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This document discusses the absorption of alcohols into poly(methyl methacrylate) (PMMA) sheets at various temperatures. It presents data on the weight gain of PMMA sheets immersed in different alcohols including methanol, ethanol, and propanol from 20-50°C. The weight gain increases with temperature according to Fick's law of diffusion. Shorter alcohol carbon chain structures like methanol resulted in greater weight gain than longer chain alcohols like propanol.

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Japanese Article
Table 1. Basic properties of alcohols at 20•Ž used as the envi- ronmental reagents Fig. 1. Variation in the weight gain of a PMMA sheet, 1 mm thick, in methanol at 20-50•Ž. –â ‚à’Z ‚-‚È ‚é ‚± ‚Æ‚ª ‚í ‚© ‚é.20•`40•Ž ‚Ì ‰· “x ”Í ˆÍ ‚É ‚¨ ‚¢ ‚Ä ‹z Žû •d —Ê ‚ÍŽž ŠÔ ‚É”ä —á ‚µ‚Ä‘• ‘å ‚· ‚é ‚± ‚Æ‚ª –¾ —Ä ‚Å ‚ ‚è,caseIIŠg ŽU ‚Æ”» •Ê ‚³‚ê ‚é19).50•Ž ‚É ‚È ‚é ‚ÆŽž ŠÔ ‚É‘Î ‚· ‚é ”ä —á ŠÖ ŒW ‚Í •ö ‚ê,Fick“I ‚ÆŽv ‚í ‚ê ‚é —l ‘Š ‚ª Œ» ‚ê ‚Ä ‚¢ ‚é.‚± ‚Ì ‚± ‚Æ ‚Í50•Ž ‚ÅPMMA•ª Žq •½ ‚Ì ”M ‰^ “® ‚ª •L •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No. 2 (2002) 94
Fig. 2. Relation of the weight gain of PMMA specimen to the thickness of surface swollen layer in methanol at 20•Ž. Fig. 3. Variation in the weight gain of PMMA specimen in ethanol at 30-50•Ž. ”Í ˆÍ ‚É ‚í ‚½ ‚Á‚Ä ‚© ‚È ‚芈 ”- ‚É ‚È ‚Á ‚Ä ‚¢ ‚Ä,”z ’uŠ· ‚¦‚ª ’Z Žž ŠÔ ‚Å ‹N ‚«‚é ‚± ‚Æ ‚𠎦 •´ ‚µ‚Ä ‚¢ ‚é.Vrentas20)‚ª ƒf ƒ{ ƒ‰ •” ‚ÆŒÄ ‚ñ ‚¾ Šg ŽU ‚Ì“Á •« Žž ŠÔ ƒÑd‚É ‚· ‚é •‚ •ª Žq ‚Ì ŠÉ ˜a Žž ‘Î ŠÔ ƒÑr‚Ì äDeb=ƒÑr/ƒÑd‚Å Œ¾ ‚¤‚È ‚ç ‚Î,20•`40•Ž ” ‚Å ‚Í ‚» ‚ê ‚ª1’ö “x ‚Å ‚ ‚è,50•Ž ‚Å ‚Í1‚æ ‚è•¬ ‚³ ‚-‚È ‚é ‚± ‚Æ ‚ðˆÓ –¡ ‚µ‚Ä ‚¢ ‚é.20•`40•Ž ‚Ì •ê •‡ ‚Ì Še ŽŽ —¿ • –Ê ‚É ‚Í –c •• ‘w ‚ª –¾ —Ä ‚É ŠÏ Ž@ ‚³‚ê ‚½ •BFig.2‚ÉFig.1(a)‚Å Ž¦ ‚µ‚½20•Ž ‚É ‚¨ ‚¯ ‚é•d —Ê ‘• ‰Á ‚Æ• –Ê –c •• ‘w Œú ‚³ ‚- •û Œü)‚Ì •• ŠÖŒW ‚𠎦‚·.•Å •¬2•æ ‹ß Ž— ‚É ‚æ ‚è–¾ Šm ‚È ”ä —á ŠÖ ŒW ‚ª “¾ ‚ç‚ê ‚é‚ª, ‹» –¡ •[ ‚¢ ‚Ì ‚ÍcaseIIŠg ŽU ‚ª Žn ‚Ü ‚é ‚Ü ‚Å ‚É(–c •• ‘w Œú ‚³ ‚ª0‚Ì •ó ‘Ô ‚Å)–ñ2wt%‚Ì ƒ• ƒ^ ƒm •[ ƒ‹‚ª ‚ ‚ç‚© ‚¶‚ß‹z Žû ‚³‚ê ‚Ä ‚¢ ‚é ‚± ‚Æ‚Å ‚ ‚é.‚± ‚Ì ‚± ‚Æ‚Í•] —ˆ ‚© ‚猾 ‚í ‚ê ‚Ä ‚¢ ‚é ‚æ ‚¤‚É,caseIIŠg ŽU ‚Ì ”- Œ» ‚É ‚Í ‚ ‚é—U “± Žž ŠÔ(induction dme)‚ª •K —v ‚Å ‚ ‚è9},‚» ‚ê ‚Í ‹° ‚ç ‚-ƒ• ƒ^ ƒm •[ ƒ‹ •ª Žq ‚ª Fig. 4. Weight gain of PMMA specimen in propanol with different structures at 40 and sot. PMMA•ª Žq •½ ŠÔ ‚Ì Ž© —R ‘Ì •Ï ‚ð–„ ‚ß ‚é ‚Ì ‚É —v ‚· ‚é Žž ŠÔ ‚Æ ‰ð Žß ‚³ ‚ê ‚é10),21).‚½ ‚µ,–{ ŽÀ Œ± ‚Å “¾ ‚½Fig.1‚Ì ‚¾ ‹z Žû •d —Ê •Ï ‰» ‚É‚Í •‰ Šú ‰ß ’ö ‚Ì ƒf •[ ƒ^•s ‘« ‚à‚ ‚Á ‚Ä —U “± Žž ŠÔ ‚Í –¾ Šm ‚ÉŒ» ‚ê ‚Ä ‚Í‚¢ ‚È ‚¢.‚È ‚¨,Thomas‚ÆWindle‚Ì ŠÏ ‘ª Œ‹ ‚É ‚Ù ‚Æ ‚ñ ‚Ç‹z Žû ‚³‚ê ‚È ‚© ‚Á ‚½ ‚Ì ‚Å,‚± ‚± ‚Å ‚Í40,50•Ž ‰Ê9}‚É ”ä ‚× ‚é ‚Æ,–{ ŽÀ Œ± ‚Å ‚ÍcaseIIŠg ŽU ‚Ì”- Œ» •ã ŒÀ ‰· “x ‚ÌŒ‹ ‰Ê ‚Ì ‚Ý ‚ðŽ¦ ‚·.40•Ž ‚Ì ŠÂ ‹« ‰· “x ‚Å ‚Í1-ƒv ƒ• ƒp ƒm •[ ‚ª ‚â ‚â •‚ ‰· ‘¤ ‚É‚¸ ‚ê ‚Ä ‚¢ ‚é ‚æ ‚¤‚Å ‚ ‚é. ƒ‹ ‚Ì •û ‚ª2-ƒv ƒ•ƒp ƒm •[ ƒ‹ ‚æ ‚è‹z Žû ‘¬ “x ‚Í‘å ‚« ‚¢ ‚ª,•½ Fig•B3‚É ƒG ƒ^ ƒm •[ ƒ‹ ‚Ì30•`50•Ž ‚É ‚¨ ‚¯ ‚é ‹z Žû ‹“ “® ‚ð •t ‹z Žû —Ê ‚Í”½ ‘Î ‚É Œã ŽÒ ‚Ì •û ‚ª ‘å ‚« ‚-,–ñ1.7”{ ‚Ì’l ‚ðŽ¦ Ž¦ ‚·.