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“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.
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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 . The au ho s also acknowledge he 382
Mic oanalysis Se ice (CITIUS-Uni e sidad de Se illa) o p o iding ull access and 383
assis ance o he LECO-CHNS-932 (TA ins umen s). 384
385
Re e ences 386
1. Tan a anakul, V., Sai hai, P. Mechanical p ope ies o bioplas ics and bioplas ic-387
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Appl.Polym. Sci.2009,114, 3057-3067. 389
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467
18
FIGURE CAPTIONS 468
469
Figu e 1. 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