在高分子材料內溶劑除吸收及其相關現象｜國立清華大學博碩士論文庫

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研究生：	劉琦崴
論文名稱：	在高分子材料內溶劑除吸收及其相關現象 Solvent Desorption in Polymer and Related Phenomena
指導教授：	李三保
口試委員:	周晟薛承輝黃健朝
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2013
畢業學年度：	101
語文別：	英文
論文頁數：	71
中文關鍵詞：	除吸收、揮發理論、擴散方程式
相關次數：	點閱：2 下載：0
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本篇論文第一部份，探討PMMA的單邊除吸收濃度分佈，我們分析在PMMA的單邊除吸收在不同的溫度中的兩個初始條件。擴散方程式以揮發理論做基礎被提出來並且利用分離係數法解出解析解。理論預測和實驗數據相當符合。利用擴散係數和揮發速率去配對曲線符合阿瑞尼士方程式。從位移數據，可以得知甲醇在PMMA中傳輸的部分莫耳體積。我們建立並分析PMMA在質傳中的彈性模型的應力分佈和縱向位移量。
第二部份探討表面波紋，表面波紋形成的條件為當高分子塊發生足夠大的壓縮應力，我們發現在PC由質傳所產生的壓縮應力在靠近雙邊除吸收表面。我們提出一個方法結合溶劑引發應力及在壓縮應力的高分子塊機械不穩定性來分析PC的溶劑引發表面波紋。計算出來的表面波長和實驗結果相符合而且趨勢相同。

Acknowledgements    i
Abstract    ii
Contents     iii
List of Tables     v
Figure Captions     vi
Chapter 1 Introduction     1
1.1 Diffusion in glassy polymers    1
1.2 Diffusion-induced stresses     5
1.3 Wrinkling phenomenon     7
1.4 Motivation and purpose of this study     10
Chapter 2 One-side desorption of a polymer slab
         －General model and analysis of PMMA data－     11
2.1 Solvent desorption in a polymer slab    12
2.1.1 Concentration profile    12
2.1.2 Total amount in the slab    13
2.2 Solvent-induced stresses in a polymer slab    15
2.2.1 Chemical stresses in a thin slab: Elastic model    15
2.2.2 Longitudinal displacement of the slab    17
2.2.3 Partial molar volume of methanol in PMMA during desorption    17
2.2.4 Stress distributions for one-side desorption of PMMA    18

Chapter 3 Solvent-induced surface pattern in polymer slab
         －A quantitative method to compare with PC data－     34
3.1 Concentration profile    35
3.1.1 Absorption    35
3.1.2 Desorption    35
3.1.3 Resorption    36
3.2 Solvent-induced surface pattern in polycarbonate    37
3.2.1 Stress distribution    37
3.2.2 Mechanical instability of a polymer slab    38
3.2.3 Pattern wavelength    41
Chapter 4 Conclusions     54
References    56
 
List of Tables
2.1    Properties of PMMA and methanol.     19
2.2    Diffusion coefficients, ratios of equilibrium concentration to saturated concentration, evaporation constant and evaporation rate for one-side desorption of methanol in PMMA for Mi /M∞=14.6%.    20
2.3    Diffusion coefficients, ratios of equilibrium concentration to saturated concentration, evaporation constant and evaporation rate for one-side desorption of methanol in PMMA for Mi /M∞=35.3%.    21
2.4    Activation energies of methanol diffusivity ED and evaporation rate Ev for one-side desorption in PMMA……………………………………………………………………22
2.5  Partial molar volume for one-side desorption of methanol in PMMA at different
    Temperature………………………..…...……………………………………….22   
3.1    Properties of polycarbonate and acetone.     45
3.2    Selected parameters of diffusion coefficients (for absorption D, desorption D1), velocity constant v, evaporation rate constant h and ratio of equilibrium concentration to saturated concentration……………………………….....................................................46
3.3    Corresponding activation energies of diffusivity and velocity for the selected parameters listed in Table 3.2.    46
3.4Selected parameters of ta and td………………….………………....................   47 
3.5 Values of x0/2l, E2/b, and E0/b for various temperatures and absorption time ta with the thickness 2l=0.8mm.     48
3.6 Values of P/b and Pc/b for various temperatures and absorption time ta with the thickness 2l=0.8mm.     49






