Ternary Systems: Review

Ternary Systems: Review
A ternary temperature-composition
Outline “phase diagram” at constant total
pressure may be plotted as a three-
dimensional “space model” within
• Ternary Phase Diagram: a right triangular prism with the
- Review equilateral composition triangle
C
- Alkemade’s Lines (……… triangle) as base and
temperature as vertical axis.
- Crystallization Path Analysis
• Vertical Sections • The three binary subsystems such as T
• Isothermal Sections A-B, B-C, and C-A, can be seen on the
vertical faces of the prism. The three
binary eutectic points are e1, e2, and e3. B
• Within the prism, the three liquidus A
surfaces descending from the melting
points of pure A, B, and C and make Space model for a simple eutectic
the ternary eutectic point E. ternary system A-B-C
Dr. M. Medraj Mech. Eng. Dept. - Concordia University Mech 6661 lecture 11/1 Dr. M. Medraj Mech. Eng. Dept. - Concordia University Mech 6661 lecture 11/2
Ternary Systems: Review Alkemade Lines

T
MC
The lines on the liquid surface are the

T
MB T1
T2 • Alkemade lines are the lines that C
T3
constant temperature lines called isotherms. e2
T4 connect the primary compositions of
T T5
MA
T6
two phase fields which share a
C
T7 common boundary.
C
Temperature
T1 T8
T2
e1
• Alkemade lines divide a phase
T3
T4
e3 diagram into compatibility triangles.
T5
e2 T6 e3 • This diagram is divided into two
T7
T8
compatibility triangles: A-C-AB and
E B-C-AB.
E
A B
• Alkemade’s theorem can be used to AB
determine the direction of decreasing
temperature on a phase diagram, as A B
B e1 A we will discuss later. AB
The plan view of the ternary space
model with the important points Each boundary line on the diagram has an
Space model for a simple eutectic Alkemades line associated with it.
ternary system A-B-C
Alkemade Lines: Ternary Invariant Points Alkemade Lines: Ternary Invariant Points
• The intersection of a boundary line (or C
extended boundary line) with its C
•The Alkemade line between C and
corresponding Alkemade line (or extended AB, in this diagram, does not cross
Alkemade line) is a maximum in the boundary line that its end
temperature on the boundary line and a components share.
minimum in temperature on the Alkemade C
line. This point is labeled “m”. C • This phase diagram is also divided
to two compatibility triangles.
• This theorem can be used to draw arrows
on the diagram showing the direction of • First draw an extension of the
decreasing temperature. boundary line so that it will
A B
• The “m” on the triangle edges are the A B intersect the Alkemade line. AB
AB
binary invariant points – ……….. points in • Then use the intersection point
this example A B where the lines meet as a guide for
A B
AB
• The point that resulted from the AB drawing the temperature arrows.
intersection of AB-C Alkemede line and The temperature arrows on the
Ternary system with a ………. Ternary system with a …………..
the boundary between C and AB is called Alkemade line will go towards the
binary compound binary compound
……….. point. intersection point.
• E1 and E2 are ternary eutectic points.
Alkemade Lines: Ternary Congruent Compound Alkemade Lines: Ternary Incongruent Compound
• As usual, we begin by highlighting
• As usual, we begin by highlighting C each boundary line and the
each boundary line and the Alkemade line associated with it. C
Alkemade line associated with it.
• Identify the compatibility triangles.
• Identify the compatibility triangles. • Label the max/min points.
• Label the max/min points.
• Draw the temperature arrows on the
• Draw the temperature arrows on the boundary and Alkemade lines.
boundary and Alkemade lines. C C ABC
The ABC/A,B,C boundary lines and the
• The binary invariant points are given associated Alkemade lines ……….. cross.
their appropriate labels. A To correct for this, draw a temporary
ABC extension of the ABC-C Alkemade line A ABC
• And the ternary invariant B and of ABC/A and B boundaries .
points are labeled. A B
• The binary invariant points are given B
A B
• The diagram is finished. their appropriate labels.
Ternary system with a congruent • And the ternary invariant
ternary compound points are labeled. Ternary system with a
• The diagram is finished. incongruent ternary compound
Crystallization Path Analysis Crystallization Path Analysis
A • Now we are ready to trace the A

