Effect of the injection moulding processing conditions on the development of pea protein-based bioplastics

Depósi o de in es igación de la Uni e sidad de Se illa h ps://idus.us.es/ Es a es la e sión acep ada del a ículo publicado en: This is a accep ed manusc ip o a pape published in: Jou nal o Applied Polyme Science (2016) ol.133 n.20 DOI: h ps://doi.o g/10.1002/app.43306 Copy igh : 1999-2025 John Wiley & Sons El acceso a la e sión publicada del a ículo puede eque i la susc ipción de la e is a. Access o he published e sion may equi e subsc ip ion. “This is he pee e iewed e sion o he ollowing a icle: Pé ez-Puyana, Vic o M; Felix Ángel, Manuel; Rome o Ga cía, Albe o; Gue e o Conejo, An onio: E ec o he injec ion moulding p ocessing condi ions on he de elopmen o pea p o ein-based bioplas ics: om Jou nal o Applied Polyme Science, ol.133 n.20 which has been published in inal o m a h ps://doi.o g/10.1002/app.43306. This a icle may be used o non-comme cial pu poses in acco dance wi h Wiley Te ms and Condi ions o Use o Sel -A chi ed Ve sions. This a icle may no be enhanced, en iched o o he wise ans o med in o a de i a i e wo k, wi hou exp ess pe mission om Wiley o by s a u o y igh s unde applicable legisla ion. Copy igh no ices mus no be emo ed, obscu ed o modi ied. The a icle mus be linked o Wiley’s e sion o eco d on Wiley Online Lib a y and any embedding, aming o o he wise making a ailable he a icle o pages he eo by hi d pa ies om pla o ms, se ices and websi es o he han Wiley Online Lib a y mus be p ohibi ed." 1 E ec o he injec ion moulding p ocessing condi ions on he 1 de elopmen o pea p o ein-based bioplas ics 2 V. Pé ez, M. Felix*,A. Rome o,A. Gue e o 3 Depa amen o de Ingenie ía Química, Uni e sidad de Se illa, Facul ad de Química, 41012 4 Se illa, Spain 5 Abs ac 6 Bioplas ic ma e ials om enewable polyme s, like p o eins, cons i u e a highly 7 in e es ing ield o impo an indus ial applica ions such as packaging, ag icul u e, 8 e c., in which he mo-mechanical echniques a e inc easingly being used. Pea p o ein-9 based bioplas ics can be made h ough a mixing p ocess ollowed by an injec ion 10 moulding. The objec i e o his s udy was o in es iga e he in luence o di e en 11 injec ion pa ame e s (moulding ime and injec ion p essu e) on he p ope ies exhibi ed 12 by he inal bioplas ics ob ained. A dynamic mechanical analysis and ensile s eng h 13 measu emen s we e pe o med, along wi h wa e abso p ion capaci y and anspa ency 14 es s. The esul s indica ed ha he majo di e ences be ween bioplas ics ob ained a 15 di e en moulding imes a e in anspa ency and in he Young's Moduli, exhibi ing 16 lowe alues as moulding ime inc eases. On he o he hand, modi ying he injec ion 17 p essu e leaded o mo e consis en bioplas ics which di e ed mainly in he elas ic 18 componen (E’ p o iles) and in he s ain a b eak. Fu he mo e, he wa e up ake was 19 mo e han 100% in almos all he di e en bioplas ics p ocessed due o i s hyd ophilic 20 cha ac e , so hey could be conside ed as po en ial sou ces o abso ben ma e ial. 21 22 Keywo ds: Pea P o ein; Bioplas ic; Dynamic Mechanical Analysis; Tensile s eng h 23 es ; Wa e Abso p ion. 24 _______________________ 25 *M. FÉLIX 26 2 Depa amen o de Ingenie ía Química, 27 Uni e sidad de Se illa, Facul ad de Química, 28 41012 Se illa (Spain) 29 E-mail: m [email protected] 30 Phone: +34 954557179; ax: +34 954556447. 