Physicochemical and biodegradation properties of flexible poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)/spent coffee grounds biocomposites

Physicochemical and biodegradation properties of flexible poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)/spent coffee grounds biocomposites | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Physicochemical and biodegradation properties of flexible poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)/spent coffee grounds biocomposites Yaowalak Srisuwan, Prasong Srihanam, Apirada Manphae, Yodthong Baimark This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6230035/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 22 Jun, 2025 Read the published version in Polymer Bulletin → Version 1 posted 9 You are reading this latest preprint version Abstract This study is aimed to prepare and characterize the poly(L-lactide)- b -poly(ethylene glycol)- b -poly(L-lactide)/spent coffee grounds (PLA-PEG-PLA/SCG) biocomposites compared to PLA/SCG biocomposites. The biocomposites were prepared by melt mixing. Fourier transform infrared (FTIR) spectroscopy shows that the PLA-PEG-PLA matrix chemically interacted with SCG but the PLA did not interact. Scanning electron microscopy (SEM) of the biocomposite fractured surfaces indicates that the phase compatibility between PLA-PEG-PLA matrix and SCG dispersed phases was better than between the PLA matrix and SCG dispersed phases. The addition of SCG decreased crystallizability of both the PLA-PEG-PLA and PLA matrices as determined by differential scanning calorimetry (DSC). The thermal stability of PLA fraction in the PLA-PEG-PLA/SCG biocomposites studied from thermo-gravimetric analysis (TGA) largely increased with an increase in the SCG content but this decreased in the PLA/SCG biocomposites. The hydrophilicity of the biocomposite surfaces and water uptake increased by the addition of SCG for both the composite types. Both the PLA/SCG and PLA-PEG-PLA/SCG biocomposites showed lower mechanical properties compared to their pure polymers. However, the PLA-PEG-PLA/SCG biocomposites were still higher flexible than the PLA/SCG biocomposites. The incorporated SCG accelerated the biodegradation in burial soil of both the biocomposite types. The results have shown that PLA-PEG-PLA/SCG biocomposites could be used as a flexible and biodegradable packaging. Polylactide Block copolymer Spent coffee grounds Biocomposites Biodegradation Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 14 1. Introduction Nowadays, the use of bio-based plastics instead of petroleum-based plastics has steadily increased due to its lower carbon footprint and greenhouse gas emissions [ 1 , 2 ]. Moreover, plastic waste problems especially from single-use applications can be reduced by using biodegradable plastics [1−5]. Therefore, biodegradable bio-based plastics have been extensively researched in both academic and industrial fields for use as sustainable and environment-friendly materials. Among biodegradable bio-based plastics, poly(L-lactide) (PLA) has attracted the most attention due to its good biocompatibility, high strength, good processability, and commercial availability [ 1 , 2 , 6 , 7 ]. However, the PLA has certain limitations. One of them is the fact that its flexibility is too low due to its high glass transition temperature (about 60 °C) [8−11]. This might limit the wider applicability of PLA. In this regard, block copolymerization of poly(ethylene glycol) (PEG) with L-lactide monomer formed high molecular weight PLA-PEG-PLA triblock copolymers which showed that the PEG blocks enhanced the plasticization effect to decrease the T g of PLA blocks [12−14]. The obtained PLA-PEG-PLA exhibited more flexible and hydrophilic compared to the PLA due to the plasticization and hydrophilicity of PEG blocks, respectively. However, the research on low cost, environment-friendly, biorenewable, and biodegradable fillers for PLA-PEG-PLA still need for reducing the production cost and fabricating the sustainable biocomposites. Spent coffee grounds (SCG) generated by the coffee industry is bio-waste that have been widely used as a bio-filler in both the biodegradable plastics such as PLA [15−22], poly(butylene succinate) (PBS) [ 23 ], poly(butylene adipate- co -terephthalate) (PBAT) [ 24 ], and thermoplastic starch/alginate [ 25 ] as well as the non-biodegradable plastics such as high-density polyethylene (HDPE) [ 26 ], low-density polyethylene (HDPE) [ 27 ], epoxy resin [ 28 ], and polypropylene (PP) [ 29 , 30 ] to reduce the production cost and to improve the biodegradability. This is because of SCG’s abundance, low cost, biorenewability, biodegradability and light weight. The addition of SCG increased opacity and brown color of the plastic matrices to protect packaged food from light [ 31 ]. Low interfacial adhesion between the hydrophobic plastics and hydrophilic SCG was found [ 15 , 20 ]. The treatment of SCG surfaces improved the interfacial adhesion in the hydrophobic plastics/SCG composites such as HDPE/SCG [ 32 ], PP/SCG [ 29 , 30 , 33 ], and PLA/SCG [ 16 , 34 ] composites compared to untreated SCG composites. However, the SCG has not been compounded with the PLA-PEG-PLA. The purpose of this work is that the hydrophilic PEG blocks could enhance the PLA-PEG-PLA/SCG interfacial adhesion. This study focuses on SCG use as a low cost and environment-friendly filler of PLA-PEG-PLA for the first time. The SCG was compounded with PLA-PEG-PLA by melt mixing and then the obtained biocomposites were compression molded. PLA/SCG biocomposites were also prepared by the same condition for comparison. The influence of SCG addition on the properties of biocomposites was evaluated through the spectroscopic, phase compatibility, crystallizability, crystalline structure, thermal stability, hydrophilicity, and mechanical property characterization of the biocomposites. Furthermore, the biodegradability of the biocomposites was also investigated through a soil burial test. 2. Materials and Methods 2.1 Materials The PLA, 3251D grade, with a melt flow rate (MFR) of 30 g/10 min at 190 °C/2.16 kg was supplied by NatureWorks LLC (MA, USA). The PLA-PEG-PLA was synthesized by in situ chain-extension and ring-opening polymerization of L-lactide monomer as described in our previous works [ 12 , 13 ]. PEG (molecular weight = 20,000)/stannous octoate and Joncryl ADR 4368 were used as an initiating system and a chain extender, respectively. Molecular weight characteristics of PLA-PEG-PLA were obtained from gel permeation chromatography (GPC) that were a number-averaged molecular weight ( M n ) of 108,500 and a dispersity ( Ð ) of 2.2. The MFR of PLA-PEG-PLA was 31 g/10 min at 190 °C/2.16 kg. SCG was obtained from a café’ at Mahasarakham University (Thailand) and washed with distilled water before drying at 80 °C in an air flow oven for 24 h. Coffee was produced by Pangkhon Coffee Roaster, Chiang Rai Province, Thailand. The size of SCG was reduced by a multipurpose blender before sieving through a 50 µm-mesh. 2.2 Preparation of biocomposites PLA and PLA-PEG-PLA were compounded with SCG powder by a melt mixing method using an internal mixer (Polylab OS System, HAAKE, USA) at 170 °C for 8 min. A rotor speed was 100 rpm. The PLA, PLA-PEG-PLA, and SCG were dried in an air flow oven at 80 °C for 24 h before melt mixing. The biocomposites with SCG contents of 5 wt%, 10 wt%, 20 wt%, and 30 wt% were prepared and investigated. The biocomposites were dried in an air flow oven at 80 °C for 24 h before film forming. The biocomposites were then hot pressed to films using a compression molding machine (Auto CH, Carver, USA). The compression molding temperature, compression force, and compression time were 180°C, 10 MPa, and 5 min, respectively. The resulting film thickness was 0.2−0.3 mm. The pure PLA and PLA-PEG-PLA films were also prepared by the same conditions for comparison. The resulting films were kept at 25 °C in a desiccator for 24 h before characterization. 2.4 Characterizations 2.4.1 Fourier transform infrared spectroscopy Fourier transform infrared (FTIR) spectra of SCG powder and film samples were recorded using an attenuated total reflectance-FTIR (ATR-FTIR) spectrophotometer (INVENIO-S, Bruker Corporation, Germany) frequency ranging from 4000 to 500 cm − 1 with a resolution of 4 cm − 1 and an accumulation of 32 scans. 2.4.2 Scanning electron microscopy The morphology of SCG powder and fractured film surfaces were observed using a scanning electron microscope (SEM, TM4000Plus, HITACHI, Japan) at an acceleration voltage of 15 kV. The film samples were fractured in liquid nitrogen. The SCG powder and film samples were sputter coated with a thin layer of gold before scanning the SEM. 2.4.3 X-ray diffractometry The crystalline structures of the SCG powder and film samples were determined using an X-ray diffractometer (XRD, D8 Advance, Bruker Corporation, Germany) with a Cu-Kα radiation set to 40 kV and 40 mA. The scanning range was 5−30 degree with a step width of 0.02°. 2.4.4 Thermo-gravimetric analysis The thermal decomposition properties of SCG powder and film samples were determined using a thermo-gravimetric analyzer (TGA, SDT Q600, TA-Instruments, USA). For analysis, 5−10 mg of each sample was heated from 50 to 800 °C at a rate of 20 °C/min in a nitrogen flow of 100 mL/min. 2.4.5 Differential scanning calorimetry The thermal transition properties of film samples were investigated using a differential scanning calorimeter (DSC, Pyris Diamond, PerkinElmer, USA) under a nitrogen flow. The samples were first heated at 200 °C for 3 min to erase its thermal history before quickly quenching to 0 °C. Subsequently, the samples were heated from 0 to 200 °C at a rate of 10 °C/min. The degree of crystallinity (X c ) for PLA crystallites was calculated from enthalpy of melting (ΔH m ) and enthalpy of cold crystallization (ΔH cc ) using the following equation. X c (%) = [(ΔH m − ΔH cc )/(93.6 × W PLA )] × 100 (1) where 93.6 J/g is 100%Xc of PLA [ 35 ]. W PLA is the PLA weight fraction (W PLA of PLA-PEG-PLA from 1 H-NMR is 0.83 [ 14 ]). 2.4.6 Water contact angle and water uptake The water contact angle of film samples was measured by the sessile drop method using a contact angle analyzer (OCA11, DataPhysics Instruments, Germany). The contact angles on the film surface were determined at 15 seconds after dropping the water from the left and right sides of the deionized water droplet (2.5 µL) and subsequently averaged. For each film sample, five determinations were made and averaged. The initial weights (W i ) of film samples (20 × 20 mm) were determined before immersing it in deionized water for water uptake test. At interval time, the films were taken from the water, any excess water on the film surface was wiped with filter paper, and the final weight (W f ) was determined. The water uptake of the film samples was calculated using the following equation. Water uptake (%) = [(W 2 − W 1 )/W 1 ] × 100 (2) 2.4.7 Tensile testing Tensile properties of film samples were studied using a universal testing machine (LY-1066B, Dongguan Liyi Environmental Technology Co., Ltd., China) at 25 °C with a cross head speed of 50 mm/min. Film samples were cut into strips with 100 mm length and 10 mm width. An initial gauge length was 50 mm. The tensile properties were measured from the average of five determinations. 