— ”õ ŽÀ Œ± ‚É ‚æ‚ê ‚Î,20•Ž ‚Å ‚Í ƒG ƒ^ ƒm •[ ƒ‹ ‚Ì ‹z Žû ‚µ‚Ä ‚¢ ‚é.—¼ ŽÒ ‚Æ ‚à‚É‹z Žû •d —Ê ‚Ì‘• ‘å ‚Í •Z ’Ð Žž ŠÔ ‚É”ä —á —Ê ‚Í ‹É ‚ß ‚Ä ‚í ‚¸ ‚© ‚Å ‚ ‚è(1000h‚Å •”wt%),Šg ŽU ‹“ “® ‚µ‚ÄcaseIIŒ^ Šg ŽU ‹“ “® ‚ðŽ¦ ‚· ‚ª,2-ƒv ƒ•ƒp ƒm•[ ƒ‹ ‚Í3500 ‚Ì —Þ Œ^ ‰» ‚Í ‚Ù ‚Æ‚ñ ‚Ç•s ‰Â ” ‚Å ‚ ‚Á‚½.‚µ ‚© ‚µ,‚± ‚Ì30•Ž h‚ð ‰ß ‚¬ ‚½ • ‚© ‚ç ‰º ‚É “Ê ‚Ì ƒJ •[ ƒu ‚ð•` ‚¢ ‚Ä ‘å ‚« ‚-‘• ‘å ˆÈ •ã ‚Ì ‰· “x ”Í ˆÍ ‚É ‚¨ ‚¢ ‚Ä ‚Í ‹z Žû •d —Ê ‚Í •Z ’Ð Žž ŠÔ ‚É”ä —á ‚µ ‚µ,Œã •q ‚· ‚ésuper caseII“I ‚ÈŒX Œü19)‚ðŽ¦ ‚µ‚Ä ‚¢ ‚é.“¯ ‚Ä‘• ‘å ‚µ,caseIIŠg ŽU ‚ª ”- Œ» ‚µ‚Ä ‚¢ ‚é ‚Æ•l ‚¦ ‚ç‚ê ‚é.ŠÂ ‰·“x ‚Å ‚Ì ƒG ƒ^ ƒm•[ ƒ‹ ‚Æ”ä Šr ‚· ‚é ‚Æ,1-ƒv ƒ• ƒp ƒm•[ ƒ‹ ‚Ì ‹z ‹« ‰· “x ‚Ì •ã •¸ ‚Æ ‚Æ ‚à‚É ‹z Žû ‘¬ “x ‚Æ•½ •t ‹z Žû —Ê ‚Í ‚â ‚Í ‚è‘å Žû ‘¬ “x ‚Í ”ñ •í ‚É’á ‚¢(1/10–¢ –ž)‚É ‚à ‚© ‚© ‚í ‚ç‚¸,•½ ‚« ‚-‚È ‚Á ‚Ä ‚¢ ‚é ‚ª,“¯ ‚¶‰· “x ‚Å ‚Ì ƒ• ƒ^ ƒm •[ ƒ‹ ‚Æ”ä ‚× ‚é ‚Æ •t ‹z Žû —Ê ‚Í ‚Ù ‚Ú “¯ ‚¶–ñ28wt%‚Ì ’l ‚É ’B ‚µ‚Ä ‚¢ ‚é•B50•Ž ‹z Žû ‘¬ “x ‚Í–ñ1Œ… •¬ ‚³ ‚-,•½ •t ‹z Žû —Ê ‚É ‚Í ‚Ù ‚Æ‚ñ ‚Ç•· ‚ª ‚Å ‚Í —¼ ƒv ƒ• ƒp ƒm •[ ƒ‹ ‚Ì‹z Žû ‹“ “® ‚Í Ž— ’Ê ‚Á ‚½ ‚à ‚Ì ‚Æ ‚È ‚Á Œ© ‚ç‚ê ‚È ‚¢.‚± ‚Ì “_ ‚É‚Â ‚¢ ‚Ä ‚ÍŒã ‚Å•Ú ‚µ ‚-ŒŸ “¢ ‚· ‚é. ‚Ä,‚Æ ‚à ‚É‘å ‚« ‚È‹z Žû ‘¬ “x ‚ðŽ¦ ‚µ‚Ä ‚¢ ‚é.2-ƒv ƒ•ƒp ƒm •[ Fig.4‚Í1-ƒv ƒ• ƒp ƒm •[ ƒ‹ ‚Æ‚» ‚Ì ˆÙ •« ‘Ì ‚Å ‚ ‚é2ˆêƒv ƒ• ƒ‹ ‚Ì •û ‚ª ‚킸 ‚© ‚È‚ª ‚ç‹z Žû ‘¬ “x ‚Í•¬ ‚³‚¢ ‚ª,•½ •t ‹z Žû —Ê ƒp ƒm •[ ƒ‹ ‚Ì ‹z Žû ‹“ “® ‚Å ‚ ‚é.—¼ ŽÒ ‚Í20,30•Ž ‚Å ‚Í–{ ŽÀ ‚Í ”½ ‘Î ‚É ‘å ‚« ‚-‚È ‚è,‚» ‚Ì’l ‚Í40•Ž ‚Ì •ê •‡ ‚Æ ‚Ù ‚Æ ‚ñ ‚Ç Œ± ‚Ì ‚© ‚È ‚è’· Šú ‚É ‚í ‚½ ‚鑪 ’è(–ñ6500h)‚Å ‚àPMMA •Ï ‚í ‚ç ‚È‚¢ ‚©,‚Þ ‚µ‚ë •- ‚µ’á ‚¢ ˆÊ ‚Å ‚ ‚é.‚È ‚¨,‚± ‚±‚Å 95 •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No, 2 (2002)
Fig.6.Relationship between the logarithm of absorpdon Fig. 5. Weight gain of PMMA specimen in butanol with rate of alcohol at 40 and 50•Ž and the molar volume of al- different structures at 40 and 50•Ž. cohol.(•œ,•›)Linear alcohols,(•£)2-propanol at 40•Ž,(•¢) 2-propanol at 50•Ž and(• )2-methyl-1-propanol at 50•Ž. ‚Ísuper caseII“I ‹“ “® ‚Í Œ© ‚ç ‚ê ‚È ‚¢.‚± ‚Ì ‚æ ‚¤ ‚É ,‹¤ ’Ê ‚µ ‚ÄcaseIIŠg ŽU ‹“ “® ‚Í Ž¦ ‚µ ‚È ‚ª ‚ç ‚à,•ª Šò • ‘¢ ‚ð ‚à ‚Â ‚± ‚Æ ‚ð• –Ê ‚© ‚ç‚ÌˆÊ ’u ‚Ì ŠÖ •” ‚Æ ‚µ‚Ä Ž¦ ‚µ‚½.‚± ‚ê ‚æ ‚è•„ —n Ž¿ •ª Žq ‚Ì •û ‚ª •ü •ó ‚Ì ‚» ‚ê ‚É ”ä ‚× ‚Ä ’á ‘¬ “x ‚Å ‚Í ‚ ‚é ‚ª ‘å ˜_ ‚· ‚é ‚Æ,caseIIŠg ŽU ‚ª •i •s ‚· ‚é ‚É‚Â ‚ê ‚Ä ”ì ‘å ‚µ‚½ • –Ê —Ê ‚É •‚ •ª Žq ‚É ‹z Žû ‚³ ‚ê ‚é. –c •• ‘w ‚̈³ •k ‰ž —Í ‚Í ’á Œ¸ ‚µ,‚» ‚ê ‚É”º ‚Á ‚Ä• –Ê ‘w “à ‚Ì•½ ŽŸ ‚É,Fig.5‚É ƒu ƒ^ ƒm •[ ƒ‹ ‚Ì ‹z Žû ‹“ “® ‚𠎦 ‚·.•¡ ‰ñ ’² •t ‹z Žû —Ê ‚Í‘• ‘å ‚· ‚é.ˆê •û,“à •” ƒRƒA ‚Å ‚Ì –c ’£ ‰ž —Í ‚¨ ‚æ ‚× ‚½4Ží —Þ ‚Ì ƒu ƒ^ ƒm •[ ƒ‹ ‚Ì ‚¤ ‚¿,2ˆê ƒu ƒ^ ƒm •[ ƒ‹ ‚Æ2ˆê ƒ• ‚Ñ ‚» ‚Ì Œù ”z ‚Í “à •” ƒR ƒA ‚ª ”– ‚-‚È ‚é ‚É•] ‚¢ ‘å ‚« ‚-‚È ‚é ‚Ì ƒ` ƒ‹ •[2-ƒv ƒ• ƒp ƒm •[ ƒ‹ ’† ‚É ‚¨ ‚¢ ‚Ä ‚Í40•Ž ‚Å ŽŽ —¿ ‚Í —n ‰ð ‚µ ‚Å,‚» ‚±‚Å ‚Ì ‹« ŠE(caseIIƒt ƒ• ƒ“ ƒg)’¼ ‘O •” ‚Å ‚Í•ª Žq ŠÔ ‚½.‚æ ‚Á ‚Ä,‚± ‚± ‚Å ‚Í1ˆê ƒu ƒ^ ƒm •[ ƒ‹ ‚Æ2-ƒ• ƒ` ƒ‹-1-ƒv ƒ• Œ„ ‚ª‹} Œƒ ‚É‘å ‚« ‚-‚È ‚è,—n Ž¿ •ª Žq ‚Ì —¬ “ü ‘¬ “x ‚à‘• ‘å ‚· ‚é•B ƒp ƒm •[ ƒ‹ ‚Ì Œ‹ ‰Ê ‚𠎦 ‚· •B ‚± ‚ê ‚ç ‚É ‚¨ ‚¢ ‚Ä ‚àPMMA‚Ì —n ‚± ‚ê ‚ç‚Ì Œ‹ ‰Ê,‰t ‘Ì ‹z Žû ‚ª ‰Á ‘¬ ‚³ ‚ê ‚Ä•ã ‹L ‚Ìsuper case ‰ð ŒX Œü ‚Í ‚© ‚È ‚è ‹- ‚¢ ‚æ ‚¤ ‚Å,50•Ž ‚Ì —¼ ƒu ƒ^ ƒm •[ ƒ‹ ‚¨ ‚æ II‹“ “® ‚ª ”- Œ» ‚· ‚é ‚à‚Ì ‚Æ•l ‚¦ ‚ç‚ê ‚é.