編輯推薦
                                      《相平衡、相圖和相變——其熱力學基礎(第二版)》是影印版英文專著,原書由劍橋大學齣版社於2008年齣版。相平衡、相變等熱力學原理是理解、設計材料屬性的基礎。計算工具的齣現使材料學傢能夠處理越來越復雜的情況,但對於熱力學基礎理論的理解也越來越重要。本書圖文並茂,深入淺齣地講解瞭熱力學原理以及在計算機計算中的應用,對於材料科學、材料工程方麵的研究者會有很大幫助。                 
內容簡介
     《相平衡、相圖和相變——其熱力學基礎(第二版)(英文影印版)》主要內容為現代計算機應用觀點下的熱力學基本原理。 化學平衡和化學變化的理論基礎也是本書的內容之一,其重點在於相圖的性質。本書從基本原理齣發,討論延及多相的係統。第二版新增加的內容包括不可逆熱力學、極值原理和錶麵、界麵熱力學等等。 平衡條件的理論刻畫、係統的平衡狀態和達到平衡時的變化都以圖解的形式給齣。
  《相平衡、相圖和相變——其熱力學基礎(第二版)(英文影印版)》適閤材料科學與工程領域的研究人員、研究生和高年級本科生閱讀。     
作者簡介
     (瑞典)希勒特(M. Hillert),瑞典皇傢工學院教授。     
目錄
   Preface to second edition page xii
Preface to first edition xiii
1 Basic concepts of thermodynamics 1
1.1 External state variables 1
1.2 Internal state variables 3
1.3 The first law of thermodynamics 5
1.4 Freezing-in conditions 9
1.5 Reversible and irreversible processes 10
1.6 Second law of thermodynamics 13
1.7 Condition of internal equilibrium 17
1.8 Driving force 19
1.9 Combined first and second law 21
1.10 General conditions of equilibrium 23
1.11 Characteristic state functions 24
1.12 Entropy 26
2 Manipulation of thermodynamic quantities 30
2.1 Evaluation of one characteristic state function from another 30
2.2 Internal variables at equilibrium 31
2.3 Equations of state 33
2.4 Experimental conditions 34
2.5 Notation for partial derivatives 37
2.6 Use of various derivatives 38
2.7 Comparison between CV and CP 40
2.8 Change of independent variables 41
2.9 Maxwell relations 43
3 Systems with variable composition 45
3.1 Chemical potential 45
3.2 Molar and integral quantities 46
3.3 More about characteristic state functions 48
3.4 Additivity of extensive quantities. Free energy and exergy 51
3.5 Various forms of the combined law 52
3.6 Calculation of equilibrium 54
3.7 Evaluation of the driving force 56
3.8 Driving force for molecular reactions 58
3.9 Evaluation of integrated driving force as function of
T or P 59
3.10 Effective driving force 60
4 Practical handling of multicomponent systems 63
4.1 Partial quantities 63
4.2 Relations for partial quantities 65
4.3 Alternative variables for composition 67
4.4 The lever rule 70
4.5 The tie-line rule 71
4.6 Different sets of components 74
4.7 Constitution and constituents 75
4.8 Chemical potentials in a phase with sublattices 77
5 Thermodynamics of processes 80
5.1 Thermodynamic treatment of kinetics of
internal processes 80
5.2 Transformation of the set of processes 83
5.3 Alternative methods of transformation 85
5.4 Basic thermodynamic considerations for processes 89
5.5 Homogeneous chemical reactions 92
5.6 Transport processes in discontinuous systems 95
5.7 Transport processes in continuous systems 98
5.8 Substitutional diffusion 101
5.9 Onsager’s extremum principle 104
6 Stability 108
6.1 Introduction 108
6.2 Some necessary conditions of stability 110
6.3 Sufficient conditions of stability 113
6.4 Summary of stability conditions 115
6.5 Limit of stability 116
6.6 Limit of stability against fluctuations in composition 117
6.7 Chemical capacitance 120
6.8 Limit of stability against fluctuations of
internal variables 121
6.9 Le Chatelier’s principle 123