2.4.8 Biodegradation test The biodegradation tests of film samples (20 × 20 mm) were carried out in soil as described in the literature with some modification [ 36 ]. The film samples were dried in an oven at 105 °C for 24 h and weighed (W 0 ). The film sample were then buried into a 1.0 mm nylon mesh at a depth of 5.0 cm from the soil surface. The soil was watered every other day. The soil’s parameters were controlled with temperature of 25−30 °C, pH of 6.0−7.0 and moisture content of 50−60%. Representative film samples were taken from the soil at different times, cleaned with distilled water. Subsequently, they were dried in an oven at 105°C for 24 h and weighed (W t ). All measurements were performed in triplicate. The weight loss in soil of the film samples was calculated using the following equation. Weight loss in soil (%) = [(W 0 − W t )/W 0 ] × 100 (3) 2.4.9 Statistical analysis The results were analyzed by one-way analysis of variance (ANOVA) and Duncan test. The data of water contact angle, water uptake, tensile properties, and weight loss in soil of the film samples were provided with mean ± standard deviation (SD) and differences were statistically significant at p ≤ 0.05. 3. Results and Discussion The chemical structures of SCG were characterized by FTIR as shown in Fig. 1(a). A broad band between 3600 and 3100 cm − 1 was assigned to −OH stretching vibration. The 2919 and 2854 cm − 1 sharp bands were observed, which means the aliphatic saturated −CH stretching vibration [37, 38]. The bands at 1705 and 1641 cm − 1 were attributed to the C = O stretching of hemicellulose and the C = N stretching of caffeine, respectively [19, 39]. The lignin characteristic band was observed at 1426 cm − 1 [40]. The SCG particles were irregular shape with particle size less than 50 µm as shown by SEM image in Fig. 1(b). XRD profile of SCG in Fig. 1(c) shows peaks at 2θ = 16.2° and 21.7° attributed to crystalline cellulose [25, 41]. Figure 1(d) shows the thermogravimetric (TG) and derivative TG (DTG) thermograms of SCG. The three steps of weight losses were observed from its TG thermogram. The first step of weight loss occurred from 50 to 150 °C due to evaporation of moisture and light volatile matter. The second step of weight loss was observed from 150 to 375 °C owing to decomposition of hemicellulose, lignin, coffee oil, and the amorphous region of cellulose [30, 42]. The third step of weight loss occurred from 375 to 550 °C due to decomposition of the crystalline region of cellulose [30, 42]. Char residue at 800 °C of the SCG was 18.6%. The DTG thermogram exhibited decomposition peaks in the first weight loss step at 97 °C and in the second weight loss step at 224, 322, and 355 °C. 3.1 FTIR spectroscopy FTIR spectra and its expanded hydroxyl regions of PLA/SCG and PLA-PEG-PLA/SCG biocomposites are shown in Figs. 2 and 3, respectively. Pure PLA exhibited the characteristics bands for ester-carbonyl (C = O) stretching vibration at 1749 cm − 1 , C−O−C bonds in ester groups at 1181, 1128, and 1081 cm − 1 , and C−H stretching vibration at 2996, 2946, and 2880 cm − 1 [43]. Pure PLA-PEG-PLA showed a small and broad band for hydroxyl end-groups (−OH) at 3380 cm − 1 . From Fig. 3, it is clearly seen that the intensity of −OH bands due to SCG steadily increased as the SCG content increased for both the PLA/SCG and PLA-PEG-PLA/SCG biocomposites. It should be noted that the −OH bands between 3100 and 3450 cm − 1 of the PLA-PEG-PLA/SCG biocomposites shifted to lower wavenumber demonstrated the hydrogen bonds between the blend components [44, 45]. The hydrogen bonds between the ether groups of PEG blocks and hydroxyl groups of SCG could be formed [46]. Whereas, the −OH bands of the PLA/SCG biocomposites did not significantly shifted. 3.2 Phase separation SEM images of cryogenic fractured surfaces of the PLA/SCG and PLA-PEG-PLA/SCG biocomposites were presented in Fig. 4. The pure PLA-PEG-PLA showed a rougher surface texture than the pure PLA indicating that the pure PLA-PEG-PLA is more flexible. SCG dispersed particles can be detected for all the biocomposites. It can be seen that interfacial voids or gaps between PLA matrix and SCG particles were noticed due to different hydrophilicity between the hydrophobic PLA matrix and the hydrophilic SCG dispersed phases [15, 21, 34]. However, the reduction of the gaps was obtained for the PLA-PEG-PLA/SCG biocomposites suggesting the better phase compatibility between the PLA-PEG-PLA matrix and the SCG dispersed phases. This may be explained by the PLA-PEG-PLA had higher hydrophilicity than the PLA because of the hydrophilic PEG blocks [47]. 3.3 Differential scanning calorimetry (DSC) analysis DSC thermograms of PLA/SCG and PLA-PEG-PLA/SCG biocomposites are shown in Fig. 5. Figure 6 shows their expanded regions of glass transition temperature (T g ) and the DSC results are summarized in Table 1. The T g values of pure PLA and PLA-PEG-PLA were 58 °C and 30 °C, respectively. The PEG middle-blocks induced a plasticizing effect to decrease the T g of PLA end-blocks [13]. The melting temperatures (T m ) values of pure PLA and PLA-PEG-PLA were 166 °C and 152 °C, respectively. The T g and T m values of both the biocomposite types did not change significantly by the addition of SCG. When the SCG was incorporated, cold crystallization temperature (T cc ) peaks of biocomposites shifted to higher temperatures suggesting that crystallization of PLA phases were suppressed [48]. This change indicates that the presence of SCG affects PLA matrices by reducing its crystallization rate, possibly due to restricted mobility within the biocomposites. This was supported by decreasing the degree of crystallinity (X c ) of both the biocomposite series. 3.4 X-ray diffraction (XRD) study Figure 7 shows the XRD profiles of PLA/SCG and PLA-PEG-PLA/SCG biocomposites. Pure PLA and all the PLA/SCG biocomposites exhibited a broad halo pattern which indicates the absence of crystalline phase. Pure PLA-PEG-PLA and all the PLA-PEG-PLA/SCG biocomposites showed a broad peak at 2θ = 16.7° corresponding to the crystalline region of PLA end-blocks [43, 47] suggesting that the addition of SCG does not change the crystalline structure of PLA-PEG-PLA. However, the XRD peaks of SCG at 2θ = 16.2° and 21.7° did not detect for all the biocomposites. These peaks may be overlapped with the halo pattern of PLA and PLA-PEG-PLA matrices. The XRD results supported the DSC results that the addition of SCG did not enhance the PLA crystallization. 3.5 Thermal decomposition study The thermal decomposition of the biocomposites were determined using TGA, and the results are illustrated in Figs. 8 and 9 for TG and DTG thermograms, respectively. The TGA results are summarized in Table 2. From TG thermograms in Fig. 8, pure PLA exhibited a single step of PLA thermal decomposition in the range of 300−450 °C, whereas pure PLA-PEG-PLA showed two thermal decomposition steps in the ranges of 250−350 °C and 350−450 °C, due to the PLA and PEG thermal decompositions, respectively [35, 36]. The plasticization of PEG middle-blocks induced faster thermal decomposition of PLA end-blocks compared to the pure PLA [13]. The PEG blocks suppressed intermolecular interactions of the PLA blocks. Decomposition temperatures at 10% weight loss (10%-T d ) of the PLA/SCG biocomposites decreased as the SCG content increased. This may be explained by the thermal stability of SCG was lower than the PLA as shown in Fig. 8. However, the 10%-T d values of PLA-PEG-PLA/SCG biocomposites tended to increase as the SCG content increased. This could be due to the lower decomposition temperature of PLA-PEG-PLA compared to SCG powder. Char residue at 800 °C of all the biocomposites steadily increased with the SCG content. The char residue is polysaccharide ashes from the natural fillers [21]. The DTG thermograms in Fig. 9 showed peaks of maximum weight loss temperature (T max ). The pure PLA and its biocomposites exhibited a single peak of PLA decomposition (PLA-T max ), whereas the pure PLA-PEG-PLA and its biocomposites showed two T max peaks of PLA (PLA-T max ) and PEG (PEG-T max ) phases. As observed from Table 2, the PLA-T max peak of PLA/SCG biocomposites shifted to lower temperatures when SCG content was increased indicating that the addition of SCG reduced thermal stability of PLA, which is in agreement with the previous works [16, 19, 21]. It is surprising that when SCG was added to PLA-PEG-PLA, the PLA-T max peaks dramatically shifted to higher temperatures, suggesting that the addition of SCG enhanced the thermal stability of the PLA blocks. The results may be explained by good interfacial adhesions of the PLA-PEG-PLA/SCG biocomposites. Thus, the TGA results supported that the interfacial adhesions between the PLA-PEG-PLA and the SCG were better than between the PLA and the SCG, which corresponded to the above FTIR and SEM analyses. Baek et al. [16] reported that the addition of a coupling agent improved the interfacial adhesion of the PLA/SCG biocomposite and then enhanced its thermal stability. However, the PEG-T max of PLA-PEG-PLA/SCG biocomposites tended to decrease as the SCG content increased. This may be due to almost PLA-PEG-PLA matrix has decomposed. Table 2 Thermal decomposition properties of PLA/SCG and PLA-PEG-PLA/SCG biocomposites. a Obtained from TG thermograms. b Obtained from DTG thermograms. 3.6 Water contact angle and water uptake tests Figure 10 shows the images of water contact angles on biocomposite surfaces. The results of water contact angle are summarized in Table 3. The pure PLA and PLA-PEG-PLA had water contact angles of 79.5° and 73.4°, respectively, which indicated that the PLA-PEG-PLA was higher hydrophilicity because of the hydrophilic PEG middle-blocks. The incorporation of SCG decreased the contact angle of the biocomposite surfaces, which indicates that the wettability of biocomposite surfaces increased by the addition of SCG. The PLA-PEG-PLA/SCG biocomposite surfaces exhibited lower contact angle than the PLA/SCG biocomposite surfaces for the same SCG content. Several reported that the incorporation of hydrophilic SCG increases the wettability of hydrophobic film surfaces [15]. The hydrophilicity of the biocomposites was also investigated from water uptake for 72 h as shown in Fig. 11. The water uptake values of the film samples were constant at 48 h. The pure PLA and PLA-PEG-PLA showed the water uptake values at 72 h of 1.6% and 4.9%, respectively supporting that the PLA-PEG-PLA was more hydrophilic due to the hydrophilic PEG blocks [47]. As would be expected, the water uptake increased with the increase of SCG content because of the hydrophilic character of SCG [18]. The PLA-PEG-PLA/SCG biocomposites showed higher water uptake than the PLA/SCG biocomposites for the same SCG content. 