NATL INST. OF STAND & TECH r a c t i c e guide

NIST

publications REFERENCE

DTA and Heat-flux

DSC Measurements

of Alloy Melting

and Freezing

W. J. Boettinger, U. R. Kattner

K.-W. Moon, and

J. H. Perepezko

/)

onal Institute of dards and Technology

nology Administration Department of Commerce

Special

Publication

960-15

NIST Recommended Practice Guide

Special Publication 960-15

DTA and Heat-flux

DSC Measurements

of Alloy Melting

W. J. Boettinger, U. R. Kattner

K.-W. Moon

*

Metallurgy Division

Materials Science and Engineering Laboratory,

National Institute of Standards and Technology

J. H. Perepezko

Department of Materials Science and Engineering,

University of Wisconsin - Madison

Special Publications

November 2006

U.S. Department of Commerce

Carlos M. Gutierrez, Secretary

Technology Administration

Robert C. Cresanti , Under Secretary of Commerce for Technology

National Institute of Standards and Technology

Dr. William Jeffrey, Director

and Freezing
Certain commercial entities, equipment, or materials may be identified in this document in order to describe an experimental procedure or concept adequately.

Such identification is not intended to imply recommendation or endorsement

by the National Institute of Standards and Technology, nor is it intended to imply that the entities, materials, or equipment are necessarily the best avail- able for the purpose.

National Institute of Standards and Technology

Special Publication 960-15

Natl. Inst. Stand. Technol.

Spec. Publ. 960-15

90 pages (November 2006)

CODEN: NSPUE2

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 2001

For sale by the Superintendent of Documents

U.S. Government Printing Office

Internet: bookstore.gpo.gov Phone: (202) 512-1800 Fax: (202) 512-2250

Mail: Stop SSOP, Washington/DC 20402-0001
Table of Contents

Part 1: Introduction 1

1. 1 Focus of the guide 1 1.2 Information sought from DTA/Heat-Flux DSC

measurements .2

1.3 Relevant standards 4

1.3.1 Terms and definitions 4

1.3.2 Calibration and sensitivity 4

1.3.3 Analysis of data 5

1.4 Major points 5

Part 2: Instruments and Operation 6

2. 1 Variations among instruments 6

2.1.1 Heat transfer between system components 6

2. 1.2 DTA / heat flux DSC vs. power compensating

(true) DSC 7

2. 1.3 How does instrument control heating rate? 8

2.1.4 What is the signal, millivolts or Kelvin? 8

2.1.5 Plotting signal vs. temperature or time 9

2.2 Samples 11 2.2.1 Mass 11

2.2.2 Shape 12

2.2.3 Powder samples 12

2.2.4 Inert powder cover 13

2.2.5 Lid 13

2.2.6 Atmosphere 13

2.2.7 Crucible selection/reaction 13

2.2.8 Evaporation 16

2.2.9 Initial metallurgical state of alloy samples 17

2. 3 Reference materials 17

2.4 Calibration and DTA signal from pure metals 18

2.4. 1 Fixed point (pure metal) enthalpy vs. temperature and

DTA response function 18

iii
DTA and Heat-flux DSC Measurements

2.4.2 Temperature calibration: effect of instrument thermal

lags on onset determination 18

2.4.3 Temperature calibration: choice of onset

temperature 20

2.4.4 Quantitative enthalpy and heat capactly calibration .22

2.5 Major points 23

Part 3: Analysis of DTA data for binary alloys 24

3. 1 General behavior for a binary eutectic system; example

Ag-Cu alloy melting 27

3. 1. 1 Enthalpy vs. temperature curves 27

3. 1.2 Derivative of enthalpy vs. temperature curves and

their relation to DTA curves 28

3.1.3 Comparison to experiment 30

3.2 Problems with solidus determination on heating 32

3.2. 1 Incipient melting point vs. solidus 32

3.2.2 Effect of hold time prior to melting 32

3.2.3 Errors caused by using extrapolated melting onset

(tangent construction) 34

3.3 Problems with liquidus determination on heating 35

3.3. 1 General DTA curve analysis 36

3.3.2 Details of computed behavior of an alloy on

melting 39

3.3.3 Small liquidus solidus separation 40

3.3.4 Resolution of difficulties using temperature cycling near the liquidus 40

3.3.5 Alloys with k<1 and k>1; peak temperature 40

3.3.6 Failure to completely melt 43

3.4 Supercooling problem with liquidus determination on

cooling 43

3.4.1 Onset of freezing 43

3.4.2 Slope of DTA curve on initial freezing 45

3.4.3 Simulation of DTA response for alloys with

supercooling .45
Table of Contents

3.5 Eutectics reactions vs. peritectic reactions 46

3.5.1 Diffusion 46

3.5.2 DTA response 47

3.6 Major points 50

Part 4: Analysis of DTA data for ternary alloys 51

4.1 Ai - rich corner of Ai-Cu-Fe phase diagram 51

4.2 Ai - 20% Cu - 0.5% Fe 53

4.3 AI - 6% Cu - 0.5% Fe 55

4.4 Major points 59

Part 5: Concluding Remarks 60

Appendices 62

A. Glossary 62

B. Recommended Reading 67

C. Model for simulating DTA response for melting and

solidification of materials with known or assumed enthalpy

vs. temperature relations. Also method for computing

thermal lags of DTA/DSC instruments 68

D. Expressions for the rate dependence of melting onset

temperatures for a pure metal 72

E. Enthalpy vs. temperature relations for dilute binary solid

solution alloy 76

F. Binary phase diagrams and DTA response 79

G Tutorial on melting and freezing of multicomponent

alloys 81

G 1 Aluminum alloy 2219 . . .81

G2 Udimet 700 85

References .87

V
OTA and Heat-flux DSC Measurements
Introduction

Part 1 : Introduction

1.1. Focus of this guide

This document is focused on differential thermal analysis (DTA)* and heatflux differential scanning calorimetry (HF-DSC)^ of metals and alloys. A ther- mal analysis guide focused only on metals and alloys is appropriate because

they behave quite differently from molecular materials such as polymers and

organics. First, metals are good conductors of heat so that temperature differ- ences at any instant can often be ignored within the small (200 mg) samples

typical of differential thermal analysis. Secondly, liquid metals and alloys are

typically monatomic. Freezing and melting occur rapidly in response to changes in temperature compared to other materials. Melting and freezing

transformations, once initiated, take place within, at most, a degree of local

j. thermodynamic equilibrium4

. Therefore the guide also focuses on melting and

solidification behavior because special methods can be employed that are not

necessarily useful for a broader class of materials and processes. The metallurgist should expect a high level of precision when proper attention is paid to technique and interpretation of data. Thermal analysis is a widely used experimental measurement technique with a long history, [49Vol], [65Gar], [66Tsa], [68Gra], [70Cun], [75McN], [78Bar],

[86Hey], [88Fly], [94Spe] and [OOOpf]. In contemporary application, most

work is performed with instruments that are commercially available and under

computer control. Under these conditions even the novice user can obtain data

and software generated analysis of measurements in a relatively short time.

However the expert may want to consider specific sample characteristics in

order to judge whether the traditional measurement protocols are satisfactory or if modifications are necessary. The specific sample characteristics also

impact the interpretation and analysis of the thermal analysis measurements

and the manner in which the software might be used. Best practice may also

require a departure from standard practice to include, for example, thermal

cycling schedules and holding treatments in order to address specific sample

characteristics. Similarly, the proper interpretation of the thermal analysis signals should include consideration of the multicomponent phase equilibrium as well as analysis of the phase evolution during solidification and melting that again is specific to a given sample. It is the intention of this guide to provide

the thermal analysis user with the considerations that are necessary for proper

* Items in blue are defined in the glossary, Appendix A.

t The Guide does not treat power-compensating scanning calorimetry (PC-DSC).

$ However, supercooling of a liquid is often required to initiate freezing (nucleation

supercooling).

1
OTA and Heat-flux DSC Measurements

sample preparation and to illustrate how the sample characteristics influence

the proper interpretation and analysis of measurements. Since the specific

characteristics of a given sample determine the best practice in measurement

and analysis, it is not possible to include all possible advice. Instead, the cornerstone of best practice should be the flexibility to alter procedures in response to specific sample characteristics and types of information sought.

In the remainder of the introduction, we describe the different types of

information usually sought from DTA/HF-DSC during the melting and

freezing of alloys. In Part 2, the details of instruments, operation and

calibration are described. The goal is to describe the thermal lags between the

sample and sample thermocouple that must be understood to enable good

analysis of data. In Parts 3 and 4, the response of the DTA to binary and

ternary alloys, respectively, is detailed. Here a strong use is made of the

enthalpy vs. temperature relation for melting and freezing of alloys with

different phase diagram features when one assumes full diffusional

equilibrium and when diffusion in the solid is so slow as to be ignored.

Part 5 makes some concluding remarks. The appendices include a glossary of

terms that are printed blue in the text, recommended reading, a heat flow

model for the DTA and a description of DTA response for alloys with more

than 3 components.

1.2. Information sought from DTA and heat-flux DSC

measurements

DTA and HF-DSC thermal measurement instruments attempt to measure the

difference in temperature between a sample and an inert standard during pro- grammed heating or cooling. As such, the measurements are sensitive to the

difference between the enthalpy vs. temperature relation of a sample and the

enthalpy vs. temperature relation of a standard. The enthalpy vs. temperature

relations of pure metals are well-known and output information from such

pure metals from a DTA/HF-DSC is used primarily for calibration.

Figure 1 . 1 shows the general shape of the DTA output for the melting and

freezing of a pure metal under ideal conditions. On heating, melting requires an input of heat and the downward peak is endothermic. On cooling, freezing

releases heat and the upward peak is exothermic. Peak shapes have a linear

portion up to the maximum deflection from the horizontal followed by an

exponential return to the horizontal. The initial detection of melting or freez- ing is indicated by the beginning of the linear portion of the peak and is used

for temperature calibration. The area of the peak is used for calibration of the

heat flow. The details of the ideal DTA shape shown in Figure 1 . 1 as well as

2
Introduction

DTA Temperature

Figure. 1.1 DTA responses to melting andfreeezing of a pure material under

ideal conditions, a-onset temperatures (taken here as equal to the melting

point, TM), b-peak signals, c-peak temperatures.

offsets from the true melting temperature and rounding of various curve

features are described in section 2.4. Once the instrument is calibrated, various types of information for melting and

solidification of alloys using a DTA/HF-DSC are sought. The most common

measurement involves liquidus and solidus temperature determination. These

terms will be used here to refer to thermodynamic quantities that depend only on the alloy composition (at fixed pressure). For phase diagram research one

might also want to determine other thermodynamic temperatures associated

with melting and freezing; e.g., in binary alloys, invariant reaction temperatures and their character; viz., eutectic and peritectic. In ternary and higher

order systems, information is sought regarding additional thermodynamic

transitions with one or more degrees of freedom.

Related measurements of interest can include the amount of supercooling

possible prior to solidification and the microstructurally and solid diffusion

rate sensitive final freezing temperature/incipient melting point. One might

want to know the supercooling tendency of a particular alloy in contact with a

certain type of crucible or in the presence of a grain refiner. These temperatures are not purely thermodynamic in origin, but are needed for the modeling

of castings, for the determination of maximum heat treatment temperature, etc. DTA/HF-DSC may at times be used for the identification of alloys from within a small class of alloys as a quality control method; i.e., the DTA plot could

be used as a "finger print" of the alloy.

3
DTA and Heat-flux DSC Measurements

A more difficult measurement is the determination of the enthalpy vs. temperature relation for the sample. One may want the thermodynamic

(equilibrium) enthalpy-temperature relation, or for practical considerations, one may want the enthalpy vs. temperature relation as it would apply under

certain casting conditions where freezing would end at a final temperature

generally lower than the solidus.

DTA and DSC are sometimes used in a non-scanning mode where the

temperature is held constant and evidence for isothermal transformation is detected. Such an approach is sometimes used for solidification studies

involving measurement of nucleation kinetics and diffusion bonding.

1 .3. Relevant standards

ASTM Subcommittee E37.01 is responsible for thermal analysis test methods.

A summary of relevant ASTM Standards is given below. Many of the methods suggested in these documents have been developed with a broad array of

materials in mind. With a focus on metal and alloy melting and freezing,

variations of these methods are sometimes more appropriate as we will

describe in this document. Various other international standards are available. In particular we note many relevant standards of the Deutsche Institut fur Normung (DIN), Association Francaise de Normalisation (AFNOR) and the

British Standard Institution (BSI). Many of these are available from the ANSI

web store (http://webstore.ansi.org).

1.3.1 Terms and definitions

ASTM E473, "Standard Terminology Relating to Thermal Analysis," is a compilation of definitions of terms used in other ASTM documents on all thermal analysis methods including techniques besides DTA and HF-DSC.

ASTM El 142, "Terminology Relating to Thermophysical Properties," is a compilation of definitions of terms used in other ASTM documents that involve the measurement of thermophysical properties in general.

1.3.2 Calibration and sensitivity

ASTM E967, "Practice for Temperature Calibration of DSC and DTA," presents simple recipes for calibration for fixed mass and heating rate using two

pure materials to obtain a linear correction for conversion of measured temperature to actual temperature. The onset temperature extracted from the melting

peak is determined by the extrapolation method, see section 2.4.3. For some

4
Introduction

materials the standard suggests using the peak for calibration, a method not recommended for metals.

ASTM E968, "Standard Practice for Heat Flow Calibration of DSC," uses

sapphire as heat capacity standard. The method is described in section 2.4.4. ASTM E2253, "Standard Method for Enthalpy Measurement Validation of

Differential Scanning Calorimeters," presents a method using three small masses to determine the detection limit of DTA/DSC.

1 .3.3 Analysis of data

ASTM E928, "Standard Test Method for Determining Purity by DSC,"

employs comparison of the shape of the melting peak of an impure sample to the shape for a high purity sample to determine the concentration of the

impurity. The method uses the "1/F plot" which examines the down slope of

the melting peak.

ASTM E794, "Standard Test Method for Melting and Crystallization

Temperatures by Thermal Analysis," employs the extrapolated onset determination method.

ASTM E793, "Standard Test Method for Enthalpies of Fusion and

Crystallization by DSC," uses area on signal vs. time plot for comparison to known heats of fusion of pure materials.

ASTM E1269, "Standard Test Method for Determining Specific Heat Capacity

by DSC," uses sapphire or aluminum as a standard.

1.4 Major points

• This guide focuses on melting and solidification of metals and alloys.

• Different types of information are sought by different users. Some deviation from standard practice may be useful for specific

measurements.

5
DTA and Heat-flux DSC Measurements

Part 2: Instruments and Operation

2.1. Variations among instruments

For precision work, it is important for users to understand the operation of

their particular DTA/HF-DSC, as different instruments employ different

designs and control features and employ different data analysis and

presentation methods.

2.1.1 Heat transfer between system components

A DTA/HF-DSC instrument consists of a single furnace and two crucibles

with thermocouples (Figure 2.1). One crucible is for the sample being tested and the other is for a reference material, often alumina powder. The sample or reference thermocouple temperatures are given by the voltage difference

between thermocouple legs A and B for either cup with suitable cold junction

compensation. In the DTA, the difference signal is obtained by shorting the B

legs and measuring the voltage between the A legs. In the heat flux DSC, the

connecting metal strip is often used as an active sensing element to obtain the

difference signal by measuring the voltage between legs B and B. Depending on the geometrical arrangement of these parts, the atmosphere, and

the temperature range of operation, heat flow will have different contributions

from radiation, convection and conduction processes. The relative contributions will change the size and heating rate dependence of the temperature

DTA Heat Flux DSC

A B A B A B A B Figure 2.1. Schematic of DTA and HF-DSC geometries (not to scale). A and

B denote the different legs of themocouples.

6
Instruments and Operation

differences and thermal lags during heating and cooling between the sample,

the reference and the thermocouples. The manner in which these lags influ- ence the interpretation of DTA data will be a central focus of this document.

Appendix C presents a model for the heat transfer within a DTA instrument

and an experimental method to determine three time constants for the instru- ment. With these time constants, the sample mass and an enthalpy vs. temperature relationship for the sample, one can calculate DTA curves. This

procedure permits one to understand an important difficulty of DTA analysis

as demonstrated by the fact that the sample thermocouple in a DTA does not remain isothermal during the melting of a pure metal. This is not due to the

kinetics of the melting process, but is due to the difference between the sample

temperature and the sample thermocouple temperature

1^. The model will be

used to clarify calibration procedures in section 2.4. 1 and aid in the

interpretation of DTA signals from alloys in Parts 3 and 4 and Appendix G.

2.1.2 DTA / heat flux DSC vs. power compensating (true) DSC

This document is limited to a description of devices with one heater. The term

differential scanning calorimeter was originally applied to instruments with

separate heaters for the reference and the sample. The differential signal of a

true DSC is the power difference required to keep the temperatures of the

reference and sample identical during a defined temperature ramp. Thus, the

signal is in units of watts per unit sample mass. This type of instrument is today called a power compensating DSC. Many instruments with a single

heater are called a DSC, but are more properly called a heat flux DSC. The

basic measurement, just as for a DTA, is a difference in voltage between the

output of the sample thermocouple and the reference thermocouple. Although

quantitative measurements of heats of transformation can be evaluated by

either DTA or heat flux DSC, there are differences in sensitivity and accuracy.