7 Applications of molar Gibbs energy diagrams 126
7.1 Molar Gibbs energy diagrams for binary systems 126
7.2 Instability of binary solutions 131
7.3 Illustration of the Gibbs–Duhem relation 132
7.4 Two-phase equilibria in binary systems 135
7.5 Allotropic phase boundaries 137
7.6 Effect of a pressure difference on a two-phase
equilibrium 138
7.7 Driving force for the formation of a new phase 142
7.8 Partitionless transformation under local equilibrium 144
7.9 Activation energy for a fluctuation 147
7.10 Ternary systems 149
7.11 Solubility product 151
8 Phase equilibria and potential phase diagrams 155
8.1 Gibbs’ phase rule 155
8.2 Fundamental property diagram 157
8.3 Topology of potential phase diagrams 162
8.4 Potential phase diagrams in binary and multinary systems 166
8.5 Sections of potential phase diagrams 168
8.6 Binary systems 170
8.7 Ternary systems 173
8.8 Direction of phase fields in potential phase diagrams 177
8.9 Extremum in temperature and pressure 181
9 Molar phase diagrams 185
9.1 Molar axes 185
9.2 Sets of conjugate pairs containing molar variables 189
9.3 Phase boundaries 193
9.4 Sections of molar phase diagrams 195
9.5 Schreinemakers’ rule 197
9.6 Topology of sectioned molar diagrams 201
10 Projected and mixed phase diagrams 205
10.1 Schreinemakers’ projection of potential phase diagrams 205
10.2 The phase field rule and projected diagrams 208
10.3 Relation between molar diagrams and Schreinemakers’
projected diagrams 212
10.4 Coincidence of projected surfaces 215
10.5 Projection of higher-order invariant equilibria 217
10.6 The phase field rule and mixed diagrams 220
10.7 Selection of axes in mixed diagrams 223
10.8 Konovalov’s rule 226
10.9 General rule for singular equilibria 229
11 Direction of phase boundaries 233
11.1 Use of distribution coefficient 233
11.2 Calculation of allotropic phase boundaries 235
11.3 Variation of a chemical potential in a two-phase field 238
11.4 Direction of phase boundaries 240
11.5 Congruent melting points 244
11.6 Vertical phase boundaries 248
11.7 Slope of phase boundaries in isothermal sections 249
11.8 The effect of a pressure difference between two phases 251
12 Sharp and gradual phase transformations 253
12.1 Experimental conditions 253
12.2 Characterization of phase transformations 255
12.3 Microstructural character 259
12.4 Phase transformations in alloys 261
12.5 Classification of sharp phase transformations 262
12.6 Applications of Schreinemakers’ projection 266
12.7 Scheil’s reaction diagram 270
12.8 Gradual phase transformations at fixed composition 272
12.9 Phase transformations controlled by a chemical potential 275
13 Transformations in closed systems 279
13.1 The phase field rule at constant composition 279
13.2 Reaction coefficients in sharp transformations
for p = c + 1 280
13.3 Graphical evaluation of reaction coefficients 283
13.4 Reaction coefficients in gradual transformations
for p = c 285
13.5 Driving force for sharp phase transformations 287
13.6 Driving force under constant chemical potential 291
13.7 Reaction coefficients at constant chemical potential 294
13.8 Compositional degeneracies for p = c 295