3.7 Tensile test The influence of SCG addition on tensile properties are displayed in Fig. 12 and the tensile results are reported in Table 4. The maximum stress, strain at break, and Young’s modulus of pure PLA were 60.2 MPa, 2.7%, and 690 MPa, respectively. While these values of pure PLA-PEG-PLA were 20.8 MPa, 72.5%, and 316 MPa, respectively. The pure PLA-PEG-PLA exhibited a yield point. These tensile results indicated that the PLA-PEG-PLA was more flexible than that of the PLA. This is because of the plasticization effect of the PEG middle-blocks. The tensile properties of both the PLA/SCG and PLA-PEG-PLA/SCG biocomposites decreased as increase of the SCG content. This suggested the poor interfacial adhesion between the hydrophobic polymer matrix and the hydrophilic SCG dispersed phases [16, 18, 30]. Although from the above FTIR, SEM, and TGA analyses suggested that the chemical interactions and phase compatibility between the PLA-PEG-PLA and the SCG was better than between the PLA matrix and the SCG because of the higher hydrophilicity of PLA-PEG-PLA compared to PLA. However, the presence of SCG might modify certain properties at the molecular level, but these changes may not be significant enough to cause noticeable improves in the tensile properties of the PLA-PEG-PLA matrix. It should be noted that maximum stress and Young’s modulus of PLA matrix decreased 78% and 85%, respectively, compared to the pure PLA when the 30% SCG was incorporated, whereas, these tensile properties of PLA-PEG-PLA matrix decreased only 38% and 41%, respectively compared to the pure PLA-PEG-PLA. This may be explained by more interfacial voids between the PLA matrix and SCG dispersed phases from above SEM analysis induced larger reduction for these tensile properties [19]. This confirms that the matrix-filler compatibility between the PLA-PEG-PLA and SCG was better than between the PLA and SCG. The strains at break of the PLA-PEG-PLA/SCG biocomposites were still higher than those of the PLA/SCG biocomposites suggesting that the PLA-PEG-PLA/SCG biocomposites were more flexible. 3.8 Biodegradation study Figure 13 shows photographs of biodegraded biocomposite films with different soil burial times for biodegradation test. The pure PLA film did not change after a 6-month biodegradation time in soil, whereas the pure PLA-PEG-PLA film exhibited many voids in film matrices from bulk erosion and easily broken. This is due to the higher hydrophilicity of PLA-PEG-PLA [36, 43, 47]. The PLA/SCG films displayed some voids in film matrices from bulk erosion and some cavity on film surfaces from surface erosion, particularly for the higher SCG content. The PLA-PEG-PLA/SCG films showed faster degradation than the PLA/SCG films, including the larger void number and the faster film shape loss for higher SCG content. Figure 14 shows the weight loss of sample films after burial in soil for 6 months. The weight loss increased with the increase of biodegradation time indicating that these films were biodegradable. The pure PLA and PLA-PEG-PLA films had weight losses at 6-month biodegradation time of 0.32% and 6.70%, respectively. The hydrophilic PEG blocks induced faster biodegradation of PLA-PEG-PLA [36, 43]. The weight loss of both biocomposite series increased as the SCG content increased. The weight losses at 6-month biodegradation time of PLA/30%SCG and PLA-PEG-PLA/30%SCG biocomposites were 17.08% and 35.55%, respectively. This may be explained by the hydrophilic SCG accelerated the biodegradation of film matrices [18]. The hydrophilicity of film matrices increased by the addition of SCG as supported from the above results of water contact angle and water uptake. 4. Conclusions This study was carried out the use of SCG as a bio-filler in the PLA-PEG-PLA compared to the PLA. The biocomposites with different SCG contents (0, 5, 10, 20, and 30 wt%) were successfully prepared via melt mixing and compression molding. The position shifting of −OH bands from FTIR spectra and the increasing of decomposition temperatures from TG/DTG thermograms of PLA-PEG-PLA/SCG biocomposites suggested chemical interactions between the PLA-PEG-PLA matrix and the dispersed SCG phases, which may due to good phase compatibility between the phases as observed from SEM. However, the no chemical interactions and poor phase compatibility between the PLA matrix and the SCG were found. The crystallization properties obtained from DSC analysis and hydrophilicity resulted from water contact angle and water uptake determinations decreased as the SCG content increased for both the biocomposite series. Tensile properties such as maximum stress, strain at break, and Young’s modulus of both the biocomposite series decreased with increasing SCG content. However, the PLA-PEG-PLA/SCG biocomposites displayed higher flexibility than those of the PLA/SCG biocomposites. From soil burial test for 6 months, the PLA-PEG-PLA/SCG biocomposites showed faster biodegradation than the PLA/SCG biocomposites. Addition of SCG has increased the biodegradation properties of both the biocomposite series. It can be concluded that the physicochemical and biodegradation properties of PLA-PEG-PLA can be controlled by adjusting the content of SCG filler. Thus, the SCG shows potential for use as a low cost, renewable and sustainable filler for flexible and biodegradable PLA-PEG-PLA. In the future, the improvement of interfacial adhesion between the PLA-PEG-PLA matrix and dispersed SCG could be proposed through treatment of SCG. Declarations Acknowledgements This work was financially supported by Thailand Science Research and Innovation (TSRI). YB is also grateful to the partially support provided by the Centre of Excellence for Innovation in Chemistry (PERCH-CIC), Office of the Higher Education Commission, Ministry of Education, Thailand. Author Contributions Y.S. and Y.B. performed most of the experimental part, A.M. performed some characterizations and formal analysis, All authors contributed to writing-original draft, and revising of the paper. Data Availability No datasets were generated or analysed during the current study. Declaration of competing interest The authors declare that they have no competing interests. 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Forests 14(2):367 Gaidukova G, Platnieks O, Aunins A, Barkane A, Ingrao C, Gaidukovs S. (2021) Spent coffee waste as a renewable source for the production of sustainable poly(butylene succinate) biocomposites from a circular economy perspective. RSC Adv 30:18580-18589 Moustafa H, Guizani C, Dufresne A (2017) Sustainable biodegradable coffee grounds filler and its effect on the hydrophobicity, mechanical and thermal properties of biodegradable PBAT composites. J Appl Polym Sci 134:44498 Nguyen VHT, Prabhakar MN, Lee DW, Lee IC, Song JI. (2023) Films derived from thermoplastic starch/alginate/spent coffee grounds for food packaging applications. J Polym Res 30:191 Cestari SP, Mendes LC, Silva DFd, Chimanowsky Junior JP, Altstädt V, Demchuk V, Lang A, Leonhardt RG, Keller JH. (2013) Properties of recycled high density polyethylene and coffee dregs composites. 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(2022) Design and development of Schiff’s base (SB)‑modified polylactic acid (PLA) antimicrobial film for packaging applications. Polym Bull 79:4627–4646 Baimark Y, Srihanam P, Srisuwan Y. (2024) Thermal, morphological, mechanical, and biodegradation properties of poly(L-lactide)- b -poly(ethylene glycol)- b -poly(L-lactide)/high-density polyethylene blends. Polymers 16(14):2078 Getachew AT, Cho YJ, Chun BS. Effect of pretreatments on isolation of bioactive polysaccharides from spent coffee grounds using subcritical water. Int J Biol Macromol 109:711–719 Atabani AE, Shobana S, Mohammed MN, Uğuz G, Kumar G, Arvindnarayan S, Aslam M, Al-Muhtaseb A. (2019) Integrated valorization of waste cooking oil and spent coffee grounds for biodiesel production: blending with higher alcohols, FT–IR, TGA, DSC and NMR characterizations. Fuel 244:419–430 Lessa EF, Nunes ML, Fajardo AR. (2018) Chitosan/waste coffee-grounds composite: an efficient and eco-friendly adsorbent for removal of pharmaceutical contaminants from water. Carbohydr Polym 189:257–266 Guan H, Cheng Z, Wang X. (2018) Highly compressible wood sponges with a spring-like lamellar structure as effective and reusable oil absorbents. ACS Nano 12:10365–10373 Mathew AP, Oksman K, Sain M. (2005) Mechanical properties of biodegradable composites from polylactic acid (PLA) and microcrystalline cellulose (MCC). J Appl Polym Sci 97:2014–2025 Tapangnoi P, Sae-Oui P, Naebpetch W, Siriwong C. (2022) Preparation of purified spent coffee ground and its reinforcement in natural rubber composite. Arabian J Chem 5:103917 Thongsomboon W, Srihanam P, Baimark Y. (2023) Preparation of flexible poly(L-lactide)- b -poly(ethylene glycol)- b -poly(L-lactide)/talcum/thermoplastic starch ternary composites for use as heat-resistant and single-use bioplastics. Int J Biol Macromol 230:123172 Weerapoprasit C, Prachayawarakorn J. (2015) Properties of biodegradable thermoplastic cassava starch/sodium alginate composites prepared from injection molding. Polym Compos 37(12):3365-3372 Noivoil N, Yoksan R. (2020) Oligo(lactic acid)-grafted starch: A compatibilizer for poly(lactic acid)/thermoplastic starch blend. Int J Biol Macromol 160:506-517 Çaykara T, Demirci S, Eroğlu MS, Güven O. (2005) Poly(ethylene oxide) and its blends with sodium alginate. Polymer 46(24):10750-10757 Srisuwan Y, Baimark Y. (2022) Thermal, morphological and mechanical properties of flexible poly(L-lactide)- b -polyethylene glycol- b -poly(L-lactide)/thermoplastic starch blends. Carbohydr Polym 283:119155 Saeidlou S, Huneault MA, Li H, Park CB. (2012) Poly(lactic acid) crystallization. Prog Polym Sci 37:1657-1677 Additional Declarations No competing interests reported. Cite Share Download PDF Status: Published Journal Publication published 22 Jun, 2025 Read the published version in Polymer Bulletin → Version 1 posted Editorial decision: Revision requested 09 May, 2025 Reviews received at journal 05 May, 2025 Reviews received at journal 21 Apr, 2025 Reviewers agreed at journal 15 Apr, 2025 Reviewers agreed at journal 01 Apr, 2025 Reviewers invited by journal 19 Mar, 2025 Editor assigned by journal 17 Mar, 2025 Submission checks completed at journal 16 Mar, 2025 First submitted to journal 14 Mar, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6230035","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":432041897,"identity":"d4f7a45f-ed07-4189-951e-107edd6c48a0","order_by":0,"name":"Yaowalak Srisuwan","email":"","orcid":"","institution":"Mahasarakham University","correspondingAuthor":false,"prefix":"","firstName":"Yaowalak","middleName":"","lastName":"Srisuwan","suffix":""},{"id":432041898,"identity":"2970cb27-35c5-4322-bb6d-ba616b4e1a7e","order_by":1,"name":"Prasong Srihanam","email":"","orcid":"","institution":"Mahasarakham University","correspondingAuthor":false,"prefix":"","firstName":"Prasong","middleName":"","lastName":"Srihanam","suffix":""},{"id":432041899,"identity":"687c1cb6-d82d-479c-ba55-6ce7285fc519","order_by":2,"name":"Apirada Manphae","email":"","orcid":"","institution":"Mahasarakham University","correspondingAuthor":false,"prefix":"","firstName":"Apirada","middleName":"","lastName":"Manphae","suffix":""},{"id":432041900,"identity":"7b6d3fed-6a0d-40a8-aabe-486b55ce3fab","order_by":3,"name":"Yodthong Baimark","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA2klEQVRIiWNgGAWjYHACA2YwJcF8ACbCRkiLYTNEC1sCVICZaC08BsRpMTjevP1xQcUduwbpnq8bf7YxyPM38B97gFfLmWOFzTPOPEtukDm77TZvG4PhjAPM7AZ4tdzIMWzmbTuczCCRu+02YxsD4wagwySI1JLz7CbQYfZEa7EDamG7AXRYIkEtkkC/zOY5cziBTeaY2W2ecxLJMw4zm+HVwne8ecNnnorD9vzSzc9u/iizse1vb3yGV4vCAQid2AahgYqZ8akHAvkGCG1PQN0oGAWjYBSMZAAAxbNIlAU24AsAAAAASUVORK5CYII=","orcid":"","institution":"Mahasarakham University","correspondingAuthor":true,"prefix":"","firstName":"Yodthong","middleName":"","lastName":"Baimark","suffix":""}],"badges":[],"createdAt":"2025-03-15 03:08:09","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6230035/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6230035/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s00289-025-05869-2","type":"published","date":"2025-06-22T15:57:45+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":79381320,"identity":"2fbd9e35-3a13-4247-889e-a3e93ccfcd2a","added_by":"auto","created_at":"2025-03-27 16:36:58","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":119077,"visible":true,"origin":"","legend":"\u003cp\u003e(a) FTIR spectrum, (b) SEM image, (c) XRD profile, and (d) TG/DTG thermograms of SCG powder.