Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations

Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations

In the present article, a set of thermodynamic problems of the temperature-induced thermoelastic martensitic transformation is discussed. It is shown that the constitutive thermodynamic force balance equations describing the temperature dependence of martensite volume fraction on the global hysteres...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Datum:2015
Hauptverfasser: Likhachev, O.A., Koval, Yu.M.
Format: Artikel
Sprache:English
Veröffentlicht: Інститут металофізики ім. Г.В. Курдюмова НАН України 2015
Schriftenreihe:Успехи физики металлов
Online Zugang:http://dspace.nbuv.gov.ua/handle/123456789/98441
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Назва журналу:Digital Library of Periodicals of National Academy of Sciences of Ukraine
Zitieren:Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations / O.A. Likhachev, Yu.M. Koval // Успехи физики металлов. — 2015. — Т. 16, № 1. — С. 1-22. — Бібліогр.: 21 назв. — англ.

Institution

Digital Library of Periodicals of National Academy of Sciences of Ukraine
id irk-123456789-98441
record_format dspace
spelling irk-123456789-984412016-04-15T03:02:28Z Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations Likhachev, O.A. Koval, Yu.M. In the present article, a set of thermodynamic problems of the temperature-induced thermoelastic martensitic transformation is discussed. It is shown that the constitutive thermodynamic force balance equations describing the temperature dependence of martensite volume fraction on the global hysteresis cycle can be directly derived from the energy conservation law where the additional irreversible work is taken into account. Resulting force balance occurs between the classical (‘chemical’) driving force, on the one hand, and the so-called nonchemical forces representing the elastic, interfacial and other energy contributions, on the other hand. The procedure of finding the nonchemical contributions from the calorimetric experiments is developed and applied to the analysis of DSC measurements for the CuZnAl and CuAlNi shape-memory alloys. Finally, the problem of thermoelastic martensitic transformation is discussed on the basis of the microscopic theoretical approach. В данной работе обсуждается ряд проблем термодинамики термически индуцированных термоупругих мартенситных превращений. Показано, что основная система уравнений баланса термодинамических сил, которая описывает температурную зависимость объёмной доли мартенсита, может быть получена непосредственно из закона сохранения энергии, где дополнительно учтены эффекты необратимой работы против внутренних диссипативных сил. Общий баланс термодинамических сил осуществляется между классическими («химическими») движущими силами, с одной стороны, и так называемыми нехимическими силами, обусловленными упругими, межфазными и другими энергетическими вкладами, с другой. Разработана процедура определения таких нехимических вкладов на основе калориметрических экспериментов, которая применена для анализа калориметрических данных в сплавах с эффектом памяти формы CuZnAl и CuAlNi. В заключение, проблемы термоупругих мартенситных превращений обсуждаются на основе микроскопического теоретического подхода. В даній роботі обговорюється ряд проблем термодинаміки термічно індукованих термопружніх мартенситних перетворень. Показано, що основна система рівнянь балансу термодинамічних сил, що описує температурну залежність об’ємної частки мартенситу, може бути одержана безпосередньо із закону збереження енергії, де додатково враховано ефекти необоротньої роботи проти внутрішніх дисипативних сил. Загальний баланс термодинамічних сил відбувається між класичними («хімічними») рушійними силами, з одного боку, та так званими нехімічними силами, обумовленими пружніми, міжфазними й іншими енергетичними внесками, з іншого. Розроблено процедуру визначення таких нехімічних внесків на основі калориметричних експериментів, яку застосовано для аналізи калориметричних даних в стопах з ефектом пам’яті форми CuZnAl та CuAlNi. Насамкінець, проблеми термопружніх мартенситних перетворень обговорюються на основі мікроскопічного теоретичного підходу. 2015 Article Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations / O.A. Likhachev, Yu.M. Koval // Успехи физики металлов. — 2015. — Т. 16, № 1. — С. 1-22. — Бібліогр.: 21 назв. — англ. 1608-1021 PACS numbers: 46.25.Hf, 62.20.fg, 64.70.kd, 65.40.De, 81.30.Kf, 81.40.Jj http://dspace.nbuv.gov.ua/handle/123456789/98441 en Успехи физики металлов Інститут металофізики ім. Г.В. Курдюмова НАН України
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
collection DSpace DC
language English
description In the present article, a set of thermodynamic problems of the temperature-induced thermoelastic martensitic transformation is discussed. It is shown that the constitutive thermodynamic force balance equations describing the temperature dependence of martensite volume fraction on the global hysteresis cycle can be directly derived from the energy conservation law where the additional irreversible work is taken into account. Resulting force balance occurs between the classical (‘chemical’) driving force, on the one hand, and the so-called nonchemical forces representing the elastic, interfacial and other energy contributions, on the other hand. The procedure of finding the nonchemical contributions from the calorimetric experiments is developed and applied to the analysis of DSC measurements for the CuZnAl and CuAlNi shape-memory alloys. Finally, the problem of thermoelastic martensitic transformation is discussed on the basis of the microscopic theoretical approach.
format Article
author Likhachev, O.A.
Koval, Yu.M.
spellingShingle Likhachev, O.A.
Koval, Yu.M.
Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations
Успехи физики металлов
author_facet Likhachev, O.A.