In a heat flux DSC, the heat flow path between the sample and the reference is provided by a metal strip whose thermal conductivity is high and well defined.

This minimizes the temperature difference between the sample and reference

and also makes the temperature difference directly proportional to the heat flux

between the two. For both, a calibration procedure can be used to relate the

difference signal integrated over time to an enthalpy (see 2.4.4). Such instruIt is to be noted that cooling and heating curves obtained with direct immersion of a thinly

protected thermocouple in the melt are often superior to conventional DTA methods because of

greatly reduced thermal lags. Such experiments require custom equipment designed for the specific alloy of interest to provide suitable atmosphere and refractory coatings; see e.g., [79Fre], [88Fre] and [03Don]. Because the DTA is a common desktop instrument available in many

laboratories, its capabilities and limitations are nevertheless worth consideration.

7
DTA and Heat-flux DSC Measurements

ments are not capable of the same accuracy as a power compensating DSC,

but are usually built to operate at the higher temperatures (>1000°C)

necessary for metallurgical work.

2.1.3 How does the instrument control the heating rate?

In its simplest configuration, the control thermocouple for a DTA* is in the

furnace. The controller applies power to maintain a linear heating or cooling

rate for this thermocouple. In this case, there is usually a thermal transient

between the furnace thermocouple and the reference and sample thermocouples, which is particularly noticeable at the beginning and end of a DTA scan. A second method uses the reference thermocouple to control the application of

power. This has the advantage of preventing the initial (and final) transients. Finally some instruments use the sample thermocouple for control in an

attempt to maintain a constant heating rate in the sample itself. However

while control of a sample thermocouple to a constant heating rate may be

possible for phase changes with sluggish kinetics or very small enthalpy of

transformation, it is practically impossible to maintain a constant heating rate during the melting or freezing of metals and alloys. This method is not recommended. Some instruments provide user selectable choices of control

method. Modulated DTA/DSC is an instrument that adds a small sinusiodally

varying temperature oscillation on the usual temperature program. This last subject, as well as power compensating DSC, are beyond the scope of the

present document.

2.1.4 What is the signal, millivolts or Kelvin?

As the name implies, the signal for a DTA is a difference. This is the y - axis

of standard DTA plots (See Figure 1.1). It is the difference in either the volt- age or the derived temperature difference between the sample thermocouple

and the reference thermocouple. When the signal is given as temperature

difference, a reference table or equation has been used by the instrument to obtain temperature difference from a voltage difference. The choice of one or

the other by individual manufacturers is mostly historical or an attempt to pro- vide numbers with which the user is comfortable. Unfortunately, both types of

output are not usually available on a single instrument. In some cases the

millivolt signal is divided by the sample mass for presentation. The signal can

either be endothermic or exothermic; i.e., indicating heat into or out of the

* In the remainder of the document, we will usually drop the distinction between DTA and HF-DSC for brevity.

8
Instruments and Operatic

sample. For transformations of materials that remain close to equilibrium,

heating scans lead to endothermic signals and cooling scans lead to exothermic

signals. Unfortunately, there is no common practice for whether a positive

y - axis is endothermic or exothermic. In this guide we will always assume

that an endothermic signal is negative on the y-axis. Some instruments use a thermopile between the sample and the reference. A thermopile is a number of

thermocouples connected in series. Connecting many thermocouples in series produces a higher differential voltage signal.

2.1.5 Plotting signal vs. temperature or time

Figure 2.2a shows experimental data for the sample and reference thermocouple temperatures plotted vs. time for the melting of pure Ag. The derived

difference between these temperatures can be plotted vs. time, vs. reference

thermocouple temperature or vs. sample thermocouple temperature as shown

in Figure 2.2b. The output table or graphics display of a particular instrument

may provide some or all of these choices as the x-axis of DTA plots.

Significant differences in the shapes of the curves are evident depending on

the x-axis choice. A display vs. temperature is useful for directly reading

temperatures of thermal events. A display vs. time is required when peak area (Kelvin second or millivolt second) is calculated from the data for quantitative measures of total enthalpy change associated with a thermal event. For

display or numerical output, some instruments choose the temperature as the

reference thermocouple temperature, while others choose the sample thermocouple temperature. For precision work the latter is preferable because the

changes in sample thermocouple temperature are more closely related to events in the material of interest. Most importantly, it is necessary for the user

to know which temperature is being used by the instrument software. Then

replotting of data can be performed using external manipulations if desired.

Parts 3 and 4 of this document will delve in considerable detail into the

expected shape and interpretation of DTA curves for alloys. For the melting

and solidification of a pure metal, DTA curves are simple and one can define

several features of the curve as seen in Figure 1.1. The baseline is the graphical feature corresponding to the AT signal over temperature ranges where no

transformation of the sample takes place. The baseline is horizontal if the

signal is a constant. The onset temperature is the beginning of the deviation

from the baseline measured by some quantitative measure as described in

2.4.3. The peak signal is the maximum deviation of the signal (Ay-value)

from the baseline and the peak temperature is the temperature (x-value) corre- sponding to the peak signal. The term peak will be used regardless of whether

it is negative or positive. The temperature at which the signal returns to the

9
DTA and Heat-flux DSC Measurements

(b)

UoH

<

time (s) 1600 1650 1700 1750 1800 1850

<

i i i i i

1000

Figure 2.2. DTA melting of a 211.6 mg ofpure Ag at 10 Klmin. (a) Reference

thermocouple temperature Ttcref and sample thermocouple temperature

Tt

sample vs time (b) Differential signal AT = TtcsamPle

- Tt^vs. time (red),

vs. sample temperature (solid black), and vs. reference temperature (dashed

black). For this data, the reference temperature remains quite linear in time as the sample melts, so that a linear scaling of the time axis makes the plots

with x-axes of time and reference temperature practically identical.

L0
Instruments and Operation

baseline has no significance with respect to thermal events in the sample and

reflects heat transfer characteristics within the instrument. See Appendix C.

2.2. Samples

2.2.1 Mass

Figure 2.3 compares the signal during melting of different masses of pure Ag

with a fixed mass of the reference. A large sample produces a larger peak

signal (deflection from the baseline). However, the larger signal delays the

temperature at which the signal returns to the baseline, making detection of

closely spaced thermal events more difficult. On the other hand, large masses

decrease the response time between the sample and sample cup. For careful

work, sample mass vs. signal output should be examined for optimal

performance. These items are discussed further in Appendix D.

>

940 960 980 1000 1020

T(°C)

Figure 2.3. Effect of sample mass on DTA signal for pure Ag. The reference mass was held constant. Heating rate is 10 Klmin.

11
DTA and Heat-flux DSC Measurements

2.2.2 Shape

Sample shape is a significant factor if the user wants to extract information on

the first melting cycle. The shape will typically not conform to the shape of

the sample cup. The thermal contact area between the sample and the cup will change during the melting process. This change can lead to a DTA peak shape

that is difficult or impossible to interpret. Sometimes the effect of changing

sample shape on first melt is more subtle. For the melting of pure Ag and for Ag-Cu eutectic, Figure 2.4 shows a shift of the baseline in the y-direction after the first melting that is not evident for the second melt. A more rounded onset and absence of linearity of the down-slope is also evident for the first melt (the

expected linearity is described in section 2.4.2). If data from a first melt is desired, success may be achieved by careful grinding of the sample to conform

to the crucible shape. In general, it is preferable to discard data obtained from

the first melting run of a sample.

2.2.3 Powder samples

In general, the use of powder sample of metals and alloys can increase

chances of contamination from atmosphere (oxidation), reduce heat flow

920 940 960 980 1000 760 780 800 820 840

T (°C) T (°C)

(a) (b)

Figure 2.4. DTA signal for melting of (a) pure Ag (211.6 mg; 10 K/min) and

(b) Ag-Cu eutectic (231.3 mg; 15 K/min) comparing first melt (red) and

second melt (blue). Note the offset of the baselines, the more rounded onsets and the lack of linearity of the down-slopes for the first melt compared to the

second.

12
Instruments and Operation

within the entire sample mass and reduce the area of contact with the sample

cup. However supercooling studies are enhanced by the use of powdered

samples due to isolation of the most active heterogeneous nucleation sites into a small fraction of the powder population [84Per].

2.2.4 Inert powder cover

Some standard practice suggests mixing A12 3 powder with powder samples

or covering samples with a layer of A12 3

. This is done in an attempt to match the heat capacity and thermal conductivity of the sample and the

(alumina) reference and produce a flatter baseline. Such practice must be

weighed against the possibility of reaction between the sample and powder

cover. If the wetting angle between the cup and sample is close to 180°, some authors suggest that use of an inert powder cover increases the thermal

conduction to the sample cup.

2.2.5 Lid

A lid is useful for high vapor pressure materials to reduce material loss and

contamination of the other parts of the instrument. A lid will also prevent

sample radiation loss and help maintain an isothermal sample.

2.2.6 Atmosphere

For precision work, the use of commercial purity inert gas is not adequate.

High purity inert gas coupled to a Ti getter furnace is usually adequate for most metals. Helium has a higher thermal conductivity than Ar; the choice can alter the thermal transport rates in the DTA instrument [03Rab].

Calibration should be performed with the same atmosphere as will be used

for samples.

2.2.7 Crucible selection/reaction

High purity alumina is a standard DTA cup material. Zirconia and yttria cups can be made/purchased for highly reactive metals. The inside of alumina cups can also be coated with zirconia or yttria washes. Coatings of boron nitride may be useful for some materials. Graphite is usually an excellent crucible

material for some non-reactive metals, like Au and Ag. For the selection of

oxide crucibles, Table 1 gives the negative of the enthalpy of formation from

the elements per mole of O (not 2

) for various oxides of the elements. Use

of this table is shown by the following example that examines the suitability of

using A12 3 or Y2 3 as a crucible for Ti. The numbers taken from the table

13
DTA and Heat-flux DSC Measurements

Table 1 - Enthalpies of Formation of Solid Oxides ({ } Liquid, < > Gas)

{H2 0} 286

{H2O2} 94 -AHf in kJ/mol for

1/2 2

U2O 595 U2O2 318 BeO 610 2/n MmOn(s) <-* 2m/n M(s) + 2 (g) AS = 1 84±1 J/K M(s) + 02(g) <-> M02 (g) AS= 15±5 J/K

2 ~2 AH*498 kJ Na2 415 Na02 261 Na02

* 130 Na2 2

* 256

MgO 601

K2O 361 KO2 142

K2O2* 142

CaO 635 SC2O3 623 Ti 2 5 490

Ti02 472

Ti2 3 507

TiO* 543

V2O 456 VO 431 V2O3* 406 VO2* 357

V2O5* 310

Cr2 3 376 Cr02 293 Cr03* 196MnO 385 Mn3 4 346

Mn203*

319 Mn03* 270

Feo.9sO 264

Fe3 4 280

Fe2 3* 274

CoO 239 C03O4 226

Rb2 330 Rb2 3 176 SrO 604 Sr02 326

Y2O3 627 Zr02 547 NbO 410 Nb02 399 Nb2 5* 380M0O2 294 M0O3 248 Tc02 216 Tc03 180 Ru02 150 Ru04 46 RhO 92 Rh2 3* 119 Rh04 96

Cs2 318

CS2O3 188 BaO 581 Ba02 318

La2 3 597 Hf02 556 Ta2 5 408 WO2 295 W3 8 284 W03* 281

Re02 213 Re03 205 Re2 7 * 178Os02 * 147 Os04 97

Ir02 111

Fr Ra Ac

Ce2 3 599 Ce02 594

Pr2 3 603 Pr02 475 Nd2 3 602 Pm Sm2 3 609

Th02 613 Pa U02 541 U4O9 502 U2 8* 447 U03* 408

Np02 514 Pu02 527

Reference: A.W. Searcy, "Enthalpy and Predictions of Solid-State Reaction Equilibria" in "Chemical and

Mechanical Behavior of Inorganic Materials," Eds. A.W. Searcy, A.V. Ragone and U. Colombo, Wiley-lnterscience, New York, NY, 1970, pp. 33-55

* O. Kubaschewski, C.B. Alcock and P.J. Spencer, "Materials Thermochemistry," 6th Ed., Pergamon Press. Oxford, UK, 1993

14
Instruments and Operation

He

B2O3 426 (CO2) 197 (CO) 111

(N2O4) -10 (N2O5) -15 O (OF2) 18 Ne

AI2O3 558 Si02 455 P2 3 273

P2O5 61 P2O5* 300

S03 151 (OCI2) -81 Ar

NiO 240 Cu2 171 CuO 155 ZnO 348 Ga2 355 Ga2 3 363 GeO 212 Ge02 363 Ge02 * 290AS2O4 198

AS2O5 185 Se02 112 Se2 5 82

Br

PdO 96 PdO* 115 Ag2 30 CdO 258 ln2 3 308 SnO 285 Sn02 290 Sb2 3 240 Sb02 290 Sb02

* 227

Te02 161 I Xe

Pt02 -85 AU2O3 1 HgO 91 TI2O 166

TI2O3 129 PbO 217 Pb3 4 179 Pb02 * 137

Bi2 3 191 Po At Rn

EuO* 590

EU2O3 554 Gd2 3 607 Tb2 3 622 Tb02 486 Dy2 3 621 H02O3 627 Er2 3 632 T1712O3 629 Yb2 3 604 Lu2 3 625

Am2 3 585 Cm Bk Cf Es Fm Md No Lw

15
DTA and Heat-flux DSC Measurements

are: A12 3 (AHf = -558 kJ/mol), Y2 3 (AHf = -627 kJ/mol), TiO AHf =

-543 kJ/mol). For the possible reaction of AI2O3 with Ti, I (Al2 3 ) +77 —> TiO + f A/

AH . = AH p

f roducts -AH

ctants reaction f f = (-543 + f 0)kJ/mol-(-558 + 0)kJ/mol =15 kJ/mol

whereas for the possible reaction of Y2 3 with Ti

}(y2 o3 )+r/->r/<9+fr

AH . = AHfpmducts - AHrf

actan,s

reaction f f = (-543 +

f • 0)kJ/mol - (-627 + 0)kJ/mol = 74 kJ/mol

The equilibrium constant, K, is given by

AM

j£ reaction RT

At the melting point of Ti, RT=\6.2 kJ/mol, so the equilibrium constant is of

order unity, exp(-l), for the reduction of A12 3

, whereas the equilibrium

constant is of order exp(-4) for the reduction of Y2 3. Thus a significant

amount of A12 3 can be reduced by Ti, whereas negligible amount of Y2 3is reduced by Ti. Yittria is a better crucible for Ti than alumina.

The observed absence of a distinct reaction product between a crucible and a sample can be misleading. Reaction products can sometimes go into liquid or

solid solution in the sample, affect the thermal measurement, and not be easily

observable; e.g., Al and O from A12 3 into Ti alloys.

2.2.8 Evaporation

Excessive evaporation can reduce the sample mass and lead to incorrect

measurement of enthalpy. Preferential loss of one or more components of an

alloy can also lead to composition change. Mass loss is one of the reasons to employ simultaneous DSC/TGA (thermal gravimetric analysis). In addition,

metals and alloys with high vapor pressure will lead to contamination of the

furnace interior and thermocouple support assemblies. A good rule of thumb

is to avoid materials with vapor pressures higher than approximately 100 Pa at the melting point, e.g., Zn and Cd.

16
Instruments and Operation

2.2.9 Initial metallurgical state of alloy samples

At heating rates typical of a DTA, one cannot be certain that the microstructure of an alloy sample is in global equilibrium prior to or during analysis. A

characteristic time required to eliminate spatial concentration gradients within

phases is X

2I4DS where Ds

is the solid diffusion coefficient and A is a distance

that characterizes the modulation of the concentration. Near the solidus, Ds

is typically 10 m /s for substitutional solutes or 10 m /s for interstitial solutes. For solidified samples cooled at between 5 K/min and 15 K/min,

typical spacings of dendritic structures are approx. 100 [im to 200 \im. Hence,

hold times of the order of 10 s or 10 s may be required for substitutional or

interstitial alloys, respectively, to become homogenized. For interstitial alloys,

normal thermal equilibration of the instrument prior to scans is usually suffi- cient to eliminate concerns about the prior homogeneity state of the sample

and global equilibrium is likely to be maintained at slow scan rates in the

DTA. However, the microstructural state of the substitutional materials must

always be considered. If the user wants to determine the thermodynamic

solidus, a series of melting runs following isothermal holds at successively

higher temperatures below the proposed solidus value should be conducted to ensure that the sample has been annealed into an equilibrium structure. See

section 3.2.2.

2.3. Reference materials

The ideal reference material is a substance with the same thermal mass as the

sample, but with no thermal events over the temperature range of interest. The

thermal mass is the product of the mass and the heat capacity. This provides

the optimum condition to obtain a horizontal baseline. When the baseline is not horizontal, various methods (see for example [OOOpf]) are used to fit and

subtract a non-constant baseline from the signal. For some instruments, such a subtraction is done by the software. A horizontal baseline is not essential for the measurement of transition temperatures, but is important for quantitative

enthalpy measurement. Alumina powder obtained from the instrument maker

is often used as a convenient reference material for DTA and DSC of metals

and alloys, even though the heat capacity differs significantly from that of

most metals.

