Biodegradable Green Composites From Thermoplastic Canola Meal Biology Essay

Abstraction

This present survey, to research the value added use of canola repast, a chief by-product from canola oil industry. The canola repast was plasticized with glycerol/water mixture, denatured by the add-on of guanidine hydrochloride ( GHCL ) were thermally processed in thaw bulge. The combined consequence of plasticization and destructerization outputs thermoplastic canola repast ( TCM ) . The TCM was blend with PBAT and PBAT/PLA biodegradable polyester to manufacture new blend green stuffs. The new blend stuff blend belongingss were characterized by thermal ( TGA, DSC ) , thermo mechanical ( storage modulus and TanI? ) , and tensile, and Izod impact measurings.

The melt-compounded blends of TCM with biodegradable polyesters give new ductile bioplastics. The higher tensile, flexural and modulus values were obtained utilizing TCM with biodegradable blends of PBAT/PLA. This survey is attributed to the plasticization consequence of glycerin to its little size which helps in its interpolation and placement within the protein construction in order to do it more compatible with polymer system.

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Keywords: Thermoplastic canola repast, PBAT, PLA and Biocomposite

*Corresponding writer. Tel. : +1 519-824-4120. Extn. 56664

Email reference: mohanty @ uoguelph.ca ( Amar Mohanty )

Introduction

In recent old ages, sustainability, environmental concerns and green chemical science have played a critical function in steering the development of the following coevals of stuffs, merchandises and engineering. The bulk of plastics come from crude oil resources and does non degrade in environments and doing serious to tellurian and aquatic home ground ( www.plasticseurope.com, 2011 ) . In this concern, renewable agribusiness and biomass feedstocks have shown much promise to replace crude oil feedstock, without viing with nutrient harvests ( Von Braun, 2007 ) .

Canola repast is the chief by merchandise of the canola oil industry. Canola repast is the 2nd largest protein repast produced in the universe, after production of soybean repast ( USDA, 2012 ) . It is presently used for comparatively low-value animate being provender ( Bell, 1993 ) . Canola repast contains 34-38 % protein, although canola protein possesses a well-balanced amino acerb composing. Due to its high content of storage proteins, canola repast has possible to be used in a assortment of possible industrial merchandise applications such as adhesives, plastics and complexs ( Manamperi et al. , 2010b ; Mooney, 2009 ) .

Proteins are natural thermoplastic polymers made up of assorted aminic acids that are readily available for broad scope of molecular interaction ( Chen et al. , 2008 ; Mo et al. , 1999 ; Zhang et al. , 2001 ) . The functional belongingss of canola protein based plastic can be prepared by either thaw processing or dissolver processing. Melt processing has been widely used in the polymer industry because it has many advantageous belongingss such as solvent-less, environment-friendly, and convenient processing. However, canola protein degrades at lower temperature during the thaw processing, and it can be overcome by plasticization and devastation of canola repast ( Mo et al. , 1999 ) . By integrating plasticisers and decently commanding treating parametric quantities, the proteins can be thermally processed with minimum thermic decomposition. This allows improved processability in thermoplastic preparation such as bulge and injection molding ( Mangata et al. , 2001 ) . For effectual plasticization, the plasticisers must hold similar mutual opposition to the proteins ( Zhang et al. , 1998 ) . Plasticizers are added to proteins to cut down their processing temperature, by increasing molecular mobility and diminishing viscousness. Plasticizers act by cut downing H bonding, new wave der Waals, or ionic interactions that hold polymer ironss together, through organizing plasticizer-polymer interactions. ( Verbeek and van lair Berg, 2010 ) . Common plasticisers are used for industrial oil co-products based plastics, such as H2O, glycerin, ethene glycerin, propene glycerin, 1,2-butanediol, 1,3-butanediol, poly ( ethylene ethanediol ) , sorghum wax, and sorbitol ( di Gioia and Guilbert, 1999 ; Woychik et al. , 1961 ) . Another destructerization procedure is by and large achieved by the use of the chemical additives or mechanical forces, such as bulge ( Aithani and Mohanty, 2006 ) . In this paper, guanidine hydrochloride ( GHCL ) and glycerin was used for devastation and plasticization of canola repast. Destructerization and plasticization methods are provided in the experimental subdivision.