‚± ‚Ì•„ ˜_ ‚Í•¶ Œ£9) ‚Ñ40•Ž ‚Ì1-ƒu ƒ^ ƒm •[ ƒ‹ ‚É ‚¨ ‚¢ ‚Ä •Z ’Ð •‰ Šú ‚É ‚í ‚¸ ‚© ‚È ‚ª ‚É Šî ‚à ‚- ‚à‚Ì ‚Å ‚ ‚é ‚ª,’J •ã ‚ç22)‚̓| ƒŠ ƒr ƒj ƒ‹ ƒA ƒ‹ ƒR ‚ç •d —Ê Œ¸ •- ‚ª Œ© ‚ç ‚ê,40•Ž ‚Ì2-ƒ• ƒ` ƒ‹•[1-ƒv ƒ• ƒp ƒm •[ ƒ‹ •[ ƒ‹(PVA)ƒt ƒBƒ‹ ƒ€ ‚Ì ƒW ƒ•ƒ` ƒ‹ ƒX ƒ‹ ƒz ƒL ƒV ƒh/•…•¬ •‡ —n ’† ‚Å ‚Í1•B5wt%’ö “x ‚Ì •d —Ê Œ¸ •- ‚ª ‚ ‚é.50•Ž ‚Ì Œ‹ ‰Ê ‚É ‚ ”} ’† ‚É ‚¨ ‚¯ ‚é–c •• ‹“ “® ‚Ì ŠÏ Ž@ ‚© ‚ç,–c ’£ •Ï Œ` ‚æ ‚è‚à ‚³ ‚ç ‚¢ ‚Ä Œ© ‚é ‚± ‚Æ ‚É ‚· ‚é ‚Æ,‚Æ ‚à ‚É •Z ’× Žž ŠÔ ‚É ”ä —á ‚µ‚½ •d —Ê ‚É•i ‚ñ ‚Å “à•” ƒR ƒA‚Å ‚Ì ”j ‰ó ‚ªsuper caseIIŠg ŽU ‚ÉŠñ —^ ‚· ‘• ‰Á ‚ª Œ© ‚ç ‚ê,caseIIŠg ŽU ‚𠎦 ‚µ‚Ä ‚¢ ‚é ‚Æ •l ‚¦ ‚ç ‚ê ‚é ‚ª, ‚é ‚Æ ‚µ‚Ä ‚¢ ‚é.‚µ ‚© ‚µ,–{ ŽÀ Œ± ‚Å ‚Í ŽŽ —¿ “à•” ‚É ‚» ‚Ì ‚æ ‚¤ •ª Šò • ‘¢ ‚ð ‚à ‚Â2-ƒ• ƒ` ƒ‹ •[1-ƒv ƒ• ƒp ƒm •[ ƒ‹ ‚Ì •û ‚ª •ü •ó ‚Ì ‚È ‚«—ô ‚â ‚» ‚Ì‘O ‹ì ‘Ì ‚Å ‚ ‚é ƒN ƒŒƒC ƒY ‚È ‚Ç ‚ÍŠÏ Ž@ ‚³‚ê ‚È‚© 1-ƒu ƒ^ ƒm •[ ƒ‹ ‚É ”ä ‚× ‚Ä ‹z Žû ‘¬ “x ‚Í •¬ ‚³ ‚¢ ‚ª ‘å —Ê ‚É ‚Á‚½.‚È ‚¨,•ã •q ‚Ì ŠÂ ‹« ‰º ‚Å ‚Ì ‚Ýsuper caseIIŒ^ ‹“ “® ‚ªŠÏ PMMA‚É ‹z Žû ‚³ ‚ê ‚é.‚Ü ‚½,2-ƒ• ƒ` ƒ‹ •[1-ƒv ƒ• ƒp ƒm •[ ƒ‹ Ž@ ‚³‚ê ‚½‚Ì ‚Í,Œ» •Û˜_ “I ‚É ‚ÍŠg ŽU ‚Ì •i •s ‚ª ‹É ‚ß ‚ÄŠÉ ‚â ‚© ’† ‚Å ‚Í2500h‚ð ‰ß ‚¬ ‚½ • ‚© ‚çsuper caseIIŒ^ ‹“ “® ‚ª ŠÏ Ž@ ‚Å ‚ ‚é ‚½‚ß ‚É•ã ‹L ‚Ì “à •” ‰ž —Í •Ï ‰» ‚Æ‚» ‚ê ‚É—U ‹N ‚³‚ê ‚éŠg ‚³ ‚ê ‚é.‚± ‚ê ‚ç ‚ÍFig.4‚É Ž¦ ‚µ ‚½40•Ž ‚Ì ƒv ƒ• ƒp ƒm •[ ƒ‹ ŽU ‹“ “® ‚ª ‚æ ‚-‘¨ ‚¦ ‚ç‚ê ‚½ ‚Ì ‚¾ ‚Ɖ𠂳‚ê ‚é.‚µ ‚© ‚µ,‚È ‚º ‚Æ —Þ Ž— ‚Ì ŒX Œü ‚Å ‚ ‚é.40•Ž ‚Ì1-ƒu ƒ^ ƒm •[ ƒ‹ ‚àcaseIIŒ^ ‚±‚ê ‚ç‚Ì ŠÂ ‹« ‰º ‚Å ‚» ‚Ì ‚æ ‚¤ ‚ÈŒ» •Û ‚ª “Á ˆÙ “I ‚É•¶ ‚¶‚½ ‚Ì ‚© ‚Æ ‚¢ ‚¦ ‚é ‚© ‚à ’m ‚ê ‚È ‚¢ ‚ª,‹z Žû —Ê ‚ª ‚í ‚¸ ‚© ‚Å ŒX Œü ‚ª ‚Í ‚Á ‚Æ‚¢ ‚¤–{ Ž¿ “I ‚È“_ ‚Í•¡ ‚Ì ‚Æ ‚± ‚ë ‚Ü‚¾ •à –¾ ‚Å ‚«‚Ä ‚¢ ‚È ‚¢ . ‚« ‚è ‚µ ‚È ‚¢ ‚½ ‚ß –¾ Œ¾ ‚Í ‚Å ‚« ‚È ‚¢.‚È ‚¨,30•Ž ˆÈ ‰º ‚Å ‚Ì ˆÈ •ã ‚ÉŽ¦ ‚µ‚½ ƒ• ƒ^ ƒm•[ ƒ‹ •` ƒu ƒ^ ƒm•[ ƒ‹ ‚Ü ‚Å ‚ÌŽÀ Œ± Œ‹ ‰Ê —¼ ƒu ƒ^ ƒm •[ ƒ‹ ‚Ì ‹z Žû ‚Í1000h‚Ì Žž ŠÔ ”Í ˆÍ ‚Å ‚Í ‚Ù ‚Æ ‚ñ ‚Ç ‚ð ˆÈ ‰º ‚É •® —• ‚µ‚Ä ‚Ý ‚é.Fig.6‚ÍFig.1,3•`5‚É ‚¨ ‚¢ ‚Ä ŒŸ •o ‚Å ‚« ‚È ‚© ‚Á ‚½. caseIIŠg ŽU ‹“ “® ‚ª Œ© ‚ç ‚ê ‚é40,50•Ž ‚Å ‚Ì ‹z Žû ‹È •ü ‚ÌŒX ‚± ‚± ‚Å,40•Ž ‚Ì2-ƒv ƒ• ƒp ƒm •[ ƒ‹ ’† ‚Æ50•Ž ‚Ì2-ƒ• ƒ` ‚« ‚ð‹z Žû ‘¬ “xD(wt%/h)‚Æ ‚µ ‚Ä,‚» ‚Ì ‘Î •” ‚ð ƒA ƒ‹ ƒR ƒ‹ •[1ƒv ƒ• ƒp ƒm •[ ƒ‹ ’† ‚Å ŠÏ Ž@ ‚³ ‚ê ‚½super caseIIŒ^ ‹“ “® ‚É •[ ƒ‹ ‚Ì ƒ‚ ƒ‹ •ª Žq —eV‚É ‘Î ‚µ‚Ä •® —• ‚µ ‚½ ‚à‚Ì ‚Å ‚ ‚é .‚± ‚ ‚¢ ‚Ä •G ‚ê ‚é.Kawagoe‚ç13)‚ÍcaseIIŠg ŽU ‚Ì ‹ì “® —Í ‚Æ ‚± ‚Å,caseIIŒ^ ‹“ “® ‚© ‚ç•- ‚µˆí ’E ‚µ‚½50•Ž ‚Ì ƒ• ƒ^ ƒm •[ ‚È ‚é “à •” ‰ž —Í ‚ð • –Ê –c •• ‘w ‚Æ “à •” ƒR ƒA ‚Ì ŠÔ ‚Å •Ï Œ` •S ‘© ‚ª ƒ‹ ‚ÆŒX Œü ‚ª•K ‚¸ ‚µ ‚à–¾ —Ä ‚Å ‚È ‚© ‚Á ‚½40•Ž ‚Ì1-ƒu ƒ^ƒm •[ ‚ ‚é ŒÅ ‘Ì —Í Šw ‚Ì •s •Ã ’è –â ‘è ‚Ì ŠÏ “_ ‚© ‚ç —L ŒÀ —v ‘f ‰ð •Í ‚µ, ƒ‹ ‚ÌŒ‹ ‰Ê ‚àŠÜ ‚ß ‚Ä ‚ ‚é.‚Ü ‚½,2-ƒv ƒ•ƒp ƒm •[ ƒ‹ ‚Ísuper • –Ê –c •• ‘w ‚É ‚Í2Ž² ˆ³ •k ‰ž —Í ‚Æ ˆø ’£ ‰ž —Í ‚ª,“à •” ƒR ƒA ‚É caseII‹“ “® ‚𠎦 ‚· ‘O ‚Ì3500h‚Ü ‚Å ‚Ì Œ‹ ‰Ê ‚© ‚çD‚ð ‹• ‚ß ‚Í ‚» ‚ê ‚Æ ’Þ ‚蕇 ‚¤3Ž² ˆø ’£ ‰ž —Í(–c ’£ ‰ž —Í)‚ª ”- •¶ ‚· ‚é ‚½.•ü •ó ƒA ƒ‹ ƒR•[ ƒ‹ ‚Í—¼ ‰· “x ‚É ‚¨ ‚¢ ‚Ä•‰ ‚ÌŒX ‚« ‚ð ‚à‚”ä 96 •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No. 2 (2002)
