Studies on the Physical and Thermal Propertiesof the Chitosan/Gelatin Blend

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(1)KOREAN J. FOOD SCI. TECHNOL. Vol. 37, No. 1, pp. 30~37 (2005). ©The Korean Society of Food Science and Technology. ÊÆÖ/J¢ :Â Ò^~ bÒ' 5 ' ßWö & \ B÷^Á;ËÖ* ããv ®>" # ®>Öë². Studies on the Physical and Thermal Properties of the Chitosan/Gelatin Blend Byung-Ho Kim and Jang-Woo Park* Department of Food and Biotechnology, and Food and Bio-industrial Research Center, Hankyong National University To mass-produce useful biopolymer films, chitosan/gelatin blend films were prepared by solution casting method. Effects of mixing ratio, tensile strength (TS), elongation (E) at break, total color difference (∆E), opacity, water vapor permeability (WVP), oxygen permeability (OP), and thermal properties on chitosan/gelatin blend films properties were investigated. TS, E, ∆E, opacity, WVP, and OP values were 58.24-22.01 MPa, 13.11-24.67%, 1.8617.45, 0.3104-1.2161 nmO.D./µm, 1.6875-1.7225 ngÁm/m2ÁsÁPa, and 2.2380Ü10−7-2.2975Ü10−7 mLÁµm/m2ÁsÁ Pa, respectively. TS of blend films decreased, while E, ∆E, and opacity increased with increasing chitosan content. WVP of blend films did not show any significant relationship with mixing ratio and thickness of blend films. Miscibility of films was examined over entire composition range by thermogravimetric analyzer (TGA) and dynamic mechanical analyzer (DMA). TGA results showed gelatin is more thermally stable than chitosan and some interactions among functional groups of two biopolymers. Glass transition temperature (Tg) of films as determined by DMA decreased with increasing content of chitosan in the blend. Results of thermal analysis indicate high miscibility among polymer components in the blend. Key words: biopolymer, chitosan, gelatin, physical properties, dynamic mechanical analysis. B. . cosamine)f Êj îj^z Î ©b Êf N-acetylD-glucosamine β-(1,4) Ö ~ ², îÖ ~ 7'~ ~ óî¾ Ï~~ b, ªU, ~~ ^ã ö 6Ò ª >Ú ®º Âª¶ bî (4). ÊÆÖö & º ®ª¢, ~ÏÒò, £® öò, Öëö> ¾ÒÏ w÷B, RFB , zË® ²Ò ' ª¢öB~ & B® ê¯> ®. (5). öê ÊÆÖf ª¶ï £ 1Ü107 Dalton~ ª¶ B ê~ Ö;¢ < ®Ú ¢>' FVÏ ¾ r¢ ÒÏöº ¾ Ï>æ pb¾, pH 6 ~~ FVÖöº Ï >Ú 6ê& ¸f Ïj ;W~æ Wîj Ï~ ªW jªj B~º & >¯> ® . KienzleSterzer (6)f ÊÆÖ~ ³êf Ï ~ «~ö V ÊÆÖ j ª~ Vê' bWö ~º 'Ëj Ò~&b, Caner (7) f Ï ÒÏ Ö~ ³êf &²B~ ³êö V ÊÆÖ jª~ ßWj Ò~& . Kim (8)f ÊÆÖ jªf ®Ö ëöB º~ ®º ªW, FW, Ôf Ö² R"ê¢ ÿö òÊº Ë6j &æ ®, &vB¾ &²B 5 Væ bî j Î&~¾ 6º ÊÆÖ FêÚ¢ æ; Úb z× Ö> bWj <º jªB& &Ë~ ~& . öê ÊÆÖ jª~ bWj BF~V * ÊÆÖ j ª¶f þ b~ jªj B êê ® î . Lazaridou (9)f chitosan" starch, chitosan" pullulan. " 2¢Ê ËÒ~ ÒÏ 5 öVö & »' B & ;z>B ' ª¢öB ¶~ã~ J"j ²z~V * ö & ¸jæ ® . ^B¢ Ö~V * O»b ~ãz' ËÒ BB . ® º>B ê>zb, Wî 5 æî ~ bî¦V ª¶ ªW jª~ BBö & & B~² Ú^ z . ª¶ jªf ÒÏ êöº ÿb~ Òò ¾ öV~z¢ ê £² ª>Ú jz& &Ë ~ãz' ËÒB " ~ Ï 5 BBö & & ¸jæ ® (1-3). ª¶ :Âº · wÏj * îÚ ßWj <º ª¶Òò¢ òº Î"' O» . ß® Vê'W 5 & W Ö> J¢ Âª¶f VËW ÚÂ ÊÆÖ Â ª¶¢ Ï~ :Â Ê VËW Ö> ª¶ Òò¢ Ï~² ò > ® . ÊÆÖ(poly-β-1,4-N-D-glu*Corresponding author: Jang-Woo Park, Department of Food and Biotechnology, Hankyong National University 67, Sukjung-dong, Ansung-si, Kyonggi-do 456-749, Korea Tel: 82-31-670-5157 Fax: 82-31-677-0990 E-mail: [email protected] 30.