The bio-fillers is renewable and cheaper replacement for man-made fibres, such as glass and C and have legion advantages, such as low cost, low denseness, high stamina, acceptable specific strength belongingss, easiness of separation and biodegradability. Many attacks have been used to turn to the jobs of biobased filler based plastics. The blending attack helps in heightening the stuff belongingss and H2O sensitiveness of the canola based plastics ( Manamperi et al. , 2010a ) . In this paper, we report our consequences on a reactive bulge procedure for production blends of other polymers with canola protein represent an of import path to get the better of the restrictions. Furthermore, the processing of canola protein is about same as that of many biodegradable polymers. Similarly, research workers have been worked on the blends of assorted biobased fillers, such as soy protein, DDGS, slang cellulosic filler, with bioplasticsA by utilizing the thaw bulge procedure techniques ( Muniyasamy et al. , 2013 ; Reddy et al. , 2010 ; Yang et al. , 2005 ; Zarrinbakhsh et al. , 2011 ) . Soy protein dressed ore was blended with Copolyester in a twin prison guard extruder ; this combination has resulted in extremely interacting blends ( Song et al. , 2011 ) . Several biodegradable polymers, such as poly ( butylene succinate adipate ) ( PBSA ) , poly ( 3-hydroxybutyrate ) ( PHB ) , poly ( butylene succinate ) ( PBS ) , and poly ( lactic acid ) ( PLA ) , are increasing in assorted sector application such as automotive, packaging, agribusiness, disposal points. In our surveies, PBAT and PBAT/PLA blend was used to manufacture with TCM explore the mechanical, thermic belongingss for obtaining new greener stuffs.

PBAT is an aliphatic-aromatic polyester with belongingss comparable to many fossil-oil-based plastics, and it is easy biodegradable ( Kijchavengkul et al. , 2010 ) ( Witt U,2001 ) . It degrades within a few hebdomads with the assistance of of course happening enzymes. PBAT is a flexible plastic designed for movie bulge and bulge coating. In position of its high stamina and biodegradability, PBAT was considered a good campaigner for toughening of PLA. PLA is a biodegradable and biocompatible crystalline polymer that can be produced from renewable resources. The belongingss of PLA are dependent on the ratio between the two enantiomorphs, D and L. PLA can demo crystalline polymorphism, which can take to different runing extremums ( Quero et al. , 2012 ) . Both PBAT and PLA are biodegradable polymers, and are used in consumer merchandises by several industrial sectors due to their biocompatibility, biodegradability and sustainability. They have comparable thermic and mechanical belongingss to those of some conventional plastics, and this has generated much involvement in researching their physical and processing belongingss for possible applications ( Quero et al. , 2012 ) . The purpose of this survey was to look into the plasticized utilizing glycerol/water mixture, denatured by the add-on of guanidine hydrochloride ( GHCL ) and the behaviour of thermic, mechanical belongingss of thermoplastic canola repast based plastics.

2. Experimental Section

2.1. Materials

The canola repast was obtained from the local canola oil treating industry- Canada. The PBAT, poly ( butylene adipate-co-terephthalate ) pellets – Biocosafe 2003 were obtained from Zhejiang Hangzhou Xinfu Pharmaceutical Co. , Ltd. , China. The PLA pellets – Ingeo were obtained from Nature Works, USA. Glycerol ( 99.9 % class ) was obtained from Sigma-Aldrich-canada. Guanidine Hydrochloride ( GHCL ) was obtained from Fisher Scientific – Canada.

2.2. Preformulation and plasticization of thermo plastic canola repast ( TCM )

The TCM was prepared in two stairss. The initial measure involved destructerization and plasticization of canola repast. During the destructerization procedure of canola repast, 7.5phr GHCL was dissolved in 10phr H2O and were premixed in canola repast 70 % ( wt % ) for 30aˆ‰min in a kitchen sociable. During the plasticization of destructerized canola repast, glycerol 30 % ( aˆ‰wt % ) was assorted in a kitchen sociable and kept for nightlong at room temperature. The 2nd measure involved, this mixture was extruded at 120aˆ‰A°C in a microcompounder ( DSM Research, The Netherlands ) , which is a sociable with duplicate perpendicular co-rotating prison guards, with a length of 150aˆ‰mm, A L/DA of 18, and a maximal capacity of 15 cm3. A abode clip of 2aˆ‰min was maintained for this procedure. The extruded canola was collected and dried in a ventilated oven for 8aˆ‰h at 80aˆ‰A°C. This stuff is referred to as TCM throughout the paper.