Fig. 7. The expected lower-limiting temperature for the ap- pearance of case II behavior in the absorption process against the molar volume of alcohol. Fig. 8 Plot of the equilibrium absorption of alcohol at 40 and 50•Ž against the molar volume of alcohol.(•œ,•›)Lin- ear alcohols,(•£)2-propanol at 40•Ž,(•¢)2-propanol at 50•Žand(• )2-methyl-1-propanol at 50•Ž. (2) ‚Æ ‹ß Ž— ‚· ‚é ‚± ‚Æ ‚É ‚æ ‚è, (3) ‚𓾠‚Ä ‚¢ ‚é.‚± ‚± ‚Å,ƒÁ ‚Í Šˆ —Ê ŒW •”,ƒÓ,‚Í •½ •t •ó ‘Ô ‚É ‚¨ ‚¯ ‚é —n Ž¿ •ª Žq ‚Ì ‘Ì •Ï •ª —¦,R,T‚Í ‚¨ ‚Ì ‚¨ ‚Ì ‹C ‘Ì ’è •”, •â ‘Î ‰· “x ‚Å ‚ ‚é.P‚Í —n Ž¿ •ª Žq ‚ª Žó ‚¯ ‚é •Z “§ ˆ³ ‚Ɖð Žß ‚³‚ê ‚é ‚ª,‚» ‚ê ‚Í “¯ Žž ‚É• –Ê –c •• ‘w ‚É‘Î ‚µ‚Ä ‚» ‚ê ‚ðŠg ’£ ‚µ ‚æ ‚¤ ‚Æ‚· ‚é–c •• ˆ³ ‚Æ ‚µ‚Ä •ì —p ‚· ‚é.Thomas‚ÆWindle, ‚¨ ‚æ‚ÑKramer‚ç ‚É ‚æ‚ê ‚Î,‚± ‚ÌP‚ð Žó ‚¯ ‚é• –Ê –c •• ‘w ‚Ì Šg ’£ ‘¬ “x ‚Í —n Ž¿ •ª Žq ‚Ì ‘Ì •Ï •ª —¦ ‚Ì ‘¬ “x4ƒÓ/4t‚É ‚æ ‚è —^ ‚¦ ‚ç‚ê,‚» ‚ê ‚Í –c •• ‘w ‚Ì ‘Ì •Ï ”S •« —¦ ‚ð ƒÅ ‚Æ‚· ‚é ‚Æ, (4) •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No. 2 (2002) 97
Fig. 9. Comparison between the experiment and the calcu- lation based on the modified Kramer theory for the results in methanol at (a) 20, (b) 30, and (c) 40•Ž. 98 •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No. 2 (2002)
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Case II Diffusion Behavior in Alcohol Absorption by Poly (methyl methacrylate) Makoto KAWAGOE,*1 Mivuki KAWAGOE,*2 Makoto NAKANISHI,*3 Jianhui QIU*4 and *1Department of Mechanical Systems Engineering, Faculty of Engineering, Toyama Prefectural University (Kurokawa, Kosugi, Toyama 939-0398, Japan) *2Education and Research Center for Engineering Materials, Toyama National College of Technology (Hongo, Toyama 939-8630, Japan) *3Toshiba Engineering Corporation (Horikawa, Saiwai-ku, Kawasaki 212-8551, Japan) *4Department of Machine Intelligence and Systems Engineering, Faculty of Science and Technology, Akita Prefectural University (Honjyo, Akita 015-0055. Javan) The structure and properties of alcohol and the ambient temperature causing the case II diffusion were investigated by studying the be- havior of alcohol absorption by poly (methyl methacrylate) (PMMA). The case II type of diffusion was newly confirmed to take place for the cases of 1-propanol, 1-butanol, and 2-methyl-1-butanol; methanol, ethanol, and 2-puropanol have already been known to show the case II behavior for PMMA. The lower temperature for the appearance of case II diffusion was raised with increasing the molar volume of alco- hol. The absorption rate was decreased with an increase in the molar volume, as with the Fickian diffusion observed for other polymer- reagent systems. Linear propanol and linear butanol showed greater absorption rate and less equilibrium solubility than the branched mole- cules. The equilibrium solubility of linear alcohol was constant or somewhat decreased with increasing the molar volume. Kramer's theory on the case II diffusion, which was modified by introducing the volume strain rate, was shown to provide good expressions for the absorp- tion behavior of methanol by PMMA, but one should compare with the behavior of other alcohols for proving the adequacy. KEY WORDS Case II Diffusion / Poly(methyl methacrylate) / Alcohol / Molecular Structure / (Received September 14, 2001: Accepted November 21, 2001)[Kobunshi Ronbunshu, 59(2), 93-100 (2002)] •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No. 2 (2002) 100