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/eba1d2039e364ba2f7a58679.png"},{"id":79381324,"identity":"a5de6391-b15e-46ab-979e-12876f267a0b","added_by":"auto","created_at":"2025-03-27 16:36:58","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":161251,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra of (above) PLA/SCG and (below) PLA-PEG-PLA/SCG biocomposites with various SCG contents.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/d1b2e8c8eb75673cd6bf1f4c.png"},{"id":79381321,"identity":"e8d079d9-691a-4b37-90d6-c15e6352980e","added_by":"auto","created_at":"2025-03-27 16:36:58","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":162502,"visible":true,"origin":"","legend":"\u003cp\u003eExpanded FTIR spectra in the region of hydroxyl groups of (above) PLA/SCG and (below) PLA-PEG-PLA/SCG biocomposites with various SCG contents.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/c201f6380a87d40bfc5a32f0.png"},{"id":79381328,"identity":"f0b9cc8e-7678-4184-9abd-715ef3b8964f","added_by":"auto","created_at":"2025-03-27 16:36:58","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":611507,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images from cryogenic fractured surfaces of (left column) PLA/SCG and (right column) PLA-PEG-PLA/SCG biocomposites (some SCG particles were indicated by red circles).\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/4d64f44921d21db7bf70505e.png"},{"id":79381869,"identity":"96e8175e-ebe3-401e-9bde-cf20743a336a","added_by":"auto","created_at":"2025-03-27 16:44:58","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":144212,"visible":true,"origin":"","legend":"\u003cp\u003eDSC thermograms of (above) PLA/SCG and (below) PLA-PEG-PLA/SCG biocomposites.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/0c71f9996253695affac218b.png"},{"id":79381870,"identity":"e22ee7dd-b33e-4f80-a959-8289763705d0","added_by":"auto","created_at":"2025-03-27 16:44:58","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":134155,"visible":true,"origin":"","legend":"\u003cp\u003eExpanded T\u003csub\u003eg\u003c/sub\u003e regions of DSC thermograms of (above) PLA/SCG and (below) PLA-PEG-PLA/SCG biocomposites.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/4c23c5d2765b280bf24efb09.png"},{"id":79382298,"identity":"ee1bcf03-4679-48ab-8a8c-deea02eaa576","added_by":"auto","created_at":"2025-03-27 16:52:58","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":166780,"visible":true,"origin":"","legend":"\u003cp\u003eXRD profiles of (above) PLA/SCG and (below) PLA-PEG-PLA/SCG biocomposites.\u003c/p\u003e","description":"","filename":"floatimage7.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/cfebf4bce63b42c04d0446ea.png"},{"id":79381330,"identity":"7d5671f0-40e7-4ab1-ab82-fa03237e29eb","added_by":"auto","created_at":"2025-03-27 16:36:58","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":295378,"visible":true,"origin":"","legend":"\u003cp\u003eTG thermograms of (above) PLA/SCG and (below) PLA-PEG-PLA/SCG biocomposites.\u003c/p\u003e","description":"","filename":"floatimage8.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/8825fa37085401b97e36d6d4.png"},{"id":79382758,"identity":"9ba71a88-7913-492e-aafc-3cf3aabc11a5","added_by":"auto","created_at":"2025-03-27 17:00:58","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":144274,"visible":true,"origin":"","legend":"\u003cp\u003eDTG thermograms of (above) PLA/SCG and (below) PLA-PEG-PLA/SCG biocomposites.\u003c/p\u003e","description":"","filename":"floatimage9.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/f4b04c284da370158f81248e.png"},{"id":79381336,"identity":"30736923-35d8-4df2-a19f-79beb5b500a8","added_by":"auto","created_at":"2025-03-27 16:36:58","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":176985,"visible":true,"origin":"","legend":"\u003cp\u003eImages of water droplets on (left column) PLA/SCG and (right column) PLA-PEG-PLA/SCG biocomposite surfaces.\u003c/p\u003e","description":"","filename":"floatimage10.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/76124fde1a32f1af7f36535c.png"},{"id":79381877,"identity":"96f72c67-9dfe-4413-ab91-f468206f1267","added_by":"auto","created_at":"2025-03-27 16:44:58","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":165813,"visible":true,"origin":"","legend":"\u003cp\u003eWater uptakes of (above) PLA/SCG and (below) PLA-PEG-PLA/SCG biocomposites.\u003c/p\u003e","description":"","filename":"floatimage11.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/c47570ca227cba03c6a77957.png"},{"id":79382296,"identity":"a00bbe05-63d8-482e-9c77-13fe646ae73b","added_by":"auto","created_at":"2025-03-27 16:52:58","extension":"png","order_by":12,"title":"Figure 12","display":"","copyAsset":false,"role":"figure","size":125755,"visible":true,"origin":"","legend":"\u003cp\u003eTensile curves of (above) PLA/SCG and (below) PLA-PEG-PLA/SCG biocomposites.\u003c/p\u003e","description":"","filename":"floatimage12.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/3cf230859eb2863d5a275589.png"},{"id":79381341,"identity":"2317f194-7507-4a3b-bbc7-dfe98569e065","added_by":"auto","created_at":"2025-03-27 16:36:58","extension":"png","order_by":13,"title":"Figure 13","display":"","copyAsset":false,"role":"figure","size":346279,"visible":true,"origin":"","legend":"\u003cp\u003ePhotographs of biodegraded films of (above) PLA/SCG and (below) PLA-PEG-PLA/SCG biocomposites.\u003c/p\u003e","description":"","filename":"floatimage13.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/4f4789beb718692ae57f937c.png"},{"id":79381343,"identity":"da04c7ff-12f3-41ad-a3ef-05ebb2801985","added_by":"auto","created_at":"2025-03-27 16:36:58","extension":"png","order_by":14,"title":"Figure 14","display":"","copyAsset":false,"role":"figure","size":147884,"visible":true,"origin":"","legend":"\u003cp\u003eWeight loss of biodegraded films of (above) PLA/SCG and (below) PLA-PEG-PLA/SCG biocomposites.\u003c/p\u003e","description":"","filename":"floatimage14.png","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/41c0c8fe1c5e40b09eaa9ba4.png"},{"id":85231384,"identity":"1b6542b7-e2ac-4e61-be9e-e3424e493a4c","added_by":"auto","created_at":"2025-06-23 16:06:57","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3719385,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6230035/v1/0699faa4-be48-4378-a65f-80e14c7a69f9.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Physicochemical and biodegradation properties of flexible poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)/spent coffee grounds biocomposites","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eNowadays, the use of bio-based plastics instead of petroleum-based plastics has steadily increased due to its lower carbon footprint and greenhouse gas emissions [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. Moreover, plastic waste problems especially from single-use applications can be reduced by using biodegradable plastics [1\u0026minus;5]. Therefore, biodegradable bio-based plastics have been extensively researched in both academic and industrial fields for use as sustainable and environment-friendly materials. Among biodegradable bio-based plastics, poly(L-lactide) (PLA) has attracted the most attention due to its good biocompatibility, high strength, good processability, and commercial availability [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. However, the PLA has certain limitations. One of them is the fact that its flexibility is too low due to its high glass transition temperature (about 60 \u0026deg;C) [8\u0026minus;11]. This might limit the wider applicability of PLA.\u003c/p\u003e \u003cp\u003eIn this regard, block copolymerization of poly(ethylene glycol) (PEG) with L-lactide monomer formed high molecular weight PLA-PEG-PLA triblock copolymers which showed that the PEG blocks enhanced the plasticization effect to decrease the T\u003csub\u003eg\u003c/sub\u003e of PLA blocks [12\u0026minus;14]. The obtained PLA-PEG-PLA exhibited more flexible and hydrophilic compared to the PLA due to the plasticization and hydrophilicity of PEG blocks, respectively. However, the research on low cost, environment-friendly, biorenewable, and biodegradable fillers for PLA-PEG-PLA still need for reducing the production cost and fabricating the sustainable biocomposites.\u003c/p\u003e \u003cp\u003eSpent coffee grounds (SCG) generated by the coffee industry is bio-waste that have been widely used as a bio-filler in both the biodegradable plastics such as PLA [15\u0026minus;22], poly(butylene succinate) (PBS) [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e], poly(butylene adipate-\u003cem\u003eco\u003c/em\u003e-terephthalate) (PBAT) [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], and thermoplastic starch/alginate [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e] as well as the non-biodegradable plastics such as high-density polyethylene (HDPE) [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e], low-density polyethylene (HDPE) [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e], epoxy resin [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e], and polypropylene (PP) [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e] to reduce the production cost and to improve the biodegradability. This is because of SCG\u0026rsquo;s abundance, low cost, biorenewability, biodegradability and light weight. The addition of SCG increased opacity and brown color of the plastic matrices to protect packaged food from light [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. Low interfacial adhesion between the hydrophobic plastics and hydrophilic SCG was found [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. The treatment of SCG surfaces improved the interfacial adhesion in the hydrophobic plastics/SCG composites such as HDPE/SCG [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e], PP/SCG [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e, \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e], and PLA/SCG [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e] composites compared to untreated SCG composites. However, the SCG has not been compounded with the PLA-PEG-PLA. The purpose of this work is that the hydrophilic PEG blocks could enhance the PLA-PEG-PLA/SCG interfacial adhesion.\u003c/p\u003e \u003cp\u003eThis study focuses on SCG use as a low cost and environment-friendly filler of PLA-PEG-PLA for the first time. The SCG was compounded with PLA-PEG-PLA by melt mixing and then the obtained biocomposites were compression molded. PLA/SCG biocomposites were also prepared by the same condition for comparison. The influence of SCG addition on the properties of biocomposites was evaluated through the spectroscopic, phase compatibility, crystallizability, crystalline structure, thermal stability, hydrophilicity, and mechanical property characterization of the biocomposites. Furthermore, the biodegradability of the biocomposites was also investigated through a soil burial test.