17
DTA and Heat-flux DSC Measurements

2.4. Calibration and DTA signal from pure metals

2.4.1 Fixed point (pure metal) enthalpy vs. temperature curves

and DTA response

Calibration is performed by melting a pure metal because a pure metal exhibits a particularly simple enthalpy vs. temperature relation Hs (Ts

) as shown in Figure 2.5a. The subscript S is used to denote sample enthalpy and sample

temperature as distinguished from, e.g., reference material enthalpy, sample

thermocouple temperature. Below the melting point, TM , the slope,

dHs (Ts)/dTs

, of the curve is the solid heat capacity. At the melting point, the curve experiences a jump in enthalpy, L, equal to the latent heat of fusion.

Above the melting point the slope is the liquid heat capacity. Figure 2.5b

shows the derivative curve, dHs (Ts)/dTs

, where we employ the delta function

LS {T$-TM) of strength L located at Ts =TM to represent the jump of the

Hs (Ts

) curve at TM. Figure 2.5c shows schematic melting and cooling DTA

curves. A useful way to think about the response of a DTA to melting and

solidification is to consider an instrument response or transfer function that converts the delta function of Figure 2.5b into the quasi-triangular shaped

peaks for melting and freezing seen in Figure 2.5c. Fourier methods are often

used to represent instrument response functions. However due to the intrinsic nonlinearity of DTA response to the enthalpy curves, the heat flow model of

Appendix C is preferred. The model confirms the central role that the rate of

change of the sample enthalpy with respect to sample temperature,

dHs (Ts)ldTs, plays in the DTA response, Eqn. C3. This derivative is usually

referred to as the heat capacity; however the term is sometimes ambiguous,

especially for alloys, in that it may or may not include the heat of fusion. In

this document, the derivative dHs (Ts)/dTs

will be taken to include the heat of

fusion. The derivative vs. temperature curve concept will be employed

throughout this document as it becomes quite useful to understand and

interpret alloy behavior in Parts 3 and 4 and Appendices F and G. 2.4.2 Temperature calibration: Effect of instrument thermal lags

on onset determination

Temperature calibration of a DTA is typically performed using the melting of a pure metal or series of pure metals. A list of commonly used calibration substances is given in Table 2. Metals of 99.99% purity are usually adequate for metallurgical work. Research involving International Temperature Standards

(ITS-90) employ higher purity metals and are available as NIST Standard

Reference Materials (www.nist.gov).

18
Sample Enthalpy,

dHs/dTs

Exothermic

DTA Signal

Endothermic

DTA Temperature

Figure 2.5. Schematic a) enthalpy vs. temperature for a pure metal;

b) corresponding derivative dHs (Ts)/dTs curve; c) DTA signal for melting

(bottom) andfreezing (top). The small difference in heat capacity of liquid

and solid leads to a small offset of the baseline before and after melting. The

onsets in the DTA curves are shown with a small deviation from the melting

point, TM , due to heat flow limitation in the DTA. This difference on melting

is adjusted to zero by the calibration procedure, at least for one heating rate.

In order to perform the calibration, the onset of melting must be determined

from the data. For precision work, one must quantify various subtleties in the

detection of melting for a pure metal and the thermal lags inherent in the

instrument.

To directly observe the effects of the thermal lags, the melting and freezing of

pure Sn was performed in a DTA instrument with an additional thermocouple

(Type K) immersed directly into the Sn. The sheathed thermocouple was only

250 Jim in diameter so that its thermal response is quite rapid. Figure 2.6a,b

instruments and Operation

(a)

Sample Temperature, TsDeltafunction

Sample Temperature, Ts

(b)

19
DTA and! Heat-flux DSC Measurements

Table 2 -Fixed Point Temperatures for Calibration [69Bar, 90Pre, 96Bed]

Substance T/gC Ref. In 156.5985 90Pre

Sn 231.928 90Pre

Bi 271.402 96Bed

Cd 321.069 96Bed

Pb 327.462 96Bed

Zn 419.527 90Pre

Sb 630.628 96Bed

Al 660.323 90Pre

Ag - 28.1 % Cu* 779.63 96Bed

Ag 961.78 90Pre

Au 1064.18 r\r\T\ 90Pre

Cu 1084.62 90Pre

Ni 1455 69Bar

Co 1494 69Bar

Pd 1554.8 96Bed

*Eutetic composition. In this document, the % symbol will refer to percentage by mass. shows the temperature vs. time and associated DTA plots obtained with the

immersed thermocouple and with the ordinary instrument thermocouple located

beneath the sample cup. One notes the perfectly isothermal plateau at 232 °C for the immersed thermocouple and the associated vertical drop in the DTA plot at the Sn melting point. The instrument sample thermocouple, on the other hand,

is not isothermal during melting nor is the drop vertical on the associated DTA

plot. This difference is due to the heat transfer limitations between the metal

sample and the sample thermocouple and gives rise to the linear section of the

DTA peak shape. In the section on supercooling effects (3.4.1), we will show

the corresponding data during cooling experiments with the immersed

thermocouple.

2.4.3 Temperature calibration: Choice of onset temperature

In normal DTA where the thermocouple is not immersed directly in the

sample, the thermal lags cause the linear portion of the peak shape as well as a

less sharp demarcation of the initiation of melting. This loss of sharpness can

lead to difficulties of calibration for highly precise work as described in Appendix D. In Figure Die, the temperature of the first detectable deviation

20
Instruments and Operation

from baseline is labeled TT

omet

. The subscript T is used to denote thermocouple temperatures. Due to the inherent trouble of picking this temperature

experimentally and due to the noise in the data, an alternative melting onset temperature is commonly employed. This procedure takes advantage of the

fact that the thermocouple temperature vs. time, TT

(t), curve quickly becomes

linear after the melting onset; the onset temperature, TT

extrap is taken as the

intersection of a linear fit to the downward sloping linear section of the

melting peak and the extrapolation of the baseline.

270-i

260-

250-

240

230-1

220 2Z—i i r

reference tc temperature

232 °C

sample tc temperature

immersed

sample tc temperature

(a)

i—|—.—|—i—|—i—|—

.

5100 5200 5300 5400 5500

time (s)

(b)

UcH

<

280

Figure 2.6. Measured (a) temperature vs. time plots and (b) associated DTA

plots for melting ofpure Sn. The instrument thermocouple readings are black

and the readings from a thermocouple immersed directly in the Sn in the sample cup is red. Mass = 163.2 mg; heating rate = 5 Klmin.

21
DTA and Heat-flux DSC Measurements

Following Eqns. D3 and D4, both TT

onset and TT

extrap deviate from TM by an amount that depends on heating rate and on sample mass through the parameter p and the time constants, which depend on the area of contact between

sample and cup. Thus calibration should ideally be conducted for a mass and

heating rate similar to those that will be used for the test samples.

In addition to this consideration, it is best to use the first deviation from baseline method. We show in Appendix D that picking the first sign of melting

actually has a smaller deviation from the true melting point and smaller heating rate dependence than the onset determined by the extrapolation procedure.

This is one reason to prefer using the first detectable deviation from baseline

for calibration. A second reason comes from the principle that the same method for the determination of the onset should be used for the calibration

and the actual measurement on alloys. Alloys usually have a melting range

and, therefore, do not melt with a linear section of the DTA curve (see e.g. Figure 3.8). Thus the onset for alloy melting is better taken using the first detectable deviation method. With these points in mind, it makes sense to use

the first detectable deviation from baseline method for the calibration.

We note that ASTM E967 and articles on instrument calibration [90H6h.

91Hoh] use the extrapolation onset temperature. JT

extraP^ to determine all onsets, even for alloys. With the use of computers for recording the thermocouple voltages, instrument manufacturers introduced software for the analysis

of the DTA curves and determination of the reaction temperatures. In most

cases the software uses the extrapolation method for the temperature

determination TT

extraP instead of TT

onset

.

2.4.4. Quantitative enthalpy and heat capacity calibration

In order to determine the quantitative heat flux, the difference signal (AT)

must be converted to one of energy units by a calibration process. The method

uses the heat of a specific transformation per unit mass in a standard sample,

such as heat of fusion. The instrument sensitivity coefficient, S. at various

temperatures is determined from the ratio ^ _ mstandard AHstandard ~ t 2

h

obtained from melting a series of standards (usually pure metals). The integral

is the area of the peak deviation from the baseline determined from a plot of

22
Instruments and Operation

AT vs. time. Alternately the original voltage difference from the thermocouples can be used instead of the temperature. The quantity mstandard AHstandard

is the product of the mass of the standard and the heat of fusion per unit mass

For an unknown sample then,

where S may be interpolated between the two standards spanning the temperature range of interest. The calibration is often performed by the instrument

software and converts the DTA signal area from units of millivolt seconds or Kelvin seconds to Joules. In order to obtain accurate heat flux information,

the same heating / cooling rate, gas flow rate, sample / reference cups, and

temperature range should be employed for standard and unknown.

After conversion of the DTA signal to energy, some instruments provide a sec- ond calibration to directly provide heat capacity measurement. For many heat

flux DSC instruments, heat capacity calibration is done by software with data

obtained by performing a heating scan with a pair of empty cups, to get the

baseline, and performing a second heating scan with the chosen reference

material in one cup and an empty second cup. More details are given in ASTME968.

2.5 Major points

• Important factors for proper technique:

• Determination of what temperatures are being recorded and presented

by the instrument and instrument software

• Calibration

• Crucible and atmosphere selection

• Consideration of thermal gradients and associated thermal lag times

within the instrument

• Determination of instrument time constants provides quantitative insight

into thermal lags important in consideration of calibration procedures and

general DTA response.

• For alloys, the microstructure and sample history may influence the

measured response to thermal analysis.

23
DTA and Heat-flux DSC Measurements

Part 3: Analysis of DTA data for binary alloys

The general response of a DTA during cooling and heating for a series of

alloys in a eutectic system where there is limited solid solubility is given

schematically in Figure 3.1. In such general descriptions it is usually assumed

that there is no barrier to nucleation on cooling and that solute diffusion is adequate to maintain the phases uniform in concentration at each temperature

during the process. Under these assumptions, the phase fractions at each

temperature follow the simple lever rule and the general shape of the DTA

response is readily predicted, if the phase diagram and heats of fusion are known.

A Composition B A Composition B Figure 3.1. Schematic DTA response on coooling and heating ofpure A and B

andfor other alloys superimposed on a simple eutectic phase diagram.

For other binary phase diagram features, such as peritectic reactions, the DTA

response is not so easily understood. Thus the model of Appendix C is used to simulate how various phase diagram features are reflected in the DTA

signals. It is our belief that such simulations can provide the DTA user with

the understanding to enable more accurate interpretation of DTA results from

samples with unknown phase diagrams.

For the simulations, we not only use the full equilibrium (lever rule) to obtain

enthalpy vs. temperature curves but also another limiting case that is important

in solidification. If an alloy has been solidified (even in the DTA), it may contain spatial gradients of composition within the phases. A limiting case of this kind of solidification is given by the Scheil (Scheil-Gulliver) approach. This

approach, well-known in the solidification and casting field, assumes that no

diffusion occurs in the solid during freezing, but that the liquid composition is uniform [74Fle]. DTA melting simulations using the lever enthalpytemperature relation apply to an alloy equilibrated prior to melting and where

diffusion was adequate to guarantee spatial concentration uniformity of all

24
Analysis of DTA data for binary alloys

=

i

1

1

1

1 1 700 800 900 1000

(b) TS (°C)

Figure 3.2. (a) Ag-Cu phase diagram; (b) Enthalpy vs. temperature curves for five Ag-Cu alloys (solid, equilibrium; dashed, Scheil); the curves have

been shifted vertically for clarity, only differences of enthalpy are relevent;

(c) dHs

I dTs

vs. Ts curves for equilibrium conditions for various Ag-Cu

alloys derivedfrom the equilibrium enthalpy curves (overleaf). The vertical arrows at the eutectic temperature (779° C) represent delta functions of the indicated strength in kJIkg.

25
DTA and Heat-flux DSC Measurements

25000'

20000-

10000-

5000-

5000

Ag-lwt%Cu

880 920

1 1 1 960

5000-

4000

J? 3000- ^ 2000 XT3 1000

760

5000-

4000- # 3000- ^ 2000-

T3 1000-

800 840

105.8

880

Ag-23wt% Cu

I ' I l 760 800 840 880 TS (°C)

(C)

Figure 3.2. (continued

)

1000 800 5000

4000

3000 H

2000

loooH

0-

47.9

Ag-15wt%Cu

760 25000

20000-

15000-

10000-

5000 H

800

144.2

840 880

Ag-28.1wt%Cu

—1 1 1 1

1 r~

760 800 840 880 TS (°C)

26
Analysis of DTA data for binary alloys

phases during melting. DTA melting simulations using the Scheil enthalpy

relations apply to a microstructure that was previously solidified and remelted

where there was no solid diffusion during both processes. Clearly these are extreme cases; interpreting DTA data from the melting of an equilibrated sample as well as an as-cast sample requires an analysis of solid diffusion for both

the freezing process and the melting process that is beyond the scope of this document ([02Boe] treat diffusion during melting). Enthalpy vs. temperature

relations can be computed more simply for the extreme cases without the

requirement of any kinetic information or geometry of the microstructure.

The enthalpy vs. temperature relations are obtained from two different

methods in this document: analytical expressions applicable to straight line phase diagrams (Appendix E) and numerical data applicable to real alloy

systems obtained from a Calphad assessment of the thermodynamic functions.

3.1 General behavior for a binary eutectic system; example

Ag-Cu alloy melting

The Ag-Cu alloy system is used to illustrate various features of DTA analysis.

3-1-1 Enthalpy vs. Temperature curves

Figure 3.2a shows the Ag-Cu phase diagram, and Figure 3.2b shows the

enthalpy vs. temperature curves for six Ag-rich Ag-Cu alloys, under

equilibrium and Scheil conditions. The thermodynamic data of [86Hay] were employed to construct the phase diagram and to produce the enthalpy vs. temperature information using code developed by [96Kat]. Other code, such

as Themocalc or Pandat, could have also been used. The 1% Cu alloy exists as a single phase solid solution alloy with liquidus and solidus temperatures

defining the temperature range where liquid phase and the Ag-rich face centered cubic (FCC) phase coexist. (In this document, the % symbol will refer

to percentage by mass.) With increasing temperature, the enthalpy curve has a sharp increase of slope at the solidus for the equilibrium curve but a smooth

increase in slope for the Scheil curved For the 5% Cu alloy, the enthalpy curve has a sharp increase of slope at the solidus for the equilibrium curve but an isothermal jump for the Scheil curve corresponding to the eutectic. The

enthalpy curve is concave up between the solidus and the liquidus, combining

the effects of changing heat capacity of the solid and liquid phases as well as the heat of fusion associated with the changing fractions of liquid and solid

phases. The 9% Cu and 15% Cu compositions are two phase alloys when

Technically, the Scheil approach predicts some eutectic for all alloys. In this case, the mass

fraction of eutectic is very small. 0.003 and would not be detected. 27
DTA and Heat-flux DSC Measurements

solid; the solidus is the eutectic temperature. The enthalpy curves for both

Scheil and equilibrium conditions have isothermal (vertical) rises in enthalpy

corresponding to the eutectic melting of a mixture of Ag-rich phase and Curich phase. The height of the isothermal rise is larger for Scheil than for equilibrium conditions and is larger for the 15% alloy than for the 9% alloy.

Upon completion of eutectic melting, all of the Cu-rich phase has

melted and the enthalpy curve rises with heating corresponding to the

continued melting of the Ag-rich phase. For the Ag-28.1% Cu alloy, the

enthalpy curves has only an isothermal rise in enthalpy corresponding the

eutectic melting.

For the Ag-15% Cu and 23% Cu alloys there is little difference between the

Scheil and equilibrium calculations**. This is because there is so little noneutectic FCC Ag-rich phase that any microsegregation within this phase has

little effect on the heat evolution and fraction of eutectic that forms. For the other alloys, significant differences arise between equilibrium and Scheil

enthalpies that are important to the interpretation of DTA curves. Most

striking is the presence of an isothermal rise in the enthalpy corresponding to the eutectic in the 5% Cu alloy for the Scheil enthalpy whereas no rise is pres- ent for the equilibrium enthalpy. The microsegregation within the Ag-rich

FCC phase predicted by the Scheil calculation leads to the formation of

eutectic, whereas when solid diffusion is adequate to keep the Ag-rich FCC

phase uniform in composition, no eutectic forms.