31 1. In oduc ion 32 P o eins, polysaccha ides and lipids a e sui able aw ma e ials o he p oduc ion o 33 bioplas ics.1,2,3 In pa icula , s a ch is widely used as a packaging ma e ial, usually 34 mixed wi h biodeg adable polyes e s4. Rega ding p o eins o manu ac u e bioplas ics, 35 esea ch s udies ha e in es iga ed no only plan p o eins such as zein, whea glu en 36 and soybean,5,6,7 bu also, in some cases, animal p o eins, such as milk p o eins, 37 collagen, gela ine, e c.8,9.Plan p o eins ha e a g ea po en ial o applying o many 38 manu ac u ing p ocesses.4 Nowadays, soy p o ein domina es he ma ke o bio-based 39 plas ic ma e ials because o i s low p ice, quali y and e sa ile applica ions. Howe e , 40 pea p o ein has inc easingly become an adequa e aw ma e ial due o i s p ice and 41 excellen p ope ies.10,11,12 P o ein concen a es ha e been widely used as aw 42 ma e ials, bu hose bioplas ics ob ained simply by he ac ion o p essu e and 43 empe a u e. Howe e , he combina ion o in e molecula disulphide bonding, hyd ogen 44 bonding, hyd ophobic in e ac ions and elec os a ic o ces be ween p o eins chains 45 ypically leads o a agile and b i le p o ein s uc u es.13Fo ha eason, p o ein 46 concen a es a e gene ally mixed wi h a plas icize . 47 Wi h ega d o plas icize s, hey a e used in o de o educe in e molecula o ces 48 among polyme chains,14,15 educing he cohesion wi hin he ma ix and acili a ing he 49 mobili y o p o ein chains.16 The use o hyd ophilic plas icize s wi h low molecula 50 weigh imp o es he lexibili y o he inal bioplas ics ob ained, bu hey canno suppo 51 a lowe mechanical s ess. The mos e ec i e plas icize , o biopolyme s, is wa e 52 because educes he glass ansi ion empe a u e acili a ing he p ocessing. Wi hou 53 3 wa e addi ion, he deg ada ion empe a u e would be easily eached be o e bioplas ics 54 would be inally p ocessed.17 Besides wa e , glyce ol is a plas icize widely used in 55 he momechanical p ocessing o p o eins.18,19 I s e ec is ela ed o he acili y o 56 glyce ol o be inse ed inside he h ee-dimensional idimensional s uc u e o 57 biopolyme s.20 58 Conside ing he p ocessing me hod, classical he moplas ic polyme p ocessing 59 echniques (ex usion, comp ession moulding, e c.) ha e been used o ob ain di e en 60 p o ein-based bioplas ic ma e ials.21,22,23 Among hese he momechanical echniques, 61 injec ion moulding is one o he mos impo an and sui able p ocesses o sys ems ha 62 may exhibi a mixed cha ac e such as p o eins,24,25,26,27 bu i needs a p e ious mixing 63 p ocess in o de o ob ain a sui able p o ein-plas icize blend. I is impo an o selec 64 he op imum injec ion pa ame e s (injec ion p essu e and moulding ime),28 bu also he 65 empe a u e in he p e-injec ion cylinde , high enough o educe he iscosi y o he 66 blend ( acili a ing he subsequen injec ion) and leading o hea ing changes he h ee-67 dimensional s uc u e o p o eins (p o ein un olding and dena u a ion) by dis up ing 68 hyd ogen bonds and