藉由溫度軌跡方法與熔融結晶法來探討可可脂與巧克力的熱性質與晶體成長

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研究生：	柯淇鏵 Chi-Hua Ko
論文名稱：	藉由溫度軌跡方法與熔融結晶法來探討可可脂與巧克力的熱性質與晶體成長 Thermal Properties and Crystal Growth of Cocoa Butter and Chocolate by Temperature History Method and Melt Crystalllization
指導教授：	李度 Tu Lee
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程與材料工程學系 Department of Chemical & Materials Engineering
論文出版年：	2019
畢業學年度：	107
語文別：	英文
論文頁數：	79
中文關鍵詞：	溫度軌跡、熔融結晶、巧克力、可可脂
外文關鍵詞：	T-history, Melt crystalllization, Chocolate, Cocoa butter
相關次數：	點閱：8 下載：0
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可可脂是組成巧克力的原料之一，是控制巧克力結晶的主要成分，本篇研究目的為藉由溫度軌跡方法來探討可可脂與巧克力的熱性質以及兩種樣品以該方法所產生的結晶型態做比較，將所得的熱性質應用在熔融結晶法的結晶層厚度預測，並同樣分析兩種樣品以熔融結晶法所產生的結晶型態來做研究。在熔融結晶法中我們研究樣品厚度與時間之關係與生長曲線，使用低溫差示掃描量熱法(LT-DSC)測定熔點、平衡狀態以及樣品之吸放熱峰值，並配合X射線衍射(XRD)來測定樣品的多晶型。溫度軌跡方法顯示:可可脂熔點=287.3±0.3 K，液態熱含量=3.46±0.34 kJkg-1K-1，固態熱含量=7.35±1.47 kJkg-1K-1，潛熱=30.1±1.7 kJkg-1K-1 以及固態導熱性=0.173±0.07 Wm-1K-1，而巧克力熔點=290.9±0.3 K，液態熱含量=2.92±0.94 kJkg-1K-1，固態熱含量=6.39±0.52 kJkg-1K-1，潛熱=12.3±2.6 kJkg-1K-1以及固態導熱性=0.215±0.006 Wm-1K-1。而低溫差示掃描量熱法以及X射線衍射顯示了由溫度軌跡方法所得到的可可脂和巧克力結晶型態分別為Form IV和Form V之結晶。熔融結晶法則證明了結晶層會隨著時間的增加而成長，可可脂經由熔融結晶法產生之厚度介於0.05至0.13cm之間且會生成 Form V之結晶，該結晶型態也是生產巧克力最合適的晶型，但經由相同方法所製造出之巧克力之厚度則介於0.46至1.27cm間，在同樣時間下之結晶厚度約為可可脂厚度的十倍，且會產生Form II、Form III和Form V之結晶，我們的系統用於探討熔融結晶法應用在傳統商業巧克力生產上減少退火步驟的可能性。

Cocoa butter is one of the components of chocolate. It is the key factor of affecting the polymorph of chocolate. In this research, we used temperature history method (T-history method) to calculated the thermal properties of cocoa butter and chocolate and compared the polymorph of two samples which made by T-history method. Otherwise, we used the thermal properties which calculated by T-history method to predict the crystal layer thickness of samples of melt crystallization and also analyzed polymorph of two samples. For melt crystallization, we investigate the crystal layer growth versus time curve of samples and compared with the theoretical calculation. We use low temperature differential scanning calorimetry (LT-DSC) to determine the melting point and the equilibrium state and combine with X-ray diffraction to characterize the polymorph of cocoa butter and chocolate. By using T-history method, thermal properties of cocoa butter are: melting point (Tm) = 287.3 ± 0.3 K, heat capacity of liquid state (Cpl) = 3.46 ± 0.34 kJ kg-1 K-1, heat capacity of solid state (Cps) = 7.35 ± 1.47 kJ kg-1 K-1, liquid-solid enthalpy change (ΔHls) = 30.1 ± 1.7 kJ kg-1 K-1, and thermal conductivity (ks) = 0.173 ± 0.07 W m-1 K-1 and the thermal properties of chocolate are: Tm = 290.9 ± 0.3 K, Cpl = 2.92 ± 0.94 kJ kg-1 K-1, Cps=6.39±0.52 kJ kg-1 K-1, ΔHls = 12.3 ± 2.6 kJ kg-1 K-1 and ks = 0.215 ± 0.006 W m-1 K-1.
The LT-DSC and X-ray diffraction showed that the cocoa butter and chocolate made by T-history are both form IV and form V, respectively. Melt crystallization showed the crystal layer of samples would increase as time went on. The layer thickness of cocoa butter from melt crystallization was between 0.05 cm and 0.13 cm, and would produce the Form V crystal, which was the most ideal form for chocolate manufacturing. The layer thickness of chocolate made by the same process was between 0.46 cm to 1.27 cm which was ten times larger than cocoa butter. However, it generated the Form II, Form III and Form V crystals. In this research, we investigated the possibility of the application of commercial manufacturing of chocolate without the annealing process.