3.1.2 Derivative of enthalpy vs. temperature curve and their

relation to DTA curves

As developed in section 2.4.1, the temperature derivative (slope) of the

enthalpy vs. temperature curve determines the DTA response. Figure 3.2c

shows these derivatives for the Ag-Cu alloys for the equilibrium enthalpy. The

delta functions corresponding to the isothermal jumps in enthalpy are labeled

with the size of the jump. Just as the DTA response to a delta function for a pure metal is altered by the instrument, so is the response to the alloy

dHsI dTs curve. This alteration can be quantitatively viewed through the

following sequence of operations. First flip a dHs

I dTsvs. Ts curve (from

Figure 3.2c) so that the positive y-axis become negative. Second, broaden this

We note the difference in solid heat capacity predicted by the equilibrium and Scheil models. This difference is due to the fact that the equilibrium computations permit the solid

state adjustment of the phase fraction and compositions of the Ag-rich and Cu-rich phases as temperature changes, whereas the Scheil calculation assumes that these phases have fixed composition and phase fractions as the temperature changes.

28
Analysis of OTA data for binary alloys

760 780 800 820 840 760 780 800 820 840 T(°C) T(°C)

Figure 3.3. Experimental DTA melting scans for a series ofAg-Cu alloys at

three different heating rates, 5 Klmin (blue), 10 Klmin (red) and 15 Klmin

(black). Note that the small signal for the eutectic melting is absent in the Ag-5 % Cu alloy at the slower heating rates. Note also the absence of a

distinct second peak in Ag-23 % Cu. Percentage is by mass. 29
DTA and Heat-flux DSC Measurements

curve in the direction of the x-axis (temperature axis). This shape is a rough

approximation to the DTA curve for melting.

The experimentally determined DTA melting responses of a series of Ag-Cu

alloys at three heating rates are shown in Figure 3.3. It can be seen that the general shapes of the DTA curves are indeed modified versions of the derivative curves, dHs

I dTsvs. Ts

. For Ag-1% Cu and Ag-28% Cu only a single peak is observed. For Ag-9% Cu and Ag-15% Cu two peaks are clearly

shown. The first peak begins near the eutectic temperature and the maximum

signal of the second peak occurs near the liquidus. The reason the maximum

signal of the second peak is associated with the liquidus temperature will be

discussed in section 3.3. For Ag-5 % Cu at the fastest heating rate, a small

signal is evident at the eutectic temperature. At the slowest heating rate, the

small signal for the eutectic melting is absent. The two peaks for Ag-9% Cu

and Ag-15% Cu are for the completion of eutectic melting and the final melting of the FCC Ag-rich phase. For Ag-23% Cu, while there are not two

distinct peaks, there is a slight bulge or shoulder for the final melting of the Ag-rich FCC phase before the return to the baseline that corresponds to the

liquidus. Clearly, the peak temperature corresponding to the end of melting of

the Ag-rich phase is too close in temperature to the strong signal from the end

of melting of the eutectic for the response times of the instrument. Thus no

distinct peak is observed for the liquidus.

3.1.3 Comparison to Experiment

Figure 3.4 shows how the measured DTA scans at 5 K/min compared to the

calculated DTA scans using the equilibrium and Scheil enthalpies. The

general agreement between the calculated and measured results validates the use of the model to simulate and assist in the data interpretation of more

complex alloys. For the 15% Cu, 23% Cu and 28.1% Cu, the model predicts

all observed features as well as trends of amplitude and observed temperatures

with alloy composition. The general shapes of the experimental curve for the

1% Cu and 5% Cu alloys generally lie between the shapes of the lever

calculation and Scheil simulation in the lack of sharpness of the onset. This

intermediate behavior indicates that solid diffusion is not sufficient to permit

full equilibration to be reached at each temperature during heating.

30
Analysis of DTA data for binary alloys

Figure 3.4. Computed DTA curves for Lever (black) and Scheil (red) at 5 Klmin. The experimental DTA curves are shown blue. Lever and Scheil curves for two alloys are essentially identical and only the Scheil curve is shown for Ag-23 % Cu, and 28.1 % Cu.

31
DTA and Heat-flux DSC Measurements

3.2 Problems with solidus determination on heating

3.2.1 Incipient melting point vs. solidus

The temperature at which a solid alloy begins to melt depends on the history

of the material. The terms solidus, nonequilibrium solidus and incipient

melting point, are variously used in the literature to describe the minimum

temperature where some liquid forms. As mentioned earlier, this Guide only

uses the term solidus to refer to the thermodynamic quantity. Cast alloys often

begin melting at temperatures below the solidus of the average composition,

the incipient melting point, which stems from the existence of composition

gradients within individual phases or the presence of extra phases in the alloy

microstructure. Whether a DTA sample is taken directly from a casting or if it has been frozen in the DTA, it is uncertain if the solid microstructure is in global equilibrium at heating rates typical of a DTA. Hence, the microstructural state of the material must always be considered when performing an alloy

melting experiment. This point was previously discussed in section 2.2.9.

3.2.2 Effect of hold time prior to melting

If the user wants to determine the thermodynamic solidus rather than the

incipient melting point, a series of melting runs following isothermal holds at successively higher temperatures below the proposed solidus value should be

conducted to ensure that the sample has been annealed into an equilibrium

structure. An example of this situation is shown in Figure 3.5 for a Ag - 5 %

Cu alloy. After a first melting scan to obtain good thermal contact with the alumina crucible, the sample was cooled at 15 K/min to 760 °C and then

immediately remelted at 15 K/min. This cycle was repeated with successively

increasing hold times at 760°C. The temperature of the large peak remains

relatively fixed, but the onset varies considerably. For the sample with zero hold time, the onset of melting occurs at the eutectic temperature, 779 °C.

This onset disappears with the 5 min hold, the onset increasing to 862 °C.

where it remains with further increase of the hold time. The lower onset occurs without hold time because of the metallurgical state of the alloy after freezing. Such a sample contains dendritic coring of the Ag-rich phase

(microsegregation) and eutectic consisting of Ag- and Cu-rich phases. The

amount of time needed to homogenize the phases and dissolve the eutectic

depends on the hold temperature, which affects the solid diffusion coefficient,

and on the distance between dendrite arms. The required hold time increases

as the square of the length scale. The finer the length scale, the shorter the

hold time. Therefore, as a corollary, more rapid preceding freezing results in a

finer spacing and a shorter hold time. Significantly, this is contrary to normally

32
Analysis of DTA data for binary alloys

779 °C

1 1 1 1

1 1

1

1 1

J 800 840 880 920 960 T(°C)

Figure 3.5. DTA signal for melting ofAg- 5 % Cu showing the effect of hold

time at 760° C and subsequent heating at 15 Klmin.

accepted DTA practice where slower cooling is usually thought to be better, an

idea based on the assumption that the slow rates in a DTA are sufficient to guarantee freezing following the lever rule.

Figure 3.6 shows the computed DTA curve for an enthalpy vs. temperature

relation when diffusion can occur in the solid as derived from a back diffusion

model of solidification, Eqn. Ell, at 5 K/min for a Ag 5 % Cu alloy. The

predicted strength of the eutectic signal is less than that for the Scheil case, but

is not as small as the measured eutectic signal with no annealing in Figure 3.5. This might indicate that the fraction of eutectic in the DTA cast alloy has

undergone further reduction during the short equilibration time required before

the heating scan was begun.

Figure 3.7 shows another example of how annealing time prior to melting

changes the DTA signal for Inconel 718 alloy [91Cao]. With annealing, the

(Fe,Cr)2Nb Laves phase present in the industrially cast sample dissolves

33
DTA and Heat-flux DSC Measurements

-2.5 r

-3 -

-3.5-

f—<

-4 -

-4.5-

-5 760 800 840 880 920

TT

(°C)

Figure 3.6. Computed DTA curve for an enthalpy vs. temperature relation

derivedfrom a back diffusion model of solidification at 5 Klmin ofAg 5 %

Cu is shown blue. Ds = 1 x 10~14 m

2

I s, A2 = 3.8 x 10~5 m. The equilibrium curve is black and the Scheil is red. The peak eutectic signal at approx.

780° C is intermediate between that for the Scheil and equilibrium cases but is not as small as the measured eutectic signal with no annealing in Figure 3.5.

and the onset of melting increases from 1163°C to 1247°C to reveal the true solidus temperature. The lower temperature is the incipient melting point of

the casting and is important for constructing heat treatment schedules for the

casting.

3.2.3 Errors caused by using extrapolated melting onset

(tangent construction)

It has already been noted (2.4.3) that the temperature of the first visible onset of melting is generally preferable over linear extrapolation methods for solidus

determination (in spite of the prevalent use of the latter). This is especially

true for solid solution alloys. Unlike a pure metal or an alloy containing

eutectic, there is no physical basis for a linear section of the DTA curve. There is thus no theoretical basis for using the intersection of the baseline with

the linear extrapolation of any portion of the DTA curve to determine the

34
Analysis of DTA data for binary alloys

1345.8 1200 1300 1200 1300 1200 1300 1200 1300 Temperature (°C)

Figure 3.7. DTA signal for Inconel 718 showing the effect of annealing time

[91Cao]. With annealing, the (Fe,Cr)2Nb Laves phase dissolves and the onset of melting increases from 1163°C to 1247°C.

solidus temperature. As soon as a deflection from the baseline occurs, melting

is surely taking place. Compare the DTA curves for the melting behavior of

pure Ag and eutectic (Figure 2.4, second melts) to the curves for Ag-1% Cu

and Ag-5% Cu (Figure 3.3); see also Figure 3.10 b,c below. For the pure

metal and the eutectic, the onset is quite sharp and the DTA curve is linear

after the onset; the DTA curves for the alloys with no eutectic have no linear

portion near the onset of melting from which to construct an extrapolated

onset. Examples of errors introduced using the extrapolation method of

determining onset compared to the first detectable departure from baseline

are shown schematically in Figure 3.8. 3.3 Problems with liquidus determination on heating

It is customary to select the peak temperature of the last thermal event on

heating as the liquidus temperature. However in the results for Ag - 23% Cu

(mass), Figure 3.3, it was seen that a distinct peak did not exist for the end of

melting because the liquidus temperature was too close to the eutectic temperature. Other subtleties of liquidus determination on melting require exposition.

35
DTA and Heat-flux DSC Measurements

Pure metal Alloy Alloy

\ Y V

j onset j extrap T onset Y

extrap j onset j extrap

Figure 3.8. Schematic DTA plots showing error introduced by using the extrapolation methodfor onset determination rather than the first detectable

departure from baseline.

3.3.1 General DTA curve analysis

The alloy, Ag - 15 % Cu, is examined in more detail to indicate which features

of its DTA curves are important and which features are unimportant during

melting and freezing. This discussion may appear obvious to some but examples abound in the literature of incorrect conclusions drawn from DTA curves. Figure 3.9 repeats the dHs

I dTs

vs. Ts using the equilibrium enthalpy for Ag - 15 % Cu from Figure 3.2c and also shows the computed DTA melting

and freezing scans at 5 K/min. As the dHs

I dTs plot shows, there are only two

temperatures that have significance: the vertical jump at 842 °C (liquidus

temperature) and the delta function at 779 °C (eutectic temperature). Features on the DTA scans are labeled with: i = important or n = not important

depending on how well they approximate these two temperatures. The

significant temperatures i are close to the liquidus and the eutectic temperature. In contrast, the heat transfer details produce other features n on the DTA

scans which bear no direct relation to the above two temperatures.

Furthermore, note the asymmetry of the interpretation of the melting and

freezing scans. For example, the peak on melting near the liquidus temperature is important but the peak just below the liquidus on cooling is unimportant. Similarly the temperature of minimum deflection from baseline between

the eutectic and liquidus temperatures on heating has no meaning yet the

minimum deflection between the liquidus and eutectic temperatures on cooling

is important; it is the onset of eutectic freezing.

We also note that after the completion of melting or the completion of

freezing, no extra heat beyond the liquid heat capacity is required for contin36
Analysis of DTA data for binary alloys

Figure 3.9. dHs

I dTs vs. Ts (top) and computed DTA scans for melting and

freezing at 5 Klmin (bottom) for Ag- 15 % Cu using equilibrium enthalpy.

Features on the DTA scans are labeled with: i = important or n = not

important.

ued sample heating or cooling. The sample temperature increases/decreases

rapidly after the completion of melting/freezing to catch up with the reference

and furnace temperatures; the shape of the return and the temperature of the return of the DTA signal to the baseline are only measures of the efficacy of

heat transfer. They have no metallurgical or thermodynamic meaning.

37
DTA and Heat-flux DSC Measurements

In solidification of binary alloys, one often employs two numbers to describe

the liquidus and solidus curves for dilute allys, the liquidus slope, m, in units

of K/% (for example) and the partition coefficient, k, which is the ratio of the

1750 - i

I i I i 1 i

1740-

1730-

-

:ure (] 1720- Tw ^ Sir I

2

empe 1710 —

i— 1700- 1690-

1680- i

i

i

1

I

1 > 1 '

Figure 3.10. a) Plot of calculated temperatures vs. time for sample (Ts), sample cup (Tc), sample thermocouple (TT) andfurnace wall (Tw)for

melting at a heating rate of 15 Klmin of a 180 mg binary alloy sample that melts following the lever rule enthalpy, with TM = 1728 K, m = -10 K I %,

k = 0.5, C = 2%. The model ofAppendix C and the instrument time constants from Table CI for Ni were employed, b) Calculated DTA curves for pure Ni and alloys with C = 2% and 5% following the lever rule at 15 Klmin. c) Calculated DTA curves for alloy with C = 5%following the lever rule at heating rates of 5 Klmin, 10 Klmin, and 15 Klmin.

38
Analysis of i data for binary alloys

solid composition to the liquid composition. So far, the DTA response has

been described for an alloy where the liquidus slope, m, is negative and the

partition coefficient, k, is less than unity. See section 3.3.5 for further

complicating factors for alloys with m>0 and k>\.

3.3.2 Details of computed behavior of an alloy on melting

For a solid solution alloy with no eutectic, the equilibrium equation for

enthalpy, Eqn. Ell, and numerical solution of Eqn. CI are employed to determine the temperature - time histories and the DTA signal for alloy melting. Figure 3.10 shows the time histories of the temperatures of the various

parts of the DTA instrument for a hypothetical Ni - base alloy of composition

of alloying addition C = 2% (k=0.5, m = -10 K / %) with solidus/liquidus

values of 1688 K/1708 K. It is important to note that the value of the thermocouple temperature at the instant when the sample completes melting at the

liquidus temperature (Figure 3.10a at « 290 s) is ~ 1720 K, 12 K higher than

the liquidus temperature. Figure 3.10b shows that the peak temperature is near 1720 K. The figure also shows the DTA plots of a 5% alloy and also pure Ni

for comparison. Figure 3.10c shows how heating rate affects the computed

DTA scan.

Figure 3.11. a) DTA peak temperature calculated at a heating rate of

15 Klminfor different alloy compositions using a lever assumption.

Peak temperature is superimposed on the phase diagram (TM = 1 728 K,

m = -10 K /%, k = 0.5). b) The difference between the peak temperature and

the liquidus temperature as a function offreezing range at three heating rates. The freezing range is given by mC [(k - l)/k)].

39
DTA and Heat-flux DSC Measurements

3.3.3 Small liquidus solidus separation

Figure 3.11a shows calculated DTA peak temperatures superimposed on the

phase diagram for 0% < C < 20%. Figure 3.11b shows the difference

between the peak temperature and the liquidus temperature. One notes that the peak temperature lies above the liquidus temperature with an error increasing as the concentration of the alloying element decreases. In other words,

if the freezing range of the alloy is small (of the order of the temperature

difference between the onset and peak temperature of a pure metal melting

DTA scan), the peak temperature of the DTA can only serve as an upper bound

on the liquidus temperature.

3.3.4 Resolution of difficulties using temperature cycling near

the liquidus

Cycling experiments can be used to determine the liquidus for small freezing

range alloys or for alloys where the fraction of the final phase on melting is small. This approach was demonstrated by [OOWu] for complex superalloys

and is shown in Figure 3.12. First an upper bound on the liquidus is deter- mined from the peak temperature of an ordinary DTA scan, 1399°C in (a). Then a lower bound is determined by the cooling curve, 1358°C in (b) as the

nucleation temperature. Clearly significant supercooling has occurred. Next

the sample is cooled, reheated and held at a temperature below the upper

bound temperature, 1380°C in (c) for 10 min, and then heating is reinitiated. Signs of an endothermic signal are sought. If absent, a fully liquid state is implied for the hold temperature and the hold temperature is above the

liquidus temperature. If present, a partially solid state is implied at the hold

temperature and the hold temperature is below the liquidus. In Figure 3.12c

with a hold temperature of 1380°C, no endothermic signal was seen. Thus the

cycle was repeated at a lower hold temperature. This process is repeated until an endothermic sign of melting is seen. With this process the liquidus

temperature can be bracketed to within a few degrees, 1378°C to 1379°C in the present case. 3.3.5 Alloys with k<1 and fc>1 ; peak temperature

A second problem with respect to liquidus temperature determination may be

encountered when dealing with an alloy for which the partition coefficient

k>\. The k> \ case applies whenever the liquidus/solidus separation (freezing

range) decreases with decreasing temperature. The more common situation,

k<\, applies whenever the liquidus/solidus separation increases with decreasing temperature. See Figure 3.13a. To demonstrate this effect we compare the

40
Analysis of DTA data for binary alloys

I

H

II H

<

i

\^interrupted and held at [38^

C

v

n interrupted and hel_d_qtJJ_7jf

^^interrupted and held at 137%' AT=2.fC

no endothermic peak

endothermic peak

1175 1200 1225 1250 1275 1300 1325 1350 1375 1400 1425 1450

Temperature (°C)

Figure 3.12. a) Normal DTA scan on heating for a small greezing range

Ni-base superally; b) Normal DTA scan on cooling. Supercooling has

occurred; c) Cycling DTA to determine the liquidus temperature [OOWu].

computed DTA response of two alloys with identical heats of fusion, and

liquidus and solidus temperatures with k = 2 and k = 0.5. Again we use the

straight line liquidus and solidus model, Eqn. El, and enthalpy given by Eqn.