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Japanese Article

  • 2. Table 1. Basic properties of alcohols at 20•Ž used as the envi- ronmental reagents Fig. 1. Variation in the weight gain of a PMMA sheet, 1 mm thick, in methanol at 20-50•Ž. –â ‚à’Z ‚-‚È ‚é ‚± ‚Æ‚ª ‚í ‚© ‚é.20•`40•Ž ‚Ì ‰· “x ”Í ˆÍ ‚É ‚¨ ‚¢ ‚Ä ‹z Žû •d —Ê ‚ÍŽž ŠÔ ‚É”ä —á ‚µ‚Ä‘• ‘å ‚· ‚é ‚± ‚Æ‚ª –¾ —Ä ‚Å ‚ ‚è,caseIIŠg ŽU ‚Æ”» •Ê ‚³‚ê ‚é19).50•Ž ‚É ‚È ‚é ‚ÆŽž ŠÔ ‚É‘Î ‚· ‚é ”ä —á ŠÖ ŒW ‚Í •ö ‚ê,Fick“I ‚ÆŽv ‚í ‚ê ‚é —l ‘Š ‚ª Œ» ‚ê ‚Ä ‚¢ ‚é.‚± ‚Ì ‚± ‚Æ ‚Í50•Ž ‚ÅPMMA•ª Žq •½ ‚Ì ”M ‰^ “® ‚ª •L •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No. 2 (2002) 94
  • 3. Fig. 2. Relation of the weight gain of PMMA specimen to the thickness of surface swollen layer in methanol at 20•Ž. Fig. 3. Variation in the weight gain of PMMA specimen in ethanol at 30-50•Ž. ”Í ˆÍ ‚É ‚í ‚½ ‚Á‚Ä ‚© ‚È ‚芈 ”- ‚É ‚È ‚Á ‚Ä ‚¢ ‚Ä,”z ’uŠ· ‚¦‚ª ’Z Žž ŠÔ ‚Å ‹N ‚«‚é ‚± ‚Æ ‚𠎦 •´ ‚µ‚Ä ‚¢ ‚é.Vrentas20)‚ª ƒf ƒ{ ƒ‰ •” ‚ÆŒÄ ‚ñ ‚¾ Šg ŽU ‚Ì“Á •« Žž ŠÔ ƒÑd‚É ‚· ‚é •‚ •ª Žq ‚Ì ŠÉ ˜a Žž ‘Î ŠÔ ƒÑr‚Ì äDeb=ƒÑr/ƒÑd‚Å Œ¾ ‚¤‚È ‚ç ‚Î,20•`40•Ž ” ‚Å ‚Í ‚» ‚ê ‚ª1’ö “x ‚Å ‚ ‚è,50•Ž ‚Å ‚Í1‚æ ‚è•¬ ‚³ ‚-‚È ‚é ‚± ‚Æ ‚ðˆÓ –¡ ‚µ‚Ä ‚¢ ‚é.20•`40•Ž ‚Ì •ê •‡ ‚Ì Še ŽŽ —¿ • –Ê ‚É ‚Í –c •• ‘w ‚ª –¾ —Ä ‚É ŠÏ Ž@ ‚³‚ê ‚½ •BFig.2‚ÉFig.1(a)‚Å Ž¦ ‚µ‚½20•Ž ‚É ‚¨ ‚¯ ‚é•d —Ê ‘• ‰Á ‚Æ• –Ê –c •• ‘w Œú ‚³ ‚- •û Œü)‚Ì •• ŠÖŒW ‚𠎦‚·.•Å •¬2•æ ‹ß Ž— ‚É ‚æ ‚è–¾ Šm ‚È ”ä —á ŠÖ ŒW ‚ª “¾ ‚ç‚ê ‚é‚ª, ‹» –¡ •[ ‚¢ ‚Ì ‚ÍcaseIIŠg ŽU ‚ª Žn ‚Ü ‚é ‚Ü ‚Å ‚É(–c •• ‘w Œú ‚³ ‚ª0‚Ì •ó ‘Ô ‚Å)–ñ2wt%‚Ì ƒ• ƒ^ ƒm •[ ƒ‹‚ª ‚ ‚ç‚© ‚¶‚ß‹z Žû ‚³‚ê ‚Ä ‚¢ ‚é ‚± ‚Æ‚Å ‚ ‚é.‚± ‚Ì ‚± ‚Æ‚Í•] —ˆ ‚© ‚猾 ‚í ‚ê ‚Ä ‚¢ ‚é ‚æ ‚¤‚É,caseIIŠg ŽU ‚Ì ”- Œ» ‚É ‚Í ‚ ‚é—U “± Žž ŠÔ(induction dme)‚ª •K —v ‚Å ‚ ‚è9},‚» ‚ê ‚Í ‹° ‚ç ‚-ƒ• ƒ^ ƒm •[ ƒ‹ •ª Žq ‚ª Fig. 4. Weight gain of PMMA specimen in propanol with different structures at 40 and sot. PMMA•ª Žq •½ ŠÔ ‚Ì Ž© —R ‘Ì •Ï ‚ð–„ ‚ß ‚é ‚Ì ‚É —v ‚· ‚é Žž ŠÔ ‚Æ ‰ð Žß ‚³ ‚ê ‚é10),21).‚½ ‚µ,–{ ŽÀ Œ± ‚Å “¾ ‚½Fig.1‚Ì ‚¾ ‹z Žû •d —Ê •Ï ‰» ‚É‚Í •‰ Šú ‰ß ’ö ‚Ì ƒf •[ ƒ^•s ‘« ‚à‚ ‚Á ‚Ä —U “± Žž ŠÔ ‚Í –¾ Šm ‚ÉŒ» ‚ê ‚Ä ‚Í‚¢ ‚È ‚¢.‚È ‚¨,Thomas‚ÆWindle‚Ì ŠÏ ‘ª Œ‹ ‚É ‚Ù ‚Æ ‚ñ ‚Ç‹z Žû ‚³‚ê ‚È ‚© ‚Á ‚½ ‚Ì ‚Å,‚± ‚± ‚Å ‚Í40,50•Ž ‰Ê9}‚É ”ä ‚× ‚é ‚Æ,–{ ŽÀ Œ± ‚Å ‚ÍcaseIIŠg ŽU ‚Ì”- Œ» •ã ŒÀ ‰· “x ‚ÌŒ‹ ‰Ê ‚Ì ‚Ý ‚ðŽ¦ ‚·.40•Ž ‚Ì ŠÂ ‹« ‰· “x ‚Å ‚Í1-ƒv ƒ• ƒp ƒm •[ ‚ª ‚â ‚â •‚ ‰· ‘¤ ‚É‚¸ ‚ê ‚Ä ‚¢ ‚é ‚æ ‚¤‚Å ‚ ‚é. ƒ‹ ‚Ì •û ‚ª2-ƒv ƒ•ƒp ƒm •[ ƒ‹ ‚æ ‚è‹z Žû ‘¬ “x ‚Í‘å ‚« ‚¢ ‚ª,•½ Fig•B3‚É ƒG ƒ^ ƒm •[ ƒ‹ ‚Ì30•`50•Ž ‚É ‚¨ ‚¯ ‚é ‹z Žû ‹“ “® ‚ð •t ‹z Žû —Ê ‚Í”½ ‘Î ‚É Œã ŽÒ ‚Ì •û ‚ª ‘å ‚« ‚-,–ñ1.7”{ ‚Ì’l ‚ðŽ¦ Ž¦ ‚·.— ”õ ŽÀ Œ± ‚É ‚æ‚ê ‚Î,20•Ž ‚Å ‚Í ƒG ƒ^ ƒm •[ ƒ‹ ‚Ì ‹z Žû ‚µ‚Ä ‚¢ ‚é.—¼ ŽÒ ‚Æ ‚à‚É‹z Žû •d —Ê ‚Ì‘• ‘å ‚Í •Z ’Ð Žž ŠÔ ‚É”ä —á —Ê ‚Í ‹É ‚ß ‚Ä ‚í ‚¸ ‚© ‚Å ‚ ‚è(1000h‚Å •”wt%),Šg ŽU ‹“ “® ‚µ‚ÄcaseIIŒ^ Šg ŽU ‹“ “® ‚ðŽ¦ ‚· ‚ª,2-ƒv ƒ•ƒp ƒm•[ ƒ‹ ‚Í3500 ‚Ì —Þ Œ^ ‰» ‚Í ‚Ù ‚Æ‚ñ ‚Ç•s ‰Â ” ‚Å ‚ ‚Á‚½.