2.3 DSM processing of biocomposite stuffs

The TCM based PBAT and PBAT/PLA composite stuffs were prepared utilizing a Micro 15-cc Twin Screw Compounder ( DSM, the Netherlands ) , paired with a Micro 12-cc Injection Moulding Unit ( DSM, the Netherlands ) . All composite samples were processed at 160A°C, with a screw rotary motion velocity of 100 revolutions per minute. Each batch was processed in the micro-compounder for 3 proceedingss prior to injection molding. After three proceedingss, the samples were transferred to the injection modeling unit utilizing a cylinder, besides heated to 160A°C. Using the injection molder, tensile, flexural, impact and DMA samples were produced for each composite stuff, every bit good as orderly PBAT. All processing stuffs were dried for 8 hours prior to processing, at 80A°C in a ventilated oven to extinguish wet from the stuff. After processing, all trial samples were stored at room temperature, and characterized after 48 hours.

2.4 Mechanical belongingss

Tensile and flexural belongingss of the complexs were measured by a Universal Testing Machine, Instron 3382, harmonizing to the ASTM D638 and ASTM D790 criterions, severally. System control and the informations analysis were done utilizing Blue Hill package. The serrate Izod impact strength was measured with a TMI Monitor Impact Tester ( theoretical account no. 43-02-01 ) harmonizing to ASTM D256, utilizing a pendulum of 5 ft-lb.

2.5. Scaning Electron Microscopy ( SEM )

The morphology of the TCM biopolymer blends was studied by SEM. The fractured samples from tensile proving were used for the morphological surveies. Hitachi instrument theoretical account S-570 SEM ( Hitachi High Technologies, Japan ) was used to obtain the SEM images for the composite specimens. A gold Pd coating of 20aˆ‰nm in thickness was coated on cryo-fractured surfaces by utilizing an Emitech K550, UK. The fractured surface of the samples was used to analyze the stage morphology.

2.6. Differential Scaning Calorimetry ( DSC )

Heat flow as a map of temperature was studied utilizing a differential scan-ning calorimeter ( DSC Q 200, TA Instruments, Inc. ) utilizing the heat-cool-heat scene. Nitrogen was used as purging gas during the experiment. The information was collected by heating the specimen from a?’50 to 200 a-¦C at a changeless warming and chilling rate of 10 a-¦C/min. The informations were analyzed utilizing Universal Analysis package ( TA Instruments ) . All the thermic belongingss were obtained from the 2nd warming tally of the DSC curves.

2.7. Thermohydrometric Analysis ( TGA )

Thermohydrometric analysis was carried out utilizing a thermohydrometric analyser ( TA Instrument Inc Q500 ) . The samples were scanned from room temperature to 800 a-¦C at heating rate of 20a-¦C/min in a N ambiance.

2.8 Dynamic Mechanical Analysis ( DMA )

A DMA Q800 from TA Instruments was used to measure the storage modulus of rectangular samples of 3.2 ten 12.5 ten 65mm3. The experiments were performed from -50 to 100A°C with a ramp rate of 3 A°C min-1. A double cantilever clinch was used at a frequence of 1 Hz and hovering amplitude of 15Aµm.

2.9 Fourier Transform Infrared spectrometry ( FT-IR )

A Thermo Scientific Nicoleta„? 6700 FTIR spectrometer was used in attenuated entire contemplation infrared ( ATR-IR ) manner with a declaration of 4A cma?’1A and a figure of 32 scans per sample were used to obtain the spectra.

3. Consequences and Discussion

It is good known that canola proteins have complex macromolecular constructions with different amino acids. Due to its strong intra- and intermolecular interactions make it hard to treat and intermix with biopolymer. Assorted surveies have been done on the interaction of GHCl with proteins, which revealed the decrease of denaturation and flowering of the protein construction ( Ahmad et al. , 2005 ; Courtenay et al. , 2009 ; Dunbar et al. , 2008 ) . Denaturation is the alternation of secondary, third and quaternate construction in the protein. The GHCl signifiers cross nexus at different locations in the side ironss and on the back bone of the protein molecule by agencies of H bonding and new wave der walls interaction ( Dunbar et al. , 2008 ) .