Figure Captions
2.1    Structural formula of (a) methanol, (b) PMMA.     23
2.2    Schematic of thin slab: one side exposed to solvent bath and the other side insulated.     23
2.3 (a) Concentration distributions at different times where  ,  , Ce/C0=0.044 and h𝓁=2 during one-side desorption…………24
2.3 (b) Concentration distributions at different times where  ,  , Ce/C0=0.137 and h𝓁=2 during one-side desorption.    24
2.4 Curves of mass versus time where  ,  , Ce/C0=0.044 and h𝓁=0.5150 during one-side desorption and  ,  , Ce/C0=0.137 and h𝓁=0.5150 during one-side desorption…...25
2.5 (a) Mass consumption of methanol in PMMA during one-side desorption at various temperatures, initiating at 14.6% of saturation…………………………25
2.5 (b) Mass consumption of methanol in PMMA during one-side desorption at various temperatures, initiating at 35.3% of saturation………………………………………….26
2.6 (a) Arrhenius plots of D1 for PMMA during one-side desorption initiating at 14.6% and 35.3% of saturation…………………………………………...........27.
2.6 (b) Arrhenius plots of ve for PMMA during one-side desorption initiating at 14.6% and 35.3% of saturation…………………………………………………………27
2.7 (a) Displacement data of PMMA at various temperatures during one-side desorption initiating at 14.6% of saturation.     28
2.7     (b) Displacement data of PMMA at various temperatures during one-side    
desorption initiating at 35.3% of saturation.     28
2.8(a) Displacement data of PMMA and partial molar volume of methanol in PMMA at various temperatures during one-side desorption initiating at 14.6% of saturation…………………………………………………………………………29
2.8 (b) Displacement data of PMMA and partial molar volume of methanol in PMMA at various temperatures during one-side desorption initiating at 35.3% of saturation…….29 
2.9 (a) Transverse stress distributions in PMMA at different times for one-side desorption at 25C, initiating at 14.6% of saturation.     30
2.9 (b) Transverse stress distributions in PMMA at different times for one-side 
      desorption at 35C, initiating at 14.6% of saturation.     30
2.9 (c) Transverse stress distributions in PMMA at different times for one-side 
     desorption at 45C, initiating at 14.6% of saturation.     31
2.9(d) Transverse stress distributions in PMMA at different times for one-side 
     desorption at 55C, initiating at 14.6% of saturation.     31
2-10(a) Transverse stress distributions in PMMA at different times for one-side 
      desorption at 25C, initiating at 35.3% of saturation.     32
2-10(b) Transverse stress distributions in PMMA at different times for one-side 
      desorption at 35C, initiating at 35.3% of saturation.     32
2-10(c) Transverse stress distributions in PMMA at different times for one-side 
      desorption at 45C, initiating at 35.3% of saturation.     33
2-10(d) Transverse stress distributions in PMMA at different times for one-side 
       desorption at 55C, initiating at 35.3% of saturation.     33
3.1    Structural formula of (a) acetone, (b) polycarbonate.     49
3.2    Pattern wavelength versus time for PC of thickness 0.8 mm immersed in acetone at various temperatures.     49
3.3    Surface patterns on PC of thickness 0.8 mm after immersing in acetone at 35°C for different times: (a) 20, (b) 40, (c) 60, (d) 80, and (e) 100 sec.     50
3.4    Schematic of thin slab located between (-l,l).    51
3.5    The model of a polymer slab on which the elastic deformation energy is calculated in the text.     51
3.6    Stress distributions for different absorption times where  ,  ,  , and   during two-side desorption     52
3.7    Stress distributions for different absorption times where  ,  ,  ,  , and   during two-side resorption.     52
3.8    Critical wavelengths versus absorption time at various temperatures and data of polycarbonate.     53

                                

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