(2) ÊÆÖ/J¢ :Â Ò^~ bÒ' 5 ' ßWö & . bjª~ thermophysical ßWj Ò~&b, Arvanitoyannis (10)f chitosan" gelatin &W jª~ Vê' 5 R" ß Wö &~ ~& . Begin (11)f HCl" formateö B B ÊÆÖ jª~ ªW Ë¾ B¢ ~ º jª BÏb~ ÒÏ &ËWj B~&b, Hoagland (12)f chitosan/pectin '[ jªj BB~&, Wong (13) f chitosan/lipid jªj BB~& . J¢f ÿb~ ., , &# Öç~ "º Wî Wª R¢¶(collagen)~ ¦ ª' &>ªö ~ áÚæº FêWîB " ® ~ Wî ºzB(gelling agent) ÒÏ> ® (14,15). J¢ f jv' Ôf Nêf ³êöBê 6Wj ¦~(16), ï 'F r J¢ Ïf F«~ êKW ®º &' º (thermoreversible gel)j ;W~V · (17). ";j J¢~ ºz(gelation)¢ ~, ¢>'b J¢~ ºzº Nê, pH, ²ªï, BO» 5 ³ê ö V¢ ² 'Ëj Aº ©b rJr (18). Bigi (19)f J¢" hydroxyapatite bjª~ f Vê' ßWö &~ ~&, 6 Bigi (20)f glutaraldehyde &vÖ* J¢ jª ~ Vê' ßWj ËçÊ, jª~ 'Wîj ~ & . Sobral (21)f sorbitol~ ·Ïö V¢ bovine hidef pigskin J¢ &W jªö ®Ú >ª R"ê, Vê' 5 ' ßWö &~ ~& . VöB ÊÆÖf &ïÖ ëbº ÒÏ ®&Ë~. º W; 6j æî ®V r^ö *Òræ ÊÆÖ~ VË j Ï jªBº þ ' O»(casting method) j îb~æ á~ ® . ~æò, ª¶ öò ÒÏ > ®º bî 7ö, R« J¢f Î&>º &²B~ «~ 5 ³êö V¢ Ï[6~ æz& ôV r^ö ÊÆÖ" J¢ j 7 >wÊ J¢ ö º bî ·Ï~ Ê ÆÖ~ ' 6j j~æ &ïÖ > ®º &ËW ôj ©b 6B . V¢B, ÊÆÖ" J¢j Ï~ bjNê jªj B~& . çVöB J«B ÊÆÖ " J¢j Ï~ bjª B bjNö V jª ßWö & º jçræ ç . öBº ÊÆÖ" J¢j Ï~ bjªj B~&j r, b jN ÊÆÖ/J¢ bjª~ Vê'(Ë;ê 5 Ë), '(ïê 5 ®R«ê), R"(>ª 5 Ö² R"ê) 5 ' ß Wö ~º 'Ëj Ò~& .. Òò 5 O» Òò þö ÒÏ ÊÆÖ(average molecular weight 40 KDa, degree of deacetylation 90%)f Ïö ²Ò Bio-Tech. Co. (Korea)¦V «~&b, JÒ;ê(jelly strength)& 240-260 bloom J¢f UNIGEL Co.(Korea)öB «~& . ÊÆÖ Ï acetic acid 5 jª~ &²B ÒÏ glycerolf Showa Chemical Co.(Japan)öB «~&, bf Ã~>(distilled water) ¢ ÒÏ~& . >jª B ÊÆÖf J¢" Ò Ã~>öB ÏW ±æ pV r ^ö 2%(v/v) acetic acid¢ Ï ÒÏ~& . b& ÊÆÖ 5 J¢~ «³ê& '' 3%(w/w)& >ê Ïî 30 gj ï~, &²B glycerol 9 gj & Ê, &jB cf 2%(v/v). 31. Table 1. Mixing ratio of chitosan/gelatin film Sample No. 0 1 2 3 4 5 6 7 8 9 10. 3% (w/w) Chitosan solution 3% (w/w) Gelatin solution concentration (%) concentration (%) 0 10 20 30 40 50 60 70 80 90 100. 100 90 80 70 60 50 40 30 20 10 0. acetic acid Ï 5 80-90oC &B Ã~> 1000 mL¢ j. . ÊÆÖ 5 J¢ Ïj hot plate stirreröB 80-90oC &v> * ''~ 3%(w/w) ÊÆÖ Ï" J¢ Ï j B~& . bjªj B~V * BB '' ~ 3%(w/w) ÊÆÖ 5 J¢ Ïj Table 1" ?f bj Nö V¢ bjªj B~& . ¯, bjNê .B ' '~ bÏ f îV¢ Ï~ 6,000 rpmöB 2ª* 7 >w 8 . Ò, hot plate stirreröB 80-90oC Ò& v>* bjª Ïj B r, bjª Ï 110 mL¢ >ï teflon glass plate(22Ü22 cm)ö V& Væ pê casting ê çNöB £ 72* ÿn 8 . B jªj teflon glass plate¦V âÚÚÚ ò ÒÏ~ & . 6 Î bjª òº þ*ö 25oC, 50% RH .B NÛV(SE-96HP, Sang Woo Scientific Co., Korea) öB 48* ç >ªïj .Î ê þö ÒÏ~&. (Fig. 1). ß® ªCÏ òº Phosphorus(V) Oxide(Kanto Chemical Co., Japan)& Ú®º VöB 1"¢ ç &~B >ªj B8, &²B& Î&>æ pf B> ¢ 6º bjªb B~& . Lþ /; BB bjª~ vþº 0.001 mm~ ;&ê¢ æîº handheld micrometer(Teclock Co., Japan)¢ Ï~ G;~& . Ë;ê 5 Ë, ïê, ®R«ê, >ª R"ê, Ö² R"ê 5 ªC G;Ï bjª~ 7¦f "æ ¦ªj G ;~ & 5 ²8j BÊ, ¾^æ 8 j Ï~ ï 5 &ÞN 8b ¾æÚî . Vê' ßW /; *¾Ò >ªïj .Î ê bjª(7Ü2.54 cm)j ASTM D 822-97 &þ»(22)ö V¢ Texture Analyzer(TAHDi 500, Stable Micro System, England)j Ï~ Ë;ê 5 Ëj G;~& . r Texture Analyzer G;öB .V grip*~ Òº 50 mm, crosshead ³êº 500 mm/minb .~& . Ë;ê 5 Ëf '' r (1)" (2) ¢ Ï~ êÖ~& . TS(MPa) = Maximum tensile force/Cross section area Elongation(%) = (∆L/L)Ü100. (1) (2).

