1
De elopmen o c ay ish p o ein-PCL biocomposi e ma e ial
1
p ocessed by injec ion moulding
2
M. Félix, A. Rome o*, J.E. Ma ín-Al onso, A. Gue e o
3
Depa amen o de Ingenie ía Química, Uni e sidad de Se illa, Facul ad de Química, 41012
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Se illa, Spain
5
Abs ac
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A combina ion o c ay ish lou (CF, wi h 60% p o ein) and Polycap olac one (PCL) was
7
success ully used o p epa e biocomposi es by a p ocess ha consis s o wo s ages:
8
mixing wi h glyce ol (GL) as plas icize and injec ion moulding o CF/GL/PCL blends.
9
Mixing heome y and Di e en ial Scanning Calo ime y (DSC) measu emen s we e
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ound o be use ul o selec sui able injec ion moulding condi ions. A ema kable
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enhancemen in mechanical p ope ies was ound o PCL con aining sys ems, e en
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when c ys alline s uc u e emains unal e ed. PCL yields a dominan con ibu ion o he
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elas ic esponse and con e a highe abili y o abso b ene gy be o e up u e, bu also
14
he p o ein/plas icise a io mus be conside ed.
15
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Keywo ds: A. Polyme -ma ix composi es (PMCs); B. Rheological p ope ies
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B. The momechanical; E. Injec ion moulding
18
_______________________
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*A. ROMERO
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Depa amen o de Ingenie ía Química,
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Uni e sidad de Se illa, Facul ad de Química,
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41012 Se illa (Spain)
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E-mail: al ome[email p o ec ed]
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Phone: +34 955420984; ax: +34 954556447.
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1. In oduc ion
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The excep ional p ope ies o plas ics, ha ha e e en lead o eplace o he
27
adi ional ma e ials such as me al and wood in many applica ions, ha e os e ed a
28
con inuous demand g ow h, ollowing a end which has been inc easing since 1950s
29
[1]. Howe e , pe oleum p oduc ion cos s ha e also been inc easing, subsequen ly
30
leading o a con inuous ise in oil p oduc s. Fo hese easons, he de elopmen o eco-
31
iendly polyme ic ma e ials ha could con ibu e o educe pe oleum dependence and
32
is becoming mo e u gen ly equi ed. In ac , he de elopmen o biodeg adable
33
ma e ials wi h sui able p ope ies has been a g ea esea ch challenge o he scien i ic
34
communi y o polyme ma e ials du ing ecen yea s [2]. Nowadays, socie y has been
35
in e es ed in he use o enewable biomass o manu ac u e high-quali y, cos -
36
compe i i e and biodeg adable consume goods as a means o educe he
37
consump ion and dependence on pe oleum, as well as, o diminish en i onmen al
38
pollu ion [3, 4].
39
Fo many yea s, p o eins, lipids and polysaccha ides ha e been selec ed as a
40
sou ce o biopolyme ma e ials [5-8]. Rega ding p o eins, mos s udies ha e used plan
41
p o eins such as zein, whea glu en o soybean in o de o manu ac u e bioplas ic
42
ma e ials [9-11]. Mo eo e , animal p o eins (milk p o eins, collagen, gela ine, egg
43
albumen…) ha e also been used o ob ain bioplas ics [12-15].
44
A u he p o ein sou ce consis s o using hose by-p oduc s, su pluses and was es
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ha a e p oduced in la ge quan i ies e e y yea by he ood indus y. This al e na i e
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also in ol es impo an en i onmen al bene i s de i ed om was e educ ion. An
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excellen example o his sou ce is ea u ed by he eshwa e ed-swamp c ay ish
48
(P ocamba us Cla kii), which has unde gone a as g ow h due o he ini ial lack o
49
p eda o s, abundan ood and a o able en i onmen al condi ions [16]. P e ious esul s
50
ha e demons a ed he abili y o p o eins om low alue-added c ay ish byp oduc s in
51
3
he s abiliza ion o emulsions [17] and he o ma ion o he mal-induced gel p oduc s
52
[18].
53
P o ein coming om c ay ish (CF) may be used o de elop bioplas ic ma e ials wi h
54
signi ican ad an ages since hey a e de i ed om a sus ainable bio esou ce and can
55
be p ocessed in much he same way as con en ional syn he ic polyme s [19].