‚µ ‚© ‚µ,‚± ‚Ì30•Ž h‚ð ‰ß ‚¬ ‚½ • ‚© ‚ç ‰º ‚É “Ê ‚Ì ƒJ •[ ƒu ‚ð•` ‚¢ ‚Ä ‘å ‚« ‚-‘• ‘å ˆÈ •ã ‚Ì ‰· “x ”Í ˆÍ ‚É ‚¨ ‚¢ ‚Ä ‚Í ‹z Žû •d —Ê ‚Í •Z ’Ð Žž ŠÔ ‚É”ä —á ‚µ ‚µ,Œã •q ‚· ‚ésuper caseII“I ‚ÈŒX Œü19)‚ðŽ¦ ‚µ‚Ä ‚¢ ‚é.“¯ ‚Ä‘• ‘å ‚µ,caseIIŠg ŽU ‚ª ”- Œ» ‚µ‚Ä ‚¢ ‚é ‚Æ•l ‚¦ ‚ç‚ê ‚é.ŠÂ ‰·“x ‚Å ‚Ì ƒG ƒ^ ƒm•[ ƒ‹ ‚Æ”ä Šr ‚· ‚é ‚Æ,1-ƒv ƒ• ƒp ƒm•[ ƒ‹ ‚Ì ‹z ‹« ‰· “x ‚Ì •ã •¸ ‚Æ ‚Æ ‚à‚É ‹z Žû ‘¬ “x ‚Æ•½ •t ‹z Žû —Ê ‚Í ‚â ‚Í ‚è‘å Žû ‘¬ “x ‚Í ”ñ •í ‚É’á ‚¢(1/10–¢ –ž)‚É ‚à ‚© ‚© ‚í ‚ç‚¸,•½ ‚« ‚-‚È ‚Á ‚Ä ‚¢ ‚é ‚ª,“¯ ‚¶‰· “x ‚Å ‚Ì ƒ• ƒ^ ƒm •[ ƒ‹ ‚Æ”ä ‚× ‚é ‚Æ •t ‹z Žû —Ê ‚Í ‚Ù ‚Ú “¯ ‚¶–ñ28wt%‚Ì ’l ‚É ’B ‚µ‚Ä ‚¢ ‚é•B50•Ž ‹z Žû ‘¬ “x ‚Í–ñ1Œ… •¬ ‚³ ‚-,•½ •t ‹z Žû —Ê ‚É ‚Í ‚Ù ‚Æ‚ñ ‚Ç•· ‚ª ‚Å ‚Í —¼ ƒv ƒ• ƒp ƒm •[ ƒ‹ ‚Ì‹z Žû ‹“ “® ‚Í Ž— ’Ê ‚Á ‚½ ‚à ‚Ì ‚Æ ‚È ‚Á Œ© ‚ç‚ê ‚È ‚¢.‚± ‚Ì “_ ‚É‚Â ‚¢ ‚Ä ‚ÍŒã ‚Å•Ú ‚µ ‚-ŒŸ “¢ ‚· ‚é. ‚Ä,‚Æ ‚à ‚É‘å ‚« ‚È‹z Žû ‘¬ “x ‚ðŽ¦ ‚µ‚Ä ‚¢ ‚é.2-ƒv ƒ•ƒp ƒm •[ Fig.4‚Í1-ƒv ƒ• ƒp ƒm •[ ƒ‹ ‚Æ‚» ‚Ì ˆÙ •« ‘Ì ‚Å ‚ ‚é2ˆêƒv ƒ• ƒ‹ ‚Ì •û ‚ª ‚킸 ‚© ‚È‚ª ‚ç‹z Žû ‘¬ “x ‚Í•¬ ‚³‚¢ ‚ª,•½ •t ‹z Žû —Ê ƒp ƒm •[ ƒ‹ ‚Ì ‹z Žû ‹“ “® ‚Å ‚ ‚é.—¼ ŽÒ ‚Í20,30•Ž ‚Å ‚Í–{ ŽÀ ‚Í ”½ ‘Î ‚É ‘å ‚« ‚-‚È ‚è,‚» ‚Ì’l ‚Í40•Ž ‚Ì •ê •‡ ‚Æ ‚Ù ‚Æ ‚ñ ‚Ç Œ± ‚Ì ‚© ‚È ‚è’· Šú ‚É ‚í ‚½ ‚鑪 ’è(–ñ6500h)‚Å ‚àPMMA •Ï ‚í ‚ç ‚È‚¢ ‚©,‚Þ ‚µ‚ë •- ‚µ’á ‚¢ ˆÊ ‚Å ‚ ‚é.‚È ‚¨,‚± ‚±‚Å 95 •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No, 2 (2002)
  • 4. Fig.6.Relationship between the logarithm of absorpdon Fig. 5. Weight gain of PMMA specimen in butanol with rate of alcohol at 40 and 50•Ž and the molar volume of al- different structures at 40 and 50•Ž. cohol.(•œ,•›)Linear alcohols,(•£)2-propanol at 40•Ž,(•¢) 2-propanol at 50•Ž and(• )2-methyl-1-propanol at 50•Ž. ‚Ísuper caseII“I ‹“ “® ‚Í Œ© ‚ç ‚ê ‚È ‚¢.‚± ‚Ì ‚æ ‚¤ ‚É ,‹¤ ’Ê ‚µ ‚ÄcaseIIŠg ŽU ‹“ “® ‚Í Ž¦ ‚µ ‚È ‚ª ‚ç ‚à,•ª Šò • ‘¢ ‚ð ‚à ‚Â ‚± ‚Æ ‚ð• –Ê ‚© ‚ç‚ÌˆÊ ’u ‚Ì ŠÖ •” ‚Æ ‚µ‚Ä Ž¦ ‚µ‚½.‚± ‚ê ‚æ ‚è•„ —n Ž¿ •ª Žq ‚Ì •û ‚ª •ü •ó ‚Ì ‚» ‚ê ‚É ”ä ‚× ‚Ä ’á ‘¬ “x ‚Å ‚Í ‚ ‚é ‚ª ‘å ˜_ ‚· ‚é ‚Æ,caseIIŠg ŽU ‚ª •i •s ‚· ‚é ‚É‚Â ‚ê ‚Ä ”ì ‘å ‚µ‚½ • –Ê —Ê ‚É •‚ •ª Žq ‚É ‹z Žû ‚³ ‚ê ‚é. –c •• ‘w ‚̈³ •k ‰ž —Í ‚Í ’á Œ¸ ‚µ,‚» ‚ê ‚É”º ‚Á ‚Ä• –Ê ‘w “à ‚Ì•½ ŽŸ ‚É,Fig.5‚É ƒu ƒ^ ƒm •[ ƒ‹ ‚Ì ‹z Žû ‹“ “® ‚𠎦 ‚·.•¡ ‰ñ ’² •t ‹z Žû —Ê ‚Í‘• ‘å ‚· ‚é.ˆê •û,“à •” ƒRƒA ‚Å ‚Ì –c ’£ ‰ž —Í ‚¨ ‚æ ‚× ‚½4Ží —Þ ‚Ì ƒu ƒ^ ƒm •[ ƒ‹ ‚Ì ‚¤ ‚¿,2ˆê ƒu ƒ^ ƒm •[ ƒ‹ ‚Æ2ˆê ƒ• ‚Ñ ‚» ‚Ì Œù ”z ‚Í “à •” ƒR ƒA ‚ª ”– ‚-‚È ‚é ‚É•] ‚¢ ‘å ‚« ‚-‚È ‚é ‚Ì ƒ` ƒ‹ •[2-ƒv ƒ• ƒp ƒm •[ ƒ‹ ’† ‚É ‚¨ ‚¢ ‚Ä ‚Í40•Ž ‚Å ŽŽ —¿ ‚Í —n ‰ð ‚µ ‚Å,‚» ‚±‚Å ‚Ì ‹« ŠE(caseIIƒt ƒ• ƒ“ ƒg)’¼ ‘O •” ‚Å ‚Í•ª Žq ŠÔ ‚½.‚æ ‚Á ‚Ä,‚± ‚± ‚Å ‚Í1ˆê ƒu ƒ^ ƒm •[ ƒ‹ ‚Æ2-ƒ• ƒ` ƒ‹-1-ƒv ƒ• Œ„ ‚ª‹} Œƒ ‚É‘å ‚« ‚-‚È ‚è,—n Ž¿ •ª Žq ‚Ì —¬ “ü ‘¬ “x ‚à‘• ‘å ‚· ‚é•B ƒp ƒm •[ ƒ‹ ‚Ì Œ‹ ‰Ê ‚𠎦 ‚· •B ‚± ‚ê ‚ç ‚É ‚¨ ‚¢ ‚Ä ‚àPMMA‚Ì —n ‚± ‚ê ‚ç‚Ì Œ‹ ‰Ê,‰t ‘Ì ‹z Žû ‚ª ‰Á ‘¬ ‚³ ‚ê ‚Ä•ã ‹L ‚Ìsuper case ‰ð ŒX Œü ‚Í ‚© ‚È ‚è ‹- ‚¢ ‚æ ‚¤ ‚Å,50•Ž ‚Ì —¼ ƒu ƒ^ ƒm •[ ƒ‹ ‚¨ ‚æ II‹“ “® ‚ª ”- Œ» ‚· ‚é ‚à‚Ì ‚Æ•l ‚¦ ‚ç‚ê ‚é.