The brickle nature of the canola protein based stuff necessities the usage of plasticisers. Glycerol has been extensively studied as a plasticiser. The plasticization consequence of glycerin is attributed to its little size which helps in its interpolation and placement within the protein web ( Cuq et al. , 1997 ) and thereby cut downing the intermolecular forces and increasing the mobility of protein ironss. The GHCL was used to interrupt down the protein construction in order to do it more flexible and compatible with the other constituents of the polymer system.

In meal processing techniques, the plasticized canola repast was processed in a DSM microcompounder, as explained in the experimental subdivision. Thermohydrometric analysis ( TGA ) was applied to look into the thermic behaviour of TCM. It is of import to correlate the thermic behaviour of pre-formulated canola with their composing. TGA consequences suggest that the pre-formulation intervention helped in bettering the thermic stableness of canola repast i.e. peculiarly the temperature scope from 50 – 200 A°C ( Figure 1 ) . Such observations are extra information to foretell the thermic stableness and processing temperature of the stuff of our chief intent of the survey for the development of thermoplastic canola repast based biocomposite stuffs.

Figure 1. TGA hints of canoal repast ( as received ) and TCM ( after modified ) .

3.1 Mechanical belongingss

Figure 2 show the tensile and flexural strength of TCM blended with PBAT and PBAT/PLA. It can be seen that the tensile strength of the TCM-PBAT is lower compared to that of TCM-PBAT/PLA blend, while per centum elongation showed the opposite tendency ( Figure 2 ) . PLA is well-known as a brickle polymer and was introduced into PBAT to equilibrate the tensile belongingss of TCM-PBAT/PLA blends. As PLA content was introduced into the TCM-PBAT system, tensile strength increased, while percent elongation decreased, demoing that the system was interacting ( Figure 2 a, B, degree Celsius ) . It can be seen from the Figure. 2c with add-on of PLA, there is a lessening in percent elongation values. With 10 % PLA add-on, the per centum elongation value reduced from 194 MPa to 67 MPa compared to the PBAT-TCM blend, bespeaking the improved stamina in the blend. However, the tensile modulus and tensile strength values increased with PLA add-on. Tensile strength and tensile modulus values were increased in this work for the canola meal-biodegradable polyester based complexs.

The TCM-PBAT blend showed a tensile strength of 5.1 MPa and flexural strength of 4.5 MPa, with 40 % burden of thermoplastic canola repast. By adding 10 % PLA into the PBAT – TCM blend systems, the stuff became tougher. It is good known that per centum elongation and tensile strength are a strong contemplation of the interface province ( Averous and Boquillon, 2004 ; Zhao et al. , 2010 ) . The ascertained tensile belongingss for TCM-based blends with polyesters show a diminishing tendency in tensile strength. This indicates hapless interfacial interactions between stages in these blends. However, the higher per centum elongation values show a high ductileness for the blends. The ground for such high ductileness is due to a high degree of which could hold led to the improved concatenation mobility ( Graiver et al. , 2004 ; Reddy et al. , 2010 ; Sue et al. , 1997 ) . These improved mobilities in the protein ironss have led to specific interactions with polyesters, particularly by the PBAT stuff. These blends did non hold any compatibilizer, taking to the improved mechanical belongingss. Glycerol is a known plasticiser for canola repast based plastics, and helps in their processing, while cut downing their tensile belongingss. The ascertained betterment in the belongingss of these blends could be due to two grounds ; the high snap of the destructured canola repast, and the compatibility between the polyesters used. The interactive consequence of flowering and destructurization of protein by GHCL and high shear forces during bulge, following the plasticization by glycerin, has caused high mobility in the protein ironss.

Impact energy is absorbed by the stuff through fictile distortions. In serrate Izod testing, the notching centre acts as the emphasis concentration point and facilitates the cleft extension for fictile distortion of the stuff after impact. The comparings of the impact strength of blends are given in Figure. 2c. The impact strength and elongation of biocomposite samples decreased as the biomass content was increased.

Figure 2. Mechanical belongingss of TCM-PBAT and TCM-PBAT/PLA blends.