13.9 Effect of two compositional degeneracies for p = c . 1 299
14 Partitionless transformations 302
14.1 Deviation from local equilibrium 302
14.2 Adiabatic phase transformation 303
14.3 Quasi-adiabatic phase transformation 305
14.4 Partitionless transformations in binary system 308
14.5 Partial chemical equilibrium 311
14.6 Transformations in steel under quasi-paraequilibrium 315
14.7 Transformations in steel under partitioning of alloying elements 319
15 Limit of stability and critical phenomena 322
15.1 Transformations and transitions 322
15.2 Order–disorder transitions 325
15.3 Miscibility gaps 330
15.4 Spinodal decomposition 334
15.5 Tri-critical points 338
16 Interfaces 344
16.1 Surface energy and surface stress 344
16.2 Phase equilibrium at curved interfaces 345
16.3 Phase equilibrium at fluid/fluid interfaces 346
16.4 Size stability for spherical inclusions 350
16.5 Nucleation 351
16.6 Phase equilibrium at crystal/fluid interface 353
16.7 Equilibrium at curved interfaces with regard to composition 356
16.8 Equilibrium for crystalline inclusions with regard to composition 359
16.9 Surface segregation 361
16.10 Coherency within a phase 363
16.11 Coherency between two phases 366
16.12 Solute drag 371
17 Kinetics of transport processes 377
17.1 Thermal activation 377
17.2 Diffusion coefficients 381
17.3 Stationary states for transport processes 384
17.4 Local volume change 388
17.5 Composition of material crossing an interface 390
17.6 Mechanisms of interface migration 391
17.7 Balance of forces and dissipation 396
18 Methods of modelling 400
18.1 General principles 400
18.2 Choice of characteristic state function 401
18.3 Reference states 402
18.4 Representation of Gibbs energy of formation 405
18.5 Use of power series in T 407
18.6 Representation of pressure dependence 408
18.7 Application of physical models 410
18.8 Ideal gas 411
18.9 Real gases 412
18.10 Mixtures of gas species 415
18.11 Black-body radiation 417
18.12 Electron gas 418
19 Modelling of disorder 420
19.1 Introduction 420
19.2 Thermal vacancies in a crystal 420
19.3 Topological disorder 423
19.4 Heat capacity due to thermal vibrations 425
19.5 Magnetic contribution to thermodynamic properties 429
19.6 A simple physical model for the magnetic contribution 431
19.7 Random mixture of atoms 434
19.8 Restricted random mixture 436
19.9 Crystals with stoichiometric vacancies 437
19.10 Interstitial solutions 439
20 Mathematical modelling of solution phases 441
20.1 Ideal solution 441
20.2 Mixing quantities 443
20.3 Excess quantities 444
20.4 Empirical approach to substitutional solutions 445
20.5 Real solutions 448
20.6 Applications of the Gibbs–Duhem relation 452
20.7 Dilute solution approximations 454
20.8 Predictions for solutions in higher-order systems 456
20.9 Numerical methods of predictions for higher-order systems 458
21 Solution phases with sublattices 460
21.1 Sublattice solution phases 460
21.2 Interstitial solutions 462
21.3 Reciprocal solution phases 464
21.4 Combination of interstitial and substitutional solution 468
21.5 Phases with variable order 469