Koval, Yu.M.
author_sort Likhachev, O.A.
title Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations
title_short Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations
title_full Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations
title_fullStr Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations
title_full_unstemmed Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations
title_sort thermoelastic behaviour, hysteresis, and dissipative forces in thermodynamics of martensitic transformations
publisher Інститут металофізики ім. Г.В. Курдюмова НАН України
publishDate 2015
url http://dspace.nbuv.gov.ua/handle/123456789/98441
citation_txt Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations / O.A. Likhachev, Yu.M. Koval // Успехи физики металлов. — 2015. — Т. 16, № 1. — С. 1-22. — Бібліогр.: 21 назв. — англ.
series Успехи физики металлов
work_keys_str_mv AT likhachevoa thermoelasticbehaviourhysteresisanddissipativeforcesinthermodynamicsofmartensitictransformations
AT kovalyum thermoelasticbehaviourhysteresisanddissipativeforcesinthermodynamicsofmartensitictransformations
first_indexed 2025-07-07T06:31:13Z
last_indexed 2025-07-07T06:31:13Z
_version_ 1836968706634153984
fulltext 1 PACS numbers: 46.25.Hf, 62.20.fg, 64.70.kd, 65.40.De, 81.30.Kf, 81.40.Jj Thermoelastic Behaviour, Hysteresis, and Dissipative Forces in Thermodynamics of Martensitic Transformations O. A. Likhachev and Yu. M. Koval G. V. Kurdyumov Institute for Metal Physics, N.A.S. of Ukraine, 36 Academician Vernadsky Blvd., UA-03680 Kyiv-142, Ukraine In the present article, a set of thermodynamic problems of the tempera- ture-induced thermoelastic martensitic transformation is discussed. It is shown that the constitutive thermodynamic force balance equations de- scribing the temperature dependence of martensite volume fraction on the global hysteresis cycle can be directly derived from the energy conserva- tion law where the additional irreversible work is taken into account. Re- sulting force balance occurs between the classical (‘chemical’) driving force, on the one hand, and the so-called nonchemical forces representing the elastic, interfacial and other energy contributions, on the other hand. The procedure of finding the nonchemical contributions from the calo- rimetric experiments is developed and applied to the analysis of DSC measurements for the CuZnAl and CuAlNi shape-memory alloys. Finally, the problem of thermoelastic martensitic transformation is discussed on the basis of the microscopic theoretical approach. В даній роботі обговорюється ряд проблем термодинаміки термічно інду- кованих термопружніх мартенситних перетворень. Показано, що основна система рівнянь балансу термодинамічних сил, що описує температурну залежність об’ємної частки мартенситу, може бути одержана безпосеред- ньо із закону збереження енергії, де додатково враховано ефекти необоро- тньої роботи проти внутрішніх дисипативних сил. Загальний баланс тер- модинамічних сил відбувається між класичними («хімічними») рушій- ними силами, з одного боку, та так званими нехімічними силами, обумо- вленими пружніми, міжфазними й іншими енергетичними внесками, з іншого. Розроблено процедуру визначення таких нехімічних внесків на основі калориметричних експериментів, яку застосовано для аналізи ка- лориметричних даних в стопах з ефектом пам’яті форми CuZnAl та CuAlNi. Насамкінець, проблеми термопружніх мартенситних перетво- рень обговорюються на основі мікроскопічного теоретичного підходу. В данной работе обсуждается ряд проблем термодинамики термически Успехи физ. мет. / Usp. Fiz. Met. 2015, т. 16, сс. 1–22 Îòòèñêè äîñòóïíû íåïîñðåäñòâåííî îò èçäàòåëÿ Ôîòîêîïèðîâàíèå ðàçðåøåíî òîëüêî â ñîîòâåòñòâèè ñ ëèöåíçèåé 2015 ÈÌÔ (Èíñòèòóò ìåòàëëîôèçèêè èì. Ã. Â. Êóðäþìîâà ÍÀÍ Óêðàèíû) Íàïå÷àòàíî â Óêðàèíå. 2 O. A. LIKHACHEV and Yu. M. KOVAL индуцированных термоупругих мартенситных превращений. Показано, что основная система уравнений баланса термодинамических сил, ко- торая описывает температурную зависимость объёмной доли мартенси- та, может быть получена непосредственно из закона сохранения энер- гии, где дополнительно учтены эффекты необратимой работы против внутренних диссипативных сил. Общий баланс термодинамических сил осуществляется между классическими («химическими») движущими силами, с одной стороны, и так называемыми нехимическими силами, обусловленными упругими, межфазными и другими энергетическими вкладами, с другой. Разработана процедура определения таких нехи- мических вкладов на основе калориметрических экспериментов, кото- рая применена для анализа калориметрических данных в сплавах с эффектом памяти формы CuZnAl и CuAlNi. В заключение, проблемы термоупругих мартенситных превращений обсуждаются на основе мик- роскопического теоретического подхода. Keywords: shape-memory alloys, martensitic transformation, hysteresis, thermoelastic equilibrium. (Received December 29, 2014) 1. INTRODUCTION As known, during the cycle of martensitic transformation the shape-memory alloys (SMA) run a sequence of heterophase states. In particular, the fraction of martensitic phase increases continuously and then returns back on heating showing a definite temperature hysteresis. At each stage both, the direct and the reverse transfor- mation the microstructure of SMAs consists of great number of plate-like martensitic crystals in austenitic matrix appearing and growing on cooling and shrinking and disappearing on heating con- tinuously and simultaneously with corresponding temperature change. Started from the works by Kurdyumov and Kurdyumov & Khandros [1–3] on the possibility of the thermoelastic equilibrium during the martensitic transformation in shape-memory alloys, this problem still remain very important for the martensitic transforma- tion physics. During the past time, the great number of problems was a subject for extended discussions and developments in the thermodynamics of thermoelastic martensitic transformations in shape-memory