3.2. Surface morphology

The morphologies of the break surfaces were investigated utilizing SEM, as shown in Figure 3a. TCM-PBAT shows irregular break surfaces of a polymer, incorporating some holes, whereas TCM-PBAT+PLA show no stage separation ( Figure 3b ) . The plasticized and destructured canola protein is really much ingrained in the PBAT matrix. The lessening in tensile strength of the blend could be due to the really low tensile strength of canola protein itself. By adding PLA into the blends TCM-PBAT80+PLA20 ( 60-40 ) that canola encapsulated itself between the matrices. This easy explains the better tensile strength and low per centum elongation when compared to that of the TCM-PBAT blend. The ascertained phenomenon explains the difference in compatibility of the destructured canola protein with PBAT and PLA. The ground for the ascertained morphology is that the sphere sort of morphology of canola protein in the blends started cut downing to fibrils with the add-on of PBAT stage ( Reddy et al. , 2010 ) . This sort of alteration in morphology was apparent that, the tensile belongingss and impact strength of these blends as explained earlier. The higher sum of PBAT showed higher per centum elongation and impact strength. This is due to the add-on of the unrestricted protein concatenation mobility in these blends. Another factor that could hold contributed to this type of behaviour is the twin screw melt bulge which could hold led to the distortion of protein from droplet to fibril due to the important elongation flow constituent. Besides, it was observed by old surveies with add-on of PCL to soy protein ( Reddy et al. , 2010 ) , fictile flow improved and led to the betterment in the stamina of the blends.

Figure 3. SEM micrographs of canola blends a ) TCM-PBAT ( 60-40 ) ; b ) TCM-PBAT80+PLA20 ( 40-60 )

3.3 Thermo hydrometric analysis ( TGA )

In general, the thermic weight losingss of agricultural biomasses were rather sensitive to temperature, with narrow decomposition ranges. The temperature matching to the oncoming of decomposition ( Tonset ) for a polymer and canola repast based blends is indispensable for measuring their thermic stableness ( Figure 4 and Table 1 ) . PBAT is more thermally stable than PLA. The add-on of thermoplastic canola repast decreased the Tonset of the PBAT and PBAT/PLA blends. PBAT and PLA undergo hydrolytic reactions by abiotic factors, and thermally degrade to bring forth polymeric ironss terminated with carboxyl and vinyl groups. The carboxyl terminal groups of the polyester catalyze the hydrolysis reactions. All of the orderly polymers exhibited a individual extremum, bespeaking that the PBAT and PLA degraded in merely one measure. The add-on of thermoplastic canola repast to the TCM-PBAT and TCM-PBAT+PLA matrix exhibited two measure thermic debasement of biopolymer blend. The first derivative extremum is the thermic debasement of thermo plastic canola repast at 212.3A°C and the 2nd extremum is the thermic debasement for PBAT and PLA at 410.2 A°C. All the biocomposites had a 13 % weight residue addition with increasing biobased content, shown in Table 1.

Figure 4. TGA hints of a ) neat PBAT, orderly PLA and TCM B ) PBAT-TCM and PBAT/PLA-TCM blends

Table 2. TGA consequences of debasement temperature of orderly PBAT, orderly PLA, TCM and their canola repast based composite stuffs.

Trial samples

T oncoming ( A°C )

Maximal debasement temperature ( A°C )

Residue weight ( % ) at 600A°C

Centimeter

63.2

331.0

28.6

TCM

150.0

212.3

23.7

PBAT

383.8

428.5

5.2

PBAT/PLA ( 90/10 )

348.9

410.2

1.9

PBAT-TCM

197.6

404.2

13.0

PBAT/PLA-TCM

204.8

408.0

12.9

T oncoming ( A°C ) – 5 % weight loss. CM- canola repast ; TCM- thermoplastic canola repast.