(3) 32. ®"²æ B 37 ² B 1 ^ (2005). ∆E = 2. 2. ( L film – L s tan dard ) + ( a film – a s tan dard ) + ( b film – b s tan dard ). YI = 142.86Üb/L. (3) (4). ®R«ê /; bjª(1.5Ü0.7 cm)~ ®R«êº BSI O»(23)j æ;~ G;~& . jªj 0.7Ü1.5 cm~ Ò';b ¶ ê ¢ Ò'~ ª7ªCÏ C' cell~ Û" 'ö ¦OÊ, ª 7ªCê(UV-530, JASCO, Japan)¢ Ï~ &7F ' 350-750 nm 2Ëj "Ò ÊB r~ 7ê¢ G;~&. . jª~ ®R«êº VB 7ê F~ 'b ;~~ &b, *º nmO.D./µm ¾æÚî .. Fig. 1. Flow chart for the preparation of chitosan/gelatin film.. VöB maximum tensile force(N)º bjªj Ë* jª .F rræ~ ·Ï &Ë ¾j ö~, cross section areaº bjª~ ï '(average thicknessÜwidth, m2)j ~ . 6 Lf Texture analyzer .V grip Ò~ Ò(mm), ∆Lf bjª .F rræ æç grip*~ Ò(mm)¢ ¾æÞ . ïê /; BB bjª(4Ü4 cm)~ ïêº ïNê(Color-eye 7000, Macbeth, USA)¢ ÒÏ~ Hunter scaleö ~ L(lightness, « ê), a(redness, 'ïê) 5 b(yellowness, ïê) 8j G;~&. . VöB L 8f ï~ CV¢ ¾æÚº ©b L = 0(black) öB L = 100(white)j ¾æÚ, a 8f ï~ ." 'ïê¢ ¾æÚº ©b a = −80(greenness)öB a = 100(redness)j ¾æ Þ . Ò b 8f Óï" ïê¢ ¾æÚº ©b b = − 80 (blueness)öB b = 70(yellowness)j ¾æÞ . ïê G;f jª ò¢ ï² 8 L = 95.91, a = 0.00 5 b = 2.27 & Wï6(calibration plate) *ö ¹, bjN ÿ¢ jª 3«~¢ ' 3²O G;~ ï 5 &ÞN 8b ~&. . Hunter L, a 5 b 8b¦V & Wï6"~ Cï N(total color difference; ∆E)f ïæ(yellowness index; YI) ¢ r~ (3)" (4)ö ~~ êÖ~& .. >ª Rê /; bjª(7Ü7 cm)~ >ª R"êº ASTM E 96-95 & þ»(24)ö V¢ Cup Method¢ Ï~ G;~& . r cup f V~ *Âj Oæ~V * Z O-ringj ËO 8b, Úã 4.6 cm, p& 2.1 cm polymethyl methacrylate(Piedmont plastic, Inc., Geenvile, SC, USA) Òî . cup Ú¦ö Ã~>¢ I, ¢ bjªb f ê ÏV~ çã" ? f çãj &ê Â÷b , &b ¹ ®º 4B~ ¾ Ò¢ ÏVÚ~ >ÃV& çã 4.6 cm~ ö; jª[j Û Bò ¦ ÿ~ê ~& . ¢ ç&Ûê& 50% .B 25oC~ NÛVö O~~B, 14* ÿn 2* *Ïb cup~ Z² 6²¢ 0.0001 g *ræ G;~& . *ö V cup~ Z² 6²~ &ê¦V cup~ *ö V Z² 6²Nj ~& . >ÃV R"N(water vapor transmission rate, WVTR)f (5)" ? cup~ *ö V Z² 6²N j jª~ 'b ¾*Ú ~&b, >ÃV R"N¦ V r (6)¢ Ï~ >ªR"ê(warer vapor permeability, WVP)¢ ~& . WVTR = Slope/Film area WVP = WVTR(L/∆P). (5) (6). r, (5)öB~ WVTRf >ÃV R"N(g/m2Á24 hr), slopeº *ö V cup~ Z² 6²N(g/24 hr), film areaº > ª ÿ ¢Ú¾ ®º jª~ 9(m2)¢ ö~, (6)ö B~ WVPº jª~ R"ê>(ngÁm/m2ÁsÁPa), Lf jª~ ï vþ(µm), ∆Pº jªj Òö z cup Ú¦f ¦~ > ÃV ¦ª{~ N(Pa) . jª~ >ª R"ê G;f ' öB 3² > þj ~ ï 5 &ÞN 8b ¾ æÚî . 6, jª~¦~ >ÃV{j jª~ ~¦f Ã~> ~ Òö ®º V~ &ö ~ 'Ëj McHugh (25)" Gennadios (26)~ O»ö V¢ ;~ ¢ >ª R "ê~ ;8(water vapor permeability by correction method, WVPC)b ~& . Ö² Rê /; Ö² R"êº OX-Tran 100A(Mocon Inc. Minneapolis, MN, USA)j ÒÏ~ ASTM D 3985-81 &þ»(27)b G; ~& . ò(5Ü5 cm)¢ 1Ë~ aluminum foil mask(5 cm2. 2.