materials for the past time [4–18]. Thermodynamic potentials dependent on the volume fraction of martensitic phase have been first introduced and analysed by Pascal & Monasevich [11, 12], who postulated existence of two fraction de- pendent Gibbs free energy potentials representing direct and reverse martensitic transformation, respectively. They also have derived the constitutive thermodynamic force balance equations describing the THERMOELASTIC BEHAVIOUR, HYSTERESIS, AND DISSIPATIVE FORCES 3 temperature dependence of martensite volume fraction on the global hysteresis cycle additionally assuming the possibility to minimize these, strictly speaking, non-equilibrium potentials. Several other authors have used a similar way. A few problems arise from such a consideration. First, the possibility to consider the configuration dependent thermodynamic functions to be dependent only on the martensite fraction can be physically reasonable if the microscopic configuration sequence passed during direct martensitic transfor- mation will remain the same for reverse transformation too. Such a ‘microscopic reversibility’ principle has been qualitatively formu- lated by Olson & Cohen [7, 8], who pointed out that growth and shrinkage of the martensitic plates take place in a well-defined se- quential order and the first plates formed on cooling being the last ones to disappear on heating. Secondly, the introduction of the non- equilibrium Gibbs free energies containing dissipative (friction) terms and especially the application of minimization principle to them can be, in general, a source for incorrect physical conclusions. And finally, a traditional scheme of splitting of the fraction de- pendent thermodynamic potentials into a pure chemical and nonchemical (elastic) components can be practically useful (in sense of their determination from the experiment) only if the pure chemi- cal equilibrium temperature value T0 were known before. However, discussions on the definition and location of T0 that have been done by different authors [9, 10] just confirm the impossibility to find this quantity directly from the experiments on the temperature in- duced transformation. In the present report (accepting in general an idea on the fraction dependent potentials and assuming that the ‘microscopic reversibil- ity’ principle as a possible background of this idea takes place), the more accurate derivation of the thermodynamic force balance equa- tions using directly the first and second Thermodynamics Laws is given. Such a way gives a possibility to avoid the above-mentioned difficulties connected with the possible incorrectness of the free en- ergy minimization procedure in presence of dissipative forces. Sec- ondly, taking into account the problem of direct measurement of T0, we propose to realize another splitting scheme for the fraction de- pendent potentials (internal energy or enthalpy) into the pseudo- chemical, linearly dependent on the martensite fraction, term and residual nonchemical energy that both can be found experimentally. This procedure gives a possibility to exclude the T0-problem from the consideration. Finally, the proposed scheme is applied to the thermodynamic analysis of the temperature induced martensitic transformation in a few copper-based shape-memory alloys to inves- tigate their thermodynamic characteristics with using DSC meas- urement data. 4 O. A. LIKHACHEV and Yu. M. KOVAL 2. ENERGY BALANCE DURING A CYCLE OF THERMOELASTIC TRANSFORMATION The following analysis is based on the first and second Thermody- namics Laws that can be represented as follows:    dis ( , ) ( , ) ( , ) ,dU z T TdS z T PdV z T dA ( , )dQ TdS z T , (1) where U, S, and V represent the total molar amounts of the internal energy, entropy and molar volume of the martensite  austenite heterophase mixture. T and P are the absolute temperature and pressure. dAdis  0 denotes the elementary irreversible work respon- sible for hysteresis and dQ is the heat flow obtained during the in- finitesimal martensitic fraction (z) change. Practically, because the most of thermoelastic shape-memory alloys usually show very small volume change, one can neglect hereafter the term PdV in Eq. (1), or include it into consideration replacing the internal energy by the enthalpy in left side of this equality. Further, we will neglect for simplicity the PdV term. The relative fraction of martensitic phase z(T) is one of the most representative macroscopic thermodynamical variables. Due to the temperature hysteresis, the temperature dependence of this variable can be represented by the main hysteresis cycle consisting from two-temperature dependent functions z(T) for cooling and z(T) for heating, respectively. The energy conservation law must be fulfilled at each point of this main loop. It is expected (as a result of ‘micro- scopic reversibility hypothesis’) that the main thermodynamic func- tions such as the internal energy U and entropy S of heterophase martensite  austenite system must be dependent on the relative volume fraction and temperature. Most of authors usually represent the total fraction dependent internal energy (or enthalpy) as con- sisting from two terms. The first one is mainly chosen and treated as completely chemical component, so as the additional term is al- ways considered as the total amount of nonchemical energy stored at the current stage of transformation. In the present paper, we propose (to avoid the problem connected with definition of T0) to split the total internal energy into the pseudo-chemical component and residual fraction dependent nonchemical energy extracting the linearly dependent part from the total nonchemical energy term and including it additionally to the chemical component. Accordingly, in this case, the total internal energy U(T, z) can be represented as fol- lows: 0 1 ( , ) (1 ) ( ) ( ) ( )a mU z T z U T zU T z     , (2) 0 ( ) (0, )aU T U T , 1 ( ) (1, )mU T U T . (3) THERMOELASTIC