PHASE DIAGRAMS 相圖

(CHAPTER 8.7-8.8)
Speaker : Yi-Hsin Chien PhD.
Date : 2023/03/06-03/13
 8.7- Binary Eutectic Alloy System
• In some binary alloy systems, components have limited solid solubility.
• Eutectic composition freezes at lower temperature than all other compositions.
• This lowest temperature is called eutectic temperature.

• 當共晶成分的液相緩慢地冷卻至共晶溫度時，
此單液相就會同時相變成兩個固相（α 及β 固溶
體）。此為共晶反應（eutectic reaction），可
以寫成下表

Eutectic temperature
Cooling
Liquid α solid solution + β solid solution
Heating
 Binary Eutectic Alloy System

⚫許多二元合金系統之組成元素彼此之間的固溶度是有限度的。

⚫在簡單的二元共晶系統（如鉛－錫系統）中，會有一個特定合金成分稱為共晶成
分（eutectic composition）。

⚫與其他成分相比，它在較低溫度時凝固。這個低溫度，相對應的是當緩慢冷卻時，
液相能存在的最低溫度，稱為共晶溫度（eutectic temperature）。

⚫在鉛－錫系統中，共晶成分及共晶溫度共同決定在相圖上的一個點，稱為共晶點
（eutectic point）。
 Slow Cooling of 60% Pb – 40% Sn alloy

⚫ Liquid at 3000C.
⚫ At about 2450C first solid forms – proeutectic solid.
⚫ Slightly above 183°C composition of alpha follows solidus and Cooling curve
composition of Sn varies from 40% to 61.9%.
⚫ At eutectic temperature, all the remaining liquid solidifies.

• 當溫度從300ºC 的a 點下降，合金將保持液相直到相交
於約245ºC 液相線上的b 點。在此溫度時，含有12%
Sn 的α 固溶體就會開始從液體中析出，這種合金形成
的 第 一 個 固 體 稱 之 為 初 晶 (primary) 或 共 晶 前
(proeutectic)α。

• 當液體從過程中的245ºC 降溫冷卻至接近183ºC 時，
會經過相圖（點b 至點d）的兩相（液相 +α）區。固
相(α)的成分會隨著固相線改變
 Various Eutectic Structures
⚫ Structure depends on factors like minimization of free energy at α / β interface.
(影響生成物外型最重要的一個因素就是在α–β介面之間自由能的最小化。 )
⚫ Manner in which two phases nucleate and grow also affects structures. (決定共
晶形狀之重要因素為兩相(α和β)凝核與成長之方式，其中也影響其結構。 )
 Example problem 8.4
Make phase analyses of the equilibrium (ideal) solidification of lead-tin alloys at the
following points in the lead-tin phase diagram of Figure.
(a) At the eutectic composition just below 183℃ (eutectic temperature)
(b) The point c at 40% Sn and 230 ℃
(c) The point d at 40% Sn and 183 ℃+ΔT
(d) The point e at 40% Sn and 183 ℃-ΔT
 8.8- Binary Peritectic Alloy System
• Peritectic reaction: Liquid phase
reacts with a solid phase to form
a new and different solid phase.

Liquid + α β
cooling

• Peritectic reaction occurs when a

slowly cooled alloy of Fe-4.3
wt% Ni passes through
Peritectic temperature of 1517℃.

• Peritectic point is invariant.

cooling
Liquid(5.4 wt% Ni) + δ (4.0 wt% Ni) γ 4.3 wt % Ni
 Binary Peritectic Alloy System

• 在包晶反應(peritectic reaction)中，液相與固相產生反應，
生成另一種新且不同的固相，可以表示為：

• 鐵－鎳相圖之包晶區域，包含了固相（δ 和）與液相。δ
相為鎳於BCC 鐵之固溶體， 相則為鎳於FCC 鐵之固溶體

• 包晶反應則會於Fe–4.3 wt % Ni 合金緩慢冷卻通過包晶溫
度1517ºC 下發生，反應式可寫為：
 Binary Peritectic Alloy System

• 具有包晶成分的合金在平衡
期間或是非常緩慢地冷卻，
通過包晶溫度，所有固相α
會與所有液相反應產生一新
的固相β
Figure 8.18 the platinum-silver phase diagram.
Binary Peritectic Alloy System
二元包晶系統
 Example problem 8.7
Make phase analyses at the following points in the platinum-silver equilibrium phase
diagram of Figure 8.18.
(a) The point at 42.4 % Ag and 1400 ℃
(b) The point at 42.4% Ag and 1186 ℃+ ΔT
(c) The point at 42.4% Ag and 1186 ℃ - ΔT
(d) The point at 60% Ag and 1150 ℃
 以快速凝固之包晶系統

Figure 8.21 A hypothetical binary peritectic phase diagram to

illustrate how coring occurs during natural freezing.