(4) ÊÆÖ/J¢ :Â Ò^~ bÒ' 5 ' ßWö & . uncovered area) Òö 7OÊ, ¢ testing cellö IÚ Ö ² R"ê¢ G;~& . Aluminum foil maskº Vê' ææ Ú, òö ¢; R" 'j Fæ~º êæ B . G;Nêº 25oC ;Ê, ò& ËOB êö ¢ b&Ê(98% N2 + 2% H2) G; cell Ú¦ ·j 16* ;ê ªÒ~, ê Ö²¢ ç[¦ö "«Ê ò¢ Û" Ö²º Ö²³ê G; bBö ~ G;B . R" cell ç [¦ö ÂB Ö²~ Fïf 15 cc/min, b&Ê~ Fï f 10 cc/minb ;~& . Ö² R"ê~ G;f 1* ÿ nö 1% ~ G; æz>æ pj r~ 8j G;~& . r jªj Òö z Ö²~ ¦ª{Kj 1V{b &;~& . ' ßW /; bjª~ n;Wf thermogravimetric analyzer(TG/DTA 6200, Seiko Instruments, Japan)¢ Ï~ ªC~& . G;f î² B~öB £ 12 mg~ ò¢ 30oCöB 600oCræ 20oC/min~ ßN³ê G;~& . 6 jª(ï 1.11Ü0.37 Ü0.008 cm)~ ÿ' ªCf dynamic mechanical analyzer (DMA 2980, TA Instruments, USA)¢ Ï~ Park (28)" Yoo (29)~ O»b G;~& . ¯, Ë;(tensile mode) ~ G;ÎöB "2>(frequency) 1 Hz, êÿV(amplitude) 5 µm ~, −30oCöB 250oCræ 2oC/min~ ßN³ê î ² B~öB G;~& . Ûê' ªC bjª~ Ë;ê, Ë, ïê, ®R«ê, >ª 5 Ö² R"ê G;8 f ï8" &ÞN ¾æÚî, ' þ ï8~ F~' N ¦;f SAS(Statistical Analysis System) Ûê package(30)¢ Ï~ Duncan’s multiple range test ¦ Ã~& .. Ö 5 8 Vê' ßW ¢>'b ª¶ jª~ ®îj Ö;~º º² 7öB V ê' ßWf &® 7º~ . &¦ª~ jªf Ëb ÒÏF r ËwKj &Ë ô AV r^ö ÿ¢ vþ 5 VËöB Ë;ê& ¸f © Vê' WËGöB J r FÒ~ > ® . Table 2º bjNö V Ê ÆÖ/J¢ bjª~ Ë;ê 5 Ë G;8j ¾æÞ © . J¢ jª~ Ë;êº 58.24 MPa &Ë ¸² G ;>î, ÊÆÖ~ ³ê& Ã&ö V¢ 57.81 MPaöB 26.54 MPa ¾æÒ . 6 ÊÆÖ jª~ Ë;êº 22.01 MPa &Ë Ô~b, ÊÆÖ~ ³ê& Ã&ö V¢ 6N'b 6 ²~º ãËj ¾æÚî . Ëf 13.11%öB 24.67% Ë;ê Ö"fº ² Ã&>î . ¢>'b jª~ Ë ;êf Ë Òöº >jf &ê& ®º, º þ ~ Ö"f ¢~~& . ¢>'b ª¶~ R Ïf ºj ;W ê ¢; Nê 5 Ûê ~öB Ê jª ;WB . J¢f &¦ª~ Wî"º Ò Nê& Ã&Nö V¢ º(gel) ç æz>º ª¶ bî . º z(gelation) ";j ÚÚ, & ÏÚöB ® coil ; Ï>Ú ®º J¢f ï'Nö V¢ 37 ¾F (triple helix structure) >òj &Jº 3B~ polypeptide ÒÒ ¦V ;WB ·f ' &vÖ(cross-linking)j Û 7. 33. Table 2. Effect of mixing ratio on tensile strength and elongation at break point of chitosan/gelatin film Sample1) No.. Thickness (µm). Tensile strength2) (MPa). Elongation (%). 0 1 2 3 4 5 6 7 8 9 10. 80.15Û2.72 80.33Û4.88 71.35Û0.88 75.18Û4.30 75.73Û1.72 75.08Û5.61 76.40Û6.16 92.53Û5.02 92.58Û6.57 86.10Û9.68 95.48Û6.17. 58.24Û1.20a 57.81Û3.20a 55.65Û0.50a 51.09Û3.53b 42.73Û1.48c 37.45Û4.06d 32.94Û1.03e 33.33Û1.86e 28.38Û1.80f 26.54Û2.72f 22.01Û1.94g. 13.11Û2.20c 13.26Û3.48c 14.43Û1.62c 16.25Û3.02c 16.90Û1.96c ,c 17.93Û4.90bc 15.10Û5.84c ,c 23.61Û3.35ab 24.20Û2.84a ,c,c 19.04Û7.37abc 24.67Û5.90a. 1) Notation of blends of chitosan/gelatin are following; 0(0/100), 1(10/ 90), 2(20/80), 3(30/70), 4(40/60), 5(50/50), 6(60/40), 7(70/30), 8(80/ 20), 9(90/10), 10(100/0). 