non-pola hyd ophobic g oups.29 Rega ding p o ein ilms, esul ing 69 elec os a ic in e ac ions, hyd ogen bonding, an de Waals o ces (non-co alen 70 o ces) and co alen disul ide b idges can imp o e he ma ix s abili y.30 Howe e , i is 71 impo an o a oid so high empe a u e in he cylinde o a oid p o ein c osslinking by 72 co alen in e molecula disul ide bonds o e en p o ein deg ada ion.26 Fu he mo e, 73 exposu e o alkaline condi ions, pa icula ly when coupled o he mal p ocessing, 74 induces o ma ion o non disulphide co alen c osslinks, such as dehyd oalanine, 75 lysinoalanine and lan hionine.31,32 On he o he hand, i is impo an o con ol he 76 condi ions in he packing s age and in he p e ious injec ion p ocess, selec ing he 77 app op ia e condi ions o ensu e an op imum injec ion speed ela ed wi h he lowe ing 78 speed o he pis on, allowing he blend o be inse ed in o he mould. Depending on he 79 condi ions selec ed, he bioplas ics ab ica ed would exhibi adequa e p ope ies o 80 conside hem o speci ic applica ions. In his way, no only p epa a ion condi ions a e 81 4 impo an , bu only o he componen s in he o mula ion such as plas icize s, pH, 82 chemicals, enzymes, nanocomposi es, lipids and as well as c oss-linking by 83 i adia ion.33 84 The main objec i e o his wo k was o explo e he po en ial de elopmen o biobased 85 plas ic ma e ials om pea p o ein p ocessed by injec ion moulding and o s udy he 86 in luence o injec ion condi ions in he packing s age (moulding ime and injec ion 87 p essu e) on hei mechanical p ope ies. Fu he mo e, a mechanical cha ac e iza ion 88 (wa e abso p ion and anspa ency measu emen s) was use ul o e alua e he e ec s 89 o he modi ica ion o he injec ion pa ame e s on he inal bioplas ics p ope ies. A 90 small-scale-plunge - ype injec ion moulding machine was used in his s udy o ob ain 91 pea p o ein-based specimens om pea p o ein/glyce ol blends, p e iously mixed by 92 means o a mixing heome e ha allows he o que and empe a u e o be eco ded 93 du ing mixing p ocess. 94 95 2. Ma e ial and me hods 96 2.1. Ma e ials 97 Pea lou was p o ided by Roque e (Les em, F ance). I s p o ein con en , ob ained in 98 quad uplica e as % N x 6.25 using a LECO CHNS-932 ni ogen mic o analyse (Leco 99 Co po a ion, S . Joseph, MI, USA) was so close o 90% (89.5±0.7%) ha i can be 100 conside ed as a p o ein isola e (PPI).33 Besides, mic oanalysis esul s e ealed a 101 sulphu con en o 0.45±0.02%, ela ed o he p esence o me hionine and cys eine and 102 i s impo ance on gene a ing c osslinking. The ash and lipids con en o he p o ein 103 isola e we e 3.5±0.2% and 1.4±0.6%, espec i ely. Besides, he pea p o ein isola e 104 p esen s a mois u e con en close o 5% (5.1±0.1%). Glyce ol (GL) wi h esidual wa e 105 con en ≤0.3% was pu chased om Pan eac Química, S.A. (Spain). 