E9, and the computation method of Appendix C. The derived dHsI dTsvs. Ts curves are shown in Figure 3.13b. The computed DTA scans for three heating

rates are shown in Figure 3.13c,d. For k<\, the DTA curve exhibits a sharp

peak at 1681 °C (for 5 K/ min). For £>1, the DTA curve has a broad peak at 1639°C and a shoulder at 1679°C (for 5 K/min). The liquidus temperature for both is 1678°C. Hence it is clear that the peak temperature for the k>\ case

bears no relationship to the liquidus. For k<l, more of the latent heat is released higher in the freezing range compared to the case for k> 1 where more

of the latent heat is released lower in the freezing range. In other words, for k<\, the value of dHs

I dTs increases with temperature, whereas for k>l, the

value of dHs

I dTs decreases with temperature, Figure 3.13b. Because the k<\

case is much more common for alloys, there is a strong association of the peak

41
DTA and Heat-flux DSC Measurements

temperature on the DTA with the liquidus temperature. This indicates that such is not always the case. This point is reinforced by the simulation shown

in Figure 3.14 using real thermodynamic data for Bi-rich and Sb-rich alloys of

the Bi-Sb isomorphous system.

12

(a)

<—i——r i 2 4 6 Composition (%)

1—i1—i——

10 1620 1640 1660 16? TS (K)

(b)

~

I

1—

1700 1720

10 C = 5%

5 K/min

K/min

K/min _

i

1—i——i——

o

10-

5 K/min

K/min

5 K/min

= 1578 K

20 K/%

C = 5%

i 1

1

1 11

1 1 r- 1620 1640 1660 1680 1700 1720 1620 1640 1660 1680 1700 1720

(c) 7>(K)

(d)

Figure 3.13. Comparison of two hypothetical alloys with identical heat of

fusion, liquidus and solidus temperatures but differing having k<l and k>l.

a) Phase diagram, b) dHs

I dTs for k<l (black) and k>l (red), c) DTAfor

k<l and d) DTA for k>l. For k<l, the latent heat is released higher in the freezing range compared to k>l where the latent heat is related lower in the freezing range.

42
Analysis of DTA data for binary alloys

g 1.2xl04- § 8.0x1 3 - H\ 4.0x1 3 - X"3

Sb-10% Bi

O.Ox 1 0° |

i 1

1—i—i—i—

r

820 840 860 880

! TS (K)

I

' I 900 920

860

' 880' 900' 920

(a) TT

(K)

4.0xl03 ~» $ 3.0xl03

2.0xl03

l.OxlO3 -

0.0x10°

(b)

Bi-10% Sb

580 600 TT

(K)

Figure 3.14. Comparison of Bi-10% Sb with k>l and Sb-10% Bi with

k<l alloys. The dHsI dTs curves computedfor lever law using the thermodynamic functions of [92Feu] and the computed DTA scans for heating and

cooling are shown.

3.3.6 Failure to completely melt

Another difficulty in the determination of the liquidus temperature can occur when the alloy contains only a small fraction of the high temperature phase

and the liquidus is very steep. Failure to run the DTA to a sufficient high

temperature to reach the liquidus and/or failure to notice a small signal can

lead to significant errors. This problem is discussed in [OOMoo] for Sn-Cu-Ag

alloys where the intermetallic compound Cu6Sn5 is the primary phase.

3.4 Supercooling problem with liquidus determination on cooling

3.4.1 Onset of freezing

Many metals and alloys are prone to supercooling prior to the initial nucleation of the solid metal from the melt. The nucleation usually occurs on

foreign crystals; examples of possible nucleating sites are the ceramic grains in the crucible, oxide on the melt surfaces or fine particles dispersed throughout

the liquid. Nucleation temperatures can vary from only a fraction of a degree

below the liquidus to 100 or more degrees below the liquidus depending on

alloy system and other factors. The failure to nucleate with small supercool43
DTA and Heat-flux DSC Measurements

ing complicates the measurement of a liquidus temperature during cooling. tt The events occurring during supercooling are demonstrated in Figure 3.15

showing data obtained with a fine thermocouple immersed in Sn in a DTA cup

(same setup as used for Figure 2.6). Here significant supercooling has

occurred. For the immersed thermocouple, the temperature reheats fully up to the melting point of 232°C as the heat of fusion is released rapidly due to the very fast dendritic freezing resulting from the large supercooling. The sample

temperature does not drop again until freezing is complete. The use of the

direct immersion thermocouple allows the determination of the temperature

where solid first forms (nucleation temperature) in this sample as 206 °C, 26 °C

below the melting point of 232 °C. Using the instrument thermocouple, the nucleation temperature would have been measured as 203 °C with a recales- cence only up to 217 °C. The presence of supercooling is detected quite easily

in the DTA plots using either temperature (Figure 3.15b) by the positive slope

of the AT vs. T graph. Supercooling provides the most extreme example of

where the instrument thermocouple temperature and the sample temperature

differ due to the limitations of heat transfer within the DTA.

7500 7600 7700 7800 7900 180 200 220 240 260

(a) time(s) (b) T (°C)

Figure 3.15. Measured (a) temperature vs. time plots and (b) associated

DTA plots for the freezing ofpure Sn. The instrument thermocouple readings

(sample and reference) are black and the readings from a thermocouple

immersed directly into the Sn in the sample cup are red. Significant

supercooling has occurred prior to freezing inducing the rapid temperature

rise upon solidification in (a) and the associated positive slope in (b); mass = 163.2 mg; heating rate = 5 Klmin.

Nucleation of liquid on melting is not difficult due to the large number of microstructural defects (grain boundaries, defects, etc.). 44
Analysis of DTA data for binary alloys

3.4.2 Slope of DTA curve on initial freezing

Smaller amounts of supercooling in some samples can be harder to detect as they may not lead to a positive sloping DTA curve. In Appendix D, we have

noted that the slope of the DTA on melting of a pure material is given by the

ratio of two heat flow response times, -twc I ts c

(wall to cup / sample to cup). This slope is easily determined experimentally by melting a pure material of similar mass. The rising linear portion of the DTA peak after the initia- tion of freezing (without supercooling) of a pure metal has the same slope.

Thus, if the measured slope after the onset of freezing is more vertical than

~*W,C / C» one can ^e certam mat supercooling has occurred and the measured onset temperature of freezing would be lower than the melting point.

This simple test for the presence of initial supercooling would not necessarily

be conclusive for an alloy because the slope during alloy freezing with no

supercooling would also be less vertical than -twc I tsc due to slope of the

liquidus curve.

3.4.3 Simulation of DTA response for alloys with supercooling

To gain insight into the DTA response when supercooling occurs for an alloy, a model of dendritic growth into a supercooled liquid for a non-dilute alloy

has been coupled to the DTA response model [02Boe]. The sample, cup, thermocouple and wall temperature histories are shown for a particular set of

materials parameters in Figure 3.16a for an initial supercooling of 5 K below

the liquidus temperature. Several features can be noted: 1) recalescence of the

sample temperature occurs as the latent heat is released during the dendritic

network propagation across the sample; 2) After the recalescence temperature

maximum, the sample temperature descends as the dendritic network thickens,

increasing the fraction solid; 3) The cup temperature exhibits a smaller

recalescence due to the heat transfer restrictions of the DTA cell and 4) the

sample thermocouple actually exhibits no recalescence.

The DTA curves for initial supercoolings of K, 5 K, 10 K, 15 K, 20 K and

30 K are shown along with the DTA curve for the Scheil path in Figure 3.16b.

The initial rise of the DTA signal departs from the baseline at a lower temperature and rises more rapidly as the supercooling increases. The latter indicates

the recalescence of the sample due to the rapid initial dendritic growth. The

rise has a backward (positive) slope for supercoolings of 10 K and above.

Here the sample recalescence is large enough that the thermocouple

temperature also recalesces (Figure 3.16a); clearly, the absence of a backward

DTA rise is not proof that supercooling is absent and that a valid liquidus

temperature has been determined.

45
DTA and Heat-flux DSC Measurements

i

1600 1620 1640 1660 1680

(b) TT (K)

Figure 3.16. a) Plot of calculated sample, sample cup, sample thermocouple

andfurnace wall temperatures vs. time curves for dendritic freezing of a 180 mg sample of alloy with C = 5% at 15 Klmin with an initial supercooling of 5 Klmin. b) Effect of supercooling on the freezing DTA signal of the same alloy. The curves are for K, 5 K, 10 K, 15 K, 20 K, 30 K

supercooling. From [02Boe].

3.5 Eutectic reactions vs. Peritectic reactions

3.5.1 Diffusion

From a purely thermodynamic point of view, eutectic reactions, L—>a+fi, and

peritectic reactions, L+oc^P, in binary alloys both take place at a fixed tem46
perature and exhibit an isothermal jump in the enthalpy vs. temperature curve

at the transition temperature. However, as is well known in the solidification

literature [74Fle], they are quite different in their diffusion kinetics. For eutectic solidification, L—>a+P, both solid phases form directly from the liquid; i.e., locally one has L—>a and L—>fi. Thus the necessary solute redistribution occurs in the liquid ahead of the individual interfaces, which are in close

proximity. On the other hand, the peritectic reaction, L+a—>f3, requires the

complete disappearance of the a phase, a process that involves solute diffusion

in two solid phases at the peritectic temperature. The kinetics is therefore

quite different for eutectic and peritectic alloys because of the extremely dif- ferent rates of diffusion in liquids and substitutional solids. (If only interstitial solid diffusion is required, the peritectic reaction occurs more easily but still not as fast as the eutectic reaction.) Very little research has been performed on DTA analysis of systems containing peritectic reactions.

If one assumes as a limiting case that no diffusion occurs in the solid upon

cooling, solidification merely switches from the freezing of the high

temperature phase, L—>a, to freezing of the low temperature phase, L—>/3,

at the peritectic temperature and below. Then the phase usually surrounds

the a phase in the microstructure resulting in a coarser two phase solid

microstructure than in a eutectic microstructure. More complex arrangements

of the two solid phases can occur for both eutectic and peritectic reactions

especially if interface attachment kinetics are sluggish (usually encountered for

crystals that grow from the liquid with crystallographic facets). Then the two

solid phases grow independently from the melt with very little communication

of the solute fields in the liquid. This leads to much coarser mixture of the two

solid phases.

When the eutectic portion of a microstructure melts, both solid phases melt

very close to a common temperature. This is because the phases usually exist as a fine two-phase intermingled microstructure. The melting DTA signal

looks like that of a pure material (Figure 2.4b). For melting of an alloy with a phase diagram containing a peritectic reaction, the two solid phases are not intermingled as closely as they would be in a eutectic alloy. The melting

response of the two-phase microstructure can occur over a range of temperatures due to the requirements of solid diffusion. The DTA response, as in freezing, again depends of the rate of solid diffusion with lever and Scheil

enthalpies representing the extremes of behavior.

3.5.2 DTA Response

To illustrate these points we have chosen an alloy in the Sn-Au system that has

both a peritectic reaction (L+Sn2Au—>Sn4Au) at 252°C and a eutectic

47
DTA and Heat-flux DSC Measurements

reaction (L—>Sn4Au+Sn) at 217 °C as shown in Figure 3.17a. Figure 3.17b

shows the enthalpy vs. temperature and dHs

I dTs

vs. temperature curves for Sn - 25% Au calculated for equilibrium (black) and Scheil (red) conditions

using the thermodynamic description of [03Liu]. For the equilibrium curves, note the presence of two isothermal jumps in enthalpy with the corresponding

delta functions in the dHs

I dTs curves at the two invariant temperatures. For

the Scheil curve the delta function is absent for the peritectic reaction. This

absence occurs because the assumption of no solid diffusion in the Scheil

model prevents the "peritectic reaction." When traversing the peritectic

temperature during solidification, the freezing process merely switches from

L—>Sn2Au to L—>Sn4Au and there is no isothermal drop in enthalpy. For

melting of an alloy frozen under these conditions, again with no solid

diffusion assumed, melting switches from Sn4Au—> L to Sn2Au—>L at the

peritectic temperature and there is no isothermal rise in enthalpy. Real solidi- fication and melting will be intermediate to these two cases. The corresponding computed DTA curves for melting and freezing are shown in Figure

3.17c,d. Note how the peak signal for the "peritectic" reaction near 252°C is much reduced when the Scheil enthalpy is used. The computed DTA response

agrees favorably with experimental results for Sn- 25% Au alloy shown in Figure 3.17e.

3000 -1 25% Au

50 60 70 80 90 100 %Sn

(a) (b)

I

1

I 1

I

1 I

1 200 220 240 260 280 300

Ts (°C)

48
Analysis of DTA data for binary alloys

i

1—i

1—i1—i

1—

r

-^

160 200 240 280 320

(e) T (°C) Figure 3.17. a) Phase diagram for Sn-rich alloys, b) Hs and dHs

I dTs curves for Sn- 25 % Au calculated for equilibrium (black) and Scheil (red)

conditions using the thermodynamic description of [03Liu]. Computed DTA

curves for c) freezing and d) melting. Note how the amplitude of the peakfor

the "peritectic" reaction near 252 °C is much reduced when the Scheil

enthalpy is used, e) Experimental melting andfreezing curves at 5 Klmin.

49
DTA and Heat-flux DSC Measurements

DTA responses for the basic cases in binary eutectic and peritectic systems are summarized in Appendix F. 3.6 Major points

• Melting onset depends on metallurgical state of sample prior to analysis.

Slow cooling and heating rates do not necessarily guarantee an

equilibrated sample at each instant.

• The melting onset during heating should be determined by the first deviation from baseline method. The common practice of using the

intersection temperature of a tangent to the DTA curve and the

extrapolated baseline can lead to significant error because alloy DTA

scans do not in general posses a linear section.

• Annealing of samples in the instrument prior to melting is sometimes

required to obtain the thermodynamic solidus.

Peak temperature on heating for alloys with small freezing ranges may

overestimate the liquidus temperature. Cycling experiments can be used

to obtain a true liquidus.

Liquidus temperature determination on heating for alloys with partition

coefficient k> 1 is more difficult than alloys with k< 1

• Peritectics do not produce as sharp a melting peak as do eutectics.

• Not all temperatures that can be extracted from alloy DTA scans have

meaning with regard to the alloy. Some temperatures are merely an

indication of thermal lags within the instrument.

50
Analysis of DTA data for ternary alloys

Part 4 - Analysis of DTA data for ternary alloys

The analysis of DTA curves for ternary and higher order systems is best

accomplished with knowledge of the general thermodynamic aspects of

multicomponent phase equilibrium. See Appendix B for selected readings.

An excellent discussion of the DTA signals obtained during the melting and

solidification of ternary alloys is given by [01 God]. In this work, Godecke

treats the situation when complete equilibrium is maintained during melting

and freezing; i.e., that all phases nucleate without superheating or supercooling

and that the compositions of all phases are uniform at every temperature and

thus follow the predictions of the lever rule. While this is an excellent starting

point for understanding alloys, we highlight here some of the different

responses obtained when interfacial equilibrium is maintained, but diffusion is not adequate to maintain uniformity of the phases during melting and

solidification. We do this by comparing the DTA response to enthalpy

temperature relations obtained from a thermodynamic calculation for two

ternary aluminum alloys using, as in previous sections, full equilibrium and

Scheil conditions.

Appendix G gives examples of similar DTA response for alloys with more

than three components.

4.1 Al-rich corner of Al-Cu-Fe phase diagram

First we discuss solidification. Figure 4.1 shows the liquidus surface (projection) of the Al-rich corner of the Al-Cu-Fe ternary system. The diagram is like a topographic map where the temperature takes the place of elevation. The

various surfaces represent the range of liquid alloy composition and the temperatures where various phases are first to solidify. The phase is labeled on

the surface. In the aluminum-rich corner, the FCC aluminum solid solution

forms. At higher Fe content and with no Cu, the Al3 Fe phase is first to form.

At high Cu content with no Fe, the 6 phase, Al2Cu, is the first phase to form.

Other regions where the a phase, Al6(Fe,Cu), and the p phase, Al7Cu2Fe, form

first are indicated. Intersections of these surfaces occur in this diagram along

lines (e.g.; ab, bd, cd, de) that descend in temperature. Many of these lines correspond to valleys$$. They represent the monovariant eutectic solidification

:

We have not discussed the situation where the liquidus surfaces intersect to form a monovariant peritectic reaction as for the intersection of Al3Fe and Al6

(Fe, Cu) liquidus surfaces on

"be" in Figure 4.1. Such an intersection is not a "valley" but a change in slope of the liquidus. Lever solidification follows this line but Scheil solidification crosses it, switching from Al3 Fe

to Al6

(Fe, Cu).