56
T adi ionally, p o ein ilms a e p ocessed by cas ing me hod [20], howe e classical
57
polyme p ocessing echniques (comp ession moulding o ex usion) a e being
58
inc easingly used in his ield [21, 22]. Among hem, injec ion moulding is a ai ly
59
a ac i e ope a ion ha dese es pa icula a en ion. Typically in his p ocess, p o eins
60
a e mixed wi h a plas icise in o de o educe in e molecula o ces among polyme
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chains, inc easing mobili y and educing he glass ansi ion [7]. The ea e , polyme ic
62
blends a e subjec ed o sui able he mal condi ions, being injec ed a high p essu e in o
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he mould ca i y [12].
64
The op imiza ion o p ocessing condi ions is essen ial in o de o achie e he
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desi able p ope ies o he inal p oduc . This ac is pa icula ly ele an in p o ein-
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based ma e ials ha equi e a p ope he moplas ic mixing wi h a sui able plas icise ,
67
and may e en come o show a p edominan he mose cha ac e upon injec ion
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moulding.
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The e is no much in o ma ion on he use o blends con aining polycap olac one
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(PCL) and p o ein blends in o de o p oduce bio-composi e ma e ials. PCL is classi ied
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as a polyes e om ossil sou ce, which has been widely used as he polyme ma ix in
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he de elopmen o new ma e ials. I is highly lexible, biodeg adable, biocompa ible
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and easy o p ocess [23, 24]. PCL can be blended wi h a a ie y o o he polyme s o
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imp o e hei p ope ies [25]. In ac , blending a na u al polyme wi h polyes e is an
75
in e es ing way o educe cos s and o imp o e he biodeg adabili y o he esul ing
76
polyme blends [26].
77
The o e all objec i e o his wo k is o de elop CF/PCL biocomposi e plas ic
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ma e ials plas icised wi h glyce ol (GL) by means o wo-s age p ocessing ha consis s
79
4
o mixing and injec ion moulding, using di e en CF/GL/PCL a ios. Rheological and
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di e en ial scanning calo ime y (DSC) measu emen s o CF/GL/PCL blends ha e
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been ca ied ou in o de o selec sui able p ocessing pa ame e s ( empe a u e and
82
esidence ime in he p e-injec ion mixing chambe as well as he empe a u e o he
83
mould). P ope ies o moulded specimens ha e been e en ually assessed by dynamic
84
mechanical analysis, X-Ray di ac ion and ensile s eng h measu emen s.
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2. Ma e ial and me hods
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2.1. Ma e ials
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C ay ish lou (CF) was ob ained om ALFOCAN S.A. (Isla Mayo , Se ille, Spain).
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The p o ein con en was de e mined in quad uplica e as % N x 6.25 using a LECO
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CHNS-932 ni ogen mic o analyse (Leco Co po a ion, S . Joseph, MI, USA) [27] being
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65 w .%. Glyce ol (GL) was pu chased om Pan eac Química, S.A. (Spain) and PCL
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(CapaTM FB100) was supplied by Pe s o p (Sweden).
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2.2. P epa a ion o samples
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Di e en CF/GL/PCL sys ems ha e been selec ed o his s udy using di e en
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CF/GL a ios (1.3, 2.0, 2.3 and 2.6) and di e en PCL con en (0, 10 and 30%). The
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PCL- ee sys em (deno ed by 70/30/0) has been used as he e e ence.
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CF/GL/PCL blends we e manu ac u ed by a he momechanical p ocedu e which
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includes wo s ages: Ini ially, hese blends we e mixed in a wo-blade coun e - o a ing
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ba ch mixe Haake Polylab QC (The moHaake, Ge many) a 25ºC and 50 pm o 60
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min., moni o ing he o que and empe a u e du ing mixing. Secondly, he biocomposi e
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blends ob ained a e he mixing p ocess we e subsequen ly p ocessed by injec ion
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moulding using a MiniJe Pis on Injec ion Moulding Sys em II (The moHaake,
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Ge many) o ob ain biocomposi es specimens. Th ee s ages a e conside ed o e his
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p ocess: he p e-injec ion s age, he injec ion i sel and he a e -injec ion packing
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s age. Table 1 shows he p ocessing pa ame e s ( empe a u e, p essu e and ime)
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alues o he injec ion moulding p ocess used in his s udy, which is simila o hose
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used in p e ious pape s [28, 29]. The alues o he p ocessing pa ame e s a he p e-
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injec ion cylinde a e selec ed o ensu e a blend iscosi y low enough o acili a e i s
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injec ion in o he mould. The esidence ime selec ed o he packing s age ( igh a e
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injec ion) has been 220 s since no u he enhancemen has been no iced by
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inc easing his pe iod. In addi ion, exposi ion o high empe a u es o a long ime
111
ypically leads o p o ein deg ada ion (i.e. ia Mailla d- ype eac ions) [30].