BEHAVIOUR, HYSTERESIS, AND DISSIPATIVE FORCES 5 Here, we have defined the energies 0 ( )aU T and 1 ( )mU T of the com- pletely transformed austenitic and martensitic phases through the total energy U(z, T) of heterophase system taken at z  0 and z  1 values of the martensite fraction. The nonchemical energy (z) is defined as a residual part between the total energy and its pseudo- chemical component that is linearly dependent on the martensite z and austenite 1  z fractions. As a result, the energy of the com- pletely martensitic state 1 ( )mU T will always contain (additionally to a pure chemical component) a constant nonchemical term represent- ing the elastic as well as the inter-variant interface energy stored in the completely martensitic state. The austenite energy 0 ( )aU T will contain only the chemical component. One can easily check that due to such a separation scheme the residual nonchemical potential will always satisfy zero conditions (0)  (1)  0 in the completely aus- tenitic and martensitic states. The entropy of austenite  martensite system can be defined as follows: ( , ) (1 ) ( ) ( ) a m S z T z S T zS T   , (4) where Sa(T) and Sm(T) are molar entropies of austenite and marten- site, respectively. Another important quantities that must be considered in the thermodynamics of martensitic transformation are the dissipative work and friction forces representing the irreversible energy loses connected, in general case, with the irreversible motion of inter- phase and inter-variant boundaries and responsible for the hystere- sis effects. These can be defined as dis dis ( )dA F z dz  , dis 0dA  . (5) Here, the dissipative work dAdis is always positively defined due to the second thermodynamics law and represents the elementary en- ergy dissipation work caused by the martensite–austenite inter- variant boundary displacements during the small change (dz) of martensite fraction. Evidently, Fdis(z)  0 and can be interpreted as a generalized dissipative (friction) force producing this irreversible work. So as the dissipative work must be always positive, the signs () must be chosen for direct (dz  0) and () for reverse transforma- tion, respectively. In a partial case of single interface, the friction force is expected to be a constant independent on the fraction, but in the general case of the multiple interfaces, a similar dependence cannot be excluded. It should be also noted, that no dissipation is expected in the completely austenitic and martensitic states. There- fore, the energies and entropies of austenite and martensite must satisfy usual relationships of non-dissipative thermodynamics: 6 O. A. LIKHACHEV and Yu. M. KOVAL 0 ( ) ( )a adU T TdS T , 1 ( ) ( )m mdU T TdS T . (6) Taking into account expressions for U(z, T), S(z, T) and dAdis and substituting them into the Eq. (1) representing the first Thermody- namics Law, one can obtain two main constitutive equations: dis ( ) ( ) ( ) ( )p d z U T T S T F z dz        , (7) (‘plus’ () for heating, while ‘minus’ () for cooling) that give the thermodynamic forces balance for the direct and reverse transfor- mations that is consistent with both the first and the second Ther- modynamic Laws. Here, 1 0 ( ) ( ) ( ) p m a U T U T U T   and S(T)  Sm(T)   Sa(T) represent in general case the temperature dependent differ- ences of the internal energies and entropies between the martensitic and austenitic states, correspondingly. As follows from the detailed analysis, one can neglect the temperature dependence of these dif- ferences and consider them as constants if only the heat capacity difference between the martensite and austenite to be small enough. In this case, the two balance equations determining the transforma- tion paths for the direct T(z) and reverse T(z) transformations can be written as follows: ( ) ( ) ( )p dis d z ST z U F z dz        , for direct dz  0, (8) ( ) ( ) ( )p dis d z ST z U F z dz        , for direct dz  0. (9) Taking a half-sum of these equations, one can obtain the relation- ship for the definition of the pseudo-chemical transformation heat flow and nonchemical energy: eq ( ) ( ) p d z ST z U dz      , where  eq 1 ( ) ( ) ( ) 2 T z T z T z     . (10) Here, Teq(z) obviously represents the non-dissipative (hysteresisless) thermoelastic equilibrium curve. Integration of this equation by z from 0 to 1 together with zero boundary conditions (0)  (1)  0 gives the expression for the pseudo-chemical transformation heat flow and the partial integration from 0 to z represents the nonchemical energy as follows: 1 eq 0 0 ( ) p p U S dzT z ST     ,  eq 0 0 ( ) ( ) z p z S dz T z T     . (11) Here, the pseudo-chemical equilibrium temperature T0p is defined as THERMOELASTIC BEHAVIOUR, HYSTERESIS, AND DISSIPATIVE FORCES 7 1 0 eq 0 ( ) p T dzT z  . (12) As follows from this equation, its value is expressed as the average taken from the fraction dependent thermoelastic equilibrium curve and can be always found from the experiment by the measurement of the temperature dependence on the martensite fraction during the main hysteresis cycle according to Eqs. (10) and (12). It is also interesting that according to Eq. (11), T0p and Up must satisfy the relationship similar to that as T0 and U in the case of pure chemi- cal equilibrium. However, because Up always differs from the cor- responding chemical value U by a positive constant nonchemical energy stored in completely martensitic state, one can expect that T0p will have the lover value than T0. The generalized dissipative force and its dependence on the mart- ensite fraction can also be easily found from the system of balance equations (see Eqs. (8) and (9)) by taking the half-difference be- tween them:  dis 1 ( ) ( ) ( ) 2 F z S T z T z       . (13) These equations give the necessary background to determine the pseudo-chemical transformation heat value, nonchemical energy and friction force from the calorimetric experiments on the transforma- tion entropy and martensite fraction vs. temperature measurement discussed in the next section. 