2) Mean standard deviation (n=5). a-g) Means with the different letter in same column are significantly different (p<0.05) by Duncan's multiple range test.. æ(cross-linking site)j ;W~æ, «'b 3Nö~ J Þò(network)¢ ;W~º ©b >î (31,32). J¢ jªf J¢ ª¶& ºj ;W ê ª¶ 7ö Ò~º b ª¶& ";j ~º ÿn z× & ¢ ;W~V r^ö, ç 27 ¾F¾ 87 ¾F¢ ;W~º ÊÆ Ö jª ¸f Ë;ê¢ <º © . V¢B ÊÆÖ~ ³ê& Ã&> ÊÆÖ/J¢ bjª~ Ë;ê& 6² >º ãËj ¾æÚî 6B . 6 öB ÒÏ &²B glycerol Î&>B ÊÆÖ" J¢ Òö ¢¦ Ö~ Ë;êº &~Êæò, glycerol öò ¶Ú~ bW r^ö bjª~ Ëf Ã&>î 6B . Ëf jª Ë>Ú 2F r~ æ;B ;ê¢ ¾æÚº, ÊÆ Ö/J¢ bjªöB ÊÆÖ~ ï Ã&ö V¢ sample No. 6" 9¢ B~º 6N'b Ã&~& . V¢B b jNö V¢ ÊÆÖ/J¢ bjª~ Ë;ê 5 Ë ¢ææ, ¢ bjª wÏ>º ª¢ö V¢ '. b jN bjªj B~º © :²ç~ 'B . ïê ïêº bjª~ &j Ö;~º 7º ßWbB b jNö V bjª~ Hunter L, a, b, ∆E 5 YI 8 j Table 3ö ¾æÚî . L 8~ ãÖ ÊÆÖ ï Ã&> bjª~ L 8f 6²>î, a f b 8f L 8ö >jf Ã&>î . 6, ÊÆÖ~ ï Ã&ö V¢ BB b jª~ ∆E 5 YI 8 f ÊÆÖ ï 90%¢ B~º . ¸f 8 G;>î . bjª~ YI 8f ïê 8 &Ë ¸f Sample No. 10 jª~ YI& 29.38 &Ë ¸~b, ¸f «ê(95.27)f Ôf ïê(3.98)¢ ¾æÞ Sample No. 0 bjª~ YI& 5.98 &Ë Ô~ . ÊÆÖ/J¢ b jª~ ïz Nº Hunter L, b 8 ~ Nö V~º © b 6B . bjª~ ïzj Gnb ç7 &V~ê ÊÆÖ~ · Ã&> R« jªöB 6N'b ÿf ¦ï~ bjªb æz~º ©j { > ®î . Rhim (33)f ÊÆÖ jª~ Hunter L, a, b 5 ∆E 8 '' 94.5,.

(5) ®"²æ B 37 ² B 1 ^ (2005). 34. Table 3. Color spectrophotometer values of mixing ratio on Hunter values(L, a, and b), total color differences (∆E), and yellow index(YI) of chitosan/gelatin film Sample1) No. 0 1 2 3 4 5 6 7 8 9 10. Thickness (µm) 77.25Û0.71 77.60Û2.40 72.10Û1.00 77.40Û1.80 80.00Û1.10 77.00Û2.40 71.50Û1.80 72.80Û4.90 78.50Û2.50 68.50Û2.50 99.75Û4.68. L2). a a. 95.27Û0.01 95.06Û0.11b 94.77Û0.05c 94.31Û0.18d 93.98Û0.05e 93.62Û0.05f 93.04Û0.12g 92.44Û0.12h 90.91Û0.62i 91.09Û0.13i 89.31Û0.01j. ∆E. b a. -0.34Û0.01 -0.76Û0.03b -0.88Û0.01c -1.03Û0.05d ,g -1.22Û0.02fg -1.30Û0.03h -1.21Û0.03f -1.17Û0.01e -0.91Û0.08c -1.00Û0.02d -1.25Û0.04g. i. 03.98Û0.01 04.38Û0.24i 05.36Û0.05h 07.28Û0.40g 09.03Û0.10f 10.53Û0.45e 12.01Û0.44d 13.31Û0.31c 17.75Û1.71b 17.39Û0.46b 18.37Û0.23a. YI i. 01.86Û0.01 02.40Û0.26i 03.41Û0.04h 05.36Û0.44g 07.13Û0.11f 08.67Û0.43e 10.23Û0.45d 11.63Û0.32c 16.30Û1.81b 15.91Û0.48b 17.45Û0.21a. 05.98Û0.01i 06.59Û0.37i 08.08Û0.07h 11.03Û0.63g 13.72Û0.16f 16.07Û0.68e 18.44Û0.70d 20.57Û0.50c 27.91Û2.89b 27.28Û0.76b 29.38Û0.36a. 1). Notation of blends of chitosan/gelatin are following; 0(0/100), 1(10/90), 2(20/80), 3(30/70), 4(40/60), 5(50/50), 6(60/40), 7(70/30), 8(80/20), 9(90/ 10), 10(100/0). 