106 2.2. Cha ac e iza ion o blends 107 5 2.2.1. Rheological measu emen s. Dough-like blends we e cha ac e ized by small 108 ampli ude oscilla o y shea (SAOS) measu emen s, using a con olled-s ain heome e 109 (ARES, TA Ins umen s, USA). A pla e-pla e geome y (dia: 40 mm) wi h a ough 110 su ace has been used, selec ing a gap be ween pla es o 2 mm. Low iscosi y Dow 111 Co ning 200 luid was used as sealan o a oid sample d ying. S ain sweep SAOS 112 es s we e also pe o med in o de o es ablish he linea iscoelas ici y ange. 113 Tempe a u e amp es s we e ca ied ou a 5 ºC/min om 20 o 100 ºC. In hese 114 measu emen s, complex iscosi y (η*) was moni o ed a a cons an equency o 6.28 115 ad/s. All he sys ems s udied had he same he mo- heological his o y be o e 116 pe o ming any heological es . 117 2.3. P epa a ion o bioplas ics 118 Bioplas ics wi h a 60PPI/40GL a io (lowe p o ein/plas icize a ios would lead o an 119 excess o plas icize ha yields oo low consis en blends o be p ope ly p ocessed and 120 an inc ease o his a io would p oduce some shea -induced c osslinking e ec s 121 leading o excessi ely b i le specimens) we e manu ac u ed by a wo-s age he mo-122 mechanical p ocedu e. Fi s ly, he selec ed blend was mixed using a wo-blade 123 coun e - o a ing ba ch mixe , HaakePolylab QC (The moHaake, Ka ls uhe, Ge many), 124 a 25ºC and 50 pm o 60 min, moni o ing he o que and empe a u e du ing mixing o 125 ob ain a dough-like blend. Secondly, bioplas ics we e ob ained by an injec ion moulding 126 p ocess in a MiniJe Pis on Injec ion Moulding Sys em (The moHaake) using he 127 blends p e iously p epa ed. A schema ic illus a ion o he injec ion moulding cell can 128 be obse ed in Figu e 1: be o e injec ion (A) and a e injec ion ook place (B).The 129 selec ed condi ions o he p e-injec ion cylinde we e 50 °C (see 3.1) and a esidence 130 ime o 100 s. As men ioned abo e, he empe a u e should no be inc eased 131 excessi ely bu in addi ion he esidence ime should no be oo long in o de o p e en 132 he mally induced p o ein c oss-linking e ec be o e he injec ion s age. On he o he 133 hand, as o he mould p ocessing condi ions, he mould empe a u e was 130 ºC and 134 6 di e en moulding imes we e selec ed (100, 200 and 300 s) o in es iga e hei e ec 135 on he p ope ies o he inal bioplas ics ob ained. I was also impo an o a oid 136 exposi ion o high empe a u es o a long ime in o de o a oid p o ein deg ada ion. In 137 addi ion, di e en injec ion p essu es (100, 300, 500 and 900 ba ) we e also e alua ed. 138 A p essu e alue o 200 ba was selec ed o he packing s age, o ensu e a sui able 139 low o blend and moulding o specimens. These condi ions should allow he 140 de elopmen o p o ein c osslinking o achie e he inal ne wo k s uc u e. Some 141 injec ion condi ions as he injec ion p essu e o he moulding ime we e modi ied in 142 o de o s udy hei in luence on he p ope ies o he inal bioplas ics ob ained. Two 143 moulds we e used o p epa e wo di e en specimens: (1) a 60×10×1 mm ec angula -144 shaped specimen o dynamic mechanical analysis (DMA) expe imen s, wa e 145 abso p ion and anspa ency measu emen s and (2) a dumb-bell- ype specimen by ISO 146 527-1:2012 o ensile p ope ies o plas ics. Bioplas ic we e s o ed a oom 147 empe a u e and 50% RH o a leas i e days in o de o each equilib ium. 148 2.4. Cha ac e iza ion o bioplas ics 149 2.4.1. Dynamic Mechanical Analysis (DMA). DMA es s we e ca ied ou wi h a RSA3 150 (TA Ins umen s), on ec angula p obes using dual can ile e bending. S ain sweep 151 es s we e also pe o med in o de