• 但在鑄造合金快速地冷卻通過包晶溫度，會產生一種稱之為環繞(surrounding)或圍
繞(encasement)的非平衡現象。在包晶反應L + α → β 進行期間，藉由包晶反應所析
出的β 相產物會環繞或是圍繞初晶α。
 Homework 8-1
Chapter 8, Problem 24
If 500 g of a 40 wt % Ag–60 wt % Cu alloy is slowly cooled from 1000°C to just below 780°C
(see Fig. 8.22):
(a) How many grams of liquid and proeutectic alpha are present at 850°C?
(b) How many grams of liquid and proeutectic alpha are present at 780°C + ∆T ?
(c) How many grams of alpha are present in the eutectic structure at 780°C - ∆T ?
(d) How many grams of beta are present in the eutectic structure at 780°C - ∆T ?
Homework 8-2
 Homework 8-3
Chapter 8, Problem 27
An alloy of 30 wt % Pb and 70 wt % Sn is slowly cooled from 250°C to 27°C (see Fig. 8.12).
(a) Is this alloy hypoeutectic or hypereutectic?
(b) What is the composition of the first solid to form?
(c) What are the amounts and compositions of each phase that is present at 183°C + ∆T ?
(d) What is the amount and composition of each phase that is present at 183°C – ∆T ?
(e) What are the amounts of each phase present at room temperature?
 Homework 8-4
Consider an Fe-4.2 wt % Ni alloy (Fig. 8.17) that is slowly cooled from 1550 to 1450°C. What weight
percent of the alloy solidifies by the peritectic reaction?
 Homework 8-5
Referring to Fig, (a) explain what happens as 23wt% salt solution is cooled from room
temperature to -30°C. Give information regarding the phases available and the compositional
changes in each phase. (b) What would you call this reaction? Can you write a transformation
equation for this reaction?
Phase diagrams 相圖
(chapter 8.9-8.12)
Speaker : Yi-Hsin Chien Ph. D.
Date: 2023/04/10
 Binary Monotectic Systems
二元偏晶系統
 Monotectic Reaction : Liquid phase transforms into solid phase
and another liquid.(偏晶反應為發生在某些二元相圖中的另一種三相
無變度反應，這種反應是指一個液相會轉變為一個固相與另一個液相)

 Over a certain range of compositions, the two liquids are

immiscible like oil in water and so constitute individual phase.

2
 Binary Monotectic Systems
二元偏晶系統

• Two liquids are immiscible. 3

• Example:- Copper – Lead system at 9550°C and 36% Pb.

 Invariant reactions
無變度反應
• Two of important invariant reactions occurring in
binary systems are the “eutectoid ( 共 析 )” and
“peritectoid (包析) types”.
• The peritectic and peritectoid reactions are the
inverse of the corresponding eutectic and eutectoid
reactions.
• The temperature and compositions of the reacting
phases are fixed for all these invariant reactions,
according to the phase rule, there are “zero” degree
of freedom at the reaction point.
 Intermediate Phases and Compounds
中間相及化合物

• Terminal phases: Phases occur at the end of

phase diagrams (ex. Pure metal..).
• Intermediate phases: Phases occur in a
composition range inside phase diagram.
• Examples: Cu-Zn diagram has both terminal
and intermediate phases.
• Five invariant peritectic points and one eutectic
point.
5
 Intermediate Phases and Compounds
中間相及化合物

• In Al2O2 – SiO2 system, an

intermediate phase called Mullite
(莫來石) is formed, which includes
the compound 3Al2O3.2SiO2

6
 Intermediate Compounds
中間體化合物
• In some phase diagrams, intermediate compound are formed – Stoichiometric
• Percent Ionic/Covalent bond depends on electronegativeness
✓ Example:- Mg-Ni phase diagram contains
✓ MgNi2 : Congruently melting compound (定組成熔解化合物)
✓ Mg2Ni : Incongruently melting compound (非定組成熔解化合物)

7
 Intermediate Compounds
Cu-Sn phase diagram Ni-Sn phase diagram
Example 8.8
 Ternary Phase Diagrams
三元相圖
• Three components
• Constructed by using a equilateral triangle
(正三角形) as base.

• Pure components at each end of triangle.

• Binary alloy composition represented on

edges.

Temperature can be represented as uniform

throughout the Whole Diagram → isothermal section. 10
 Ternary Phase Diagrams
三元相圖
Example:- Iron-Chromium-Nickel phase diagrams.

• Isothermal reaction at 650 °C for this system

• Composition of any metal at any point on the

phase diagram can be found by drawing
perpendicular from pure metal corner to
apposite side and calculating the % length of
line at that point
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Soldering Reaction : Eutectic SnPb-Cu foil

Ref : https://www.youtube.com/watch?v=MvKmI_lqzAI&feature=emb_logo
 Homework-1
Chapter 8, Problem 40
Consider the aluminum-nickel (Al-Ni) phase diagram of Fig. P8.40. For this phase diagram:
(a) Determine the coordinates of the composition and temperature of the invariant reactions.
(b) Write the equations for the three-phase invariant reactions and name them.
(c) Label the two-phase regions in the phase diagram.
 Homework-2
Chapter 8, Problem 42
Consider the titanium-aluminum (Ti-Al) phase diagram of Fig. P8.42.
(a) What is the maximum solubility of Al in Ti while maintaining a single phase?
(b) At what temperature does this happen?
(c) Identify as many intermediate phases as you can.
Homework-3
Homework-4
 Homework-5
Chapter 8, Problem 49
A number of elements along with their crystal structures and atomic radii are listed in the
following table. Which pairs might be expected to have complete solid solubility in each other?