• First, identify the compounds on
cooling path of any ternary
the diagram and their corresponding
composition.
primary crystallization fields.
• Then connect compounds, whose
• First locate the composition of a
interest (co) on the diagram.
primary crystallization fields share a AC
• Next determine its primary
AC
boundary, with Alkemade lines.
crystallization field.
• The Alkemade lines form
compatibility triangles. • Identify the compatibility
triangle: in our example, it is AC –
ac
• Remember that where Alkemade
B–C
lines cross boundary lines the
boundary lines are at a local • And final liquid composition: b
maximum and the Alkemade lines The final liquid composition is the co c
are at a local minimum in ternary invariant point where all
temperature three compounds in the
B C compatibility triangle meet. B C
Crystallization Path Analysis Ternary Isothermal Sections
• Now draw a tie line from the A  Isothermal sections in ternary

primary phase B through the point phase diagrams are horizontal slices
to the boundary with ac. through the three dimensional
diagram. All points on the section
• The crystallization path begins at a are at the same temperature, unlike
the point and moves away from
Temperature
AC the normal view of the ternary T = value
the the primary phase as B begins
diagram where the liquidus surface
to crystallize out of the
is seen.
composition.
• Now AC begins to crystallize out ac  A Ternary diagram is a flat
as the path follows the boundary representation of the curved liquidus
line to its ternary invariant point. surface. Therefore, in a normal
b ternary diagram, everything shown
• Finally, at the ternary invariant A B
point all of the remaining liquid c is liquid.
crystallizes.  In an isothermal section both
liquid and solid can be present. C
B C
CaF2-LiF-MgF2 Isothermal Section at 1100°C LiF-RbF-BeF2 Isothermal Section at 700°C
• Identify and trace all of the isotherms for the

temperature for isothermal section of 1100oC. • Trace all isotherms on this diagram at 700°C,
and draw the tie lines.
• Then fill in for the region of the diagram
where the liquidus area is still below the Every phase field left at this
temperature of 1100°C. point will consist of three
Two phase regions occur when the phases. There will either be
intersection between the isotherm and a two solids and a liquid of a
single phase region (e.g. liquid) is a line specific composition, or there
(not a point). will be three solid phases.
• Draw both lines that intersect with the

phase boundary line and surround the The three phase region shown here
two-phase region. consists of Rb2BeF4 – Rb3BeF5 – L1.
• Finally, draw in dashed tie lines
from the composition to the liquidus
region of 1100oC.
Ternary Isothermal Sections Three-Phase Regions

• There are 4 types of phase fields in the isothermal section of a ternary LiF-RbF-BeF2 Isothermal Section at 400°C
system: Remember that the
– The single phase region. The phase can be a liquid or a solid regions with one • Trace all isotherms on this diagram at 400°C,
solution. Liquid is more common. In the previous examples, this corner in contact identify the liquid and draw the tie lines in
region is composed entirely of a liquid of varying composition. with the liquidus the two phase regions.
have liquid in them
– The two Phase region, containing both solid and liquid. The with the comp. of The remaining portion has either three
composition of the liquid is found using the tie lines that were the contact point. solids, or a liquid and two solids.
drawn in on the second slide. The solid is of a single, unvarying
composition. This region shares a border with the liquid region. Liquid
•Trace all Alkemade lines that do not
– The three Phase region, composed of two solid compositions and come into contact with the liquidus
one unvarying liquid composition. This region is easily recognized lines, or cross any of the tie lines.
by its sole point of contact with the liquid region, labeled L1 in the
previous slide. • Identify all the regions that contain
……...
– The solid region, contains three distinct solids. This region is
triangular, and has no contact with the liquid region. • Everything that is left is all …….
None that the previous examples do not contain all four types (three-……….. region).
of phase fields. Therefore the next example will be at 400°C.
LiF-RbF-BeF2 Isothermal Section at 400°C
 Liquid and two solids regions:



A) L1 & Li2BeF4 & Li2RbBe2F7
B) L2 & Li2RbBeF7 & LiRbBeF4
10 minutes Break
 C) L3 & LiRbBeF4 & Rb2BeF4
 D) L4 & RbBrF3 & Rb2BeF4
Liquid
L1 L
L2 L3 4  Three solids regions :
D
A I) LiF & Li2RbBe2F7 & Li2BeF4
B C
II
II) LiF & RbBe2F7 & LiRbBeF4
I III IV
III) LiF & Rb2BeF4 & LiRbBeF4
VI IV) LiF & Rb2BeF4 & Rb3BeF3
V
V) LiF & LiRbF2 & Rb3BeF5
VI) RbF & LiRbF2 & Rb3BeF5
Ternary Vertical Sections: Introduction Constructing Vertical Sections