o es ablish he linea iscoelas ici y ange.The 152 selec ed hea ing a e was 5 ºC·min−1 and he empe a u e ange co e ed was om 153 -30ºC by he use o an ai chille connec ed o he o ced con ec ion o en (Polycold, 154 TA Ins umen s) o 130ºC. Linea iscoelas ic modulus (E’) and an δ (E’’/E’) we e 155 moni o ed a cons an s ain (0.05%, wi hin he linea iscoelas ic egion) and 156 equency (6.28 ad/s). All he samples we e coa ed wi h Dow Co ning high acuum 157 g ease o a oid wa e loss and showed he same he mo- heological his o y. 158 2.4.2. Tensile s eng h measu emen s. Tensile es s we e pe o med by using he 159 Insigh 10 kN Elec omechanical Tes ing Sys em (MTS, Eden P ai ie, MN, USA), 160 acco ding oby ISO 527-2:1993 o Tensile P ope ies o Plas ics. Young’s Modulus, 161 7 s ain a b eak and maximum ensile s eng h we e e alua ed using ype IV p obes and 162 an ex ensional a e o 10 mm·min−1 a oom empe a u e. 163 2.4.3. Wa e abso p ion capaci y. Wa e up ake capaci y o bioplas ics was measu ed 164 acco ding o he s anda d me hod o de e mining wa e abso p ion in plas ics 165 ASTMD570, 2001. Rec angula specimens o 60×10 ×1 mm we e used. The 166 specimens we e subjec ed o d ying (condi ioning) in an o en a 50±2 ºC o 5-6h o 167 de e mine d y weigh , hen in oduced in o dis illed wa e and weighed a e 24h 168 imme sion. Finally, i was subjec ed o d ying ( econdi ioning) again and weighed o 169 de e mine he soluble ma e ial loss. All he expe imen s we e pe o med in iplica e a 170 oom empe a u e. Acco ding o he me hodology used, wa e abso p ion capaci y and 171 soluble ma e ial loss we e de e mined by he ollowing equa ions: 172 % 𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊 𝑢𝑢𝑢𝑢𝑊𝑊𝑊𝑊𝑢𝑢𝑊𝑊 = 𝑊𝑊𝑊𝑊𝑊𝑊 𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊ℎ𝑊𝑊 − 𝐼𝐼𝐼𝐼𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝐼𝐼 𝐷𝐷𝑊𝑊𝐷𝐷𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊ℎ𝑊𝑊 𝐼𝐼𝐼𝐼𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝐼𝐼 𝐷𝐷𝑊𝑊𝐷𝐷𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊ℎ𝑊𝑊 ·100 (1) 173 % 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 𝐿𝐿𝑜𝑜 𝐿𝐿𝐿𝐿𝐼𝐼𝑢𝑢𝑠𝑠𝐼𝐼𝑊𝑊 𝑚𝑚𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝐼𝐼 = 𝐼𝐼𝐼𝐼𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝐼𝐼 𝐷𝐷𝑊𝑊𝐷𝐷𝐷𝐷𝑊𝑊𝑊𝑊𝑊𝑊ℎ𝑊𝑊 − 𝐹𝐹𝑊𝑊𝐼𝐼𝑊𝑊𝐼𝐼 𝐷𝐷𝑊𝑊𝐷𝐷𝐷𝐷𝑊𝑊𝑊𝑊𝑊𝑊ℎ𝑊𝑊 𝐼𝐼𝐼𝐼𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝐼𝐼 𝐷𝐷𝑊𝑊𝐷𝐷𝐷𝐷𝑊𝑊𝑊𝑊𝑊𝑊ℎ𝑊𝑊 ·100 (2) 174 2.4.4. Colou de e mina ion. A Colo ime e CM-700D (Konica, Japan) was used o 175 measu e he colou o he bioplas ics. Acco ding o EN ISO 11664-4, he CIE s anda ds 176 a e used o calcula e colou di e ences. I is desc ibed by a h ee-dimensional 177 coo dina e sys em (L*, a* and b*) ha loca es a colou in a colou space. The 178 pa ame e L* e e s o he ligh ness o he colou (L* = 0 indica es black and L* = 100, 179 whi e). Pa ame e s a* and b* can be ei he posi i e o nega i e: Pa ame e a* ex ends 180 om g een (-a*) o ed (+a*) and b* om blue (-b*) o yellow (+b*). 