‚± ‚Ì•„ ˜_ ‚Í•¶ Œ£9) ‚Ñ40•Ž ‚Ì1-ƒu ƒ^ ƒm •[ ƒ‹ ‚É ‚¨ ‚¢ ‚Ä •Z ’Ð •‰ Šú ‚É ‚í ‚¸ ‚© ‚È ‚ª ‚É Šî ‚à ‚- ‚à‚Ì ‚Å ‚ ‚é ‚ª,’J •ã ‚ç22)‚̓| ƒŠ ƒr ƒj ƒ‹ ƒA ƒ‹ ƒR ‚ç •d —Ê Œ¸ •- ‚ª Œ© ‚ç ‚ê,40•Ž ‚Ì2-ƒ• ƒ` ƒ‹•[1-ƒv ƒ• ƒp ƒm •[ ƒ‹ •[ ƒ‹(PVA)ƒt ƒBƒ‹ ƒ€ ‚Ì ƒW ƒ•ƒ` ƒ‹ ƒX ƒ‹ ƒz ƒL ƒV ƒh/•…•¬ •‡ —n ’† ‚Å ‚Í1•B5wt%’ö “x ‚Ì •d —Ê Œ¸ •- ‚ª ‚ ‚é.50•Ž ‚Ì Œ‹ ‰Ê ‚É ‚ ”} ’† ‚É ‚¨ ‚¯ ‚é–c •• ‹“ “® ‚Ì ŠÏ Ž@ ‚© ‚ç,–c ’£ •Ï Œ` ‚æ ‚è‚à ‚³ ‚ç ‚¢ ‚Ä Œ© ‚é ‚± ‚Æ ‚É ‚· ‚é ‚Æ,‚Æ ‚à ‚É •Z ’× Žž ŠÔ ‚É ”ä —á ‚µ‚½ •d —Ê ‚É•i ‚ñ ‚Å “à•” ƒR ƒA‚Å ‚Ì ”j ‰ó ‚ªsuper caseIIŠg ŽU ‚ÉŠñ —^ ‚· ‘• ‰Á ‚ª Œ© ‚ç ‚ê,caseIIŠg ŽU ‚𠎦 ‚µ‚Ä ‚¢ ‚é ‚Æ •l ‚¦ ‚ç ‚ê ‚é ‚ª, ‚é ‚Æ ‚µ‚Ä ‚¢ ‚é.‚µ ‚© ‚µ,–{ ŽÀ Œ± ‚Å ‚Í ŽŽ —¿ “à•” ‚É ‚» ‚Ì ‚æ ‚¤ •ª Šò • ‘¢ ‚ð ‚à ‚Â2-ƒ• ƒ` ƒ‹ •[1-ƒv ƒ• ƒp ƒm •[ ƒ‹ ‚Ì •û ‚ª •ü •ó ‚Ì ‚È ‚«—ô ‚â ‚» ‚Ì‘O ‹ì ‘Ì ‚Å ‚ ‚é ƒN ƒŒƒC ƒY ‚È ‚Ç ‚ÍŠÏ Ž@ ‚³‚ê ‚È‚© 1-ƒu ƒ^ ƒm •[ ƒ‹ ‚É ”ä ‚× ‚Ä ‹z Žû ‘¬ “x ‚Í •¬ ‚³ ‚¢ ‚ª ‘å —Ê ‚É ‚Á‚½.‚È ‚¨,•ã •q ‚Ì ŠÂ ‹« ‰º ‚Å ‚Ì ‚Ýsuper caseIIŒ^ ‹“ “® ‚ªŠÏ PMMA‚É ‹z Žû ‚³ ‚ê ‚é.‚Ü ‚½,2-ƒ• ƒ` ƒ‹ •[1-ƒv ƒ• ƒp ƒm •[ ƒ‹ Ž@ ‚³‚ê ‚½‚Ì ‚Í,Œ» •Û˜_ “I ‚É ‚ÍŠg ŽU ‚Ì •i •s ‚ª ‹É ‚ß ‚ÄŠÉ ‚â ‚© ’† ‚Å ‚Í2500h‚ð ‰ß ‚¬ ‚½ • ‚© ‚çsuper caseIIŒ^ ‹“ “® ‚ª ŠÏ Ž@ ‚Å ‚ ‚é ‚½‚ß ‚É•ã ‹L ‚Ì “à •” ‰ž —Í •Ï ‰» ‚Æ‚» ‚ê ‚É—U ‹N ‚³‚ê ‚éŠg ‚³ ‚ê ‚é.‚± ‚ê ‚ç ‚ÍFig.4‚É Ž¦ ‚µ ‚½40•Ž ‚Ì ƒv ƒ• ƒp ƒm •[ ƒ‹ ŽU ‹“ “® ‚ª ‚æ ‚-‘¨ ‚¦ ‚ç‚ê ‚½ ‚Ì ‚¾ ‚Ɖ𠂳‚ê ‚é.‚µ ‚© ‚µ,‚È ‚º ‚Æ —Þ Ž— ‚Ì ŒX Œü ‚Å ‚ ‚é.40•Ž ‚Ì1-ƒu ƒ^ ƒm •[ ƒ‹ ‚àcaseIIŒ^ ‚±‚ê ‚ç‚Ì ŠÂ ‹« ‰º ‚Å ‚» ‚Ì ‚æ ‚¤ ‚ÈŒ» •Û ‚ª “Á ˆÙ “I ‚É•¶ ‚¶‚½ ‚Ì ‚© ‚Æ ‚¢ ‚¦ ‚é ‚© ‚à ’m ‚ê ‚È ‚¢ ‚ª,‹z Žû —Ê ‚ª ‚í ‚¸ ‚© ‚Å ŒX Œü ‚ª ‚Í ‚Á ‚Æ‚¢ ‚¤–{ Ž¿ “I ‚È“_ ‚Í•¡ ‚Ì ‚Æ ‚± ‚ë ‚Ü‚¾ •à –¾ ‚Å ‚«‚Ä ‚¢ ‚È ‚¢ . ‚« ‚è ‚µ ‚È ‚¢ ‚½ ‚ß –¾ Œ¾ ‚Í ‚Å ‚« ‚È ‚¢.‚È ‚¨,30•Ž ˆÈ ‰º ‚Å ‚Ì ˆÈ •ã ‚ÉŽ¦ ‚µ‚½ ƒ• ƒ^ ƒm•[ ƒ‹ •` ƒu ƒ^ ƒm•[ ƒ‹ ‚Ü ‚Å ‚ÌŽÀ Œ± Œ‹ ‰Ê —¼ ƒu ƒ^ ƒm •[ ƒ‹ ‚Ì ‹z Žû ‚Í1000h‚Ì Žž ŠÔ ”Í ˆÍ ‚Å ‚Í ‚Ù ‚Æ ‚ñ ‚Ç ‚ð ˆÈ ‰º ‚É •® —• ‚µ‚Ä ‚Ý ‚é.Fig.6‚ÍFig.1,3•`5‚É ‚¨ ‚¢ ‚Ä ŒŸ •o ‚Å ‚« ‚È ‚© ‚Á ‚½. caseIIŠg ŽU ‹“ “® ‚ª Œ© ‚ç ‚ê ‚é40,50•Ž ‚Å ‚Ì ‹z Žû ‹È •ü ‚ÌŒX ‚± ‚± ‚Å,40•Ž ‚Ì2-ƒv ƒ• ƒp ƒm •[ ƒ‹ ’† ‚Æ50•Ž ‚Ì2-ƒ• ƒ` ‚« ‚ð‹z Žû ‘¬ “xD(wt%/h)‚Æ ‚µ ‚Ä,‚» ‚Ì ‘Î •” ‚ð ƒA ƒ‹ ƒR ƒ‹ •[1ƒv ƒ• ƒp ƒm •[ ƒ‹ ’† ‚Å ŠÏ Ž@ ‚³ ‚ê ‚½super caseIIŒ^ ‹“ “® ‚É •[ ƒ‹ ‚Ì ƒ‚ ƒ‹ •ª Žq —eV‚É ‘Î ‚µ‚Ä •® —• ‚µ ‚½ ‚à‚Ì ‚Å ‚ ‚é .‚± ‚ ‚¢ ‚Ä •G ‚ê ‚é.Kawagoe‚ç13)‚ÍcaseIIŠg ŽU ‚Ì ‹ì “® —Í ‚Æ ‚± ‚Å,caseIIŒ^ ‹“ “® ‚© ‚ç•- ‚µˆí ’E ‚µ‚½50•Ž ‚Ì ƒ• ƒ^ ƒm •[ ‚È ‚é “à •” ‰ž —Í ‚ð • –Ê –c •• ‘w ‚Æ “à •” ƒR ƒA ‚Ì ŠÔ ‚Å •Ï Œ` •S ‘© ‚ª ƒ‹ ‚ÆŒX Œü ‚ª•K ‚¸ ‚µ ‚à–¾ —Ä ‚Å ‚È ‚© ‚Á ‚½40•Ž ‚Ì1-ƒu ƒ^ƒm •[ ‚ ‚é ŒÅ ‘Ì —Í Šw ‚Ì •s •Ã ’è –â ‘è ‚Ì ŠÏ “_ ‚© ‚ç —L ŒÀ —v ‘f ‰ð •Í ‚µ, ƒ‹ ‚ÌŒ‹ ‰Ê ‚àŠÜ ‚ß ‚Ä ‚ ‚é.‚Ü ‚½,2-ƒv ƒ•ƒp ƒm •[ ƒ‹ ‚Ísuper • –Ê –c •• ‘w ‚É ‚Í2Ž² ˆ³ •k ‰ž —Í ‚Æ ˆø ’£ ‰ž —Í ‚ª,“à •” ƒR ƒA ‚É caseII‹“ “® ‚𠎦 ‚· ‘O ‚Ì3500h‚Ü ‚Å ‚Ì Œ‹ ‰Ê ‚© ‚çD‚ð ‹• ‚ß ‚Í ‚» ‚ê ‚Æ ’Þ ‚蕇 ‚¤3Ž² ˆø ’£ ‰ž —Í(–c ’£ ‰ž —Í)‚ª ”- •¶ ‚· ‚é ‚½.•ü •ó ƒA ƒ‹ ƒR•[ ƒ‹ ‚Í—¼ ‰· “x ‚É ‚¨ ‚¢ ‚Ä•‰ ‚ÌŒX ‚« ‚ð ‚à‚”ä 96 •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No. 2 (2002)