2) Mean standard deviation (n=9). a-j) Means with the different letter in same column are significantly different (p<0.05) by Duncan’s multiple range test.. Table 4. Effect of mixing ratio on opacity values of chitosan/ gelatin film Sample1) No.. Thickness (µm). Opacity2) (nmO.D./µm). 0 1 2 3 4 5 6 7 8 9 10. 75.64Û0.45 73.60Û3.78 69.40Û2.19 75.40Û1.67 76.20Û1.92 66.60Û1.34 66.60Û2.88 68.80Û1.79 90.40Û6.88 76.80Û2.39 87.70Û3.12. 0.3104Û0.018g 0.3757Û0.0189f 0.3524Û0.0113fg 0.7539Û0.0165cd 0.7286Û0.0188d 0.5069Û0.0102e 0.9931Û0.0430b 0.7967Û0.0207c 0.9938Û0.0796b 1.2016Û0.0372a 1.2161Û0.0420a. 1) Notation of blends of chitosan/gelatin are following; 0(0/100), 1(10/ 90), 2(20/80), 3(30/70), 4(40/60), 5(50/50), 6(60/40), 7(70/30), 8(80/ 20), 9(90/10), 10(100/0). 2) Mean standard deviation (n=3). a-g) Means with the different letter in same column are significantly different (p<0.05) by Duncan’s multiple range test.. Fig. 2. Effect of mixing ratio on water vapor permeability of chitosan/gelatin films (n=3). ø-ø: Corrected water vapor permeability value (correction method), ù-ù: Measured water vapor permeability value (ASTM method). a-b) Means with the different letter in same column are significantly different (p<0.05) by Duncan’s multiple range test.. −0.19, 10.3 5 8.6¢ ~&º, öB J¢ Î&>æ pf ÊÆÖ jª" jv~&j r, Rhim (33)~ Ö" ïêf CïNöB £ 2V ;ê ¸f 8j ¾æÚ î . º ÊÆÖ Ï B ÊÆÖj cf .ÖÏö Ï * ÊÆÖ~ -NH2V& ÖW" ç æz>º êV r^ö &>ª* Ã&ö V¢ ïê& Ã&>î 'B .. R«êº J¢ jª(Sample No. 0)~ ®R«ê £ 4V ¸² ¾æÒ . º B J«B ïê G;ö V «ê& 6 N'b 6²>, ïê~ 8 Ã&>º Nö V~º ©b 6B . jª~ R«êº ®Ëö 'Ï r 7º º . ®R«ê~ G;~& º ©f >B ' 9f ©j ~~, R« ;ê& Ôf ©j ~ .. ®R«ê ïêf îR&æ jª~ &j Ö;~º 7º ßWb B BB bjª~ ®R«êº Table 4ö ¾æÞ ©" ? 0.3104 nmO.D./µmöB 1.2161 nmO.D./µm~ º* G;> î . ÊÆÖ~ ³ê& Ã&> &Ú'b ®R«êê Ã &~º ãËj ¾æÚî . ÊÆÖ~ ï 20%ræº N ¢ ¾æÚæ p~ . 6 ÊÆÖ jª(Sample No. 10)~ ®. >ª Rê bjNê BB ÊÆÖ/J¢ bjª~ >ª R"ê º Fig. 2öBf ? 1.6875 ngÁm/m2ÁsÁPaöB 1.7225 ngÁ m/m2ÁsÁPa G;>î . ÊÆÖ" J¢~ bjN 80:20 Sample No. 8~ >ª R"ê(1.6271 ngÁm/m2ÁsÁPa)& & Ë Ô~b, bjN 40 : 60 Sample No. 4~ >ª R"ê (1.7756 ng"m/m2"s"Pa)& &Ë ¸~ . ~æò, Duncan~.