112
Two ypes o moulds we e used o p epa e CF/GL/PCL specimens: a 60×10×1 mm
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ec angula shape mould o DMTA expe imen s and a Dumpbell ype specimen
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de ined by ISO 527-2 [31] o Tensile P ope ies o Plas ics.
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2.3. Cha ac e iza ion o blends
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2.3.1. Di e en ial Scanning Calo ime y (DSC). DSC expe imen s we e pe o med wi h
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a Q20 (TA Ins umen s, USA), using 5 o 10 mg samples, in he me ic aluminium pans.
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A hea ing a e o 10 ºC/min was selec ed. The sample was pu ged wi h a ni ogen low
119
o 50 mL/min.
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2.4. Cha ac e iza ion o biocomposi es
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2.4.1. Dynamic Mechanical Tempe a u e Analysis (DMTA). DMTA es s we e ca ied
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ou wi h a RSA3 (TA Ins umen s, New Cas le, DE, USA), on ec angula specimens
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using dual can ile e bending. All he expe imen s we e ca ied ou a cons an
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equency (1 Hz) and s ain (be ween 0.01 and 0.30%, wi hin he linea iscoelas ic
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egion). The selec ed hea ing a e was 3 ºC·min−1. All he samples we e coa ed wi h
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Dow Co ning high acuum g ease o a oid wa e loss.
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2.4.2. X-Ray di ac ion (XRD). XRD s udies o he specimens we e ca ied ou using a
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D8 Disco e (BRUKE, Massachuse s, USA) (45 kV, 100 mA) equipped wi h Cu Kα
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adia ion (λ = 0.1516 nm) in o de o isualise di e en c ys alline phases ha may
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indica e sys ems whose mic os uc u e could be di e en .
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2.4.3. Tensile s eng h measu emen s. Tensile es s we e pe o med by using he
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Insigh 10 kN Elec omechanical Tes ing Sys em (MTS, Eden P ai ie, MN, USA),
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acco ding o by ISO 527-2 [31] o Tensile P ope ies o Plas ics. Tensile s eng h
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pa ame e s we e e alua ed om a leas h ee duplica es o each p oduc using ype
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IV p obes and an ex ensional a e o 1 mm·min−1 a oom empe a u e.
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2.5. S a is ical analysis
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S a is ical analysis was pe o med using - es and one-way analysis o a iance
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(ANOVA, p0.05) by means o he s a is ical package SPSS 18. S anda d de ia ions
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om some selec ed pa ame e s we e calcula ed.
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3. Resul s and discussion
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3.1. P epa a ion o blends by he moplas ic mixing
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Fig. 1 exhibi s o que and empe a u e p o iles as a unc ion o mixing ime o
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di e en CF/GL/PCL blends. Fig, 1A, shows bo h p o iles o blends main aining he
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same CF/GL a io a ca. 2.3, using di e en PCL con en , whe e he blend wi hou PCL
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is used as he e e ence sys em. On he o he hand, hose blends con aining 10% PCL
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a di e en CF/GL a ios a e plo ed in Fig. 1B.
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These esul s pu o wa d he ele an dependence o o que and empe a u e on
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he CF/GL/PCL a io. Thus, a apid inc ease in o que up o a maximum alue akes
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place, ollowed by an asymp o ic dec ease owa ds a pla eau alue. Tempe a u e
150
p o iles gene ally ollow an inc ease owa ds a pla eau alue. The ime equi ed o
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each he pla eau alues o bo h a iables ( o que and empe a u e), which is oughly
152
he same, is clea ly dependen on he CF/GL/PCL a io. This coincidence may be seen
153
as a consequence o he de elopmen o exo he mic c osslinking eac ions du ing he
154
mixing p ocesses ha in ol e bo h an inc ease in empe a u e and consis ency
155
( e lec ed in o que). Bo h p o iles show also an ini ial induc ion pe iod, being mo e
156
e iden o hose blends displaying he slowes e olu ion. I is wo h men ioning ha a
157
o que peak appea s when unmel ed PCL is p esen in he blend. Thus, he PCL mel
158
poin , which is eached a abou 55ºC, is coinciden wi h he maximum o que alue. In
159
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o he wo ds, he o que does no s a o dec ease un il he PCL mel ing poin is
160
exceeded.
161
As may be obse ed in Fig. 1A, an inc ease in PCL con en leads o a as e o que
162
and empe a u e kine ics and, as a consequence, o an an icipa ion o bo h p o iles.
163
The e ec also gi es ise o a gene al inc ease in o que and empe a u e alues a any
164
ime. Simila beha iou can be obse ed by inc easing he CF/GL a io (Fig. 1B).