51
DTA and Heat-flux DSC Measurements

Figure 4.1. Liquidus surface ofAl-rich corner ofAl-Cu-Fe alloy with lines of

constant temperature (labeled), monovariant lines (ab, be, bd, cd, de, ef and

eg) and invariant points (a, b, c, d, e) at 654°C, 623°C, 608°C, 592°C, and

548°C, respectively. Diagram is computedfrom thermodynamic data of

[96Saul]. The calculated paths of the liquid concentration for the two alloys

discussed in Figures 4.2, 4.3, 4.4 are indicated: Al - 6% Cu - 0.5% Fe

equilibrium is black (ends along line de), Scheil is red (ends at point e) and

Al-20 wt% Cu- 0.5% Fe equilibrium and Scheil are blue (both end at point

e and are essentially identical).

of two solid phases whose liquidus surfaces have intersected. Where two

monovariant eutectic valleys join to form a third monovariant valley that continues to descend, such as at (d), an invariant occurs, variously termed a transi- tion reaction, Class II four-phase invariant reaction [56Rhi], quasi-peritectic

[66Pri] or ternary peritectic [60Mas]. When three descending monovariant

valleys intersect, such as at (e), a different type of invariant occurs, termed a ternary eutectic reaction or Class I four-phase invariant reaction.

The solidification path is the entire history of how the liquid composition,

whose concentration is assumed uniform at each temperature, changes as the

various solids form from the melt. During primary (or first) solidification, the

52
Analysis of DTA data for ternary alloys

path moves away from the composition of the primary phase, until it intersects one of the valleys. Solidification proceeds down in temperature following the

valley and traversing whatever invariant reaction is encountered. The paths of

liquid concentration superimposed on the liquidus surface for the two alloys

discussed below, Al - 20% Cu - 0. 5% Fe and Al - 6% Cu - 0.5% Fe for the

equilibrium calculation are shown in Figure 4.1.

For illustrations of the DTA responses, we employ the model of Appendix C,

using an alloy mass of 200 mg, heating and cooling rates of 5 K/min and

instrument time constants obtained by linear interpolation to 600°C between

the results obtained experimentally for Sn and Ag in Appendix D; i.e.,

ts c = 9.8 s, twc = 23.6, tTC = 20.9 s.

4.2 Al - 20% Cu - 0.5% Fe

With the brief preceding description of the phase diagram, we proceed to describe the DTA response. The alloy Al - 20% Cu - 0.5 % Fe has been

chosen for exposition because it exhibits the most common behavior for a ternary alloy; i.e., a three stage process on cooling that progresses from

freezing of one, then two and finally three solid phases from the melt.

Figure 4.2 shows the DTA and dHsI dTs

plots under equilibrium conditions.

The solidification sequence is: L^FCC,

L^FCC+Al7Cu2Fe,

L^FCC+Al7Cu2Fe+Al2Cu.

With decreasing temperature, the dHs

I dTs plot first encounters a jump in value at the liquidus temperature, ~ 598 °C. The derivative value then slowly

decays until another jump occurs when the monovariant valley (de) is encountered at ~ 584°C. The value of dHs

I dTs then slowly decays again

until the delta function associated with the ternary eutectic temperature (e) is encountered at ~ 548 °C. The corresponding DTA plot on cooling shows an

onset associated with the liquidus, a second onset associated with encountering

the monovariant valley and a third onset associated with the ternary eutectic. Supercooling may be required to enable the nucleation of each new solid

phase. Thus, problems can occur in identification of onsets during cooling

not only for the first phase to form from the melt but also for each new phase

in the various later stages of solidification.

53
OTA and Heat-flux DSC Measurements

Al - 20% Cu - 0.5% Fe

Lever

5 K/min

520 560

Ts (°C)

600

Figure 4.2. DTA and dHs

I dTs plots for Al - 20 % Cu - 0.5 % Fe under

equilibrium conditions. The aluminum alloy thermodynamic database

[96Saul] was employed. The solidification sequence is: L—>FCC, L^FCC+Al7Cu2Fe, L-^FCC+Al7Cu2Fe+Al2 Cu.

54
Analysis of DTA data for ternary alloys

On heating, an onset is encountered that is associated with the ternary eutectic

melting. All three solid phases are melting, but only one, Al2Cu, is completely

consumed by this process. The other solid phases, FCC and Al7Cu2Fe,

although reduced in amount, still remain. The temperature associated with the

maximum deflection does correspond to the time when Al2Cu is gone, but the

temperature of the sample thermocouple at this time has no significance due to the thermal lags of the instrument; this case is analogous to the peak shape

during melting of a pure metal in that the peak temperature after an invariant

reaction has no thermodynamic meaning.

On continued heating, according to the dHs

I dTsplot, the rate at which the

remaining FCC and Al7 Cu2Fe melt increases with increasing temperature until a sudden drop in the dHs

I dTs value occurs. This drop indicates that all of the

Al7 Cu2Fe has melted. This drop in the dHs

I dTs value produces the maximum deflection in the DTA plot associated with the temperature where all of

the Al7 Cu2Fe has melted. According to the dHsI dTsplot, the rate at which

the remaining FCC melts increases with increasing temperature until a sudden

drop in the dHsI dTs value occurs. This drop indicates that all of the FCC has

melted. The final peak temperature in the DTA scan is thus associated with

the temperature when all of the FCC has melted. We have used the term

"associated with" to indicate that the measured onset and peak temperatures

suffer from same thermal lags from the temperatures where the events are

truly taking place in the instrument; this deviation appears in Figure 4.2 as the

offset of the DTA peaks from the dashed vertical lines indicating the thermodynamic temperatures. We note finally that, for this alloy, there is little difference between the lever and Scheil enthalpies because the fraction of the

FCC phase (in which dendritic coring can exist) occupies a relatively small

amount of the total alloy.

4.3 Al - 6% Cu - 0.5% Fe

This alloy has been chosen for exposition because it exhibits the second most

common behavior for a ternary alloy, i.e., a four (five for Scheil) stage process on cooling that progresses from the freezing of one solid phase, then two solid

phases, interrupted by an invariant reaction, continued freezing of two solid

phases and finally three solid phases. The solidification sequence is: L^FCC,

L-^FCC+Al6(Fe,Cu),

L+Al6(Fe,Cu)^Al7Cu2Fe+FCC (invariant); Lever path only.

55
DTA and Heat-flux DSC Measurements

L^FCC+Al7Cu2Fe,

L-^FCC+Al7Cu2Fe+Al2Cu (invariant); Scheil path only.

Solidification first involves the formation of the FCC phase from the melt.

The liquid is enriched in Cu and Fe as the temperature drops until the concentration reaches the monovariant valley (bd), L^FCC+Al6(Fe,Cu), at 616°C.

Then simultaneous liquid freezing to FCC and Al6(Fe,Cu) phases occurs with

decreasing temperature until the valley encounters a second valley that is between the FCC and Al7Cu2Fe liquidus surfaces (de). Under the equilibrium

assumption, all of the Al6(Fe,Cu) dissolves at the invariant temperature

(d) at 592°C, in the process forming more FCC and the new phase, Al7Cu2Fe. Subsequently, solidification continues with decreasing temperature (along de)

forming more FCC and Al7 Cu2Fe. Solidification is completed at 556°C on

(de) between (d) and (e) at 556 °C). In contrast, under Scheil assumptions, the

invariant temperature (d) is merely the temperature (592 °C) where solidifica- tion switches from L^FCC+Al6(Fe,Cu) to L^FCC+Al7Cu2Fe as the

temperature drops. For Scheil conditions, the curve (de) is followed as FCC

and Al7 Cu2Fe solids form, the temperature descending and the liquid concentrations increasing to the end of (de) until the ternary eutectic temperature at (548 °C) and liquid concentration are reached at (e). Here all liquid disappears

via the ternary invariant eutectic, L-^FCC+Al7Cu2Fe+Al2Cu.

Figure 4.3 shows dHs

I dTs and melting and freezing DTA plots under equilibrium conditions for this alloy. Figure 4.4 shows dHs

I dTs and melting and

freezing DTA plots under Scheil conditions. Note the presence of the delta function at ~ 592 °C in the dHs

I dTs plot corresponding to the invariant reaction, L+Al6(Fe,Cu)-^FCC+Al7Cu2Fe, in the equilibrium case but not for the

Scheil case. Also note the presence of the delta function corresponding to the

ternary eutectic at 547 °C in the Scheil case and its absence in the equilibrium

case (Figure 4.4). These differences are due to the assumptions of complete

diffusional equilibrium in the first case and no solid diffusion in the second

case, again representing extremes of behavior. Just like a peritectic reaction in a binary alloy (section 3.5), the reaction L+Al6(Fe,Cu)^FCC+Al7Cu2Fe

requires solid state diffusion and thus does not occur under the Scheil assumption. On solidification, one merely switches at 592 °C from the formation of

FCC+Al6(Fe,Cu) to the formation of FCC+Al7Cu2Fe. Al6(Fe,Cu) is not consumed on continued cooling but remains in the alloy's microstructure.

These differences in the dHs

I dTs curves are then reflected in the DTA scans.

56
Analysis of DTA data for ternary alloys

20—,

oo

00

Al - 6% Cu - 0.5% Fe

Lever

5 K/min

25000-,

20000-

15000

10000-

5000-

560 600 640 680

To (°C)

Figure 4.3. DTA and dHs

I dTs plots for Al-6 % Cu-0.5 % Fe under

equilibrium conditions. The aluminum alloy thermodynamic database

[96Saul] was employed. The solidification sequence is:L—>FCC,

L^FCC+Al6(Fe,Cu), L+Al6(Fe,Cu)-^FCC+Al7Cu2Fe, L->FCC+Al7Cu2Fe. Note the delta function at ~ 592°C corresponding to the invariant reaction,

L+Al6(Fe,Cu)->FCC+Al7Cu2Fe.

57
DTA and Heat-flux DSC Measurements

Al - 6% Cu - 0.5% Fe

on HT3

25000 -i

20000 -

15000 -

X 10000

-a

5000 -

520 560 600

To (°C)

640 680

Figure 4.4. DTA and dHs

I dTs plots for Al-6 % Cu-0.5 % Fe under Scheil

conditions. The aluminum alloy thermodynamic database [96Saul] was

employed. The solidification sequence is: L—>FCC, L—>FCC+Al6(Fe,Cu),

L—>FCC+Al7Cu2Fe, L->FCC+Al7Cu2Fe+Al2 Cu. Note the delta function in the dHs

I dTs plot at ~ 592 °C in Figure 4.3 corresponding to the invariant

reaction, L+Al6(Fe,Cu)—>FCC+Al7Cu2Fe is gone.

58
Analysis of DTA data for ternary alloys

.4 - Major points

Knowledge of ternary alloy phase equilibrium is necessary to interpret

data for ternary and higher order systems.

Ternary invariant transition reactions may have quite different

DTA signals compared to ternary invariant eutectic reactions.

Failure to nucleate during cooling DTA scans can occur with solid phases

that form through secondary solidification processes in addition to primary

solidification.

59
DTA and Heat-flux DSC Measurements

Part 5: Concluding remarks

We have attempted to highlight two important effects that must be carefully

considered in the measurement of alloy melting and freezing using a DTA/HF-DSC. The first is concerned with the heat flow and the small but

important temperature differences that exist within the different parts of the

instrument. Thermocouple signals are the only information available and the thermocouple, not directly immersed in the metal, is not at the sample temperature. This is most easily seen in the shape of the DTA curves for the melting

of a pure material, where one might naively think that the sample temperature

ranges from the onset temperature to the peak temperature during melting due

to an erroneous concept of kinetics. This is clearly not the case. Thus the heat

transfer between sample, through the sample container and finally to the thermocouple must be considered. A model is presented to quantify these

effects and to determine heat transfer characteristic of any DTA/HF-DSC

instrument.

The second important effect is that deviations from full equilibrium can and do

occur during the melting and freezing of alloy samples at the rates encountered

in DTA. Indeed the small sample in the DTA cup is best viewed as a small

casting with all of the complications that can occur in castings. However, the

loss of full equilibrium is due mostly to the slow rate of solute diffusion in alloys and is thus analyzable without recourse to complex models that involve

so-called reaction kinetics. This concept is widely used in the successful

modeling of castings and can be applied to DTA response. This idea has

been developed in the current document in the broad usage of the comparison

of full equilibrium and Scheil approaches to place bounds on expected DTA

response. The heavy use of simulations of the DTA response in this document should not be taken to imply that measurements are unnecessary. The simulations were

performed using thermodynamic data that remains under constant revision by

the Calphad community. Indeed these thermodynamic assessments are constructed from data sometimes obtained from incorrect interpretations of

transformation temperatures using the DTA. In addition many complications

of diffusion kinetics and microstructure variations can occur that are not considered here. The emphasis of this document on problems with DTA analysis may also have

led the reader to the impression that accurate temperature determination with

the DTA is nearly impossible. This is not true and it is not the intention of this guide to discourage DTA measurements. The intention is to increase user

60
Concluding Remarks

awareness of the factors that influence the DTA signal by providing physical

explanations that enable thorough and meaningful analysis of the results and

temperature determinations.

61
OTA and Heat-flux DSC Measurements

Appendices

Appendix A: Glossary

Back (solid) diffusion: Diffusion in the solid phase(s) to attain equilibrium

composition throughout the solid phase during solidification.

Baseline: The signal recorded without a thermal event such as melting taking

place.

Calphad: Calculation of phase diagrams. The Gibbs energy of each phase is represented as a function of composition, temperature and pressure. The

adjustable parameters of the functions for the individual phases are derived

from experimental phase equilibria and thermochemical data. The descriptions of constituent subsystems can be combined for the calculation of a multicomponent system.

Degrees offreedom: Number of variables that can be changed without

changing the identity of the phases in equilibrium. The number of degrees of

freedom, F, can be obtained from the phase rule, F = N-P+2, where TV is the

number of components and P is the number of phases in equilibrium. For

condensed phase systems the pressure is usually dropped as a variable and the

phase rule is modified to F = N-P+l

Delta function: A function d\x) that has the value of infinity for x=0, the

value zero elsewhere. The integral from minus infinity to plus infinity is 1.

Differential scanning calorimetry (DSC): See Heat-flux differential scanning

calorimetry (HF-DSC) or Power-compensating differential scanning

calorimetry (PC-DSC).

Differential thermal analysis (DTA): Thermal analysis using a reference.

Sample and reference are heated in one furnace. The difference of sample

temperature and reference temperature is recorded during programmed heating

and cooling cycles.

Endothermic: Heat is consumed during a reaction or transformation, i.e. the

enthalpy change is positive.

Enthalpy (H): Heat content of a phase.

62
Appendix A

Equilibrium: State of the lowest free energy when no further change of a system is possible. Phases in equilibrium at a given composition, temperature

and pressure have no driving free energy to react or transform. See Global

equilibrium and Local equilibrium.

Eutectic: Thermodynamic situation where a liquid is simultaneously saturated

with respect to several solid phases and cooling decreases the amount of liquid

and increases the amount of all solids. The situation may have zero or more

degrees of freedom depending on the number of phases and components.

Exothermic: Heat is released during a reaction or transformation, i.e. the

enthalpy change is negative.

Fraction of solid versus temperature: Amount of solid phase(s) formed

during the solidification of an alloy.

Gibbs-Thomson effect: The contribution of the interface energy to the Gibbs

free energy due to the effect of the shape (curvature) of the interface between

phases. Phases with high curvature interfaces exhibit altered melting

temperatures and solubilities.

Global equilibrium: A complete equilibrium where there are no gradients of

temperature or pressure and the compositions of coexisting phases are uniform.

Heat capacity (Cp): Rate of enthalpy (heat content) change of a phase with

respect to temperature at constant pressure.

Heat-flux differential scanning calorimetry (HF-DSC): Sample and reference

are heated in one furnace. The difference of sample temperature and reference

temperature is proportional to the heat flux between the sample and reference.

Contrast with: Power-compensating differential scanning calorimetry.

Incipient melting: Initial melting of an alloy. This may occur below the

solidus temperature of the average alloy composition due to microsegregation

from prior solidification.

Interface undercooling: The departure of the interface temperature (and

interface phase concentrations) from that given by the phase diagram.

The interface undercooling that drives the kinetic processes involved in solidification and melting is typically quite small (< 1 K) for metals and

alloys.

63
DTA and Heat-flux DSC Measurements

Interstitial solutes: Elements that occupy positions between the solvent

element atoms in a crystal lattice. Diffusion of interstitial solutes is rapid

because of the large number of vacant sites.

Invariant reaction: A reaction with zero degrees of freedom. Also called

invariant equilibrium. Examples are eutectic and peritectic in a condensed

phase system consisting of two components at constant pressure.

Latent heat: Heat change during a reaction or transformation. This quantity is only exactly defined for invariant reactions or transformations.

Lever rule: An expression of conservation of matter in which the relative

phase amounts are determined from the overall alloy composition and the

coexisting phase compositions assumed to be in global equilibrium at each

temperature.