\u003c/p\u003e"},{"header":"2. Materials and Methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Materials\u003c/h2\u003e \u003cp\u003eThe PLA, 3251D grade, with a melt flow rate (MFR) of 30 g/10 min at 190 \u0026deg;C/2.16 kg was supplied by NatureWorks LLC (MA, USA). The PLA-PEG-PLA was synthesized by \u003cem\u003ein situ\u003c/em\u003e chain-extension and ring-opening polymerization of L-lactide monomer as described in our previous works [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. PEG (molecular weight\u0026thinsp;=\u0026thinsp;20,000)/stannous octoate and Joncryl ADR 4368 were used as an initiating system and a chain extender, respectively. Molecular weight characteristics of PLA-PEG-PLA were obtained from gel permeation chromatography (GPC) that were a number-averaged molecular weight (\u003cem\u003eM\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e) of 108,500 and a dispersity (\u003cem\u003e\u0026ETH;\u003c/em\u003e) of 2.2. The MFR of PLA-PEG-PLA was 31 g/10 min at 190 \u0026deg;C/2.16 kg. SCG was obtained from a caf\u0026eacute;\u0026rsquo; at Mahasarakham University (Thailand) and washed with distilled water before drying at 80 \u0026deg;C in an air flow oven for 24 h. Coffee was produced by Pangkhon Coffee Roaster, Chiang Rai Province, Thailand. The size of SCG was reduced by a multipurpose blender before sieving through a 50 \u0026micro;m-mesh.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Preparation of biocomposites\u003c/h2\u003e \u003cp\u003ePLA and PLA-PEG-PLA were compounded with SCG powder by a melt mixing method using an internal mixer (Polylab OS System, HAAKE, USA) at 170 \u0026deg;C for 8 min. A rotor speed was 100 rpm. The PLA, PLA-PEG-PLA, and SCG were dried in an air flow oven at 80 \u0026deg;C for 24 h before melt mixing. The biocomposites with SCG contents of 5 wt%, 10 wt%, 20 wt%, and 30 wt% were prepared and investigated. The biocomposites were dried in an air flow oven at 80 \u0026deg;C for 24 h before film forming. The biocomposites were then hot pressed to films using a compression molding machine (Auto CH, Carver, USA). The compression molding temperature, compression force, and compression time were 180\u0026deg;C, 10 MPa, and 5 min, respectively. The resulting film thickness was 0.2\u0026minus;0.3 mm. The pure PLA and PLA-PEG-PLA films were also prepared by the same conditions for comparison. The resulting films were kept at 25 \u0026deg;C in a desiccator for 24 h before characterization.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Characterizations\u003c/h2\u003e \u003cdiv id=\"Sec6\" class=\"Section3\"\u003e \u003ch2\u003e2.4.1 Fourier transform infrared spectroscopy\u003c/h2\u003e \u003cp\u003eFourier transform infrared (FTIR) spectra of SCG powder and film samples were recorded using an attenuated total reflectance-FTIR (ATR-FTIR) spectrophotometer (INVENIO-S, Bruker Corporation, Germany) frequency ranging from 4000 to 500 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e with a resolution of 4 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and an accumulation of 32 scans.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section3\"\u003e \u003ch2\u003e2.4.2 Scanning electron microscopy\u003c/h2\u003e \u003cp\u003eThe morphology of SCG powder and fractured film surfaces were observed using a scanning electron microscope (SEM, TM4000Plus, HITACHI, Japan) at an acceleration voltage of 15 kV. The film samples were fractured in liquid nitrogen. The SCG powder and film samples were sputter coated with a thin layer of gold before scanning the SEM.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section3\"\u003e \u003ch2\u003e2.4.3 X-ray diffractometry\u003c/h2\u003e \u003cp\u003eThe crystalline structures of the SCG powder and film samples were determined using an X-ray diffractometer (XRD, D8 Advance, Bruker Corporation, Germany) with a Cu-Kα radiation set to 40 kV and 40 mA. The scanning range was 5\u0026minus;30 degree with a step width of 0.02\u0026deg;.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section3\"\u003e \u003ch2\u003e2.4.4 Thermo-gravimetric analysis\u003c/h2\u003e \u003cp\u003eThe thermal decomposition properties of SCG powder and film samples were determined using a thermo-gravimetric analyzer (TGA, SDT Q600, TA-Instruments, USA). For analysis, 5\u0026minus;10 mg of each sample was heated from 50 to 800 \u0026deg;C at a rate of 20 \u0026deg;C/min in a nitrogen flow of 100 mL/min.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section3\"\u003e \u003ch2\u003e2.4.5 Differential scanning calorimetry\u003c/h2\u003e \u003cp\u003eThe thermal transition properties of film samples were investigated using a differential scanning calorimeter (DSC, Pyris Diamond, PerkinElmer, USA) under a nitrogen flow. The samples were first heated at 200 \u0026deg;C for 3 min to erase its thermal history before quickly quenching to 0 \u0026deg;C. Subsequently, the samples were heated from 0 to 200 \u0026deg;C at a rate of 10 \u0026deg;C/min. The degree of crystallinity (X\u003csub\u003ec\u003c/sub\u003e) for PLA crystallites was calculated from enthalpy of melting (ΔH\u003csub\u003em\u003c/sub\u003e) and enthalpy of cold crystallization (ΔH\u003csub\u003ecc\u003c/sub\u003e) using the following equation.\u003c/p\u003e \u003cp\u003eX\u003csub\u003ec\u003c/sub\u003e (%) = [(ΔH\u003csub\u003em\u003c/sub\u003e\u0026thinsp;\u0026minus;\u0026thinsp;ΔH\u003csub\u003ecc\u003c/sub\u003e)/(93.6 \u0026times; W\u003csub\u003ePLA\u003c/sub\u003e)] \u0026times; 100 (1)\u003c/p\u003e \u003cp\u003ewhere 93.6 J/g is 100%Xc of PLA [\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e]. W\u003csub\u003ePLA\u003c/sub\u003e is the PLA weight fraction (W\u003csub\u003ePLA\u003c/sub\u003e of PLA-PEG-PLA from \u003csup\u003e1\u003c/sup\u003eH-NMR is 0.83 [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section3\"\u003e \u003ch2\u003e2.4.6 Water contact angle and water uptake\u003c/h2\u003e \u003cp\u003eThe water contact angle of film samples was measured by the sessile drop method using a contact angle analyzer (OCA11, DataPhysics Instruments, Germany). The contact angles on the film surface were determined at 15 seconds after dropping the water from the left and right sides of the deionized water droplet (2.5 \u0026micro;L) and subsequently averaged. For each film sample, five determinations were made and averaged.\u003c/p\u003e \u003cp\u003eThe initial weights (W\u003csub\u003ei\u003c/sub\u003e) of film samples (20 \u0026times; 20 mm) were determined before immersing it in deionized water for water uptake test. At interval time, the films were taken from the water, any excess water on the film surface was wiped with filter paper, and the final weight (W\u003csub\u003ef\u003c/sub\u003e) was determined. The water uptake of the film samples was calculated using the following equation.\u003c/p\u003e \u003cp\u003eWater uptake (%) = [(W\u003csub\u003e2\u003c/sub\u003e \u0026minus; W\u003csub\u003e1\u003c/sub\u003e)/W\u003csub\u003e1\u003c/sub\u003e] \u0026times; 100 (2)\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section3\"\u003e \u003ch2\u003e2.4.7 Tensile testing\u003c/h2\u003e \u003cp\u003eTensile properties of film samples were studied using a universal testing machine (LY-1066B, Dongguan Liyi Environmental Technology Co., Ltd., China) at 25 \u0026deg;C with a cross head speed of 50 mm/min. Film samples were cut into strips with 100 mm length and 10 mm width. An initial gauge length was 50 mm. The tensile properties were measured from the average of five determinations.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section3\"\u003e \u003ch2\u003e2.4.8 Biodegradation test\u003c/h2\u003e \u003cp\u003eThe biodegradation tests of film samples (20 \u0026times; 20 mm) were carried out in soil as described in the literature with some modification [\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e]. The film samples were dried in an oven at 105 \u0026deg;C for 24 h and weighed (W\u003csub\u003e0\u003c/sub\u003e). The film sample were then buried into a 1.0 mm nylon mesh at a depth of 5.0 cm from the soil surface. The soil was watered every other day. The soil\u0026rsquo;s parameters were controlled with temperature of 25\u0026minus;30 \u0026deg;C, pH of 6.0\u0026minus;7.0 and moisture content of 50\u0026minus;60%. Representative film samples were taken from the soil at different times, cleaned with distilled water. Subsequently, they were dried in an oven at 105\u0026deg;C for 24 h and weighed (W\u003csub\u003et\u003c/sub\u003e). All measurements were performed in triplicate. The weight loss in soil of the film samples was calculated using the following equation.\u003c/p\u003e \u003cp\u003eWeight loss in soil (%) = [(W\u003csub\u003e0\u003c/sub\u003e \u0026minus; W\u003csub\u003et\u003c/sub\u003e)/W\u003csub\u003e0\u003c/sub\u003e] \u0026times; 100 (3)\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section3\"\u003e \u003ch2\u003e2.4.9 Statistical analysis\u003c/h2\u003e \u003cp\u003eThe results were analyzed by one-way analysis of variance (ANOVA) and Duncan test. The data of water contact angle, water uptake, tensile properties, and weight loss in soil of the film samples were provided with mean\u0026thinsp;\u0026plusmn;\u0026thinsp;standard deviation (SD) and differences were statistically significant at \u003cem\u003ep\u003c/em\u003e \u0026le; 0.05.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\u003cp\u003eThe chemical structures of SCG were characterized by FTIR as shown in Fig.\u0026nbsp;1(a). A broad band between 3600 and 3100 cm\u003csup\u003e− 1\u003c/sup\u003e was assigned to −OH stretching vibration. The 2919 and 2854 cm\u003csup\u003e− 1\u003c/sup\u003e sharp bands were observed, which means the aliphatic saturated −CH stretching vibration [37, 38]. The bands at 1705 and 1641 cm\u003csup\u003e− 1\u003c/sup\u003e were attributed to the C = O stretching of hemicellulose and the C = N stretching of caffeine, respectively [19, 39]. The lignin characteristic band was observed at 1426 cm\u003csup\u003e− 1\u003c/sup\u003e [40]. The SCG particles were irregular shape with particle size less than 50 µm as shown by SEM image in Fig.\u0026nbsp;1(b). XRD profile of SCG in Fig.\u0026nbsp;1(c) shows peaks at 2θ = 16.2° and 21.7° attributed to crystalline cellulose [25, 41]. Figure\u0026nbsp;1(d) shows the thermogravimetric (TG) and derivative TG (DTG) thermograms of SCG. The three steps of weight losses were observed from its TG thermogram. The first step of weight loss occurred from 50 to 150 °C due to evaporation of moisture and light volatile matter. The second step of weight loss was observed from 150 to 375 °C owing to decomposition of hemicellulose, lignin, coffee oil, and the amorphous region of cellulose [30, 42]. The third step of weight loss occurred from 375 to 550 °C due to decomposition of the crystalline region of cellulose [30, 42]. Char residue at 800 °C of the SCG was 18.6%. The DTG thermogram exhibited decomposition peaks in the first weight loss step at 97 °C and in the second weight loss step at 224, 322, and 355 °C.