165
3.2. The mal cha ac e iza ion o blends
166
Hea low pa e ns ob ained om Di e en ial Scanning Calo ime y (DSC)
167
measu emen s a e shown in Fig. 2. Fig 2A shows he he mog am o CF lou and o
168
he e e ence sys em (CF/GL/PCL, 70/30/0), as well as he p o iles co esponding o
169
CF/GL/PCL blends a cons an CF/GL a io, as a unc ion o PCL con en . On he o he
170
and, Fig. 2B displays he DSC esul s o CF/GL/PCL blends con aining 10% PCL as a
171
unc ion o he CF/GL a io.
172
CF lou displays a ypical endo he m o a ai ly dena u ed p o ein sys em. This
173
p o ile exhibi s an endo he mic i s peak a 68ºC, a glass ansi ion (Tg) a ca. 92ºC, as
174
well as a b oad endo he mic e en be ween he Tg and 130ºC. The i s he mal e en
175
can be a ibu ed o he physical aging e ec , which was p e iously epo ed o his CF
176
lou [32]. Physical aging is a gene al phenomenon ha occu s o e ime in glassy o
177
pa ial glassy polyme s below hei Tg and is a mani es a ion o he non-equilib ium
178
na u e o he glassy s a e [33, 34]. The glass ansi ion a a ound 90ºC is consis en
179
wi h p e ious esul s epo ed by Fa ahnaky e al. [32] o c ay ish lou and Hashimo o
180
e al. [35] o ish muscle p o eins. On he o he hand, he b oad endo he mic e en
181
may be ela ed o he huge a ie y o p o ein ac ions o di e en molecula weigh ha
182
cons i u e he CF lou a epo ed in a p e ious pape [36].
183
Wi h ega d o he endo he ms ob ained o he e e ence sys em he wo
184
endo he mic e en s anish. The o al disappea ance o he i s endo he mic peak,
185
mos p obably as a consequence o mixing, con i ms i s physical ageing-d i en na u e.
186
8
Howe e , he glass ansi ion emains oughly a he same empe a u e o all he
187
blends s udied.
188
In addi ion, i is wo h men ioning ha all he sys ems con aining PCL display an
189
appa en endo he mic peak a ca. 55 ºC, which is a ibu ed o he PCL mel ing poin .
190
This peak becomes mo e p onounced wi h inc easing PCL con en , as may be
191
obse ed in Fig. 2.
192
The esul s ob ained om DSC measu emen s also con i m he sui abili y o he
193
empe a u e selec ed o he cylinde and mould, since he o me (60ºC) is highe han
194
he endo he mic peak co esponding o he PCL mel ing whe eas he la e empe a u e
195
(100ºC) is highe han he glass ansi ion in o de o a ou mobili y and empe a u e-
196
induced p o ein c osslinking (in combina ion wi h p essu e).
197
3.3. Mechanical cha ac e iza ion o biocomposi es
198
3.3.1. Dynamic Mechanical Tempe a u e Analysis
199
Fig. 3 shows he alues o he elas ic modulus, E’ (Fig. 3A), and he loss angen ,
200
an  (Fig. 3B), as a unc ion o empe a u e ( om -30ºC o 140º) ob ained om DMA
201
measu emen s. The e e ence sys em is compa ed wi h hose specimens wi h he
202
same p o ein/plas icise a io (CF/GL/PCL: 63/27/10 and 49/21/30).
203
As may be obse ed in Fig. 3A, all he specimens s udied show a simila p o ile o
204
E’ a low and medium empe a u e. In his way, an inc ease in empe a u e leads o a
205
dec ease in elas ic modulus (E’) ha ends o each a pla eau alue. I is ema kable,
206
howe e , ha PCL con aining samples exhibi highe elas ic modulus p o ided ha
207
empe a u e emains below he PCL mel ing poin . A he mel ing poin he h ee
208
samples show a he coinciden alues ha unde go a dec ease wi h inc easing
209
empe a u e. In ac , he e is a egion whe e he PCL- ee specimen shows sligh ly
210
highe E’ alues. E en ually a empe a u e is eached abo e which he dec ease in E’
211
ound o he e e ence specimen becomes as e whe eas he PCL-con aining
212
composi es end o each a pla eau egion.