181 2.4.5 T anspa ency measu emen s. T anspa ency measu emen s we e pe o med on a 182 Genesys-20 (The mo Scien i ic, USA) spec opho ome e . In his de ice, he 183 ansmi ance (%) o ec angula specimens, 1mm hickness, a a selec ed wa eleng h 184 o 600 nm is measu ed. Ai is used as blank (100% ansmi ance). In o de o compa e 185 he anspa ency o di e en bioplas ics, a ansmi ance index (IT) was used: 186 𝐼𝐼𝑇𝑇=% 𝑇𝑇𝑊𝑊𝑊𝑊𝐼𝐼𝐿𝐿𝑚𝑚𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝐼𝐼𝑇𝑇𝑊𝑊 %𝑇𝑇𝑊𝑊𝑊𝑊𝐼𝐼𝐿𝐿𝑚𝑚𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝐼𝐼𝑇𝑇𝑊𝑊𝐿𝐿𝑜𝑜𝑊𝑊𝑊𝑊𝑜𝑜𝑊𝑊𝑊𝑊𝑊𝑊𝐼𝐼𝑇𝑇𝑊𝑊 𝑠𝑠𝑊𝑊𝐿𝐿𝑢𝑢𝐼𝐼𝑊𝑊𝐿𝐿𝑊𝑊𝑊𝑊𝑇𝑇 (3) 187 8 2.5. S a is ical analysis 188 A leas h ee eplica es o each measu emen we e ca ied ou . S a is ical analyses 189 we e pe o med wi h es s and one-way analysis o a iance (ANOVA, p < 0.05) by 190 means o he s a is ical package SPSS 18 (IBM, Chicago, IL, USA). S anda d 191 de ia ions om some selec ed pa ame e s we e calcula ed. 192 193 3. Resul s and discussion 194 3.1. P epa a ion and cha ac e iza ion o blends 195 As indica ed abo e, mixing is he i s s age in he he mochemical p ocessing o he 196 p o ein-based bioplas ics s udied. The 60PPI/40GL a io was an adequa e p opo ion 197 because doughs wi h a highe o lowe con en in p o ein would no be sui able o 198 p ocessabili y because hey we e oo consis en o he inal bioplas ics exhibi glyce ol 199 exuda ion, espec i ely ( esul s no shown). Besides choosing an app op ia e 200 p o ein/plas icize a io, a sui able selec ion o he mixing condi ions is e y impo an , 201 howe e i is no always easy. An ex ensi e mixing was equi ed o ob ain a 202 homogeneous dough-like blend, bu long mixing pe iods mus be a oided o limi shea 203 induced s uc u a ion e ec s. Fo ha eason, bo h o que and empe a u e alues 204 we e moni o ed as a unc ion o mixing ime o he 60PPI/40GL sys em (Figu e 2). The 205 p o ile shows a maximum o que alue ollowed by a con inuous dec ease and a 206 endency o each an e en ual cons an alue, whe eas he empe a u e exhibi ed a 207 cons an inc ease o e he mixing ime. 208 F om he o que and empe a u e p o iles, i may be deduced ha a balance o he 209 mixing ime, long enough o a sui able homogeniza ion deg ee bu sho enough o 210 a oid p ema u e c oss-linking eac ions o p o ein chains is needed. The e o e, h ee 211 di e en mixing imes we e s udied: one ela ed o he minimum o que (10 min), 212 ano he when he inc ease in o que was p oduced (21 min) and he hi d when he 213 15 Acknowledgemen s 378 This wo k is pa o a esea ch p ojec sponso ed by MINECO, “Minis e io de Economía 379 y Compe i i idad”, om he Spanish Go e nmen (Re . MAT2011-29275-C02-02/01) 380 and by he Andalousian Go e nmen , (Spain) (p ojec TEP-6134). The au ho s 381 g a e ully acknowledge hei inancial suppo . 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Diag am o he lab-scale plunge - ype injec ion moulding de ice: (A) Be o e 470 injec ion; (B) A e injec ion. 471 Figu e 2. E olu ion o mixing o que and empe a u e o e he mixing p ocess o he 472 60PPI/40GL blend. Pic u es o he esul ing blends a di e en mixing imes a e 473 inse ed. 474 Figu e 3. Complex iscosi y (η*) o e hea ing a cons an a e (5 ºC/min) o 60/40 and 475 70/30 PPI/GL a ios. 476 Figu e 4. Resul s om mechanical es s ca ied ou o 60PPI/40GL biobased 477 specimens ob ained a di e en moulding imes (100, 200 and 300 s): (A) S o age 478 modulus (E’) and (B) loss angen ( an δ) alues om Dynamic Mechanical The mal 479 Analysis (DMTA) empe a u e amp measu emen s pe o med a cons an equency 480 (6.28 ad/s) and hea ing a e (3oC·min-1). Values o LDPE and Soy biobased 481 specimens (SPI) we e also included. 