3. CALORIMETRIC EXPERIMENTS AND RESULTS Two copper-based polycrystalline shape-memory alloys have been investigated by using heat flow measurement on the differential scanning calorimeter ‘Perkin Elmer’ and analysed in accordance to the above-proposed scheme. The first one denoted here as (A) was the 56 mg sample of CuZnAl alloy prepared from the round cross- section wire extruded and subjected to 5 min heat treatment at 800C and then quenched into the water at room temperature. The 48 mg sample of CuAlNi alloy (B) has been prepared from the pre- viously hot rolled at 850C and quenched into the water at room temperature, which then was aged during 60 min and cooled on air at room temperature [16]. After the heat treatment, the DSC heat flow measurements have been carried out. Corresponding data ob- tained after a few stabilizing cycles of the martensitic transforma- tion (that have been made to achieve a good reproducibility) are represented in Figs. 1 and 2. 8 O. A. LIKHACHEV and Yu. M. KOVAL The initial data obtained has been also subjected to a special process- ing directed on the best extraction of the base-line effects. Second or- der polynomial base line parameters were found from the best-fit re- quirements with the measurement data in the temperature intervals corresponding to completely martensitic and austenitic states. Then, these data were used to find the relative transformation entropy and relative fraction change during the complete cycle of Fig. 1. The relative differential heat flow data extracted from DSC meas- urements in CuZnAl. Fig. 2. The relative differential heat flow data extracted from DSC meas- urements in CuAlNi. THERMOELASTIC BEHAVIOUR, HYSTERESIS, AND DISSIPATIVE FORCES 9 transformation as a function of temperature (see Figs. 3 and 4). The relative entropy change  ( ) ( ), ( ) a S T S z T T S T      as a func- tion of the temperature caused martensitic transformation along the global transformation cycle and its overall value S have been found using the following equations: ( ) fA T dQdT S T T dT       , f f A M dQdT S T dT       . (14) According to zero entropy production during the full direct and re- Fig. 3. The temperature dependence of martensite fraction obtained from the DSC measurement in CuZnAl. Fig. 4. The temperature dependence of martensite fraction obtained from DSC measurement in CuAlNi. 10 O. A. LIKHACHEV and Yu. M. KOVAL verse martensitic transformation cycle, it is expected S  S. Experimentally found values were S  0.011 J/(gK) for alloy A and S  0.02 J/(gK) for alloy B, respectively. The martensite fraction behaviour has been obtained by using the normalization method as z(T)  S(T)/S and shown in Fig. 2. It should be noted that the definition of transformation entropy from the Eq. (14) are good in the limit of small heat capacity difference between the austenite and martensite. Ortin and Planes [13, 14] have ana- lysed the more accurate procedure of the entropy calculation taking into account heat capacity effect in details. As follows from our analysis, the corresponding heat capacity corrections must be con- sidered in the force balance equation too taking into account a weak temperature dependence of Up and S in Eqs. (8) and (9). The pseudo- equilibrium temperatures and transformation heats have been ob- tained according to Eqs. (11) and (12) and were T0p  308.7 K, Up  3.38 J/g for alloy A and T0p  403 K, Up  8.06 J/g for alloy B, respectively. Finally, the fraction dependent residual nonchemi- cal energies and dissipative forces have been calculated according to Eqs. (11) and (13) and represented in Figs. 5–8. Therefore, using directly the first and second Thermodynamic Laws and without application of any minimization procedures, one can accurately derive the main thermodynamic force balance equa- tions taking into account the energy dissipation processes caused by hysteresis. The proposed scheme of splitting of the total amount of nonchemical energy into the pseudo-chemical component linearly dependent on the martensite fraction and a residual part of the Fig. 5. Fraction dependence of the nonchemical potentials in CuZnAl. THERMOELASTIC BEHAVIOUR, HYSTERESIS, AND DISSIPATIVE FORCES 11 fraction dependent nonchemical energy has two physical reasons. As it was earlier mentioned, both the pure chemical and the total nonchemical energies are not directly measurable quantities in case of multi-variant temperature-induced martensitic transformation. Unlike to these, the linearly dependent on the martensite fraction contributions of chemical and nonchemical energies combined to- gether as pseudo-chemical energy and the residual potential (z) will remain the only really measurable quantities in absence infor- mation on T0. On the other hand, the linear contribution extracted from the to- tal nonchemical energy and combined together with a similar linear term of chemical energy is responsible only for a simple renormali- Fig. 6. Fraction dependence of the dissipative forces in CuZnAl. Fig. 7. Fraction dependence of the nonchemical potentials in CuAlNi. 