\u003c/p\u003e\n\u003cdiv id=\"Sec16\"\u003e\n \u003ch2\u003e3.1 FTIR spectroscopy\u003c/h2\u003e\n \u003cp\u003eFTIR spectra and its expanded hydroxyl regions of PLA/SCG and PLA-PEG-PLA/SCG biocomposites are shown in Figs.\u0026nbsp;2 and 3, respectively. Pure PLA exhibited the characteristics bands for ester-carbonyl (C = O) stretching vibration at 1749 cm\u003csup\u003e− 1\u003c/sup\u003e, C−O−C bonds in ester groups at 1181, 1128, and 1081 cm\u003csup\u003e− 1\u003c/sup\u003e, and C−H stretching vibration at 2996, 2946, and 2880 cm\u003csup\u003e− 1\u003c/sup\u003e [43]. Pure PLA-PEG-PLA showed a small and broad band for hydroxyl end-groups (−OH) at 3380 cm\u003csup\u003e− 1\u003c/sup\u003e. From Fig.\u0026nbsp;3, it is clearly seen that the intensity of −OH bands due to SCG steadily increased as the SCG content increased for both the PLA/SCG and PLA-PEG-PLA/SCG biocomposites.\u003c/p\u003e\n \u003cp\u003eIt should be noted that the −OH bands between 3100 and 3450 cm\u003csup\u003e− 1\u003c/sup\u003e of the PLA-PEG-PLA/SCG biocomposites shifted to lower wavenumber demonstrated the hydrogen bonds between the blend components [44, 45]. The hydrogen bonds between the ether groups of PEG blocks and hydroxyl groups of SCG could be formed [46]. Whereas, the −OH bands of the PLA/SCG biocomposites did not significantly shifted.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec17\"\u003e\n \u003ch2\u003e3.2 Phase separation\u003c/h2\u003e\n \u003cp\u003eSEM images of cryogenic fractured surfaces of the PLA/SCG and PLA-PEG-PLA/SCG biocomposites were presented in Fig.\u0026nbsp;4. The pure PLA-PEG-PLA showed a rougher surface texture than the pure PLA indicating that the pure PLA-PEG-PLA is more flexible. SCG dispersed particles can be detected for all the biocomposites. It can be seen that interfacial voids or gaps between PLA matrix and SCG particles were noticed due to different hydrophilicity between the hydrophobic PLA matrix and the hydrophilic SCG dispersed phases [15, 21, 34]. However, the reduction of the gaps was obtained for the PLA-PEG-PLA/SCG biocomposites suggesting the better phase compatibility between the PLA-PEG-PLA matrix and the SCG dispersed phases. This may be explained by the PLA-PEG-PLA had higher hydrophilicity than the PLA because of the hydrophilic PEG blocks [47].\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec18\"\u003e\n \u003ch2\u003e3.3 Differential scanning calorimetry (DSC) analysis\u003c/h2\u003e\n \u003cp\u003eDSC thermograms of PLA/SCG and PLA-PEG-PLA/SCG biocomposites are shown in Fig.\u0026nbsp;5. Figure\u0026nbsp;6 shows their expanded regions of glass transition temperature (T\u003csub\u003eg\u003c/sub\u003e) and the DSC results are summarized in Table\u0026nbsp;1. The T\u003csub\u003eg\u003c/sub\u003e values of pure PLA and PLA-PEG-PLA were 58 °C and 30 °C, respectively. The PEG middle-blocks induced a plasticizing effect to decrease the T\u003csub\u003eg\u003c/sub\u003e of PLA end-blocks [13]. The melting temperatures (T\u003csub\u003em\u003c/sub\u003e) values of pure PLA and PLA-PEG-PLA were 166 °C and 152 °C, respectively. The T\u003csub\u003eg\u003c/sub\u003e and T\u003csub\u003em\u003c/sub\u003e values of both the biocomposite types did not change significantly by the addition of SCG. When the SCG was incorporated, cold crystallization temperature (T\u003csub\u003ecc\u003c/sub\u003e) peaks of biocomposites shifted to higher temperatures suggesting that crystallization of PLA phases were suppressed [48]. This change indicates that the presence of SCG affects PLA matrices by reducing its crystallization rate, possibly due to restricted mobility within the biocomposites. This was supported by decreasing the degree of crystallinity (X\u003csub\u003ec\u003c/sub\u003e) of both the biocomposite series.\u003c/p\u003e\n \u003cdiv\u003e\n \u003cdiv align=\"left\"\u003e\u003cimg 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XdR+Pn2/smJFxEyFQYXy2iHeqzcILldXV+EZ+fI329vbC4HJ6kgY3cvLS5ABg+Mlci0Bk5dK0MyX88FAV1ZWwj0EIq4j2HKePPVgwZT+WJ0QVYKNLywshHytVntj84C9mn1ji6IamumdsumcVDbZTgl2jNj9KdtN+Cz6OljZqgaF8YJRHuWhoaGw7VeGbQ/4ZTjLWIyFgOOV//z8nM3MzIQ8gYXgc3d392aLgfu4zvLNthJttWQrJ2SFdrYKvzL/8z//k/3Hf/xHUeoPeNf2vnst/9PTU92Gl5eXP2R/KfXjPZAT+VKRs129p9YP5Nne3g4pXiB4+6iavl9ZsdqJsYDjFYkCbZuNoMSK6L2/tBkcHMwODw+L0ivUsYKyF8Kx1S1FWy1Z8kFPtM4///M/Z//1X/8VJiv9AHb2v//7v9n/+3//Lzgcjsj/WYO6GTxzYmKiKL1+a2Ni14osKfXjPZDvb//2b4N8//AP/5D9+7//e/aP//iPxdnu067eU+sH4FeZ4JuftXHo7eNTyJ1mwGX7Bv4yJQ88QXaS/WWgkQeH+jnyHn+fpTLy1VL9vP3VC8+xOtrJV0n1sr+ev+axMtdRtnMk345dZ3JafT9Rtbyxfoy///u/r+uzCqqU29ucyUc//vu//zsk6v71X/811FPuhHbkxoZNPp/Qrz8X2yv9qrIftFkVjezEj1fk5dgp7crdSO9//dd/Xc+bvLENVdEP2uoU64P3pSYnCbnMPjqlTF79HyxEZXTLhpjZDQ8Ph5lqFX/B+dlyM+M8Pj4OMv/f//t/s7/7u7/L/vIv/zJ8v+hkdd3tMVtlPz5bdlYsrEj+6Z/+KaxE+EOA6+vr+h9htUu3dV5VP7oht7cPPpt0Qpm8ClaiMrphQwxe/qCFIPVv//Zv2d/8zd8UZ9qnX22/n8esdN5d+k3uMnn7/puV+Fr8xV/8Rfaf//mfYZ/8r/7qr4paIcSfjlZWojI06+wu/TxmpfPu0m9yl8mrlZUQQojkUbASQgiRPApWQgghkkfBSgghRPIoWAkhhEgeBSshhBDJo2AlhBAieRSshBBCJI+ClRBCiORRsBJCCJE8ClZCCCGSR8FKCCFE8ihYCSGESJ4vH6zsp+4/wvz8fPi/Asc/q0498JtLlhdCiD8B85Uc8X+np6ehDPg8fhQV+BFGy1fJlw5WKP3y8rIoNYfAxAvhRQD/+/rDw8OQB17O+fl5yPOrqSsrKwpYbWADgsEQTwjQvdWjb3sn6JljL+lXufsZ6bx7mK8kQM3OzmYPDw/Z0dFRcTbL9vb26r9ezA+j8mvBVQesLxusMN7t7e2Wf47bB6YYBgY/N+1ZXFzMZmZm3sw+RHNwLPf39+HdMBj879mg46mpqXo9+t7c3Ay/GswkYXR0tGdOqF/lRl7sk2SO3U+wOF+GOf1eIp13D2Rq5ivpy/LyclF6xX7WnndRGfnLDLjslyA32CL38+fc3Fzo/8nJSagnf3Nz83NnZyfkc2MPR6u36zkPtVotHGPs2q8COmkXdIi+DNO36Rg9Wt7gfdk9uWNqW9dfUW5k8nIhU2zHsdweru/EtqXz7uq8E7m9rwTzkcgDcR+Msv61Spm89ZpOOtOPlL0AjNjnMW4zcH/ew8ugnheDDr0xUR8/50+mygERQ9veQZXR6B29x1eTm2fFTi92LMj8nkw4VnNYH0U6767OP0vf1ifk4hlxf6oMrvprwILV1dXs7OwsLFvZkyX//fv3sP/aCK5li4Hl8dbWFtqt14vWYYvDvj90Am2w1dMt+lVubJtvqs3A9m3bx7arLJl9T0xMvPlu0Q2k8+7rvBFs/+H3gM8k+D++a33WFquCVQFGcHV1lT0/P4f9V/LvcXx8HL5NNYLBUMXAEln4zsC76TdSlPvx8TEbHBwsSs3BSeaz5eCI8hl9ls+g6xO4gYGB8N0oNaTz7nB9fd10Ms87aPVvAlrhywYrVlLMDAyUfnFxUc9jEENDQ6EMBB0Ggc1w+Ni5vr4e8sAHSGZAYC+QmdJ7synx+teT7w1A9Lu0tPRm1sZfG/l3SBsM5m7Rr3K/Bza+sLAQ8mbL2Db9YFLXS6Tz7hP7SsAf2l//AdcgL7tSFqAIZvEfXnREHr0DLvtlYC+2nX3rVuhkv7Zf6cSG2Ot+7zsDe/U8w5Lfuy/7JtAqX03usu8elKkHOwJ982VP1d8kWkU6/7jsnegbPuor6RvvqV3K5K3XdNqZfoWXUDWdDIZ+plMb6uT+TiYeX01ub584P9rx48A7Sq7lvE9GmQNuFd9OO3Ry/1fUuW+jXby8zaB/nQQqKJO3XlNFZ8TXppsDwoMTaNf5wFeUG6fnHWQjcIxeRiu3O8M3pPPGfIbOq9B3NymTV39gIZLive8RZfAfelb5Ibcd+k1u+482428RMXx3yINC+B5Bogx8F0L+XiKdfy2+EbFCJldKkRWiLfrVhiR395HOu0u/yV0mr1ZWQgghkkfBSgghRPIoWAkhhEgeBSshhBDJo2AlhBAieRSshBBCJI+ClRBCiORRsBJCCJE8ClZCCCGSR8FKCCFE8ihYCSGESB4FKyGEEMmjYCWEECJ53vxf14UQQogUiP+v6/qJEFEZ+vmE7tLPY1Y67y79JneZvNoGFEIIkTyVBasfP36EaOjT7u5uODc2Nlavu729DXVlcF2jX9G0ttbW1kI7HK3OoGzPoR2uMbx8PAc54mdRtntjaKuRbKlB3+bn54uSEEL8AeRLrYDLts3Dw8PP0dHRovTa5s3NTchTz/lGcF2tVvs5NzdX1LxlZ2cnXGPnT05O3sjMef9s2rLzPNfLYmXuieE+2v5ToK9l/fwM/PvoJyR395HOu0u/yV0m76duA+aOP/v+/XtRag7X7e/vZxcXF2EV5GGlsLCwEPL39/fhuLi4GNo3Njc3s6Ojo6KUhbbs/N7eXshPTk6G8sjICJrINjY2QvlP5uzsrMgJIUT/8qnB6vLyMpuYmChKzXl8fAxHgsrd3V3IGwQyAgzBxrYU2ZIjIIFtLVowMuw8ckxPT4d8Kzw9PdW3DMG2B+05frvRb0Vand9+tDoS2L3WJtt1tGt5oI8k2/K0Z8RbmQZlrrXnWplnEMRJ/pydB5OHo/VPCCGS43WBVc0y0bbXLOWBpzjTfBuQett681t9RryNZc+xbT/uaSY/1/mtPdorkxEoW7tcZ+eRiefwbC8fbZjMts1IHddxr9XRlt3H0Z7B0eqtzvpnMlt7XMcRaNva5zqSnSNvcvNc05+Xh2eZjGDXdAJy9iOSu/tI592l3+Quk7fylVXuBHlKSLayeQ9WUktLS2GGPzU19WYr0G8Bkme1YNt4s7OzoTwwMBDOx9uHBqsQv0XI9l/u0MMqrkzG7e3tcCxbFSIrzzdo4/n5OWxP2soO2biGFZ3JRh9sCxPiLUvD+oAe2eqEPEiFI3qxZy8vL4dreSa6I8Ur0hiuR7/oOQ9U4frh4eFQPjw8LK4SQoj06NmfrrMNZY6ZbTcLcCQCgDle2wI0tra2itwvOM89BC8PQYpnEAxw9H7LrhWOj4+DM/cMDg5mBwcHddk5jo+Ph2cROD3U8b0MXl5efpOvVSxIEcCsDwTImZmZkDe9+QBYBm3kK6v69QRDArfd+1H9CCFE18gdVcBl24ItJdqw5GHLyZ8jUQdWti0v3w7bXn57yra8/HkPW1p2jmTbYhDLR7ItsRg7T3uADFYXl8vkJlnbVrb++ntNXs7RF8vHbTXSDcT68Ndwzs5bX+wcCRn9u2mkj1ahjX5Ecncf6by79JvcZfLq/2CRIKzWWIX5bcN+oF9tSHJ3H+m8u/Sb3GXy9mwbUDSGQJWvkOp/sSeEEF8draxEZWjW2V36ecxK592l3+Quk1crKyGEEMmjYCWEECJ5FKyEEEIkj4KVEEKI5FGwEkIIkTwKVkIIIZJHwUoIIUTyKFgJIYRIHgUrIYQQyaNgJYQQInkUrIQQQiSPgpUQQojkUbASQgiRPApWQgghkkfBSiQLv+fFTwWQ+EHKRnUpgUwm3+7ublGbntynp6d1eTzITN38/HxRUw7nb29vi1JvKJPfGBsbC+e8rpG3lb59NrHu3tO5t51uY7J5WwZkLas3/Dio6nf5FKxEskxPT4fftCGNjIyEAXB5eRnKJycn2d7eXnFlOtgPZyLj4eFhkDlFua+vr+vymMPBgV5dXYX6mZmZENDKoP7i4qIo9Q7kLAMHubq6Gs5jN4DMU1NT4d2cn5+Hul4Q6+49nXPexkGtVqvM8bfKxsZGtrOzU5RewV6QFZmQ3U8IjLu7u3CetL+/X9R2hoKVSBIGxNLS0m+DE2djDA8PF7m0MAeJwzw7Owv5lOTGuZgDIWgtLCyE/Pfv37OVlZWQp+7o6CjkY7hnbm6uKKUFM36cOk7WoL/Y0s3NTf3d9IpYd+/pfHJyMltcXAz59fX10sDQbQhQZjPIbjbuQd9MGqqUV8FKJAmDgVkZxm4BC0fDLI9BwKD3DikVCEp+iwdSk9scNvKw4rPy4+NjNjg4GPJwf39f5H7Bu6hqplw12AqrFo70zewGZ0qAYGVFffx+ukWZ7lrRuafXwRaQ0ctBHzzon7HL5GB0dLSygKVgJZLEBgNbNjhUY2hoKDj+g4ODygZBlbCtZk5xc3MzyAspyo1DYfUXr14bYVtSqfLy8hKC0tbWVuib6Rpnij1Rx/vZ3t4u7ugeVeiO7eNUJwoeG7usCtF32cqrHRSsWgCDx/mQev1x9ivCdyDgPdjKhFlbq062m7Blg1O0bT/KKcuNTBY82Z58fn4OeRw/f6TgOT4+rm/vsIIhKPdqldIMnCQQuOgHWKAYHx9/d/XyGTTS3Xs6N1KaKCCj2czT01PTbW30XRUKVi1gszJSLz/OfnUYzLbKGhgY6InTaRW2PwhMkLLcOEE+lsPExET9m4n/lmIwq7dxQCCgfxYYUgBZ0K05UvLULS8v1/vFu7DJTzdppLv3dA68I1aDTHzIk3oJ9mKrJf/9qgyua3b+Q+TKC7isEG1RpQ3lzj60F7eZD/R6fT7gi9rO+Ay585VVUfNKSnLzfJMFuTy1Wu23evI7OztF6RXqOulHu7J7rA/o3PB98/JZv/y17UAbnRLrrpnOT05O6v3pRP525UYGezayGGbn3i4o0y8vc2w3rcK9Md/4Jz8RlqdFVoi26FcbktzdRzrvLv0md5m82gYUQgiRPApWQgghkkfBSgghRPIoWAkhhEgeBSshhBDJo2AlhBAieRSshBBCJI+ClRBCiORRsBJCCJE8ClZCCCGSR8FKCCFE8ihYCSGESB4FKyGEEMmjYCWEECJ5FKyEEEIkj4KVEEKI5FGwEkIIkTwKViX8+PEj/FIlaW1tLdRx9GVjfn6+yImqMZ2TeCdgZdLY2FioSwlvO7u7u0VteV96iZfHgz2X1Runp6f187e3t0Vtb2gmJ7bBOa9r5KWuV2PW687w9tJItl7qHBvmud6WwewkrjfMvpC9Mn4WuOyX5+TkpMi98vDw8HN0dDTk7Qg7OzvhnHilahuK30NcrtVqRa4zqpQb+zCbsLy3H/rQa7lvbm7qukQWk4f6ubm5kMe2SR7fD59vh6p0XtYOdbHs9Jd6ezft0oncpmdkMfm8TSPbZ+m8E7ljW/Bl7KWRTumv799HKJNXK6sSlpaWwqyg2QzYzo2MjISjqBZmbLwHv5IdHx8vcq+z5Onp6aKUFmYTq6ur2dnZWcjnAzocYXh4uMj1hsnJyWxxcTHk19fX39j5/f19kcuyoaGhIvfKy8tLNjs7G/L0kdVLr1dXMcz4cyeZbWxsFDWvYxVbyoNxz8YrMuzv74f89fV1trCwEPLepu/u7rKJiYmi9EqKOr+6uqrLv7KyUrfxz0bBKgKjyoN4MOx8FhPKGAkGQwAzw9nb23szIES1MBh4D+jfApZ3NMfHx3WHmxIEpdiZIHc+Ew32g6NKzW5MrwQxs3Mo0+/BwUGRSw9s5eLiIhzpg9kNzjRfAWRTU1OhvhfO3nTM8y8vL+tlb9PYBu8gJjWdM6Hxcj8+Pha5z0XBKsIP3HwJW581MCvCeXJk1r+8vByMHuNL8dtJv2Pv4fz8PAzufgGbMae4ublZX51wJGDheHCmqcCky2b8wKoPOZE9hjHBqoW+kQgMAwMDxdnewyqEoLS1tRXGqukaZ4o9Ucf72d7eLu7oPsjAitvvGDQjdZ13EwWrJvglumGOBiPC6JlJMxut9EOieIOtZg0mCaluAbIawSHZth9lbMZWVKzYW3VUn02sR1txICdOvUxOm7RxnsDgZ9ipYKsT5COAgfWTMe23OnsB+o0nLPgPJsBlpKZzJucm/9PTU9e2tRWsmsCqyvZmDW3/9Z7v37+XTiRSgi1kAhPgMG11yKy4184SCExMtgim5EnPz8/hewQMDg7+5lANruUbEKvelCBIoVuTmzx1BIGjo6NQ578B9Qr0NzMzU5ReabQFaKSkc2S3HSf//erTySN2wGW/NPnsJeiCZH/xYvDXLfzFlEGe6zr5q6g/iSptCJ3ae4jhPVTJZ8gd/4VUPiOu98fbUCe0K7e3cZK3X6936wOyMxYox9e3C+10isnp5bExSfJ6xmbia9uBNtrBy4U+Y2Kbrlrn7cqNDCY3dmOYnXgfSdl0bvr2dR+B+2K+8U9+IuyHFlkh2qJfbUhydx/pvLv0m9xl8mobUAghRPIoWAkhhEgeBSshhBDJo2AlhBAieRSshBBCJI+ClRBCiORRsBJCCJE8ClZCCCGSR8FKCCFE8ihYCSGESB4FKyGEEMmjYCWEECJ5FKyEEEIkj4KVEEKI5FGwEkIIkTwKVkIIIZJHwUoIIUTyKFgV7O7uhl+n5OhZW1sL9RyN+fn50mupF9Vhuif9+PGjYV0KmEwe5CuT1ezn9va2qOk+Xo8eky2uN/x5Ui/fQTM5x8bG3siHru36eNx2i9PT099k9jZCKvMhdp/3Qd2ikV80O2ikS5OZ91AVClYFGxsb2c7OTlF6BYWD/bwyBm8OhrrDw8OQBwzp/Py8KIkqmJ6eDnomjYyMhIF9eXkZyicnJ9ne3l5xZe8xG/HMzs5mDw8PIXlHg53Mzc0Vpe6DDZtua7VaXTZv24yF2BGh/62trXDe7uW99IoynQNOcnV1NZw3+Z6fn+tyM9Z7wfX1dXg+tmu6vbu7q8uFnczMzIR6z+LiYrinF5T5RWRHTmS+urr6bcLi7WR7e7thQPsoClZNwLiWl5dDnuPx8XHIx9jgF9WBgS8tLf02m2RAG8PDw0UuPRiwzCpxluYw40HdKyYnJ4MDhPX19Tdy3d/fF7ksGxoaKnK/4N6UYcZPEPUBif5hSwSxXoEM+/v7IY9fWVhYCPnx8fFwBALXxMREUUoXApTJv7Kykp2dnYW8QT+YLAB25if1naBg1QQMbGBgoCi9lm2w2uwNCGI2+