Lever rule solidification: One limiting case of solidification where complete

diffusion for the liquid phase and the solid phases is assumed. The phases are

in thermodynamic equilibrium and phase amounts and compositions are linked

by the lever rule at each temperature during cooling.

Liquidus: Boundary in a phase diagram between phase field regions

containing only the liquid phase and phase fields regions containing liquid and

solid phase(s). This boundary represents the limit where the fraction of solid

is zero.

Local equilibrium: Equilibrium conditions are only fulfilled at the interface

between phases.

Metastable equilibrium: Equilibrium when one or more of the stable phases

are absent.

Microsegregation: Concentration gradients in the solid phase formed during

solidification because of insufficient diffusion in the solid phase.

Nucleation supercooling: Extent of supercooling needed for nucleation to occur. See: Supercooling.

Onset temperature: The temperature where the signal first departs from the

baseline and which corresponds to the leading portion of a peak. Two onset temperatures are described in this document: one obtained by an extrapolation

method and the other obtained as the first detectable deviation from baseline.

64
Appendix A

Peak: The entirety of the deviation and return of the DTA signal from and to the baseline.

Peak signal: The amplitude of the maximum deviation of the signal from the

baseline. Can be exothermic or endothermic.

Peak temperature: The temperature corresponding to the peak signal.

Peritectic: Thermodynamic situation where a liquid is simultaneously

saturated with respect to multiple solid phases and cooling decreases the

amount of liquid and at least one of the solid phases while increasing the

amount of the other solid phases. The situation may have zero or more

degrees of freedom depending on the number of phases and components.

Phase: A portion of a material that is distinguishable by its state, composition

and/or crystal structure. A phase may exhibit smooth variations in composition.

Power-compensating differential scanning calorimeter (PC-DSC): Sample

and reference are heated independently in two furnaces so that their temperature difference stays zero. The difference in power used to heat the

sample and reference is a measure of the enthalpy of the sample.

Contrast with: Heat-flux differential scanning calorimetry.

Recalescence: The rapid increase in temperature due to release of the latent heat due to the solidification from a supercooled condition.

Scheil-Gulliver solidification: One limiting case of solidification where

complete diffusion for the liquid phase and no diffusion for the solid phases

are assumed. This type of solidification produces the worst case of

microsegregation. Also called Scheil solidification.

Solidification path: The change in liquid composition and the sequence of

solid phases that form as temperature decreases.

Solidus: Boundary in a phase diagram between phase field regions containing

only solid phase(s) and phase fields regions containing solid and liquid

phase(s). This boundary represents the limit where the fraction of liquid is zero.

Supercooling: Failure of a solid phase to nucleate at the temperature given by

the phase diagram (thermodynamic equilibrium). See: Nucleation

supercooling

65
DTA and Heat-flux DSC Measurements

Substitutional solutes: Elements that replace the solvent element randomly in

its crystal lattice. Diffusion usually occurs by a vacancy mechanism.

Thermal conductivity: The time rate of heat flow, under steady conditions,

through unit area, per unit temperature gradient in the direction normal

to the area.

Tie line: An isothermal, isobaric line connecting the compositions of a pair of

phases in equilibrium

Transition reaction: Invariant reaction in a multicomponent system where a number of phases react to form a number of different phases. This reaction is neither a eutectic nor a peritectic reaction. However, since this reaction is somewhat similar to a peritectic reaction it is also called quasi-peritectic.

Another term for this reaction is Class II reaction.

Variant eutectic reaction: A multiphase equilibrium with liquid and at least one degree of freedom with eutectic character. A monovariant (one degree of

freedom) eutectic is also called a eutectic valley.

66
Appendix B

Appendix B: Recommended Reading

[56Rhi], [60Mas], [66Pri], [82Wes], [02Wes]; Monographs on ternary phase

diagrams.

[65Gar]; A classic in the field, general focus on a wide range of materials, not

specific to alloys.

[88Bro]; A concise summary of techniques and interpretation.

[88Met]; A general treatment of solidification.

[96BH]; A general treatment of solidification.

[OlGod]; An excellent summary of the DTA response to the solidification of

ternary alloys under equilibrium (lever law) melting and solidification (in

German).

[03Fer]; A general guide to good technique for phase diagram determination

[04Sta]; Focused on Al alloys, reviews DTA techniques with a major focus on

solid state reactions with some melting work. Effect of prior sample history

made clear.

67
OTA and Heat-flux DSC Measurements

Appendix C: Model for simulating DTA response for melting

and solidification of materials with known or assumed enthalpy

vs. temperature relations. Also method for determining thermal

lag time constants of DTA/DSC instruments [02Boe]

We employ an approach using ordinary differential equations (ODE) in which

Ts(t), Tc(t), and Tj(t) are the sample, sample cup and thermocouple temperatures. Thus thermal gradients within these three objects are ignored.^ As

described in section 2.1.3, different instruments control the heating rate in different ways. For this model, we will assume that the furnace wall temperature, Tyy(t), is controlled by the instrument to be a prescribed linear function of

time. An additional triplet of variables can be used to describe the temperatures of the reference sample, cup and thermocouple. A system of ODE's that describes these six unknown temperatures is given in [02Boe] as well as the

reduced set that we employ here. We consider only heat flow between: a) the

sample and the sample cup; b) the sample cup and the furnace wall; and c) the

sample cup and the thermocouple. We neglect heat flow between the sample

and reference cups.***

We let hscAsc, hwcAwc and hTCATC be the products of the heat transfer coefficients hx Y and areas Ax Y

for the heat flow a), b), and c) described

above, respectively. We also let ms and Hs be the sample mass and

enthalpy/unit mass, mc

and C

p

be the crucible mass and heat capacity/mass

and mT, and C

p

be the thermocouple mass and heat capacity/mass.

Defining instrument time constants ts c, twc and tTC by

h.c = m c C

c

p

1 ^sx^sx

' '»,c = m c C

c

p

1 h A ' n w x w x

}t,c = mT C

T

p

1 hT C AT Q

8S A similar treatment is found in [92Shu] and one explicitly dealing with radiative heat

transfer is found in [05Dom]. A finite element treatment that includes thermal gradients is given by [95Ban]. ***

Examination of experimental temperature-time data for the reference thermocouple during

the melting of small (180 mg) samples of pure Ni at 5 K/min in a DTA show less than 0.8 K

variations from linearity. This indicates that very little heat flows beetween the reference and

sample cups in these experiments and validates the use of the simple model. 68
Appendix C

a heat balance gives

mc Cp

*s,c tc =—{Ts -Tc ) + -±-{Tw -Tc ), [C2]

^s.c *w,c

tT =—{Tc -TT )

where the dot represents time differentiation. For situations where transformation kinetics can be ignored, the enthalpy is only a function of temperature and ^

dHs dHs dTs dHsf s dt dTs dt dTs

s [C3]

Inclusion of kinetic effects produces a time dependent sample enthalpy

function that is described in [02Boe].

The time parameter, ts c, is the characteristic response time for heat flow

between the metal sample and the crucible cup; twc is the response time

between the furnace wall and the cup; and tTC is the response time between

the thermocouple and the cup. Due to the presence of the area of contact between the sample and the cup in Eqns. CI, the response time, tsc depends on the size and thus the mass of the sample. We will assume that these

response times are independent of temperature over the course of melting or

solidification. We will further assume that the furnace heating rate, a, is constant such that the interior furnace wall temperature is given by

Tw(t) = constant + at . [C4]

Analytic solution of these equations is possible for a pure material and is given

in [02Boe], the results of which are given in Appendix D with respect to melting onset analysis. Numerical solution is necessary for alloys and is possible using standard software packages, such as Mathematica or Matlab.

Simulation of DTA plots for alloys with known or assumed enthalpy vs. temperature curves are reported throughout this document.

The time constants appropriate to a particular instrument were obtained as follows. Using a least squares procedure, measured DTA data was compared to

69
DTA and Heat-flux DSC Measurements

the computed DTA response for initial guesses of the time constants. Minimization of the error using an iterative procedure led to values for the

thermal lags given in Table CI for a Perkin-Elmer DTA 1600 using the

melting of ~ 200 mg samples of Sn, Ag, and Ni. The decrease in the size of

the thermal lags with increasing melting point suggests the increasing importance of radiation in the heat flow. We have also found that the parameter,

ts q, is approximately inversely proportional to the 1/3 power of the sample

mass, rather than a 2/3 power that might be expected from the increased

contact area between the sample and the sample cup. This may be due to the high contact angle of the samples with the alumina cup. Parameters for a HFDTA (Netsch DSC 404C) are given in Table C2. Note the much smaller value

of tjQ for this instrument are probably due to the direct welding of

thermocouple wires to the platinum cup support structure. Please note that the parameters given in these tables are meant only as a guide. Each user should

determine a set of lag parameters for the specific instrument and operation

conditions being used. We also note that a more complex heat flow model of

the DTA can be employed (see for example the appendix in [02Boe]) that can

include additional time parameters that characterize the heat transfer between

the sample and reference cups as well as other effects that are likely more

important for a HF/DSC.

70
Appendix C

Table CI - Thermal lag time constants determined for a DTA using the

model of Appendix C

on

(2329C)

AA rrg

(961 9C)

INI (14532C) Mass (g) 0.163 0.237 0.180

Heating rate (K/min)

5 10 15 5 10 15 5 10 15

<S,C (s) 13.5 15.3 15.9 6.2 6.7 6.7 6.5 6.0 5.5

*W,C (s) 34.5 29.2 26.3 13.0 12.7 13.1 5.1 5.0 4.7

tTC (s) 27.6 18.9 17.0 14.5 12.4 11.7 7.4 6.5 6.7

lw,c 1!s,c 2.56 1.91 1.65 2.10 1.90 1.96 0.78 0.83 0.85

Table C2 - Thermal lag time constants determined for a HF/DTA using

the model of Appendix C

Ag (961 2C) Mass (g) 0.214 0.214 0.214 Heating rate (K/min) 5 10 15

<S,C (s) 12.5 12.0 11.7

tw>c (s) 18.2 18.3 18.7

tTC (s) 0.82 0.37 0.11

lw,c 1

rS,C 1.46 1.53 1.60

71
DTA and Heat-flux DSC Measurements

Appendix D. Expressions for the rate dependence of melting

onset temperatures for a pure metal

For a pure metal, analytical solution to the differential equations in Appendix

C is possible [02Boe] if one takes an enthalpy function given by

where C

p

is the (constant) heat capacity per unit mass (assumed the same for

liquid and solid) and L is the heat of fusion per unit mass. For convenience

we define the ratio p as

where ms

is the sample mass and mcand C

p

are the crucible mass and heat

capacity/mass. The solution is broken into three time regimes: before melting,

during melting and after melting. For DTA instruments, the 'DTA signal' is the

difference between the sample and reference thermocouple temperatures,

which is the same in this simplified model as the difference between the

sample temperature and the furnace wall temperature.

Figure Dl shows the calculated temperature vs. time behavior and the

associated DTA curve, which is a plot of (TT - Tw) vs. TT

. Prior to melting

(t < 0), the temperatures are all linear in time, with the same slope a, but with

different temporal or temperature offsets. These offsets are established during

the initial transient of the instrument after heating is initiated. The sizes of all temperature offsets are directly proportional to the heating rate. During

melting, < t < tM, the sample temperature is assumed constant consistent

with negligible temperature differences within the metal sample and the

assumption of equilibrium, Ts

(t) = TM. During this regime both the cup and

thermocouple temperature-time curves exponentially approach linear behavior

with slope a ts c

I (ts c + twc), where a alpha is the heating rate as in Appendix C. The corresponding slope on the DTA plot is - twc I ts c, which

is independent of heating rate. For t > tM, the sample, sample cup and thermocouple return as the sum of three exponential functions of time to the linear

temperature behavior obtained during the first regime, t < tM.

[Dl]

P

= [D2]

72
Appendix D

1770-

(a)

l 1 1

1

1

1 11 r 40 80 120 160 Time (s)

= -8 -

Time (s)

1—i—|—i—|—i—|—i—|—

r

1720 1730 1740 1750 1760 1770 1780

(C) TT (K)

Figure Dl. a) Calculated temperatures within a DTA instrument as functions

of time for pure Ni, sample (Ts), sample cup (Tc), thermocouple (TT) andfur- nace wll (Tw), b) enlarged region near t =0, c) associated DTA curve. The

figures show the possible sources of error in determining the melting onset temperature for calibration purposes.

73
OTA and Heat-flux DSC Measurements

The difficulty of picking the melting onset is shown in Figure Dlb, which is an enlarged view of the temperature histories near the initiation of melting at

t =0. It is seen that only a gradual change in slope of the thermocouple

temperature begins alt=0 marked TT

onset

. The onset temperature of the

sample thermocouple, TT

onset differs from melting point of the sample TM, the

two related by

TT—=TM+ a(tsc p-tTC ), [D3]

which can either increase or decrease from TM with increasing heating rate depending on the values of the time constants and the ratio p. In principle the deviation from the melting point with heating rate might be zeroed by a proper

heat flow arrangement.

An extrapolation procedure is commonly used to determine an alternate melting onset. This procedure takes advantage of the fact that the thermocouple

temperature vs. time, TT(t), curve becomes linear quickly after the melting

onset as described above. Then the onset temperature is taken from the DTA

curve as the intersection of the extrapolated linear portion with the

extrapolated baseline. The melting onset picked in this way is denoted

TT

extrap

. It is always above TM with a deviation from the melting point that increases with heating rate according to

T

eXtraP=T T M

h,c + *w,c

[D4]

For the values of the time constants given in Table CI for Ni, and a typical

value of p = 0.5, these two choices for onset temperature can be compared

numerically. TT

onset

is a times 2.6 s below TM, which equals 0.6 K for a heating rate of 15 K/min. TT

extrap

is a times 5.2 s above TM, which equals 1.3 K at a heating rate of 15 K/min. Thus picking the onset (or calibrating the

instrument) by the extrapolation method is more heating rate sensitive than

using the first sign of deflection from the baseline. One might argue, however, that noise in the baseline makes the latter choice less preferable. In any case, using the same heating rate and method for picking the onsets for calibration and measurements on alloy samples reduces the errors. Another important piece of information that can be obtained from the

analytical solution is the characteristic time it takes for the sample

74
Appendix D

thermocouple temperature behavior to return to a slope of cc; or equivalently

the temperature change that occurs before the DTA plot returns to the baseline.

The smaller this time is, the closer detectable thermal events can be. The

return to baseline is the sum of three exponential functions in time [02Boe].

The characteristic times are:

tTC and

2^.cVc

, [D5]

(fwjc + Phe + PVc )± V vW + pts c + ptw c ) ~ 4pts,c

tw,c

which, for the parameters in Table CI for Ni and p = 0.5 are 7.4 s, 1.8 s and

9.0 s, respectively.

If we assume that the longest time above dominates and is denoted by T, the

temperature interval of a DTA scan over which the signal returns from the

peak temperature to baseline is approximately I ATpea^ + ax or ax more than

the peak height. Thus detecting two events within this temperature interval is very difficult in a DTA instrument. Reduced peak signals are inherent in the

heat flux DSC, and thus provide some advantage for detecting events

separated by small temperature intervals.

75
DTA and Heat-flux DSC Measurements

Appendix E: Enthalpy vs. temperature relations for dilute

binary solid solution alloy

For simulation and understanding of DTA response to simple alloys, it is useful to examine a hypothetical alloy with straight line liquidus and solidus curves, TLiq and TSoh both terminating at a eutectic temperature TE

. The lines are given by

TT. = Th1 + m Cn Liq M

T Sol =TM +(m/k)C [El

where C is the composition, TM is the pure solvent melting point, k is the

partition coefficient, and m is the liquidus slope taken as negative for a

j. j.j. eutectic type diagram. "r

'r'r Equivalently, m I k is the slope of the solidus.

If C is such that TSol > TE, the equilibrium freezing range is given by _ _T _ m{k-\)C

Liq 1

Sol ^

[E2]

First we examine different models for the liquid composition, CL (fs) as a function of fraction solid, fs, where 0<fs<l and then the corresponding

enthalpy curves.

For an equilibrium liquid - solid mixture (Lever law), CL (fs) is given by

CL (/s

) = C [l-d-A:)/s J

1 |E31

For Scheil behavior CL (fs

) is given by

CL (fs ) = C [l-fs p [E4]

^"r * For a dilute alloy, m and k are related by the expression, m = —(l — k) where R is the

gas constant and LM is the heat of fusion per mole of the pure solvent. This reduces to the normal melting point depression law (van't Hoff Law) if k — 0. 76
For the Ohnaka [860hn] model for back diffusion _ k ~l ( i„h Ylr

CL (fs) = C l-fs 1 2ak

\ + 2a

2ak \+2a [E5]

with a = —~y~ and tj and A the local freezing time and dendrite spacing

respectively. Here, the local freezing time is taken as the equilibrium freezing

range divided by the cooling rate. The Ohnaka form recovers the equations

for Scheil and lever as the parameter a spans the range from to °o, respectively.

It is important to determine if the liquid concentration increases to the eutectic

composition when using Eqns. E3-E5; i.e., whether some value of/5 gives

CL (fs ) = CE

. [E6]

The value of fraction solid fsp

if and where this occurs is the fraction of

primary phase and the fraction of eutectic will be (1 -f$

P

)- The enthalpy is given by

H(T) = C

sp T+L(l-fs (T))

where L is the heat of fusion and where fs

(T) is obtained by solving the

expression

T=TM +mCL (fs ),

[E7]

[E8]

forfs

in terms of T. Eqn. E8 is the liquidus curve combined with one of the

forms for CL (fs

) from Eqn. E3-E5. Then the enthalpy can then be expressed

as a function of temperature. For an equilibrium liquid - solid mixture (Lever

law), the enthalpy is given by

H(T) = C

sp °T +L 1- l-/c Sol [E9]

V

Li<i J J

11
DTA and Heat-flux DSC Measurements

For Scheil behavior, the enthalpy is given by

H(T ) = C

S0T +L 1-

v * J

T, -T ]

Liq T -T y Liq Sol J

l/(*-D [E10]

For the back-diffusion form, the enthalpy is given by

h(t)=cs

p °t+l

x 1-2^/(1 + 2a)

l- 1- Jfc-lY Ti k

Liq

TLiq ~ TSol

2ak

l+2a

k-\

JJ

[Ell]

In these equations, TSol is strictly given by Eqn. El for the alloy composition

of interest, C , even if TSol < TE. These enthalpy expressions are only valid

for if no eutectic forms. If the eutectic is encountered, the enthalpy suffers a jump discontinuity at TE

of height L(l -fs

).

78
Appendix F

Appendix F. Binary phase diagrams and DTA response

To illustrate the general shape of DTA curves for different cases in binary

eutectic and peritectic systems we have chosen hypothetical systems based on Ni. The parameters used for the calculation of the DTA curves are: a = 15 K/min, tsc = 5.67 s, twc = 4.65 s, tTC = 5.5 s, L = 290 kJ/kg,

Cp = 0.75 kJ/kg and ms = 111 mg. Three alloy compositions were chosen for each system and the results for the eutectic system are shown in Fig. Fl and

the results for the peritectic system are shown in Fig. F2.

o| V

L

•

of

1700 L ; 1650

160O

155a a \ 1500

5 10 15 20 25 30 Composition (%)

Figure Fl. Phase diagram, enthalpy, dHsI dTs and computed DTA curves for three different compositions in a hypothetic binary eutectic system. The

blue curves are for equilibrium conditions (Lever) and the red curves are for

Scheil conditions.

19
DTA and Heat-flux DSC Measurements

Figure F2. Phase diagram, enthalpy, dHs

I dTs and computed DTA curves for three different compositions in a hypothetic binary peritectic system. The

blue curves are for equilibrium conditions (Lever) and the red curves are for

Scheil conditions.

80
Appendix G

Appendix GL Tutorial on melting and freezing of

multicomponent alloys

We now explore the DTA melting response of a pair of complex alloys. These were first described in [02Boe]. As input to the calculation we use enthalpy

vs. temperature values obtained for full equilibrium (lever law) and for Scheil

freezing assumptions. DTA melting simulations, using the lever enthalpy-temperature relation, would apply to an alloy equilibrated prior to melting and

where diffusion was adequate to guarantee spatial concentration uniformity of

all phases during melting. DTA melting simulations, using the Scheil enthalpy

calculations, would apply to a microstructure that was solidified and remelted

with no solid diffusion. Clearly these are extreme cases. The melting of an

equilibrated alloy as well as an as-cast sample requires an analysis of solid dif- fusion for both the freezing process and the melting process. The thermodynamic parameters of [96Saul] [96Sau2] were used in conjunction with the

methods of [98Boe] to give the enthalpy - temperature relations. GL1- Aluminum Alloy 2219

Al alloy 2219 has typical mass composition of 6.63 % Cu, 0.03 % Mn, 0.2 %

Fe and 0.1 % Si. Table Gl gives the sequence of phase formation 'reactions' listed in the order of decreasing temperature. More phases occur, and the final solidification temperature is lower for the Scheil assumption due to the

microsegregation. Figure Gl shows the phase fractions as a function of

1 -

£0.01

0.001

(a)

Lever L

r FCC

Al

2Cu /

\ / AUCu2 Fe

Al20Cu^\ \Al6Mn

'

I

'

I

' I

r K 0.1-

'—oCO

o - c3

0.001

Scheil

Al2 Cu f^"^ FCC

L

ALCiuFe

780 800 820 840 860 880 900 920 940

Temperature (K)

780 800 820 840 860 880 900 920 940

(b) Temperature (K)

Figure Gl. Phase fraction vs. temperature computed using an aluminum

alloy thermodynamic database [96Saul] for a) lever and b) Scheil conditions

for Al 2219 alloy.

81
DTA and Heat-flux DSC Measurements

temperature. Off of the scale of Figure Fl are the oc-AlSiFe and Si phases

with maximum phase fractions of 8 x 10"4 and 3 xlO"4 respectively.

Figure G2 shows the values of dHs

I dTs obtained from the calculated

Table Gl - Sequence of phase formation during lever and Scheil freezing

of 2219 Al Alloy

Lever Scheil L^FCC

L^FCC+Al6Mn

L+Al6Mn<->FCC+Al7Cu2Fe

L->FCC+Al7Cu2Fe

L^FCC+Al7Cu2Fe+Al20Cu2Mn3 L^FCC+Al7Cu2Fe+Al20Cu2Mn3+Al2Cu

L^FCC

L^FCC+Al6Mn

L^FCC+Al7Cu2Fe L^FCC+Al7Cu2Fe+Al2Cu

L^FCC+Al7Cu2Fe+Al2Cu+oc-AlFeSi

L^FCC+Al7Cu2Fe+Al2Cu+oc-AlFeSi

+Si (invariant reaction @797K)

enthalpy temperature - curves and the DTA simulation for 5 K/min.

Comparison of Figure Gl with the dHsI dTs curves allows one to recognize

the cause of the various peaks in the DTA signal. During melting, a peak

occurs when all of a particular phase has completely melted (see however

problems associated with phase diagram lines that are converging with

decreasing temperature, 3.3.5). For example, for the lever melting, the first peak on heating at ~ 820 K indicates that all of the Al2Cu phase has melted.

The second peak is barely detectable at ~ 840 K and indicates that all Al2oCu2Mn3 has melted. The third peak at ~ 855 K indicates that all of

Al7Cu2Fe has melted and similarly for other peaks. Note that for the Scheil

DTA calculation, a peak is visible at ~ 797 K. This is due to the melting of the

invariant quinary eutectic at 797K (Table Gl) where the Si phase

completely disappears and reductions also occur in the phase fractions of the

other phases. The alloy under consideration has five components, the reaction

involves six phases, and there are zero degrees of freedom. Thus despite the

small fraction of Si phase, the signal from the invariant eutectic melting is relatively large.

Simulations of alloy freezing were performed. Figure G3 compares the

melting and freezing signals for the Al 2219 alloy at 5 K/min (Scheil enthalpy

used for both). The vertical dashed lines are the liquidus temperature and the

temperature where the Al2Cu phase disappears, or first appears, on melting or

solidification, respectively. The peak temperatures are clearly offset from

these dashed lines and should not be used to characterize the melting or freezing process.

82
References

3E+004-

<50 S 2E+004-

I I I I I I I

1E+004-

OE+000 —|—i—

|—i—

|—i—|—i—

|—i—|—i—

|—i—j—

r

780 800 820 840 860 880 900 920 940

Temperature (K)

1

1

I

1

I

1 I1 I (0 800 820 840 860 880 900 920 940

TT(K)

Figure G2. Top) dHs

I dTs obtained from the enthalpy-temperature

predictions for Al 2219 alloy computed using thermodynamic database

[96Saul] for lever and Scheil conditions for Al 2219 alloy. The curve for 'Scheil' is shifted by 5X103 JIkg Kfor clarity. Bottom) Corresponding

DTA plots for melting at 5 Klmin. The curve for 'Lever is shifted up 1 K

for clarity.

83
DTA and Heat-flux DSC Measurements

TT(K)

Figure G3. Calculated DTA plots for melting andfreezing at 5 Klmin of

Al 2219 alloy using the Scheil enthalpy-temperature relation.

1400 1450 1500 1550 1600 1650 1400 1450 1500 1550 1600 1650

Temperature (K) Temperature (K)

(a) (b)

Figure G4. Phase fraction vs. temperature computed using Ni alloy

thermodynamic database [96Sau2] for lever and Scheil conditions for

Udimet 700 alloy.

84
Appendix G

G2 - Udimet 700

A second example is the Ni alloy, Udimet 700, with mass composition of

15 % Cr, 18.5 % Co, 5 % Mo, 3.5 % Ti, 4.4 % Al, 0.07 % C, and 0.025 % B. The thermodynamic parameters were taken from [96Sau2]. The phase

formation sequences are given in Table G2, the phase fractions in Figure G4

and dHs

I dTs and the DTA signals in Figure G5. To be noted here is the very

large difference between the sizes of the freezing ranges of the two cases. The particular peaks and their sizes for real DTA signals for this alloy would

be difficult to predict given the large difference between the diffusion rates of

the interstitials B and C and the substitutional elements in the FCC phase.

Table G2 - Sequence of phase formation during lever and Scheil freezing

of Udimet 700

Lever Scheil

L

L->FCC

L^FCC+MC

L-^FCC+MC+MB2

L->FCC

L^FCC+MC

L^FCC+MC+MB2 L^FCC+MC+MB2+M3B2 L^FCC+MC+MB2+M3B2+o

L^FCC+MC+MB2+M3B2+G+y

L->FCC+MC+o+y+MB2

85
DTA and Heat-flux DSC Measurements

1450 1500 1550 1600

Temperature (K)

1450

I

1 I 1500 1550

TT(K)

1600

1650

1650

Figure G5. Top) dHsI dTs obtainedfrom the enthalpy-temperature

predictions for Udimet 700 alloy computed using thermodynamic database

[96Sau2] for lever and Scheil conditions for Udimet 700 alloy. Bottom)

Corresponding DTA plots for melting of 180 mg sample at 15 K/min.

86
References

References

49Vol M. J. Void, Analyt. Chem. 21 (1949) 683-688.

56Rhi F.N Rhines., Phase Diagrams in Metallurgy. McGraw-Hill Book

Comp., 1956.

60Mas Massing G and Rodgers BA, Ternary Systems . Dover Publications.

NY 1960 p 49.

65Gar P.D.Garn, Thermoanalytical Methods of Investigation. Academic

Press, New York, 1965, Chapter 4 and 5.

66Pri A. Prince, Alloy Phase Equilibria. Elsevier Amsterdam (1966),

pp. 211.

66Tsa N.F. Tsang, Handbook of Differential Thermal Analysis, Eds. W.J. Smothers and Y. Chiang, Chem. Publ. Comp., New York, NY,

1966, pp. 91-123.

68Gra A.P Gray, Analytical Calorimetry, Vol.1, Eds. R.S. Porter and

J.F. Johnson, Plenum Press, New York, NY, 1968, pp. 209-218.

69Bar C.R. Barber, Metrologia 5, 35-44 (1969).

70Cun A.D. Cunningham and F.W. Wilburn, Differential Thermal Analysis . Vol.1, Ed. R.C. Mackenzie, Academic Press, London, UK, 1970, pp. 31-62.

74Fle M.C. Flemings, Solidification Processing. McGraw Hill, New York,

1974, pp. 177-183.

75McN J.L. McNaughton and C.T. Mortimer, in Thermochemistry and

Thermodynamic

s

, edited by Henry Alistair Skinner, International Review of

Science: Physical Chemistry. Series Two. Vol. 10, Butterworths, London,

1975, pp. 1-44. 78Bar E.M. Barral and R.J. Glitter, in Systematic Materials Science. Volume

IV, edited by J.H. Richardson and R.V Peterson, 1978, Academic Press, New

York, Chapter 39. 79Fre H. Fredriksson and B. Rogberg, Metal Science 13 (1979) 685-690.

87
DTA and Heat-flux DSC Measurements

82Wes D.R.F. West, Ternary Equilibrium Diagrams, 2nd Edition.

Chapman-Hall, London UK 1982.

84Per J.H. Perepezko, Mat. Sci. and Eng. 65 (1984) 125-135.

86Hay F. H. Hayes, H. L. Lukas, G. Effenberg and G. Petzow,

Z. Metallkunde 77(1986) 749-754.

86Hey W. Heyroth, J. Thermal Analysis 31 (1986) 61-72.

860hn I. Ohnaka, Transactions of the Iron And Steel Institute of Japan 26

(1986) 1045-1051.

88Fly J.H. Flynn, J. Thermal Analysis 34 (1988) 367-381.

88Fre H. Fredriksson, ASM Metals Handbook ( 1 988) 9th Edition

Volume 15 "Casting", pp. 182-185.

88Bro M. E. Brown, Introduction to Thermal Analysis; Techniques and

Applications, Chapter 4: Differential thermal analysis (DTA) and differential scanning calorimetry (DSC), Chapman & Hall, 1988, New York.

88Met Principles of Solidification, in Volume 15: Casting, Metals Handbook

9th. Edition., (ASM, Metals Park, OH 1988)

90Pre H. Preston-Thomas, Metrologia, 27, 3-10 (1990).

90H6h G.W.H. Hohne, H.K. Cammenga, W. Eysel, E. Gmelin and

W. Hemminger, Thermochim. Acta 180, 1-12 (1990).

91Cao W.D. Cao, R.L. Kennedy & M.P. Willis, in Superallovs 718,625

and Various Derivatives , Ed. E. A. Loria, TMS, Warrendale, PA, 1991,

pp. 147-160.

91H6h GW.H. Hohne, J. Thermal Analysis 37, 1987-2000 (1991).

92Shu R.D. Shull, Thermal Analysis in Metallurgy. Eds. R.D. Shull and

A. Joshi, TMS, Warrendale, PA, 1992, pp. 95-119.

92Feu Y. Feutelais, G. Morgant, J. R. Didry and J. Schnitter, CALPHAD 16,

1992, pp. 111-119.

88
94Spe R. F. Speyer, Thermal Analysis of Materials , Marcel Dekker, Inc. (1994) New York, NY.

95Ban D. K. Banerjee, W. J. Boettinger, R. J. Schaefer, M. E. Williams,

Modeling of Casting, Welding and Advanced Solidification Processes. VII,

Eds. M. Cross and J. Campbell, TMS, Warrendale, PA, 1995, pp. 491.

96Bed R.E. Bedford, G. Bonnier, H. Maas and F. Pavese, Metrologia, 33,

133-154 (1996).

96Kat U.R. Kattner, WJ.Boettinger, S.R. Coriell, Z. Metallkunde 87 (1996)

522-528.

96Saul N. Saunders, Mater. Sci. Forum, 217-222, 1996, pp. 667.

96Sau2 N. Saunders, Superalloys 1996, Eds. R. Kissinger et al. TMS,

Warrendale, PA, (1996) pp. 101. 96BH H. Biloni and W. J. Boettinger, Physical Metallurgy, 4th edition, Eds.

P. Haasen and R. W. Cahn, 1996, North Holland, Amsterdam, pp. 669-842.

98Boe W.J. Boettinger, U.R. Kattner and D.K. Banerjee, Modeling of

Casting, Welding and Advanced Solidification Processes, VIII, Eds. B.G.

Thomas and C. Beckermann, TMS, Warrendale PA, 1998, pp 159-170.

00Wu R.I. Wu and J.H. Perepezko, Metall. and Matls. Trans. A 31

A

(2000) 497.

OOOpf J. Opfermann, ThermoKinetics: A Software Module for the Kinetic

Analysis of Thermal Measurements using Multivariate Linear Regression

Software. Netzsch-Geratebau GmbH, Selb, Germany, (2000).

OOMoo K.-W Moon, W.J. Boettinger, U.R. Kattner, F.S. Biancaniello and

C.A. Handwerker, J. Electronic Materials, 29 (2000), pp. 1122 - 1136.

OlGod T. Godecke, Z. Metallkd. 92(2001) 966 [in German].

02Boe W.J. Boettinger and U.R. Kattner, Metall. and Matls. Transactions,

33A (2002), 1179.

02Wes D.R.F. West and N. Saunders, Ternary Phase Diagrams in Materials

Science. Maney-Institute of Materials, London UK 2002.

89
DTA and Heat-flux DSC Measurements

03Don H.B. Dong, M.R.M. Shin, E.C. Kurum, H.Cama, J.D. Hunt,

Metallurgical and Materials Transactions A34 (2003) 441-447.

03Fer R. Ferro, G. Cacciamani and G. Borzone, Intermetallics 11(2003)

1081-1094.

03 Liu H.S. Liu, C.L. Liu, K. Ishida and Z.R Jin, J. Electron. Mater. 32

(2003) 1290-1296.

03Rab A. Rabinkin, Solidus-Liquidus. Brazing Course Lecture Notes,

ASM/AWS "International Brazing and Soldering Conference 2003."

04Sta M.J. Starink, Internbational Materials Rev. 49(2004) 191-226

05Don H.B. Dong and J.D. Hunt, Matls Sci and Eng A 413-414

(2005) 470-473.

90

November 2006