(6) ÊÆÖ/J¢ :Â Ò^~ bÒ' 5 ' ßWö & . 35. ~ >ª R"êº vþ~ æzfº &êì ¢;~&æò, >W ª¶ jª~ >ª R"êº jª~ vþf çF' j f&êö ®b, º Ûb cJB jªÚ Z;; ¦ªj Û jªÚ¦öB~ >ª{Ö >WVf b ª¶ ~ zKö ~B ³ê ¢Ú¾V r^ ©b ~& . ~æò, ÊÆÖ/J¢ bjªf bjNê vþ & 77.00 möB 87.96 m~ º* vþö V >ª R"ê~ 'Ëf ìº ©b G;>î . 6 Park (36)f ÊÆÖ j ª~ >ª R"êº Ï ö ~~ 'Ëj Ab &²B~ ³ ê& Ã&> >ª R"ê& Ã& ~&º, öBº ÊÆÖ/J¢ bjª~ bjN 5 vþº > ª R"êö 'Ëj ~æ pº ©b ¾æÒ .. Fig. 3. Effect of mixing ratio on the oxygen permeability of chitosan/gelatin films (n=3). a-d) Means with the different letter in same column are significantly different (p<0.05) by Duncan’s multiple range test.. 7jv ªCÖ" ÊÆÖ~ ³ê& Ã&ö V¢ bjª ~ >ª R"êº F~'(p < 0.05) N¢ ¾æÚæ p~b æ, ÊÆÖ/J¢ bjª~ >ª R"êö ®Ú bjN ~º 'Ëf ~ ìº ©b ¾æÒ . ª¶ jª ~ R"êö ~º &' ºbº ª¶ öò~ ª ¶ï, jªÏ Bö jº '; Ï , 6 Î&>º & ²B~ «~ 5 ³ê b ª > ® . Wî" ?f >W ª¶ jªf &²B& Î&>º · Ã&ö V¢ Z;; ¦ª~ ª¶ ÒÒ~ &÷B ;ê& £^ >ª R "êº Ã&~º ©b >îº(34), ÊÆÖ/J¢ b jªö Î&B &²B(glycerol)~ ·f bjNê Îv ÿ ¢~&V r^ö bjª~ >ª R"êöº 'Ëj ~æ á ©b 6B . ®ÏW ÊÆÖ" >ÏW J¢j Ï ~ B ÊÆÖ/J¢ bjªöB ÊÆÖ cf .Ö Ïö Ï>Ú >W "~ ; *~>Ú J¢" z ®Ú *Ú'b bjªf >W ª¶ jª~ Wîj ¾ æÚº ©b ÒòB . Banker (35)f FW ª¶ jª. Ö² Rê ÊÆÖ/J¢ bjª~ Ö² R"êº bjNö V¢ Fig. 3" ? 2.2380Ü10−7 mLÁm/m2ÁsÁPaöB 2.2975Ü10−7 mLÁm/m2ÁsÁPa ¾æÒ . ¢>'b ª¶ jª~ R "êº ª¶~ &ê, ª¶ï, Ö;ê, &²B~ «~ 5 ·, Ûê, jª~ vþ ö V¢ ôf 'Ëj Aº ©b rJ^ ® . çë 5 ëË ÒòB ÒÏ>V * ª¶ j ªf Ë ÚÏbj ^~V *~ ¦~ ÛV 5 Ö²¢ N~º Î"& ®Ú¢ . Fellows(37)º 25oC, 45% RHö B vþ& 0.025-0.200 mm LDPE(low density polyethylene)j ª~ Ö² R"ê& 8,000 mL/m2Á24 hr, 25oC, 45% RHö B vþ 0.020-0.030 mm OPP(oriented polypropylene) jª~ Ö² R"êº 1,600-2,000 mL/m2Á24 hr¢ ~& . º þöB~ Ö"& ºÏ jª LDPEf OPP jª~ Ö² R"ê ú® Ôf Ö² R" ßWj ¾æÚæ ÚRV W jº ®Ëö 'Ï &Ë ©b 6B . ' ßW Fig. 4f 5º >ª" &²B¢ Î&~æ pf B> J¢ jª, bjª 5 ÊÆÖ jª~ ' n;Wj î² B~ öB TG/DTA ªC ©, ò~ Nêçßö V 7 ï~ æz 5 ª¢ ¾æÚ ® . Fig. 4º B> J¢ jª(A)~ TG Ff "ê~ ª& 270oC ¦"öB ¢Ú ¾ ®rj ", B> ÊÆÖ(F)~ "ê ªº 230oC. Fig. 4. Effect of mixing ratio on the thermal gravity analysis of chitosan/gelatin films without H2O and glycerol. Notation of mixing of chitosan/gelatin are following; A(0/100), B(20/80), C(40/60), D(60/40), E(80/20), F(100/0). The measurement was conducted at a 20oC/min heating rate under nitrogen flow..