21.6 Ionic solid solutions 472
22 Physical solution models 476
22.1 Concept of nearest-neighbour bond energies 476
22.2 Random mixing model for a substitutional solution 478
22.3 Deviation from random distribution 479
22.4 Short-range order 482
22.5 Long-range order 484
22.6 Long- and short-range order 486
22.7 The compound energy formalism with short-range order 488
22.8 Interstitial ordering 490
22.9 Composition dependence of physical effects 493
References 496
Index 499      
前言/序言
   
 
 
    
				 
				
				
					《相平衡、相圖與相變:其熱力學基礎》(第二版)(英文影印版)圖書簡介  深入理解物質世界轉變的基石  《相平衡、相圖與相變:其熱力學基礎》(第二版)是一部全麵而深入的專著,旨在為材料科學、化學工程、物理化學以及相關領域的研究人員和高年級本科生/研究生提供一個堅實的理論框架,用以理解和預測物質在不同溫度、壓力和組分條件下的行為。本書的核心聚焦於相平衡現象的驅動力——熱力學原理,並係統地闡述瞭如何利用這些原理構建和解讀相圖,從而指導實際過程的設計與優化。  本書的第二版在繼承第一版嚴謹性和全麵性的基礎上,進行瞭大量的修訂和增補,以反映近年來該領域的新進展和教學實踐中的反饋。它不僅是一本教科書,更是一本深入的參考手冊,強調理論的內在邏輯和實際應用之間的緊密聯係。   第一部分:熱力學基礎的迴顧與深化  要掌握相平衡,必須首先對熱力學有透徹的理解。本書伊始,即以一種高度聚焦的方式迴顧並深化瞭讀者對基礎熱力學概念的掌握,特彆是那些直接與相態和相變相關的概念。  1. 熱力學勢與化學勢的再審視: 重點闡述瞭吉布斯自由能(G)作為最關鍵的熱力學勢在恒溫恒壓條件下的指導意義。書中詳盡地討論瞭化學勢($mu$)的概念,將其定義為物質在混閤物中傾嚮於遷移的驅動力。通過微觀和宏觀的視角相結閤,讀者可以清晰地理解,相平衡的本質是係統中所有組分的化學勢達到相等。  2. 偏摩爾量與活度: 針對非理想溶液,本書深入探討瞭偏摩爾量(Partial Molar Quantities)的計算方法及其物理意義。活度(activity)的概念被引入,用以修正理想溶液模型下的不足。詳細推導瞭活度係數的意義,並展示瞭如何通過不同的模型(如Wilson, NRTL, UNIQUAC)來描述溶液的非理想性,這對處理復雜的多組分體係至關重要。  3. 功、熱與熵的關聯: 雖然這些是基礎概念,但本書強調瞭它們在描述相變過程中能量轉換的重要性。特彆是在涉及潛熱(Latent Heat)的相變過程中,熵變的精確計算被放在突齣位置,為理解剋拉佩龍方程的推導奠定基礎。   第二部分:相平衡的理論構建  這是本書的核心部分,係統地將熱力學原理應用於描述不同類型的相平衡係統。  4. 單組分係統的相平衡: 從最簡單的純物質齣發,本書詳盡地推導瞭剋拉佩龍方程(Clapeyron Equation),並闡述瞭其在固-液、液-氣、固-氣三相綫上的應用。剋勞修斯-剋拉佩龍方程(Clausius-Clapeyron Equation)作為其在氣液平衡中的重要簡化形式,被用來精確計算飽和蒸汽壓和沸點。三相點(Triple Point)和臨界點(Critical Point)的特性在相圖中的體現被詳細分析。  5. 多組分係統的相平衡——溶液熱力學: 本部分是本書的精髓之一。它涵蓋瞭氣-液平衡(VLE)、液-液平衡(LLE)以及固-液平衡(SLE)。     VLE的理論基礎: 詳細分析瞭拉烏爾定律(Raoult's Law)在稀溶液和理想溶液中的適用範圍。隨後,重點講解瞭非理想體係中如何利用活度係數模型(如Wilson, NRTL)來校正偏離,從而精確預測閃點、露點和泡點。    LLE的相容性: 探討瞭溶液中存在兩相的條件,特彆是液體的部分互溶性。著重分析瞭三組分係統中的三角形相圖(如Ternary Diagram)的繪製和解讀,包括共軛綫的意義。    SLE與凝固點下降: 闡述瞭溶解的溶質對純溶劑凝固點的影響,這對於閤金學和結晶過程至關重要。  6. 擴散相變與化學平衡: 本書並未局限於物理相變,還整閤瞭化學反應在相平衡中的作用。化學反應平衡常數 ($K$) 與熱力學量的關係被清晰闡述,展示瞭如何將化學平衡納入更宏觀的相圖分析中。   第三部分:相圖的構建與解讀  相圖是信息的載體,是熱力學術語嚮直觀圖形轉化的橋梁。本書花費大量篇幅指導讀者如何“閱讀”和“繪製”這些圖。  7. 相律的普適性: 吉布斯相律(Gibbs Phase Rule, F = C - P + 2) 被視為指導所有相圖分析的根本法則。書中通過大量實例,演示瞭如何利用相律來確定特定區域或綫上自由度(Degrees of Freedom),從而理解相圖中“相場”的性質。  8. 二元和三元係統的相圖:     二元相圖(Binary Diagrams): 詳細分析瞭共晶(Eutectic)、共熔(Eutectoid)、包析(Peritectic)等各種拓撲結構。對於閤金係統,書中特彆強調瞭固溶體(Solid Solution)的形成、亞共晶和超共晶冷卻路徑的分析。    三元相圖(Ternary Diagrams): 深入講解瞭等溫截麵、垂直截麵以及連綫上分析法。特彆關注在冶金和陶瓷領域中常見的,如液相燒結過程中相的形成與轉化。  9. 壓力對相圖的影響: 討論瞭高壓對相平衡的顯著影響,例如在地球物理學和高壓閤成中常見的相變,如冰的不同多晶型物。   第四部分:應用與現代方法  本書的深度體現在它不僅停留在經典理論,還觸及瞭現代工程應用中必須掌握的工具。  10. 範特霍夫/愛倫特定律與溶解度: 係統地分析瞭溫度對固體和氣體在液體中溶解度的影響,包括使用範特霍夫方程預測溫度依賴性。  11. 反應平衡與化學勢的聯係: 重新審視化學平衡在多相體係中的地位,如何通過最小化總吉布斯自由能來定位反應的終點,這對於反應工程至關重要。  12. 實驗技術與數據擬閤: 簡要介紹瞭測定相平衡數據的主要實驗技術(如DSC, DTA, TGA, 氣相色譜分析等),並介紹瞭用於處理這些實驗數據的熱力學數據庫和計算方法,如計算化學方法(CALPHAD方法的基礎思想),強調瞭實驗數據與理論模型的反饋循環。   總結  《相平衡、相圖與相變:其熱力學基礎》(第二版)以其無與倫比的清晰度和嚴謹性,成為連接基礎物理化學與材料科學、化學工程等應用學科的橋梁。它不僅教授讀者“是什麼”,更重要的是教會讀者“為什麼”以及“如何計算”,是任何希望在物質轉變領域取得深入研究成果的專業人士不可或缺的工具書。通過係統學習本書內容,讀者將能夠自信地分析復雜的材料體係,設計高效的提純或閤成過程,並對物質在極端條件下的行為做齣準確的預測。