5b.

Fig. 4-4: Change in density on the addition of CaO to ZrO2 in

solid solution quenched from (a) 1600 C and (b) 1800 C . At
1600 C each Ca2+ addition is accompanied by the formation of
33
a vacant lattice site. At 1800 C there is apparently a change in
defect type with composition.
Fig. 4-5: When (a) CaCl2 is added to KCl. (b) Al2O3 is added to MgO, vacant cation lattice
sites are created.
34
Interstitial Solid Solutions. If added atoms are small, they can go on interstitial sites
in the crystal to form solid solutions. This type of solution is particularly common
with metallic bonding, in which added H, C, B, and N fit easily into interstitial sites.

The ability to form interstitial solid solutions depends on the same factors, except for
structure type, that apply for substitutional solid solution-size, valency, and chemical
affinity. The size effect depends on the original host crystal structure. In face-
centered cubic structures, such as MgO, the only available interstitial sites are
tetrahedral sites surrounded by four oxygen ions. In contrast, in TiO2 there are
normally vacant octahedral interstices; in the fluorite structure there are larger
interstices with eightfold coordination; in some of the network silicate structures
such as the zeolites the interstitial positions are very large. Therefore, we expect the
order of ease for forming interstitial solid solutions to be zeolite > ThO2 > TiO2 >
MgO, and this is found to be the case.

35
The addition of ions on interstitial sites requires some associated charge balance to
maintain electrical neutrality. This can be accomplished by vacancy formation,
substitutional solid solution, or changes in the electronic structure. All occur. For example,
when YF3 or ThF4 is added to CaF2, a solid solution is formed in which Th4+ or Y3+
substitute for Ca2+ and at the same time F－ ions are placed on the interstitial sites so that
electrical neutrality is maintained (see Fig. 4.6a).

Likewise, the addition of ZrO2 to Y2O3 creates oxygen interstitials to maintain the proper
site relation and electrical neutrality. The measured density data are given in Fig. 4.6b and
favor Eq. 4.8 (oxygen interstitials) rather than Eq. 4.9 (yttrium vacancies).

In many silicate structures the additional charge due to an interstitial Be 2+ , Li + ,

Na+ is balanced by the replacement of some of the Si 4+ by Al 3+ in solid solution.
36
Fig. 4-6: Addition of (a) YF3 to CaF2 and (b) ZrO2 to Y2O3 give rise to the formation of
interstitial anions.
37
氧化鋯補充資料

純ZrO2從高溫到室溫會發生液相（L）→（~2680℃）立方相（c）→（~2370
℃）正方相（t）→ （~1000℃）單斜相（m）的同素異構轉變，圖二示出
ZrO2三種晶型的單位晶胞結構。當ZrO2中加入穩定劑（Y2O3，MgO，CaO，
CeO2等）構成二元系時，則使相變點降低並變成一個溫度區間，如圖4.16所
示。由於穩定劑的種類與含量不同及加熱冷卻不同，則相變將以不同的方式
進行。

38
當純氧化鋯添加某些相安定劑(如氧化鎂、氧化鈣、氧化釔)，將使只能
在高溫下才能產生安定之正方晶相(t 相)及立方晶相(c相)，亦能在常溫
下安定存在，而因其添加了相安定劑後，(如：氧化釔)即具有高強度、
高韌性和化學抵抗力的材料，因此常被使用於結構陶瓷方面，如射出
件、刀具、光纖陶瓷套圈(ferrule)等。

39
完全安定氧化鋯由於較部份安定氧化鋯添加較多的安定劑(如氧化鎂、
氧化鈣、氧化釔)，於室溫下可完全形成立方晶相，因其高氧離子傳導
性，完全安定氧化鋯亦常被氧氣偵測器及燃料電池工業(做為固態電解
質）使用。雖然如此，氧化鋯的不安定性，必須添加氧化釔等材料作
為安定劑是一種使用上的障礙。

氧化物法製備安定或者部分安定的氧化鋯，常會發生成分不均勻的現
象，甚至經過煆燒反應之後粉末粒徑增加，無法使燒結溫度下降，會
造成不穩定相的產生，這些都是急待克服的問題。

40
釔安定化氧化鋯(Yttrium stabilized Zirconia, YSZ)是 ZrO2中加入Y2O3 所形成，
為立方螢石結構，主要是以陽離子所構成的面心密堆為基礎，其所有的四面
體間隙位置由陰離子填充。每一個金屬陽離子被八個陰離子所包圍，每一個
陰離子則被四個陽離子包圍。在結構中有一個極大的八面體格隙孔洞，因此，
此結構也造成了開放與離子容易擴散的特性。其晶格結構如圖一，如此藉以
安定正方結構之ZrO2，ZrO2在低溫會由正方結構轉換為單斜結構，因而失去
原有的離子導體特性，而加入Y2O3可穩定此一非平衡結晶結構，其中Y2O3的
含量，若低於7-8 mol.%穩定的相是tetragonal相，高於此成份時，ZrO2的穩定
相是正方晶系[1-3]。