213
9
In addi ion, i is in e es ing o ema k ha he e e ence sys em shows a minimum in
214
E’ close o 100ºC, ollowed by an appa en enhancemen o elas ic p ope ies inc ease,
215
which is cha ac e is ic o a he mose ing po en ial [37-39]. In o he wo ds, an inc ease
216
in he empe a u e o he packing s age would lead o a ein o cemen o he
217
biopolyme ma ix. In con as , he addi ion o PCL leads o a educ ion in his po en ial
218
han ends o disappea a he highes PCL con en , whe e elas ic p ope ies emain
219
a he independen on empe a u e. These esul s sugges ha he mel ing o PCL
220
esul s in a ce ain educ ion in he ee olume leading o an inc ease in physical
221
in e ac ions. In any case, he esponse in he high empe a u e egion seems o be
222
domina ed by he p esence o mel ed PCL.
223
Fu he mo e, all p obes s udied display simila loss angen p o iles (Fig. 3B)
224
showing one single peak, which is ela ed o a glass-like ansi ion o he plas icized
225
p o ein-based ma e ial. These unimodal p o iles indica e a good compa ibili y be ween
226
compounds, ob ained o all sys ems a e he injec ion moulding p ocess. Howe e ,
227
he inc ease in PCL con en gi es ise o a plas icising e ec leading o a dec ease in
228
he peak empe a u e ( om ca. 100 o 50ºC).
229
Figu e 4 shows he alues o some pa ame e s selec ed in o de o compa e he
230
beha iou o di e en biocomposi e ma e ials. The i s one (shown in Fig. 4A)
231
co esponds o he alue o he s o age modulus a 1 Hz and 20ºC (E’1,20) and he
232
second is he alue o he loss angen a he peak empe a u e ( an δmax), whose
233
alues (Tpeak) a e also included in he plo (Fig. 4B). These esul s con i m he e ec o
234
PCL-induced inc ease in elas ici y ha akes place also a a highe CF/GL a io.
235
Mo eo e , a cons an PCL con en , an inc ease in CF/GL a io also p oduces an
236
inc ease in E’ alues. This e ec is pa icula ly no iceable a he highes PCL
237
concen a ion, which sugges s occu ence o a syne gis ic e ec be ween CF and PCL.
238
Simila esul s we e epo ed by Ai hani and Mohan y [40], which ound an inc ease in
239
s o age modulus o bioplas ics con aining PCL and co n glu en meal as he p opo ion
240
o PCL inc ease.
241
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In e acial and emulsi ying beha iou o c ay ish p o ein isola e. Lw -Food Science and
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Figu e Cap ions
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Fig. 1. E olu ion o o que and empe a u e o e he mixing p ocess o c ay ish
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lou /glyce ol/polycap olac one (CF/GL/PCL) sys ems: (A) a cons an CF/GL a io:
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70/30/0, 63/27/10 and 49/21/30; (B) a cons an PCL concen a ion: 65/25/10, 63/27/10
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and 60/30/10.
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Fig. 2. DSC p o iles o c ay ish lou and CF/GL/PCL blends: (A) a cons an CF/GL
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a io: 70/30/0, 63/27/10 and 49/21/30; (B) a cons an PCL concen a ion: 65/25/10,
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63/27/10 and 60/30/10.
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19
Fig. 3. DMA empe a u e amp measu emen s pe o med a cons an equency (1 Hz)
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and hea ing a e (3ºC·min-1) o CF/GL/PCL injec ion moulded specimens a cons an
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CF/GL a io: 70/30/0, 63/27/10, 49/21/30: (A) S o age modulus (E’); and (B) loss
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angen ( an δ).
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Fig. 4. Linea iscoelas ic unc ions om DMA measu emen s o all CF/GL/PCL
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s udied sys ems: 70/30/0, 65/25/10, 63/27/10, 60/30/10, 55/15/30, 49/21/30 and
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40/30/30: (A) S o age modulus (E’); (B) loss angen ( an δ).
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Fig. 5. X-Ray Di ac ion measu emen s (XRD) o CF/GL/PCL specimens: (A)
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con aining 10 w .% PCL: 65/25/10, 63/27/10 and 60/30/10, as well as he e e ence
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specimen 70/30/0; (B) con aining 30 w .% PCL: 55/15/30, 49/21/30 and 40/30/30, as
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well as PCL powde .
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Fig. 6. Resul s om uniaxial Tensile S eng h measu emen s o he specimens s udied
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70/30/0, 65/25/10, 63/27/10, 60/30/10, 55/15/30, 49/21/30 and 40/30/30: (A) Tensile
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s ess-s ain cu es (only o specimens a cons an CF/GL a io: 70/30/0, 63/27/10 and
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49/21/30); (B) Young’s modulus (E); (C) s ain a b eak (ƐMax); (D) Toughness (T)
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Figu e 1
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Figu e 2
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Figu e 3
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Figu e 4
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Figu e 5
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