摘要    i
Abstract    iii
Acknowledgement    v
Table of Contents    vii
List of Figures    x
List of Tables    xiii
Chapter 1    1
Background    1
1.1    Chocolate    1
1.2    Cocoa butter    2
1.3    Conceptual Framework    7
1.4    References    9
Chapter 2    11
Analytical Methods    11
2.1    Thermal Analysis Methods    11
2.1.1    Low Temperature Differential Scanning Calorimetry (LT-DSC)    
              11
2.1.2    Thermocouple    14
2.1.3    Temperature-history Method (T-history Method)    18
2.2    Crystallographic Analysis Methods    18
2.2.1    Powder X-ray Diffraction (PXRD)    18
2.3    References    22
Chapter 3    23
Materials and Experimental Procedure    23
3.1    Introduction    23
3.2    Materials    24
3.3    Analytical Instruments and Experimental Procedures    25
3.4    References    40
Chapter 4    42
Results and Discussion    42
4.1    Results of Experiment    42
4.1.1    The Results of DSC Scans and XRD Patterns of samples from T-history Method    42
4.1.2    Melt Crystallization    47
4.2    References    56
Chapter 5    57
Conclusion and Future works    57
5.1    Conclusions    57
5.2    Future works    59
5.3    References    60

 
List of Figures
Figure 1.1 Molecular structures of (a) POP, (b) POS, (c) SOS    3
Figure 1.2 Molecular structures of (a) palmitic acid, (b) oleic acid, (c) stearic acid    4
Figure 1.3 Molecular arrangement of (a) α-form (b) β’-form, (c) β-form    5
Figure 1.4 Possible transformations of cocoa butter    6
Figure 1.5 Tempering sequence during lipid crystallization in chocolates10    6
Figure 2.1 Schematic diagrams of (a) heat-flux DSC, and 
(b) power-compensated DSC.    12
Figure 2.2 Low temperature differential scanning calorimetry. 
(Perkin Elmer DSC 7, Norwalk, CT, U. S. A.)    13
Figure 2.3 Schematic diagrams of thermocouple basics.    15
Figure 2.4 The thermometer used is Lutron Electronic TM-947SD 
(Taipei, Taiwan).    16
Figure 2.5 Diffraction of Bragg’s Law    19
Figure 2.6 Bruker Axs D8 Advance PXRD    21
Figure 3.1 Three identical heating-cooling cycles for sample analysis    25
Figure 3.2 Heating-cooling cycles for polymorph characterization    26
Figure 3.3 (a) A typical T-history curve for samples, and 
(b) typical T-history curve for distilled water sample.    29
Figure 3.4 Experimental setups for temperature-history method. 
(a) 4 channels thermometer, (b) water bath, (c) K-type thermocouple, and (d) samples in the test tube.    30
Figure 3.5 Experimental set up for melt crystallization: (a) cooling finger, 
         (b) crystallized cocoa butter layer, and (c) molten cocoa butter    31
Figures 3.6 (a) LT-DSC scan of cocoa butter, (b) T-history curve of cocoa butter, 
         (c) LT-DSC scan of chocolate, and (d) T-history curve of chocolate.    37
Figure 4.1 PXRD pattern of cocoa butter from T-history method    43
Figure 4.2 LT-DSC scan of cocoa butter made from T-history method    44
Figure 4.3 PXRD pattern of chocolate from T-history method    45
Figure 4.4 LT-DSC scan of chocolate from T-history method    46
Figure 4.5 Photo images of crystal layer thickness of cocoa butter at different time    48
Figure 4.6 Photo images of crystal layer thickness of chocolate at different time    48
Figure 4.7 (a) Solid layer growth of cocoa butter at T0=5oC Tb=50oC
-Theoretical value of solid layer growth
                  ▓Experimental value of solid layer growth,
                  ▓calculate value of convective heat-transfer coefficient,
         (b) Solid layer growth of chocolate at T0=5oC Tb=50oC  
             -Theoretical value of solid layer growth
             ▓Experimental value of solid layer growth,
             ▓calculate value of convective heat-transfer coefficient,    50
Figure 4.8 PXRD pattern of cocoa butter from melt crystallization.    51
Figure 4.9 LT-DSC scan of the cocoa butter from melt crystallization    52
Figure 4.10 PXRD pattern of chocolate from melt crystallization    53
Figure 4.11 LT-DSC scan of chocolate from melt crystallization    54
Figure 5.1 LT-DSC scan of purchased chocolate    58
Figure 5.2 PXRD pattern of purchased chocolate    59
 
List of Tables
Table 1.1 Melting points of different polymorphs of cocoa butter7,8    5
Table 2.1 Seven kinds of thermocouples from TM-947SD operation manual.    15
Table 2.2 Descriptions of analytical instruments in this study.    21
Table 3.1 Thermal properties of cocoa butter and dark chocolate (literature value)-    35
Table 3.2 Nomenclatures of all symbols used for temperature-history method.6    38
Table 3.3 Nomenclatures of all symbols used for melt crystallization.    39
Table 4.1 Density of cocoa butter and chocolate    42
Table 4.2 Thermal properties of cocoa butter and chocolate    47
Table 4.3 Layer thickness versus time of cocoa butter and chocolate from 
melt crystallization    49


                                

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