12 O. A. LIKHACHEV and Yu. M. KOVAL zation of the latent transformation heat value by a constant nonchemical energy stored in the completely martensitic state. As a result, the temperature T0 is also shifted and replaced by the pseudo-chemical equilibrium temperature T0p being defined by Eq. (12). Therefore, all the essential information on the thermoelas- tic equilibrium can be obtained from the detailed investigation of the residual nonchemical energy (z) and its dependence on the martensite fraction. One can easily check the following general properties of this potential. (i) Residual potential is always negative (z)  0 and takes zero val- ues at z  0 and z  1. (ii) (z) has positive curvature: eq ( ) ( ) 0z ST z     , because S  0 and eq ( ) 0T z  . (iii) (z) has a single minimum, because (z)  0, if only Teq(z)  T0p. The item (ii) can be considered as the general thermodynamic stability condition of the thermoelastic hysteresisless equilibrium curve which must be always monotonically decreasing function of z ( eq ( ) 0T z  ). It is important that the total nonchemical energy that differs from (z) only by a linearly dependent on martensite frac- tion term must also satisfy this condition. In both cases experimen- tally analysed here and indicated in Fig. 5, one can observe the faster increase of the residual potential as z  1 and shift of its minimum to the martensitic phase side. It is assumed that such be- haviour is a result of the inter-variant interactions when each newly formed martensitic crystal contacting with earlier formed multi-variant microstructure will produce an additional amount of elastic energy due to the incompatibility at the martensite– Fig. 8. Fraction dependence of the dissipative forces in CuAlNi. THERMOELASTIC BEHAVIOUR, HYSTERESIS, AND DISSIPATIVE FORCES 13 martensite interfaces. On the other side, these additional internal stresses will make the inter-variant boundaries to occupy the more appropriate positions producing, therefore, some additional amount of irreversible work. This effect is expected to be responsible for the significant fraction dependence of the dissipative force and aus- tenite–martensite asymmetry of nonchemical potential, which is found for the CuZnAl alloy. In case of CuAlNi containing two types Ti-rich X-phase and 2-phase precipitates [16], both effects are pre- sent too, but increase of nonchemical energy becomes stronger nearly z  1, so as the fraction dependence of dissipative force is not so sharp in comparison to the CuZnAl alloy. This shows that differ- ent types of quenched inhomogeneities can essentially influence on the processes of nonchemical energy storage and thermoelastic properties of shape-memory alloys. In this sense, the investigation of microscopic mechanisms of thermoelastic equilibrium is one of the interesting problems for the martensitic transformation physics that have been partially discussed in [17–19]. Some ideas and re- sults following from the analysis proposed there will be briefly re- viewed in the next sections. 4. INTERNAL STRESSES, QUENCHED INHOMOGENEITIES, AND THERMOELASTIC EQUILIBRIUM IN SHAPE-MEMORY ALLOYS It is known that a great number of shape-memory alloys, having the small temperature hysteresis, usually show thermoelastic behaviour. Macroscopically, the thermoelastic equilibrium can be considered as a coexistence of the martensite and parent phase in the wide tem- perature region between two characteristic temperatures, Ms and Mf. Microscopically, the thermoelastic equilibrium is displayed as a self-accommodated ensemble of plate-like martensitic crystals, which can grow continuously on cooling and, correspondingly, dis- appear on heating. These continuous martensite microstructure variations are always accompanied with the corresponding marten- sitic volume fraction change [2]. From a general point of view, the thermoelastic equilibrium in SMAs can be considered as a result of the local balance between so- called ‘chemical’ driving forces and mechanical driving forces, which are connected with the elastic stress field. It is produced by the martensitic crystals system together with other stress field sources [20]. Although this conception of thermoelastic equilibrium nature has been generally accepted for a long while, no adequate mathematical methods have been proposed for solution of the prob- lem. Different types of so-called ‘quenched’ inhomogeneities are known 14 O. A. LIKHACHEV and Yu. M. KOVAL to play an important role in martensitic transformation physics. First of all, the strongest effects are expected from the microscopic composition and ordering inhomogeneities, interstitial point de- fects, dislocations and stacking faults, grain boundaries, etc. that cannot relax in time and change rapidly their spatial configuration in a martensitic transformation temperature intervals. Following [17–19], the main aim of the present section is to rep- resent a general method for systematic analysis of the thermoelastic equilibrium states in SMAs. Here, we are taking into account the important role of the random internal driving forces produced by various randomly distributed elastic stress sources, including a self- consistent incompatibility stress fields generated by the martensite– austenite system. Here, we will be restricted with a simple case when only a single variant of martensitic phase is realized. It is also considered a com- pletely plane shear structure distortion matrix 1 0 0 ˆ 0 1 0 0 0 0             , (15) which has two invariant shear planes with normal vectors m1  (110) and m2  (110 ). Introduce the microscopic configuration function (x) to describe an arbitrary two-phase state containing a system of the multiple martensite–austenite interfaces. It is defined in such a way to have (x)  1 and (x)  0 values in martensite and austenite, respectively. Then one can easily express the inelastic strain distribution in the material as follows: ˆ ˆ( ) ( )x x   . (16) The definite amount of elastic energy  ˆ( ) e U x is stored in the two- phase state due to incompatibility of the martensite-structure lat- tice distortion with undistorted parent phase crystal structure. Ac- cordingly, the internal stress field produced by a system of marten- sitic crystals ensemble in the material ˆ ( ) m x can be found from the elastic energy functional as functional derivative:  ˆ( ) ˆ ( ) ˆ( ) e m U x x x       . (17) By the way, it is important to take into account the elastic interac- tion energy between the martensite and different type defects pro- ducing inhomogeneous stress fields ˆ ( ) r x in the material: THERMOELASTIC BEHAVIOUR, HYSTERESIS, AND DISSIPATIVE FORCES 15    3ˆ ˆ ˆ( ) ( ) ( ) r r U x d x x x      . (18) Therefore, the total Gibbs free energy of heterophase