而Y2O3 被廣泛的當成氧化鋯的添加劑的原因，就是基於上述的理由。當Y2O3
的添加量在2-3 mol%時，氧化鋯會有極優異的機械性質，且在室溫下保持在
一個均一的正方晶相結構。隨著Y2O3 的添加量在8-12 mol%，氧化鋯即轉變成
立方晶相結構。而Y-TZP 陶瓷是指含單一正方晶相氧化鋯之材料，其主要是
利用添加Y2O3 為穩定劑，並控制其晶粒大小(<1μm)，使介穏態之正方晶相可
以在室溫存在。

41
氧化鋯應用

﹡高密度氧化鋯磨球
﹡高溫爐用加熱器
﹡高溫耐火材
﹡固態燃料電池
﹡氧氣偵測器
﹡分鋼槽流嘴

42
 添加Y2O3對氧化鋯在高溫還原氣份的穩定性之研究
A Study of Phase Stability of Yttria Doped Zirconia on the
High-Temperature in Reducing Atmosphere

43
 表1. ZrO2試片編號與摻雜Y2O3量對照表。

試片編號
3YSZ 6YSZ 7.5YSZ 10YSZ 12.5YSZ 15 YSZ
Y2O3添加量
3 6 7.5 10 12.5 15
(mol.%)

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 Cube-ZrO2
monoclinic-ZrO2
tetragonal-ZrO2
lntensity (arb.unit)

15Y
12.5Y
10Y
7.5Y

6Y
3Y

20 30 40 50 60 70 80

2θ (dgree)
圖2. 添加不同Y2O3於ZrO2在1500℃燒結3小時之XRD繞射圖。 45
 7.5Y 10Y 12.5Y 15Y

老化循環30次
7.5Y 10Y 12.5Y 15Y

圖3. 不同含量釔安定ZrO2於在1500℃燒結3小時 (a：7.5YSZ、c：10YSZ、e：

12.5YSZ、g：15YSZ ) 及老化循環30次(b：7.5YSZ、d：10YSZ、f：12.5YSZ、h：
15YSZ )SEM影像
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 (a) (a)：7.5YSZ cubic-ZrO2
monoclinic-ZrO2

30 circle 於在1500℃燒結3小時及不
同老化循環次數之XRD繞射
Intensity (arb. unit)

20 circle 圖。
10 circle

5 circle

0 circle

20 30 40 50 60 70 80

2 degree (b)：10YSZ
(b)
cubic-ZrO2

30 circle
Intensity (arb. unit)

20 circle

10 circle

5 circle

0 circle

20 30 40 50 60 70 8047

2 degree
 (c)：12.5YSZ cubic-ZrO2
(c)
30 circle
Intensity (arb. unit)

20 circle
於在1500℃燒結3小時及不
10 circle
同老化循環次數之XRD繞射
5 circle 圖。

0 circle

20 30 40 50 60 70 80

2 degree
(d)：15YSZ
(d) cubic-ZrO2

Intensity (arb. unit) 30 circle

20 circle

10 circle

5 circle

0 circle

20 30 40 50 60 70 80

2 degree 48
 表2. 材料粉末粒徑尺寸、相對密度及晶格常數。

單斜晶之晶格常數(Å )
試片編號 相對密度(%) 晶體結構
a軸 b軸 c軸
5.1501(56) 5.1936(65) 5.2881(46)
7.5YSZ 96.82 ± 1.21 Cubic + Monoclinic 立方晶之晶格常數(a軸, Å )
5.13974(15)
10YSZ 93.12 ± 0.77 Cubic 5.14436(10)
12.5YSZ 92.06 ± 0.88 Cubic 5.14966(10)
15YSZ 91.35 ± 1.22 Cubic 5.15678(12)
5.131Å

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表3. 10 – 15 mol% Y2O3添加至ZrO2經過不同老化循環次數之晶粒尺寸。

試片編號 老化循環次數
晶粒尺寸(μm) 0 5 10 20 30
10YSZ 6.17 4.33 4.51 4.46 4.73
12.5YSZ 6.46 3.11 3.55 3.70 4.44
15YSZ 6.55 3.23 3.59 3.60 4.70

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表4. 7.5 mol% Y2O3添加至ZrO2經過不同老化循環次數之晶粒尺寸及面積。

老化循環次數
7.5YSZ
0 5 10 20 30
小晶粒(μm) 0.40 0.29 0.31 0.27 0.72
大晶粒(μm) 1.90 1.59 1.48 1.34 1.73
小晶粒面積(%) 5.78 9.80 12.19 14.12 14.53

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結論
添加Y2O3的氧化鋯在還原氣氛高溫熱處理時，晶粒
中的釔元素之擴散對還原氣氛有一定的影響，而會造成
有晶粒細化的現象，當氧化釔添加低於10 mol.%時，立
方晶與單斜晶會共存，而且單斜晶的存在對增加在還原
氣氛中熱處理次數會造成小晶粒面積的增加。

然而，從XRD分析中沒有發現單斜晶有增加的趨勢。氧
化釔添加量在10 -15 mol.%與的氧化鋯陶瓷經過30次的
老化循環後，立方晶結構仍然穩定存在，添加15 mol.%
Y2O3時，晶粒細化程度最大為50 %。

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