• Vertical sections are two
dimensional representations of ZrO2 • Identify primary phase fields
the crystallization paths for a
• Draw Alchemades lines
series of points that lie along a
chosen line on a ternary phase • Identify direction of falling
diagram. temperature on boundary lines.
• There are three main lines in a C
ZrTiO4 ZrO2
vertical section which divide
the various solids and liquid E
phases. These three lines are 1610°
ZrTiO4 1590°
called the liquidus, subliquidus, T
and solidus lines, and will be
1580°
explained in more detail later.
B Al2O3
TiO2
Vertical sections in ternary systems A Al2TiO5
can be very complicated due to the
crossing of Alkemedes’ lines and Space model for a simple eutectic TiO2 Al2O3
Al2TiO5
changing crystallization paths. ternary system A-B-C
Constructing Vertical Sections Constructing Vertical Sections
Step 1 - Solidus lines
• Choose the section line (x - y). • Which compatibility triangles are crossed?
• Find the associated ternary invariant points.
• Draw diagram framework. ZrO2
ZrO2
• Indicate temperatures on (x - y) diagram.
• Draw Solidus lines on (x - y) diagram.
ZrTiO4 ZrO2 ZrTiO4 ZrO2
1610°
1590° 1610°
ZrTiO4 x ZrTiO4 1590° y
1580° 1610°
1580°
1590°
Al2O3
TiO2 1580°
Al2TiO5 Al2O3
TiO2
Al2TiO5
TiO2 Al2TiO5 Al2O3
x y
TiO2 Al2TiO5 Al2O3 x y
Constructing Vertical Sections Vertical Section: Important Compositions

Step 2 - Liquidus line
• The top view of the liquidus line can be seen on • The essential compositions used to develop the sub-liquidus line
the ternary diagram. in a vertical section are called important compositions. The
purpose of these important compositions is to reduce the work
ZrO2 • Find the end points and points where the
load on the investigator.
liquidus line crosses any boundary lines.
• Estimate and plot relative temperatures of these • These compositions separate regions of similar crystallization
points. paths. Therefore, the crystallization paths of these compositions
• Draw liquidus line - estimate curvature. directly intersect important features of the ternary diagram. Some
ZrTiO4 ZrO2 examples of these features are given.
1590°
1610° Examples:
x ZrTiO4 y
 Ternary Invariant Points
1580° 1610°
 m – Points
Al2O3 1590°
TiO2 1580°  Alchemades Lines
Al2TiO5
 Diagram Boarders
Now we must Find and indicate all of the important compositions.

Constructing Vertical Sections Constructing Vertical Sections
Step 3 - Sub-liquidus line Step 4 - Alchemades line Intersection
• Find and indicate all of the important compositions. • Find and indicate all compositions where
• Perform isoplethal analysis - record temperature section line crosses an alchemades line.
ZrO2
where boundary line is intersected. ZrO2 • Perform isoplethal analysis and plot final
• Draw sub-liquidus line. crystallization temperature.
• Check each segment with an intermediate • Draw lines which indicate material is all solid
isoplethal analysis.
ZrTiO4 ZrO2
ZrTiO4 ZrO2
1610°
x ZrTiO4 1590° y 1610°
x ZrTiO4 1590° y
1580° 1610°
1580° 1610°
Al2O3 1590°
TiO2 1580° Al2O3 1590°
Al2TiO5 TiO2 1580°
Al2TiO5
Constructing Vertical Sections
Step 5 - Labels
• Refer to the ternary diagram and label vertical section
…………..
The End
……….
Liq. + Al2TiO5
…………. Liq.
ZrO2 …….
Liq.
ZrO2
THANK YOU VERY MUCH
Liq. Liq. Al2TiO5 Al2O3
1610° ZrO2
TiO2 Liq.
ZrTiO4 ZrTiO4 Al2TiO5
Al2TiO5
1590° ………
ZrO2 + Al2O3 +
1580° Al2TiO5
TiO2 + ZrTiO4 + ……………
Al2TiO5
x y

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Ternary Systems: Review

Ternary Systems: Review Alkemade Lines

The lines on the liquid surface are the

A • Now we are ready to trace the A

Crystallization Path Analysis Ternary Isothermal Sections

• Now draw a tie line from the A  Isothermal sections in ternary

• Identify and trace all of the isotherms for the

• Draw both lines that intersect with the

Ternary Isothermal Sections Three-Phase Regions

 Liquid and two solids regions:

Ternary Vertical Sections: Introduction Constructing Vertical Sections

ZrTiO4 ZrO2 ZrTiO4 ZrO2

Constructing Vertical Sections Vertical Section: Important Compositions

Now we must Find and indicate all of the important compositions.

Constructing Vertical Sections

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