3.4 DSC analysis

Table 3 shows the thermic behaviour for the blends with different composings. DSC scans identified the glass passage stage, crystallisation and runing behavior for the blends studied. By adding plasticized canola repast to the PBAT matrix, there was addition in the thaw and glass passage temperature ( Table 3 ) . This consequence was likely due to the little, all right atoms of canola repast is moving as a nucleating agent ( Averous and Boquillon, 2004 ) . In contrast, consequences showed a reduced Tm and Tg in the PBAT/PLA blend with the add-on of canola repast. This consequence is due to the PLA playing as a suppresser in the runing behaviour of the PBAT matrix ( Averous and Boquillon, 2004 ) . On the other manus, the DSC curves of PBAT90/PLA10 blends exhibit two Tg values, which indicate that these blends are non-miscible systems. This is likely due to the little, finely dispersed PLA crystals moving as nucleating agents in PBAT ( Averous and Boquillon, 2004 ; Kumar et al. , 2010 ) . However, the add-on of TCM to the PBAT/PLA sample resulted in a lessening of the PLA thaw and glass passage temperature. In this survey, the Tm of PBAT did non alter significantly, except in TCM-PBAT from -121.5 to -125.1 ( Table 3 ) . This consequence suggests that the interfacial interaction between the polymer and blends might connote the formation of a more stable construction, possibly due to increased motion of the polymer sections that facilitate polymer concatenation mobility.

Table 3. DSC consequences of PBAT, PLA and their canola repast based composite stuffs.

Trial samples

Tm 1 ( A°C )

Tm 2 ( A°C )

Tg 1 ( A°C )

Tg 2 ( A°C )

Tc ( A°C )

PBAT

121.5

-31.6

PLA

169.4

61.3

101.3

PBAT/PLA ( 90/10 )

118.4

168.4

-34.8

59.5

99.4

PBAT-mPCM

125.1

-35.1

PBAT/PLA-mPCM

119.2

149.2

-34.7

45.2

86.7

Tm 1 – thaw temperature of PBAT ; Tm 2 – thaw temperature of PLA ; Tg 1 – glass passage temperature of PBAT ; Tg 2 – glass passage temperature of temperature of PLA ; Tc – crystallisation temperature of PLA.

3.5 Dynamic mechanical analysis

DMA reveals the sum of energy stored in a stuff as elastic energy and sum of energy dissipated during mechanical strain, which strongly depends on the geometric analysis and degree of scattering of fillers and fibres within the matrix. The temperature dependences of virgin PBAT, PBAT/TCM, and TCM-PBAT/PLA biodegradable complexs are represented in Figure 5a. In the instance of biodegradable canola protein composite, a important addition in storage modulus compared to neat biodegradable polymer was observed over the temperature scope from -50 A°C to 100 A°C. At the low temperature of -20 A°C, the polymer matrix TCM-PBAT/PLA is somewhat increased compared to the neat PBAT, and PBAT/TCM ( 60/40 ) . This shows that biocomposite are in glassy province. The PBAT-TCM complex showed similar storage modulus at that of the orderly PBAT matrix which reveals a deficiency of polar interaction between PBAT and TCM. The Tg of orderly PBAT matrix corresponds to the lower temperature of its passage part ( -32A°C ) . The incorporation of TCM into the matrix resulted in a lower Tg of the matrix up to -35.1A°C. Further add-on of TCM-PBAT/PLA shows displacements in the Tg to relatively higher temperature to -34.7A°C of PBAT and Tg of PLA from 61.3 to 45.2A°C. This indicates an sweetening of the interfacial adhesion between the filler and the biodegradable polymer matrices ( Figure 5b ) .

Figure 5. a ) Storage modulus and 5 B ) Tan delta thermoplastic canola repast based composite stuffs.

3.6 FT-IR analysis

The combined consequence of glycerin and GHCL has allowed for the production of canola meal-based bioplastics utilizing melt bulge. The denaturation of canola protein by GHCL was confirmed by FTIR ( Figureure 6 ) , where it was observed that the strong extremum for the amide group, around 1626cm-1, in canola repast shifted to 1649cm-1, bespeaking H bonding. This phenomenon is likely responsible for the betterment of the mechanical belongingss of the protein based blends ( Reddy et al. , 2010 ) . The obtained thermoplastic canola repast was used to intermix with polyesters, i.e. , PBAT and PLA separately and in loanblends.

4. Decisions

Biodegradable thermoplastic canola meal-reinforced PBAT/PLA complexs have been successfully prepared via thaw processing. Preformulation and plasticization techniques provided better scattering and bettering the belongingss. The interfacial adhesion between filler and matrix was observed utilizing SEM. The biocomposite stuffs analysis utilizing DSC and TGA showed some interactive features between the TCM and polymer matrix. DMA consequences revealed that the scattering of the filler in the polymer matrix well enhanced the storage modulus and TanI? . Structural analysis besides farther confirmed that thermoplastic canola protein plasticization and the devastation of biofiller aid for the formation of H bonding.

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