martensite– austenite system in this case can be always written in the following form:    3 0 ( ) ( ) ( ) ( )G x d xg x x V x     , (19) where the first term represents the total chemical energy with the specific Gibbs free energy difference per unit volume between the martensite and austenite, 0 ( ) ( ) ( ) M Ag T G T G T  . The second one V[(x)] is the nonchemical energy functional:    ˆ( ) ( ) ( ) e r V x U x U x    . (20) Taking the variational derivative of the total Gibbs free energy functional in respect to (x), one can define the local thermome- chanical driving force applied to the martensite–austenite interface  for x  :     ( ) ˆ ˆ ˆ( ; ) ( ) ( ) ( ) ( ) ( ) m r G x g x T g T g T x x x             . (21) The martensitic crystal ensemble can be in a thermomechanical equilibrium state only if the above-defined thermomechanical driv- ing force will zero for all x   at the inter-phase boundaries. In other words, the balance equation between the ‘chemical’ g(T) and mechanical (x) driving forces is fulfilled at all the boundaries  between the martensite and parent phase. That is g(T)  (x) if x  . (22) Here, ˆ ˆ( ) ( )x x     . (23) ̂ is the shear distortion matrix associated with the martensitic transformation of the parent phase lattice structure, and ˆ ( )x is the total internal stress tensor caused both the martensite crystal system and other randomly distributed sources of the elastic stress. In particular, it is important that in equilibrium the martensitic phase can occupy that region of space where g(T)  (x). In other words, the equilibrium spatial distribution of the mart- ensitic phase can be explicitly expressed by the configuration func- tion (x): 16 O. A. LIKHACHEV and Yu. M. KOVAL  ( ) ( )x x g     , (24) which takes the values (x)  1 in the region occupied by martensite and (x)  0 in the parent phase region, respectively. Here, () is the well-known Heaviside function:         1 for 0, ( ) 0 for 0. (25) In general, the total internal stress ˆ ( )x may be expressed as a su- perposition ˆ ˆ ˆ( ) ( ) ( ) m r x x x     , (26) where ˆ ( ) m x is the stress field associated with the martensitic crys- tals ensemble and ˆ ( ) r x is caused by the random defect system. Similarly, in accordance with Eq. (23), the mechanical driving force (x) can be written as ( ) ( ) ( ) m r x x x     . (27) Using the elasticity theory, the martensitic stress field ˆ ( ) m x can be found as a linear functional of the martensitic configuration func- tion (x) [21]. The corresponding result can be expressed in the fol- lowing general form:     ˆ( ) ( )x E x , (28) where the evident form of the integral-differential linear operators Ê follows immediately from the direct solution of the theory elas- ticity equations. In particular, the martensitic component of the mechanical driving force m(x) has the following form: ˆ( ) ( ) m x E x    , (29) with ˆ ˆE E    . Combining the Eqs. (24), (27), and (29), one can obtain a self-consistent nonlinear thermoelastic equilibrium equa- tion for the mechanical driving force (x):  ˆ( ) ( ) ( )rx x E x g       . (30) It should be also noted that the linear operator Ê has a diagonal form in the Fourier representation. That is, the plane waves exp(ikx) corresponding to the wave-vector k are evidently the eigen- functions of Ê : THERMOELASTIC BEHAVIOUR, HYSTERESIS, AND DISSIPATIVE FORCES 17    ˆ ( ) ikx ikxE e n e  , (31) where the eigenvalues (n) are always the positive functions, de- pending only on the direction vector n  k/k in k-space. In special cases, if the structure distortion matrix ̂ can be represented as the invariant plane shear with the shear plane normal vectors m1 or m2, then 2 ( ) ( )n G f n   , (32) where G is the shear modulus, ̂ is the structure strain value and f(n) is the dimensionless positive function taking zero value f(n)  0 if n  m1 or m2. 5. SOLUTION AND ANALYSIS The thermoelastic equilibrium Eq. (30) cannot be solved exactly be- cause of the nonlinear term in the right side of the Eq. (30). How- ever, an effective approximation method based on the linearization of the nonlinear term in the Eq. (30) has been proposed in Ref. [18]. In accordance with that one, the configuration function ((x)  g) is approximated as follows:  ( ) ( ) ( ) ( )x g z g P g x      , (33) where the identification of the coefficients z(g) and P(g) can be found from the evident equations:  ( ) ( )z g x g    ,  ( ) ( ) ( ) P g x g x       , (34) after …-averaging the configuration function  and its first de- rivative value /. Both parameters z(g) and P(g) have an evident physical interpretation. In particular, function P() represents the probability distribution function of the mechanical driving force field (x). Here, ()  d()/d is the well-known Dirac’s function. Besides, z(g) represents the volume fraction of martensite as a function of ‘chemical’ driving force g. As a result of Eq. (33),  ˆ ˆ( ) ( ) ( )E x g P x E x     , (35) because the action of Ê on the spatially homogeneous function z(g) gives 0. Substituting Eq. (35) into Eq. (30), one can obtain the lin- earized thermoelasticity equation for a self-consistent mechanical driving force (x): 18 O. A. LIKHACHEV and Yu. M. KOVAL  ˆ ˆ( ) ( ) ( )rI P g E x x    . (36) A simple relationship between the Fourier transform coefficients (k) and r(k) of (x) and r(x) follows immediately from Eqs. (31), (32), and (36). As a result, the solution of the self-consistent ther- moelastic equilibrium Eq. (30) can be expressed in the following analytic form:   1 ( ) ( ) 1 ( ) ( ) r k k g f n       , (37) where (g)  G2P(g). The linear relation between (k) and r(k) de- notes that the random self-consistent field (x) can be considered as a Gaussian random field only if r(k) is also Gaussian. In particular, the probability distribution function P() can be expressed as fol- lows:     1/2 2 2 2 ( ) 2 expP        , (38) where the statistical dispersion 2 of (x) and (g) can be found from the Eqs. (37) and (39): 22 3 ( )d k k   . (39) Here, (k)2 is the Fourier power spectrum of (x). Using Eq. (37) and substituting it into Eq. (39), one can obtain the equations de- termining the dependence of (g) and 2 on the ‘chemical’ driving force, respectively. As follows from our analysis, the functions (g) and 2 show the following properties:  2 1 2 0 1 4 rg       , 2 2 rg    , (40) 2 0 2 g   , 0 g  . (41) Here,   1/2 2 2 r G      , 22 3 ( )r rd k k   . (42) Because     2 22 2 ( ) ( ) r r r x x      , then an important parame- ter  can be expressed as a ratio   /r between the structure dis- tortion  and elastic strain level r corresponding to the internal stress field ˆ ( ) r x :   1/2 1 2 ( ) r r G x   . (43) THERMOELASTIC BEHAVIOUR, HYSTERESIS, AND DISSIPATIVE FORCES 19 Only the large values of  can be a subject of analysis because, in most of cases, r is much smaller than the structure distortion pa- rameter . The quantitative representation of (g) and 2 behaviour are shown in Figs. 9, 10. Here, g is represented in units 2 r  . Some interesting conclusions follow immediately from the sim- plest analysis of Eq. (37). In particular, one can conclude that the Fourier power spectrum (k)2 is always localized in that region of k-space where the angle  between n and shear plane normal vector m1(or m2) takes the small values: Fig. 9. Normalized value of (g) as function of chemical driving force. Fig. 10. Relationship between mean square nonchemical and chemical driv- ing forces. 20 O. A. LIKHACHEV and Yu. M. KOVAL 1/2 ( )g   ,         ,n m . (44) A similar anisotropic Fourier power spectrum distribution is known to be a consequence of the plate-like structure of martensite in real space. In particular, the habit planes of martensitic plates will coin- cide with the shear planes of the structure distortion, and the aver- age thickness and radius of the plates can be estimated as   0 ,d 1/2 0 ( )R g   . (45) Therefore, the plate radius can strongly increase on cooling and ap- proach the largest value Rmax  0 at g  0. Here, 0 is the character- istic spatial scale of the random stress field ˆ ( ) r x . The martensitic volume fraction as a function of ‘chemical’ driv- ing force g can also be obtained from the present theory. The corre- sponding results are represented in Eq. (34).  2 2 ( ) ( ) erfz g x g    . (46) Here, the brackets … denote the statistical averaging procedure and erf(p) is a well-known ‘error function’. The graphic representa- tion of volume fraction behaviour is shown in Fig. 11, where g is represented in units of 2 r  . In particular, the martensitic trans- formation interval for chemical driving force g can be estimated as   1/2 2 2 2g G      (47) Fig. 11. Martensite fraction as function of chemical driving force change. THERMOELASTIC BEHAVIOUR, HYSTERESIS, AND DISSIPATIVE FORCES 21 and considered as a characteristic energy scale for the nonchemical interactions. The total nonchemical energy and its martensite frac- tion dependence has been also calculated and plotted in Figs. 11, 12. The nonchemical energy is given in units of g. These model calcu- lations are in good qualitative agreement with the residual nonchemical energy behaviour obtained from DSC measurement and discussed in the preceding sections. Naturally, the experimentally found asymmetric shape of the fraction dependent potentials mainly connected with the inter-variant interaction effects cannot be satis- factorily reproduced in the framework of present single variant model. Similar effects are assumed to be a subject of further devel- opments in this field of investigations. Therefore, in accordance with the present studies, the random stress fields produced by the different quenched defects in parent phase play an important role in thermodynamic driving force bal- ance. They and should be always taken into account to understand the nature of thermoelastic equilibrium and to describe quantita- tively the macroscopic and microstructure properties of SMAs. REFERENCES 1. G. V. Kurdjumov, Tech. Phys. U.S.S.R., 18: 999 (1949). 2. G. V. Kurdjumov and L. C. Khandros, Dokl. Acad. Nauk. SSSR, 66: 211 (1949) (in Russian). 3. G. V. Kurdjumov, J. Metals, 11: 449 (1959). 4. L. Delaey, R. V. Krishnan, H. Tas, and H. Warlimont, J. Mater. Sci., 9: 1521 (1974). Fig. 12. Nonchemical energy and its fraction dependence calculated within the present model. 22 O. A. LIKHACHEV and Yu. M. KOVAL 5. R. V. Krishnan, L. Delaey, H. Tas, and H. Warlimont, J. Mater. Sci., 9: 1536 (1974). 6. H. Warlimont, L. Delaey, R. V. Krishnan, and H. Tas, J. Mater. Sci., 9: 1536 (1974). 7. G. B. Olson and M. Cohen, Scr. Metall., 9: 1247 (1975). 8. G. B. Olson and M. Cohen, Scr. Metall., 11: 345 (1977). 9. H. C. Tong and C. M. Wayman, Acta Metall., 22: 887 (1974). 10. C. M. Wayman and H. C. Tong, Scr. Metall., 11: 341 (1977). 11. Y. I. Paskal and L. A. Monasevich, Sov. Phys. J., 78: 1466 (1979). 12. Y. I. Paskal and L. A. Monasevich, Phys. Met. Metall., 52: 95 (1981). 13. J. Ortin and A. Planes, Acta Metall., 36: 1873 (1988). 14. J. Ortin and A. Planes, Acta Metall., 37: 1433 (1989). 15. C. Segui, E. Cesari, and J. Pons, Mater. Trans., JIM, 33: 650 (1992). 16. E. Cesari, C. Segui, J. Pons, and F. Perelló, J. Phys. IV France, 6, C8: 413 (1996). 17. A. A. Likhachev and Yu. N. Koval, Samosoglasovannye Polya Napryazheniy i Termouprugoe Ravnovesie Faz v Neodnorodnykh Tverdykh Rastvorakh [The Self-Consistent Field Stresses and Thermoelastic Phase Equilibrium in Heterogeneous Solid Solutions] (Kiev: 1988) (Prepr./N.A.S. of Ukraine. Inst. for Metal Physics. No. 20.88, p. 18) (in Russian). 18. A. A. Likhachev and Yu. N. Koval, Scr. Metall. Mater., 27: 1623 (1992). 19. A. A. Likhachev and Yu. N. Koval, Fazovye Prevrashcheniya Martensitnogo Tipa [Martensitic-Type Phase Transformations] (Kiev: Naukova Dumka: 1993), p. 39–52 (in Russian). 20. A. L. Roytburd, Usp. Fiz. Nauk, 113: 69 (1974) (in Russian). 21. A. G. Khachaturyan, Fiz. Tverdogo Tela, 8: 2709 (1966) (in Russian).

Ähnliche Einträge