  • 5. Fig. 7. The expected lower-limiting temperature for the ap- pearance of case II behavior in the absorption process against the molar volume of alcohol. Fig. 8 Plot of the equilibrium absorption of alcohol at 40 and 50•Ž against the molar volume of alcohol.(•œ,•›)Lin- ear alcohols,(•£)2-propanol at 40•Ž,(•¢)2-propanol at 50•Žand(• )2-methyl-1-propanol at 50•Ž. (2) ‚Æ ‹ß Ž— ‚· ‚é ‚± ‚Æ ‚É ‚æ ‚è, (3) ‚𓾠‚Ä ‚¢ ‚é.‚± ‚± ‚Å,ƒÁ ‚Í Šˆ —Ê ŒW •”,ƒÓ,‚Í •½ •t •ó ‘Ô ‚É ‚¨ ‚¯ ‚é —n Ž¿ •ª Žq ‚Ì ‘Ì •Ï •ª —¦,R,T‚Í ‚¨ ‚Ì ‚¨ ‚Ì ‹C ‘Ì ’è •”, •â ‘Î ‰· “x ‚Å ‚ ‚é.P‚Í —n Ž¿ •ª Žq ‚ª Žó ‚¯ ‚é •Z “§ ˆ³ ‚Ɖð Žß ‚³‚ê ‚é ‚ª,‚» ‚ê ‚Í “¯ Žž ‚É• –Ê –c •• ‘w ‚É‘Î ‚µ‚Ä ‚» ‚ê ‚ðŠg ’£ ‚µ ‚æ ‚¤ ‚Æ‚· ‚é–c •• ˆ³ ‚Æ ‚µ‚Ä •ì —p ‚· ‚é.Thomas‚ÆWindle, ‚¨ ‚æ‚ÑKramer‚ç ‚É ‚æ‚ê ‚Î,‚± ‚ÌP‚ð Žó ‚¯ ‚é• –Ê –c •• ‘w ‚Ì Šg ’£ ‘¬ “x ‚Í —n Ž¿ •ª Žq ‚Ì ‘Ì •Ï •ª —¦ ‚Ì ‘¬ “x4ƒÓ/4t‚É ‚æ ‚è —^ ‚¦ ‚ç‚ê,‚» ‚ê ‚Í –c •• ‘w ‚Ì ‘Ì •Ï ”S •« —¦ ‚ð ƒÅ ‚Æ‚· ‚é ‚Æ, (4) •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No. 2 (2002) 97
  • 6. Fig. 9. Comparison between the experiment and the calcu- lation based on the modified Kramer theory for the results in methanol at (a) 20, (b) 30, and (c) 40•Ž. 98 •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No. 2 (2002)
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  • 8. Case II Diffusion Behavior in Alcohol Absorption by Poly (methyl methacrylate) Makoto KAWAGOE,*1 Mivuki KAWAGOE,*2 Makoto NAKANISHI,*3 Jianhui QIU*4 and *1Department of Mechanical Systems Engineering, Faculty of Engineering, Toyama Prefectural University (Kurokawa, Kosugi, Toyama 939-0398, Japan) *2Education and Research Center for Engineering Materials, Toyama National College of Technology (Hongo, Toyama 939-8630, Japan) *3Toshiba Engineering Corporation (Horikawa, Saiwai-ku, Kawasaki 212-8551, Japan) *4Department of Machine Intelligence and Systems Engineering, Faculty of Science and Technology, Akita Prefectural University (Honjyo, Akita 015-0055. Javan) The structure and properties of alcohol and the ambient temperature causing the case II diffusion were investigated by studying the be- havior of alcohol absorption by poly (methyl methacrylate) (PMMA). The case II type of diffusion was newly confirmed to take place for the cases of 1-propanol, 1-butanol, and 2-methyl-1-butanol; methanol, ethanol, and 2-puropanol have already been known to show the case II behavior for PMMA. The lower temperature for the appearance of case II diffusion was raised with increasing the molar volume of alco- hol. The absorption rate was decreased with an increase in the molar volume, as with the Fickian diffusion observed for other polymer- reagent systems. Linear propanol and linear butanol showed greater absorption rate and less equilibrium solubility than the branched mole- cules. The equilibrium solubility of linear alcohol was constant or somewhat decreased with increasing the molar volume. Kramer's theory on the case II diffusion, which was modified by introducing the volume strain rate, was shown to provide good expressions for the absorp- tion behavior of methanol by PMMA, but one should compare with the behavior of other alcohols for proving the adequacy. KEY WORDS Case II Diffusion / Poly(methyl methacrylate) / Alcohol / Molecular Structure / (Received September 14, 2001: Accepted November 21, 2001)[Kobunshi Ronbunshu, 59(2), 93-100 (2002)] •‚ •ª Žq ˜_ •¶ •W, Vol. 59, No. 2 (2002) 100