(7) 36. ®"²æ B 37 ² B 1 ^ (2005). Fig. 5. Effect of mixing ratio on differential thermogravimetric analysis of chitosan/gelatin film without H2O and glycerol. Notation of mixing of chitosan/gelatin are following; A(0/100), B(20/80), C(40/60), D(60/40), E(80/20), F(100/0). The measurement was conducted at a 20oC/min heating rate under nitrogen flow.. Fig. 6. Effect of mixing ratio on dynamic mechanical analysis of chitosan/gelatin film without H2O and glycerol. The measurement was conducted at a 2oC/min heating rate under nitrogen flow.. ¦"öB ¾æÒ . Ö"¢ " r J¢ ÊÆÖ. n;W Ö>j r > ®î . v B> Wª~ bjª (B-E)öBº bjNö V¢B n;W~ N¢ ¾æÚ ® . *Ú'b 370oC çöBº /Ï ª¢ ¾æÚæ p~b, 550oC çöBº j*²& >î . ºFb~ 7 ïf ÊÆÖ~ ï Ã&ö V¢ 25.7%öB 37.2% 6N 'b Ã&~& . º J¢~ Ïæ ÒÒ Ò~ ; >²Ö ÊÆÖ~ jVf b>B >²ÖK £z>îV r^b 6B . 6 Fig. 5º 7ïê> (derivative thermogravimetric, DTG) Fb ª¶~ ª & ¢Ú¾º ;ê¢ r > ® . J¢ jª(A)~ G; Ö", ®n;~² æò 120oC ¦"öB~ ·f Ff &ª¶ W ª~ ª, 330oC ¦"öB~ Ff "ê~ ª & ®rj " ® . F Fº B> ÊÆÖ~ DTG Fb 140oC, 190oC 5 270oC ¦"öB F ¾æÒ, & ¦ª~ ªº 270oC ¦"öB ¢ÚÒ . ª¶ "ê~ & ªNê¢ ¾æÚº F(B-E)f J¢~ Wª Ã&ö. V¢ Ã&~&, &ª Ff ¢ Fb ¾æÒ . º ÊÆÖ" J¢ ª¶ ~ &ËV(functional groups) Ò ö ç^·Ï(molecular interaction) Ò~, W ª ¶& çÏW ®rj ¾æÚº © . Fig. 6öBº ÊÆÖ" J¢ ''~ ¢ 6º bjª ~ ª¶*(molecular relaxation)ö & Ö"¢ ¾æÚ ® . ¢>'b DMAº ª¶f ª¶ Ò~ ç^·Ïj > ®º ;& V V çÏW ®º ª¶ bjªöB W ª¶~ F Ò*Nêº W ª¶Ò~ Wö V¢B FÒ*Nê & æz~º j~ çÏW ìº ãÖöº W ª¶~ F FÒ*Nê¢ '' ¾æÞ (38). Fig. 6öB º © " ? B> ÊÆÖ~ ãÖ FÒ*Nêº 144oC ¾æÒ , >ö J¢ jª~ tan δ Ff 240oC ¦"öB ¾æ Ò . ©f TG/DTA ªCÖ"öB J¢~ ªö V relaxation~ F, J¢~ FÒ*Nêº J¢ ~ ãçWö V¢ ªNê ¸jB G; Ú[ . 6 ÊÆÖ" J¢~ bjN 20/80 ãÖ 2B~ relaxation Fj ¾æÚîº, 200oC ¦"öB ¾æ¾º © bjª ~ FÒ*Nê, 240oC ¦"~ tan δ Ff J¢~ ª ö V relaxation F, bjN 40/60~ ãÖê f ÿ¢~ . *Ú' tan δ Fj &V r bjNö V ¢ FÒ*Nêº ¢ Fj ¾æÚî, J¢~ ï Ã&ö V¢ FÒ*Nêº Ã&~& . -² >V * Bº Wª¶ ~ ^bÞ ÒöB :²ç ç^·Ï (interaction) ®Ú¢ . ÊÆÖ" J¢ Ò~ ¸f çÏ Wf J¢~ ®Vf ÊÆÖ~ ®V 6º j V ~ WV Ò~ ª¶Ú 5 ª¶*ö Ò~º ; ç^·Ïö V . V¢B Ö"º ÊÆÖ" J¢ ª¶ Òö çÏW ®rj ¾æÚº © .. º. £. FÏ ª¶ jªj B~V * Ï'b ÊÆÖ" J¢j Ï~ solution casting O»b bjNö V¢ bjªj B~& . 6 ÊÆÖ/J¢ bjª~ Ë ;ê, Ë, ïê, ®R«ê, >ª 5 Ö² R"êf ?f b Ò' ßW" ' ßWö ®Ú bjN ~º Î"ö &.

(8) ÊÆÖ/J¢ :Â Ò^~ bÒ' 5 ' ßWö & . ~ Ò~& . bjNê BB ÊÆÖ/J¢ bj ª~ Ë;êº 58.24 MPaöB 22.01 MPa 6N'b 6² ~º ãËj ¾æÚî, Ëf 13.11%öB 24.67% Ë ;ê Ö"fº ² Ã&>º ãËj & . jª~ &j Ö;~º 7º ßW ïê G; Ö", L 8~ ãÖ ÊÆÖ ï Ã&> 6²>î, af b 8f L 8ö >jf Ã&>î . 6 ÊÆÖ~ ï Ã&ö V¢ BB b jª~ ∆E 5 YI 8 f ÊÆÖ ï 90%¢ B~º . ¸f 8 G;>î . bjª~ ®R«êº 0.3104 nmO.D./µmöB 1.2161 nmO.D./µm~ º* G;>î . >ª R"êº 1.6875 ngÁm/m2ÁsÁPaöB 1.7225 ngÁm/m2ÁsÁPa G;>îæò, Duncan~ 7jv ªCÖ" ÊÆÖ~ ³ ê& Ã&ö V¢ bjª~ >ª R"êº F~'(p < 0.05) N¢ ¾æÚæ p~ . Ö² R"êº bjNö V¢ 2.2380 Ü10−7 mLÁm/m2ÁsÁPaöB 2.2975Ü10−7 mLÁm/m2ÁsÁPa ¾æÒ . 6 ' ßWj ªC Ö" bjNö V¢ FÒ*Nêº ¢ Fj ¾æÚî, J¢~ ï Ã &ö V¢ FÒ*Nêº Ã&~&V r^ö Ö" j " r, ÊÆÖ" J¢ ª¶ Òö çÏW ®rj r > ®î .. ^. ò. 1. Krochta JM, Mulder-Johnsotn CD. Edible and biodegradable polymer films: challenges and opportunities. Food Technol. 51: 61-74 (1997) 2. Deveaufort F, Quezada-Gallo J, Voilley A. Edible films and coatings: Tomorrow's packagings: A review. Crit. Rev. Food Sci. Nutr. 38: 299-313 (1998) 3. 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