482 Figu e 5. Young’s modulus, maximum s ess and s ain a b eak om Tensile S eng h 483 measu emen s ca ied ou o 60PPI/40GL biobased specimens ob ained a di e en 484 moulding imes (100, 200 and 300s). Values o Soy biobased specimens (SPI) we e 485 also included. Columns wi h di e en le e s a e signi ican ly di e en (P ≤ 0.05). 486 Figu e 6. (A) E olu ion o wa e abso p ion capaci y (%) a e imme sion o 24 h and 487 soluble ma e ial loss (%) and (B) Colo s anda ds and anspa ency measu emen s: 488 ligh ness (L*), yellow/blue alue (b*) and ansmi ance ca ied ou o 60PPI/40GL 489 biobased specimens ob ained a di e en moulding imes (100, 200 and 300s). 490 Columns wi h di e en le e s a e signi ican ly di e en (P ≤ 0.05). 491 Figu e 7. Resul s om mechanical es s ca ied ou o 60PPI/40GL biobased 492 specimens ob ained a di e en injec ion p essu es (100, 300, 500 and 900 ba ): (A) 493 S o age modulus (E’) and (B) loss angen ( an δ) alues om Dynamic Mechanical 494 The mal Analysis (DMTA) empe a u e amp measu emen s pe o med a cons an 495 equency (1 Hz) and hea ing a e (3oC·min-1). 496 Figu e 8. Young’s modulus, maximum s ess and s ain a b eak om Tensile S eng h 497 measu emen s ca ied ou o 60PPI/40GL biobased specimens ob ained a di e en 498 injec ion p essu es (100, 300, 500 and 900 ba ). Columns wi h di e en le e s a e 499 signi ican ly di e en (P ≤ 0.05). 500 Figu e 9. (A) E olu ion o wa e abso p ion capaci y (%) a e imme sion o 24 h and 501 soluble ma e ial loss (%) and (B) Colo s anda ds and anspa ency measu emen s: 502 ligh ness (L*), yellow/blue alue (b*) and ansmi ance ca ied ou o 60PPI/40GL 503 biobased specimens ob ained a injec ion p essu es (100, 300, 500 and 900 ba ). 504 Columns wi h di e en le e s a e signi ican ly di e en (P ≤ 0.05). 505 506 19 FIGURE 1 507 508 509 510 511 512 20 513 FIGURE 2 514 020 40 60 0 5 10 15 20 25 30 To que (N·m) (min) To que (N·m) T(ºC) 20 40 60 80 T (ºC) 515 516 517 518 519 21 520 FIGURE 3 521 522 20 30 40 50 60 70 80 90 100 6.0x10 4 8.0x10 4 1.0x10 5 1.2x10 5 1.4x10 5 1.6x10 5 60PPI/40GL 70PPI/30GL T (ºC) η∗ (Pa·s) 523 524 525 526 22 527 FIGURE 4 528 -40 -20 020 40 60 80 100 120 140 10 6 10 7 10 8 10 9 A E' (Pa) T(ºC) LDPE E' (Pa) (100 s) E' (Pa) (200 s) E' (Pa) (300 s) E' (Pa) SPI (500 s) 529 -40 -20 020 40 60 80 100 120 140 0.0 0.1 0.2 0.3 0.4 0.5 T(ºC) LDPE an δ (100 s) an δ (200 s) an δ (300 s) an δ SPI (500 s) an δ B 530 531 532 533 534 23 535 FIGURE 5 536 0 10 20 30 40 50 60 70 80 90 100 S ain a B eak (%) SPI (500 s)300 s 200 s 100 s δ C b Moulding ime Maximum S ess (MPa) Young's Modulus (MPa) S ain a B eak (%) Young's Modulus (MPa) Maximum S ess (MPa) A a α B a β A a γ 0 2 4 6 8 10 537 538 539 540 541 24 542 FIGURE 6 543 544 545 546 547 548 549 550 551 552 553 554 555 556 557 558 559 560 561 562 563 564 565 566 100 s 200 s 300 s 0 40 80 120 Soluble Ma e ial Loss (%) a a a C B A Wa e Up ake (%) Moulding Time Wa e Up ake (%) Soluble Ma e ial Loss (%) A