EU1MBiYmaFzC1g4fWZ56J4B36sZciu8vLz8tuqgLkVMTmyb1aA59dimfX/YdbCJXCpgKxcXF+FIH/xEB1tiddKrgGW64/nsDljZ6xSbTn0yAExovNyPj49F7pWnp6c3Ex0/wewEBas2YBsH48dZMiCYndoebdmes/g4NhjQNYPbYBAQsA4ODoJTEp3BVqrN+IHVKvrd3NwsaspJ0bEyGWB71bagzEbMlgi+9M2293sBcjHJjXcMxPsoWDUBI7fZMHvefjYBtv1HvQ0QqxfVwWwfcDy2orq5uUl6wLMi98GU2ahfpadAvH1tdot+WYX0q0O1IErgilezKWyzod94opXiSrURbG+b/Kyi4u14JpTUA9eNjo6GfKcoWDWBgWzfqXCSsTFp+6+74HhslYXj999XUoMJDPIxWEn2/SoVCEx8/MZ+yZOYkPE9AgYHB39zqEYc5FKBIGU6B/Lx6i+FMYv+4j+k6JctQEB2+07lv18ZfIez71T++1XH5KuBgMt+SXZ2doIOSPmssqj9+TOfnYW6Wq1W1LxC/cPDQ1H6Ge7hOuq/KlXaUD4bq78Pj70PUr66Kmo7owq5TSbkNpDP6r2t+D74+o/C/e1gtmrJy+z1brIhL+PDiMdCO9B+p5TJ73Vu9tFobLcDbbSDl6vMR5T5F9O5f1/+PXyEduVupDuzEy8P5Vjn/t18BO6N+cY/+YnwvaXICtEW/WpDkrv7SOfdpd/kLpNX24BCCCGSR8FKCCFE8ihYCSGESB4FKyGEEMmjYCWEECJ5FKyEEEIkj4KVEEKI5FGwEkIIkTwKVkIIIZJHwUoIIUTyKFgJIYRIHgUrIYQQyaNgJYQQInkUrIQQQiSPgpUQQojkUbASQgiRPApWBfPz8+EHv/j5cc/a2lqo52jYtbu7u0XNK9SL6jDdk+ynyjlanX8nvcZk8nhZ/U/EYzfU9dJevG5jkDUeB4bZviXfr27TSH5A/li+Zv3qBqenp6Uyt2oPZX3qFjzTZG8kq+8fP91fNQpWOSh5a2sr/DIlBmFBiHqwX6zkBdhLoO7w8DDkgcF/fn5elEQVTE9PBz2TRkZGQt3d3V29bn9/P9SlAPLEzM7OZg8PDyFZYMV+rq6uwvUzMzN1G+smyGC6rdVqvwX9RpMAHJaNE7vX3ksvKNM54CxXV1fDeS9fo351i+vr6yDTyclJ3ce0ag+N+tQt/LjDnpHV422D8ysrK8WZ6lCwyllcXMwmJydDHoU/Pj6GPMa1vLwc8hyPj49DPsYGv6gOBvPS0tJvDoY6Bm4vZpcfAfmY+OBYzLlQ9/379/pAXlhYyI6OjkK+m2Dr2Dysr6+/0SXOspmjsXGSKsz4CaIbGxtFzSvv9euzQcc2ucKv8O6hFXto1KduMj4+XuReA9fExERReuXl5SVMzgB7x/ZtYl8VClYlDA8PhyMGNjAwEPJA2QarzXSAIGaDX1QDA5dZGjq3gEWeupubm2x0dDSUU4XBG8+AqWMiNDg4WNRk2f39fZHrHV5OHKl3TB5/Hc7fJnKpgD1cXFyEI+PTT3Sa9asbmO6Q6/Lysl5+zx6a9ambxDZSNmk5ODgocp+DglUEgee9GQzbfThNrsN4mJ0yeDGm9/adRWvY4EDXDG6wOgYKWylnZ2ehLNpnb2+vPuPHllvdWm3ksHoJk4G5ubn6dhTOEyf/kX59NsjFJLfVoNOoT6mBLbD6wweSCLB+ol8FClaOeLaIc8RY4Pn5+c3sAmz7j3ozJqsX1WHbC55ezpJbgYHqnQozZupYtWNLgG318oN/vH2NI8TRsGrlu0MvZesEC6I4eXScWr+Y5JpttGoPcZ96RbMVNRMCfCATSeSM/WWnKFgV8BJstkgeY2Ig23cqzsUvSdt/vYNVle37pwgDlQCFHZFwQtSx12/fJfz3im5DoNre3g72S56EoyHh0HHsjbYo4yCXCoxd0zmQp67VfnUL9Gd/oPCePTTqU694b0VN3/iu/Cl/bJa/xIDLfjl2dnZC/y3ls4LizM+Qpy5f4hY1r1CfG39R+vkzn038du9Xg/5XRe5U6u/DMB2TeGdVUYXcJhdyGzc3N/V6byvYEnWd2gpttIPXI8nLDMjq65DT6zseC+3QruyeMvm9zsl74n61Q7tye7ni915mD17nzfrUKtxbBWV+EDnRLc/oVL9Gmbzf+Cc/EZbJRVaItuhXG5Lc3Uc67y79JneZvNoGFEIIkTwKVkIIIZJHwUoIIUTyKFgJIYRIHgUrIYQQyaNgJYQQInkUrIQQQiSPgpUQQojkUbASQgiRPApWQgghkkfBSgghRPIoWAkhhEgeBSshhBDJo2AlhBAieRSshBBCJI+ClRBCiORRsBJCCJE8ClYFu7u74dcpx8bGippX1tbWQj1HY35+PtRxj4d6UR2me9KPHz9CnZVJ8bvqJSaTB5mt3uQ3KPdSfq/bmNvb21BfZs9m+5bifnUTk6EMdOvlsz6R4nHbLU5PT0tlNp0iYxkp6Jxnehma+bpY91WhYJVjSuVnlFdXV4NRgR3t55UxJjMo6g4PD0MeGPzn5+dFSVTB9PR00DNpZGQkvA8rk2ZnZ4srew/yxCDfw8NDSH6yA3G5m2DDpttarfZGFnQ8NTUVZI7tmXGytbVV1z/38l56RZnOAUfJOOa8yff8/FyXe2NjI9R1m+vr6/D8k5OTNwETPc/NzRWlt6Si87u7u7oM2MbMzExx5i1luq8KBasCM+Crq6tscXEx5DGu5eXlkOd4fHwc8jE2+EV1MJiXlpbeONLx8fEil77OcTLMMBmwNmhtUkRAWFlZCfleMDk5Wbfx9fX1ulwc0fnNzU1DR8O9KcOMH4fuA5L1C0faK5Bhf38/5PErCwsLId8KKejcjz0C18TERFH6RZnuq0TBKoeBiTHFxkzdwMBAUXotm+HYDAIIYjb4RTUwmJmdoXMLWN6Bpq7zl5eX3xw+dYCz8oO/15icZ2dnYYbPygr7tl0Ew/eHgGsTuVTAVi4uLupj2U90sCVWNL0KWKY7nn95efmbbTQiFZ17ObDfOIA2031VKFgV8DJs6frenjbLdq5lBsFLYXaKIfGSmu3litaxwYGuGdx/CtiLzbBTYG9vry7P4+NjfRzg2Le3t0N9GWUOq9cwGSDY2rbZwcFBcJ5mS0xudnZ2wljtFcjFJLcdZ56izo1Guq8SBasIAg+DFjBymw2z521Gb9hWFPX2kqxeVEf8baoftl1ZkfvBen9/H+oYxExqRkdHw95/L//IokyPVmblh8z9iDl0nKeNX6Ns+6rbMMmt2pF3i/dWd8103ykKVhHsx9qA5WjfqZjVxC9J23+94fv370lto5XBBAZnj1Mi2fcrJjQkAhUBq1cBgUDFygn7JU/Cvo+OjsJ5HE2jP2BJdbKAozSdA/l4JZLCmEV/jf5AoRGp6LzR6q4V3XdMPnACLvvlODk5Cf0n1Wq1ovaVfIbQsD53OEXpVxvUf1WqtKHckdffSUz8LjqlCrlNVuQ2bm5u6vXeVoCyv7Yd2pXb2zvJy4Fu4zpsemdnpyhVo/92ZfeUye91Th6Q3eroeyfQRjt4uWIfYT6GZHZStc7blTumzA+anGW6b5cyeb/xT34ibE0UWSHaol9tSHJ3H+m8u/Sb3GXyahtQCCFE8ihYCSGESB4FKyGEEMmjYCWEECJ5FKyEEEIkj4KVEEKI5FGwEkIIkTwKVkIIIZJHwUoIIUTyKFgJIYRIHgUrIYQQyaNgJYQQInkUrIQQQiSPgpUQQojkUbASQgiRPApWQgghkkfBSgghRPJ0NVjd3t6GX4D06fT0NJzzdfY7/jHUNzsPtOfbIvHcsmeTdnd3izvfyjc/Px/aoi5mbW3tTRsk8M/m/kbwzEbn6RvtWF9J5L2c/lyZnF4+zlEWQoi+5meBy34q/DY/v9sPDw8P4bkc4T0Z+K3/Wq1W/83/RpycnITrgOdZu/7ZwHOtLbvOZLEybZVB+3aONqxd/+xGcH50dLT+LI/JQ3vIAFxr9aYzOxfLSdu+j5St/59Nt55TNZK7+0jn3aXf5C6Tt6fbgCMjI1nuWLO7u7ui5n2Wl5ezw8PDovQ+k5OTWe7sS1dIe3t72cbGRshvb29neUAIMgH35frJFhcXQ7kZCwsL2cXFRVFqDqui6enpbHZ2Njs7OytqfzE0NFTksuz5+TkcLy8vwxGQOQ9AQT7gmAeskKftg4ODbH9/P5SBPP0QQoh+puffrHDy4+PjRakxOGIwJ23l9+C6fDVSv4/n2RaZh/qJiYmi9DEItgTdViBA0V+C7tXVVVH7iu/T1tZWtrS0lI2NjYUAakGVwEWw89A3gipyEJgt4AohxJ9CT4KVDxh+NdMMHDErGFhdXS1dlXhYYdA+zvvk5KSozUJQYaXx3mrDf/fx34s8BBPOc/SrmfegvwSY+/v7NwGKPtlKjvPIyAqMZ/DtqR2sD6RWA7wQQqRGT4KVDxi2YniP6+vrEHhwupubm2+2All9mEM22CqzZzTayvMBhraPj4+L0us5AimJIGnt+z+MIAjaM1pdzSC7tcWKzwddvwVofxSBHFzHSgvo69PTU8jHDA4Ohmv9liey0TfqteISQvQrPd8GbIYPDMPDw/XAQAJbKbBC8fUfwZ5xdHQUVmNlKxicvLV/fn5e1LYGMlrgoW2ChrXFtybbCoxXPZTLZCFoEfB8QGLlR2I1RpCempoqzgghxB9C7jQDLvtp2F+ukfLZflH7itX7xF+1+XtyRx+u5S/frM7+Ss7w57jf8O34xF/LGWXX2DM99hd2JP98/2yfqLd7vEzk7Zo8ABW1r9Cufw6yGbGcsQ78fST/zM+EZ/Ujkrv7SOfdpd/kLpP3G//kJ8K2VJEVoi361YYkd/eRzrtLv8ldJm/S24BCCCEEKFgJIYRIHgUrIYQQyaNgJYQQInkUrIQQQiSPgpUQQojkUbASQgiRPApWQgghkkfBSgghRPIoWAkhhEgeBSshhBDJo2AlhBAieRSshBBCJI+ClRBCiORRsBJCCJE8ClZCCCGSp6+CFT9Bz49yldGoPkX4mfuyn6wXQghRTt/9UnC//eLle+zu7mYLCwvZyMhIUdO/9Ou7kdzdRzrvLv0md5m82gbsMYeHh0VOCCFEI/oyWLEaIfKynQZsD46NjYU8kOc86cePH6GObTeru729/a3O2uJekj2Dazhnee4lb+dJ9gxfRx789SR7JvXI/fDwkI2OjoZymYzWN5NPCCG+JPlSK+CySYOcOzs7IZ87+Z83Nzc/c4cf8sC5k5OTkOdIvT9P3dzcXMhbHZDnHNfaM2ibPPXka7VauJZzpi9rj/usXeA893At50xm4DrOgclneeCctcUzOc9zUsd00m9I7u4jnXeXfpO7TN6+XFltbGyE4+zsbDh6rq6ussHBwZBfXFwMK5eXl5f6tdSdn5+HlYtfja2urmZPT08hnweN+jPyoBHuAVtBQR58wnF8fDwc7+7u3nx3yoNM9vz8nE1MTIT2Njc339wfwzlkZVU1NTWVXVxc1Ou5//r6OpSFEOIr0tffrA4ODrKBgYGi9AoBY3t7O+Rx9AQbruFaD3UEBNtue3x8DIHlo1iQIkDyDAtIHAlkk5OTTBFCaraVRxsEJbuWBARW8sPDw3VZhRDiy5E7woDLJg3bYchK8ltplG2bzsq+T7Z1R+I8+LZsm863Zed8nut8WyTD19u2XbN7ge0+8vTFy4McbP9ZmZQ6/SBjGZK7+0jn3aXf5C6Tt+/+dD0F7I8nbKtQvNKvNiS5u4903l36Te4yeRWsPghbcXxTgnw1FLb5xCsayN2ln8esdN5d+k3uMnkVrERlaCB3l34es9J5d+k3ucvk1X8ULIQQInkUrIQQQiSPgpUQQojkUbASQgiRPApWQgghkkfBSgghRPIoWAkhhEgeBSshhBDJo2AlhBAieRSshBBCJI+ClRBCiORRsBJCCJE8ClZCCCGSR8FKCCFE8ihYCSGESB4FK5EkP378CL9pQ+IHL43T09NQNzY2VtSkBb8ibXKTkBd8f9bW1kJdLzE9lsmCvjk3Pz9f1PyC660fvaaRHNgG9d5G7Npe6t50HsuMnpvJ5u/zY6EbmGxel2YfJLPvGG8n2H4l/CxwWSHaokobqtVq4fjw8PBzbm6unh8dHQ35k5OTnzs7OyHfKVXKjVwG8iEz+Pqq6FRuZDI9G9TRrsntubm5qfeD++J7P0JVOo/bQcZYdi8n13NNu3Qit8mBDs12yZs82Hksu7d5n/8o7cgdy2YyWz84V9aul5M22rGTsnbrNZ28BCGgShuyQYuxkyzvA1S7AzfmM+SG2EmS/PlO6VTu2JEgG2224sy51iYR7VCVzuN2kIk6s5kY7KfRuVZoV+7YLqzs68v0ybvw74hrWnk/MZ3qO5bDQB7fB6Bsz4vHbKuUyattQJEkIyMjYQtiaWkpGx8fD3VPT0/Z0NBQyEM+KIpcOiA3sPUxPDxcz+djLcsHfJYH2Oq2RSrm7Owsy51PNjU1FbZv3ttysr6mxP7+ftA1dtNoi2pwcLDIdQ/TFXq9vLyslznaNt/MzEyoizk4OChyvcXsOSa2A8p5gAp9ur6+zjY2NooznaFgJZLl/Pw8OPjZ2dmipn+4u7vLJiYmQt4G8+TkZJbPNENQSJHHx8cgK84eObe3t4szv7O3txcCQ2qYrpnIHB0dhbyHPvIeegW6XV1dffN9anFxMdQfHh7+NkFA1nxFExw/6eLiIhsYGCjOdo/j4+Pfgg6yrqysFKW3MKkkYBFoq5qcKVi1AMo2Yyn76Cw+DwarfdxlALC6At4Jq5RUYUZZ5hRtlZgq09PT4Yic9/f3IR+Dk7LrUoWgZYHLIECkEGBx+mUOnMnB8/NzUfqFrRaZQLDyjfv12bDyW15eLkq/IIARaGPom62omGxW9UctClYtYLNNErN90RtwoMw+gZULM9R+g1XVwsJCUUoLHJKtRl5eXkpXtAQqnCpOiny8EkiFOKDiMK3MX2z2EmQr2/LDwTeazHAPW5vd9j8EKpt4kbcgywRyfX095GN9YjtsdQKrwEaTng+TO+CAywrRFlXaEG1Z8vCxlrqq/rgCqpQb+KjsP4JTtr6087G5EZ3I3UgmPqJT5/XLR3Su8ffE13wU7u+UWA77sE9CZoO81ZM6eQfc3w7Ygz3fy2b6JqFfw3RuferU3mnjo/B8k41kcvs6ktm6z3ud+7HQKtwX841/8hNhi6vICtEW/WpDkrv7SOfdpd/kLpNX24BCCCGSR8FKCCFE8ihYCSGESB4FKyGEEMmjYCWEECJ5FKyEEEIkj4KVEEKI5FGwEkIIkTwKVkIIIZJHwUoIIUTyKFgJIYRIHgUrIYQQyaNgJYQQInkUrIQQQiSPgpUQQojkUbASQgiRPApWQgghkkfBqoQfP36EX6okra2thTqOvmzMz88XOVEl/h3c3t4WtVl2enoa6sbGxoqatCizHQ/1KWB6LLPnZvq1+0jke4nJEYPscR/s2rJ30i3Mh8Qym87jeqOXOt/d3Q3P5WgwHt+Tx95Bpf7xZ4HLfnlOTk6K3CsPDw8/R0dHQ96OsLOzE86JV6q0oVqtFo7od25urp43/fOO0H8VVC232Q+yevvgXJXP6rQt5DQ9A/o0nfq8x/rk30U7VKWHuJ2bm5s3OgffR67nmnZpV26eaXaBPCYT9Wbfn6nzTvQdy+VlL2uXa+0dIG/sT1uhrF2trEpYWloKswJmyY2wcyMjI+EoqmV9fT0c7+7uspWVlXp+dXU15BcXF7PDw8OQT42np6ci98s+mI1OT0+HfKo8Pj5mExMTIb+wsNBQvy8vL+GY4up2e3s7yx3kmxn//v5+kcuy3JFmz8/PRal7TE5OBpsFbNv7lvv7+yKXZUNDQ0XuLSnp3PRJn/JA+5uf3NjYqNs978OPh05QsIpA8XkQz/JZQzB6yih+dnY2BDCOsLe3F16K+BzQOVsITBzGx8dDHUbvB3M+eyty6cBA3tzcDLZyeXlZ1GbZ8fFx3VmlDHI24+joKJuamgrj4Pz8vKhNB/TP+MVuGm1RDQ4OFrneYc4ch2++BcpsJHWdW18a0SgAfxQFqwhvRPnyNTs7OwtlGwQc2b9dXl6u792mOMP8E2BgMmmwCUK/wOydiQ4TGsBebKWYMtj2wcFBsGnkL7PrgYGB0D8mCt3+ftIKNn6RDycfw+qRsd1LsAt0bQwPDwedMskpI1Wd4/9s16MR19fXlU3SFKyaYDN6jy15MXiWuBgQzjTFgfsngJ7NaTJDsy0F3gMONTX4iM4WGls7yMiAZjsNWW32bMcUYUJGYnunzBHRP3YUbPWSKgSteMaP7D5I9IJ4O5gyoFMmx2V/AJKqzt/bLah6kqZg1QRWVTgej7b/egeTB/uO4r9fpQQBCtkAZ8n3EQKXBQGwY6rgHJG9zBFdXFzUJ2y2TZ4icVCgT1b2f9nWTZCJCS56JU/CPq6ursJ5tifL9JmizplAWiAq06fVYUeV6TsfOAGX/dLwlyvogpQvvYvaV/grGP4CxrC/hskNqKj52lRpQ/YO4jZ5J1XrvEq5zSZI9ldeniqf1UlbZXZuuo3tnn7E15Rd9xG4v1NMDrOFh4eHep3XPXmrJ/VCbq9vkrdf8lZPH6BqnXNvO/hn0wewsiXziZbHT/rz9teDH4H7Yr7xT34ibE0UWSHaol9tSHJ3H+m8u/Sb3GXyahtQCCFE8ihYCSGESB4FKyGEEMmjYCWEECJ5FKyEEEIkj4KVEEKI5FGwEkIIkTwKVkIIIZJHwUoIIUTyKFgJIYRIHgUrIYQQyaNgJYQQInkUrIQQQiSPgpUQQojkUbASQgiRPApWQgghkkfBqoCfXuYHv+KfYObnsKnnaMzPz5deS72oBn66Gx2T+Plv4/T0NNTxs9op4uX2NmN2lIqNmB69jGC23Ui/vn+9/nl1kyMG2eM+2LVxf7uJ2YCX2euTVGYf9k4sdVPvZX6R8WiyYEfN4JqqULAq2NjYyHZ2dorSK/Yi7BcreUnmOKk7PDwMecAQz8/Pi5LolL29vaDjh4eHbHt7O9QxSLe2tkI9dfFkIQWQ++TkJMh4eXkZZMZmpqenQ93IyMib4NsrFhcXg5we9DkzMxPkXF1dLdXv7OxseCekXjp+QM4YdIveOXd/fx/qkJMy6eDgoCf69zZQq9Xquru7u6vLhk7Rv8fbvN2LDXWLMr94fHwcZLm5ucmWlpaK2t+p2j4UrJpwfX2dLS8vhzxHXlIZZoiiOtbX18ORwbyyslLP40QBZ+snCynx9PRU5LLgWAYGBoK8gPOZnJwM+dR4fHzMJiYmQn5hYeE3/SI7qxX6ZA6TupRgEjM6Ovpmxr+/v1/ksuB4n5+fi1L34J2bDWDbprfx8fFwBOzb9O9JzV5Mn8g1NzdXagOf4RMVrJrAS8DRGJTNcFjemuMkiJkhimrAGbL9wczNBjRBYGhoKOSBmWhqMJA3NzeDfTDDB/rC4KXOnHyqNJqQwcvLy2/yU5cS6J9ZP3bTaItqcHCwyPUO06PXJ5PjODD58/THJs8pUWbTn+ETFazagO0+BgRLZJa6zJQwJJxRKt8k/gTQM1sNbD31E8zemd2zJWjghLAZJjyNnGivwdGzTYYdI3+q3wWbYY6TiczR0VHIe1g99nqlgl341V6rlAWzXsIEzHY9PGwf285IlShYNQHDt5kjWwfxDMKWutTbvrLVi2pgcJrTZFVlW2w4fRxqajB5YQuN7yXIGNsCduK3CVMDGyaxvRM7InYZ6JNBH/3OQ0owJuPxyrtpJ0hUifmMmFRXTc1otHpi+5ixyaQH7NgpClZNwKhsW8R/vzK0/ddd2A607yj++1VK4MyRDXCW8feR79+/l36XSAmcOrLHtk2dBWGSfb9KkTgo0Ccr9+oPc5CJb2rolbyfyLy3amoU5HoF795WT7E+sRGb9IAdOyZvKOCyX5KdnZ2gA9LJyUlR+/NnPsMMdbVarah5hfqHh4ei9DPcw3XUf1WqtCF7F3Gb9p7ymVtR0zlVyn1zc1OX22zB2xb5quhEbrNXL5PJGctIP6zO98/b/0fh/k4xOcwWkMfq/Dgkb/WkTt4B97eD1zcptt8y/+LljM9/lHblNpsgmV+0siVswuotb1DXDmX3feOf/ERYqhVZIdqiX21Icncf6by79JvcZfJqG1AIIUTyKFgJIYRIHgUrIYQQyaNgJYQQInkUrIQQQiSPgpUQQojkUbASQgiRPApWQgghkkfBSgghRPIoWAkhhEgeBSshhBDJo2AlhBAieRSshBBCJI+ClRBCiORRsBJCCJE8ClZCCCGSR8FKCCFE8ihYFczPz4dfpxwbGytqXllbWwv1HA27dnd3t6h5hXpRDT9+/Ag6Jt3e3ha1WXZ6elr6nlLBy+1txqA+BUyPXkYvO6nMnsvu6xUmZwy2Qb23Ebu2l3Lz7EYyo/tGNm06L7vvs8HH8dzY17Uij9lTVWNVwSoHY9ja2go/o4xi7cVQD/bzyjhNc5zUHR4ehjxgiOfn50VJdMre3l7Q8cPDQ7a9vR3qMH57T9TFAygFkPvk5CTIeHl5GWQ2UnDwxuLiYpDTc3d3F+Q2vc/MzBRnflF2X69AzhjGJ3rn3P39fahD79avg4ODN5OfbsEzp6engwy1Wu03W2hmG9fX1+E+9N5tm9/Y2Mh2dnaK0i+Qpxn0d3R0NLu5uam/h05RsMphAE5OToY8zvDx8THkMZLl5eWQ53h8fBzyMWaIojrW19fDEQe6srJSz6+uroY878xPFlLi6empyGXZyMhIOPaDjYyPjxe5V11PTEwUpf6BSQxO0iaasL+/X+Sy4Hifn5+LUvfAv2CzgG37SQyymo3HcJ3Jjz9aWFgI+dSZmpoKwdX8ahUoWJUwPDwcjhjKwMBAyANlUz7LW3OcBDEzRFENOHm2oZaWlupOlCAwNDQU8sDsPzVwLJubm8E+mOEb/WAjFlgBx1ilo+kW6J9ZP3bjA5ZncHCwyPWOWNd+ouCx68ye/H2pgt6ZMDDxR+5G7+GjKFhF4FRY+jaD7T4GBNexfGemxAvhxei7VXWgZ7YRZmdni5r+gNk7g5UtQWDrxlaK4nMxZ85E5ujoKOQ97Jr0OghjF7Zawn/4lV8j8DdMjpttF6YCk0rGLMGV8UvQqgIFKwcBx7b9AMN/eXkJebYO4lmNbe1Qb99SrF5UA47FPtCyqrItNla5BITUwJmwVcM+PTJiC2xXIiuTGbBjqsTjoB9hTMbjtdXA8JnE28F8Q8MesA8CbLM/RmByjE31A+xOoX/Gb1U7IApWBQxQ2/ogj1FgVPadyn+/MrT9113YKrHvVP77VUpgN8gGDFYmOQQuJjI2mbFjqvTrFqAnDgoEKiv36g9zkIlvavgM8iSzCxw6AavZHyNwfdkfvaQGkzUbp4yHubm5kO+YXFEBl/1y7OzshP5bypVbnPkZ8tTVarWi5hXqcwMrSj9/npyc/HbvV4P+V4W9i7hNe1f5wC5qOqdKuW9ubupyl9lClc/qpC2zVxI69ZTZul3T7L6P0InshslhtsB4tDqve/JWT+qF3F5vpNh+kd3Xmc7fs6dW4f52QAZ7Pn0wrM7LTBl5wd/XDmX3feOf/ERYihZZIdqiX21Icncf6by79JvcZfJqG1AIIUTyKFgJIYRIHgUrIYQQyaNgJYQQInkUrIQQQiSPgpUQQojkUbASQgiRPApWQgghkkfBSgghRPIoWAkhhEgeBSshhBDJo2AlhBAieRSshBBCJI+ClRBCiORRsBJCCJE8ClZCCCGSR8FKCCFE8ihYFezu7oZfpxwbGytqXllbWwv1HI35+flQxz0e6kU1/PjxI+iYdHt7W9Rm2enpael7SgUvt7cZg/oUMD3GMpptl8kOdh/Jv5deYHLEYBvUexuxaxv1qxvw7DKZzfc08h+N3lU3MNliX1fWjzJauaZVFKxycDDAzyivrq4G4wA72s8rMzhtgFJ3eHgY8oAhnZ+fFyXRKXt7e0HHDw8P2fb2dqjjPW1tbYV66uIBlALIfXJyEmS8vLys2xb00lHGLC4uBjk92LvpF7m97OD1z3tZWVkpzvQG5IhhfKJ3zt3f34c69E6ZdHBw0JMgyzOnp6eDDLVarW4L1F9dXYX6mZmZus/xlL2rbrGxsZHt7OwUpV8g73tUbe8KVgW8FMBwMA64vr7OlpeXQ57j8fFxyMeYIYrqWF9fD8e7u7u6UyTPZAJ4R36ykBJPT09FLstGRkbCsR9sZHx8PJucnCxKv2Q3Xl5estnZ2ZDnHCuXXjj+ZjCJGR0dfeP09/f3i1wWHO/z83NR6h7o1fwKtm0Tge/fv9fte2FhITs6Ogr5fucz7F3BKoeBh/HES1bqBgYGitJr2QYz15rjJIiZIYpq4J2wLbK0tBScKBAEhoaGQh6Y3acGjnFzczPYBzN8ox9sBJ3j5JGdWX4ZrExSBv0z68duylYpMDg4WOR6h00EHh8f38hjq8F+5zPsXcGqAOPByDm+t73Edh/XshpjqctMyQa5vltVB3q+ubmpz+b7BWbvzO7ZEgTsyVaKqYODwbZZtcarJiZqbGFh56SLi4s3k7kUsCDARKZslUJw8KvHXoBd+NXen8Zn2buCVQRKxqABw2frA9g6sIFg2FKXetvLt3pRDTgW+1DOqsq22FjlEhBSg8kL2znMkJERW8DxIysOHuyYMmynlW2X2cqFbyhzc3O/jYlUQK5YNt5Nr4NEvD02PDxc1zO+JtU/HPoIn2XvClYRfBcxY+Jo36n89ytD23/dhe1A+07lv1+lBAEK2QBniSMicOHgbTJjx5TB3m37NQaHyzZbyn9QFAcFApWVe/WHOcjEJACfQZ40MTFRXwH671f9zKfZe95QwGW/HPksMfSfVKvVitpX8tljw/qHh4ei9KsN6r8qVdqQvY+4zZ2dnVCXz9yKms6pUu6bm5u63GW2UOWzOmnL2zw6BWzc6jhv0A+uwd45V4XuaadTTFaTx+Qjed2Tt3qS9bcduL8dvL5JXoem91hmk7PsXX0U7m0HnmfP9jZhdb4flLF/D3XtUHbfN/7JT4SlWpEVoi361YYkd/eRzrtLv8ldJq+2AYUQQiSPgpUQQojkUbASQgiRPApWQgghkkfBSgghRPIoWAkhhEgeBSshhBDJo2AlhBAieRSshBBCJI+ClRBCiORRsBJCCJE8ClZCCCGSR8FKCCFE8rz5v64LIYQQKRD/X9frwUoIIYRIFW0DCiGESB4FKyGEEImTZf8/F5sLy1mKf5sAAAAASUVORK5CYII=\"\u003e\u003c/div\u003e\n \u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec19\"\u003e\n \u003ch2\u003e3.4 X-ray diffraction (XRD) study\u003c/h2\u003e\n \u003cp\u003eFigure 7 shows the XRD profiles of PLA/SCG and PLA-PEG-PLA/SCG biocomposites. Pure PLA and all the PLA/SCG biocomposites exhibited a broad halo pattern which indicates the absence of crystalline phase. Pure PLA-PEG-PLA and all the PLA-PEG-PLA/SCG biocomposites showed a broad peak at 2θ = 16.7° corresponding to the crystalline region of PLA end-blocks [43, 47] suggesting that the addition of SCG does not change the crystalline structure of PLA-PEG-PLA. However, the XRD peaks of SCG at 2θ = 16.2° and 21.7° did not detect for all the biocomposites. These peaks may be overlapped with the halo pattern of PLA and PLA-PEG-PLA matrices. The XRD results supported the DSC results that the addition of SCG did not enhance the PLA crystallization.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec20\"\u003e\n \u003ch2\u003e3.5 Thermal decomposition study\u003c/h2\u003e\n \u003cp\u003eThe thermal decomposition of the biocomposites were determined using TGA, and the results are illustrated in Figs.\u0026nbsp;8 and 9 for TG and DTG thermograms, respectively. The TGA results are summarized in Table\u0026nbsp;2. From TG thermograms in Fig.\u0026nbsp;8, pure PLA exhibited a single step of PLA thermal decomposition in the range of 300−450 °C, whereas pure PLA-PEG-PLA showed two thermal decomposition steps in the ranges of 250−350 °C and 350−450 °C, due to the PLA and PEG thermal decompositions, respectively [35, 36]. The plasticization of PEG middle-blocks induced faster thermal decomposition of PLA end-blocks compared to the pure PLA [13]. The PEG blocks suppressed intermolecular interactions of the PLA blocks.\u003c/p\u003e\n \u003cp\u003eDecomposition temperatures at 10% weight loss (10%-T\u003csub\u003ed\u003c/sub\u003e) of the PLA/SCG biocomposites decreased as the SCG content increased. This may be explained by the thermal stability of SCG was lower than the PLA as shown in Fig.\u0026nbsp;8. However, the 10%-T\u003csub\u003ed\u003c/sub\u003e values of PLA-PEG-PLA/SCG biocomposites tended to increase as the SCG content increased. This could be due to the lower decomposition temperature of PLA-PEG-PLA compared to SCG powder. Char residue at 800 °C of all the biocomposites steadily increased with the SCG content. The char residue is polysaccharide ashes from the natural fillers [21].\u003c/p\u003e\n \u003cp\u003eThe DTG thermograms in Fig.\u0026nbsp;9 showed peaks of maximum weight loss temperature (T\u003csub\u003emax\u003c/sub\u003e). The pure PLA and its biocomposites exhibited a single peak of PLA decomposition (PLA-T\u003csub\u003emax\u003c/sub\u003e), whereas the pure PLA-PEG-PLA and its biocomposites showed two T\u003csub\u003emax\u003c/sub\u003e peaks of PLA (PLA-T\u003csub\u003emax\u003c/sub\u003e) and PEG (PEG-T\u003csub\u003emax\u003c/sub\u003e) phases. As observed from Table\u0026nbsp;2, the PLA-T\u003csub\u003emax\u003c/sub\u003e peak of PLA/SCG biocomposites shifted to lower temperatures when SCG content was increased indicating that the addition of SCG reduced thermal stability of PLA, which is in agreement with the previous works [16, 19, 21].\u003c/p\u003e\n \u003cp\u003eIt is surprising that when SCG was added to PLA-PEG-PLA, the PLA-T\u003csub\u003emax\u003c/sub\u003e peaks dramatically shifted to higher temperatures, suggesting that the addition of SCG enhanced the thermal stability of the PLA blocks. The results may be explained by good interfacial adhesions of the PLA-PEG-PLA/SCG biocomposites. Thus, the TGA results supported that the interfacial adhesions between the PLA-PEG-PLA and the SCG were better than between the PLA and the SCG, which corresponded to the above FTIR and SEM analyses. Baek et al. [16] reported that the addition of a coupling agent improved the interfacial adhesion of the PLA/SCG biocomposite and then enhanced its thermal stability. However, the PEG-T\u003csub\u003emax\u003c/sub\u003e of PLA-PEG-PLA/SCG biocomposites tended to decrease as the SCG content increased. This may be due to almost PLA-PEG-PLA matrix has decomposed.\u003c/p\u003e\n \u003cdiv\u003e\n \u003cdiv align=\"left\"\u003e\u003cstrong\u003eTable 2\u003c/strong\u003e Thermal decomposition properties of PLA/SCG and PLA-PEG-PLA/SCG biocomposites.\u0026nbsp;\u003c/div\u003e\n \u003cdiv align=\"left\"\u003e\u003cimg 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\"\u003e\u003c/div\u003e\n \u003c/div\u003e\n \u003cp\u003e\u003csup\u003ea\u003c/sup\u003e Obtained from TG thermograms.\u003c/p\u003e\n \u003cp\u003e\u003csup\u003eb\u003c/sup\u003e Obtained from DTG thermograms.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec21\"\u003e\n \u003ch2\u003e3.6 Water contact angle and water uptake tests\u003c/h2\u003e\n \u003cp\u003eFigure 10 shows the images of water contact angles on biocomposite surfaces. The results of water contact angle are summarized in Table\u0026nbsp;3. The pure PLA and PLA-PEG-PLA had water contact angles of 79.5° and 73.4°, respectively, which indicated that the PLA-PEG-PLA was higher hydrophilicity because of the hydrophilic PEG middle-blocks. The incorporation of SCG decreased the contact angle of the biocomposite surfaces, which indicates that the wettability of biocomposite surfaces increased by the addition of SCG. The PLA-PEG-PLA/SCG biocomposite surfaces exhibited lower contact angle than the PLA/SCG biocomposite surfaces for the same SCG content. Several reported that the incorporation of hydrophilic SCG increases the wettability of hydrophobic film surfaces [15].\u003c/p\u003e\n \u003cdiv\u003e\n \u003cdiv align=\"left\"\u003e\u003cbr\u003e\u003cimg 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\"\u003e\u003c/div\u003e\n \u003c/div\u003e\n \u003cp\u003eThe hydrophilicity of the biocomposites was also investigated from water uptake for 72 h as shown in Fig.\u0026nbsp;11. The water uptake values of the film samples were constant at 48 h. The pure PLA and PLA-PEG-PLA showed the water uptake values at 72 h of 1.6% and 4.9%, respectively supporting that the PLA-PEG-PLA was more hydrophilic due to the hydrophilic PEG blocks [47]. As would be expected, the water uptake increased with the increase of SCG content because of the hydrophilic character of SCG [18]. The PLA-PEG-PLA/SCG biocomposites showed higher water uptake than the PLA/SCG biocomposites for the same SCG content.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec22\"\u003e\n \u003ch2\u003e3.7 Tensile test\u003c/h2\u003e\n \u003cp\u003eThe influence of SCG addition on tensile properties are displayed in Fig.\u0026nbsp;12 and the tensile results are reported in Table\u0026nbsp;4. The maximum stress, strain at break, and Young’s modulus of pure PLA were 60.2 MPa, 2.7%, and 690 MPa, respectively. While these values of pure PLA-PEG-PLA were 20.8 MPa, 72.5%, and 316 MPa, respectively. The pure PLA-PEG-PLA exhibited a yield point. These tensile results indicated that the PLA-PEG-PLA was more flexible than that of the PLA. This is because of the plasticization effect of the PEG middle-blocks.\u003c/p\u003e\n \u003cp\u003eThe tensile properties of both the PLA/SCG and PLA-PEG-PLA/SCG biocomposites decreased as increase of the SCG content. This suggested the poor interfacial adhesion between the hydrophobic polymer matrix and the hydrophilic SCG dispersed phases [16, 18, 30]. Although from the above FTIR, SEM, and TGA analyses suggested that the chemical interactions and phase compatibility between the PLA-PEG-PLA and the SCG was better than between the PLA matrix and the SCG because of the higher hydrophilicity of PLA-PEG-PLA compared to PLA. However, the presence of SCG might modify certain properties at the molecular level, but these changes may not be significant enough to cause noticeable improves in the tensile properties of the PLA-PEG-PLA matrix.\u003c/p\u003e\n \u003cp\u003eIt should be noted that maximum stress and Young’s modulus of PLA matrix decreased 78% and 85%, respectively, compared to the pure PLA when the 30% SCG was incorporated, whereas, these tensile properties of PLA-PEG-PLA matrix decreased only 38% and 41%, respectively compared to the pure PLA-PEG-PLA. This may be explained by more interfacial voids between the PLA matrix and SCG dispersed phases from above SEM analysis induced larger reduction for these tensile properties [19]. This confirms that the matrix-filler compatibility between the PLA-PEG-PLA and SCG was better than between the PLA and SCG. The strains at break of the PLA-PEG-PLA/SCG biocomposites were still higher than those of the PLA/SCG biocomposites suggesting that the PLA-PEG-PLA/SCG biocomposites were more flexible.\u003c/p\u003e\n \u003cdiv\u003e\n \u003cdiv align=\"left\"\u003e\u003cbr\u003e\u003cimg 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8biWApexd8T3cK0BK1Puw3vKE4+3iuMIjIt55OeorPfJQ/uURn3Ki1/5ePKe4l8j9O2pRDmDrh8kO7k4NsgzPkFy513Fx7Kb/NRXHU+ecRybynsKlNEL6LnaEd+V/se2IasoP733P//zP+241qLc9utd8kUkg9h/jQNpVZRPaXXlKg9OY60waaoT12lNaIK8nYhjXe1DVYZQJ8eYL/Yx6qjiqlT1OBL7G8uN4wBRRrQPYrlKh1iO0uQnDfDHPFFGONURIV74/0xhssY62T+W3XB4Trlyotf1MFTDr4koZ/+fKYwx5oWg71Nyfws+UZmssU72j2U3HCzX0RDl7BOVMcaYrLGhMsYYkzU2VMYYY7LGhsoYY0zW2FAZY4zJGhsqY4wxWWNDZYwxJmtsqIwxxmSNDZUxxpissaEyxhiTNTZUxhhjssaGyhhjTNbYUBljjMkaGypjjDFZY0PVA9PT06Xv8fAO/7v6+FPL/GQzP48N/LSz/Mb8DWgeeW48DX7G/7//+7+TDPWT/hFkSRpO+aJr+un4LOX+J1AJmkAvstHPL+tnsPmZ5fiT1EoX/Dx0Nc7ckYNO8hPcj/2Z8pzIcT7zU+TMh5c8N3KQKzLTT9nr5+WrP+eueEEYB8hfPztfRw5yj233ieoRsLtoKUUZ6s7e3l7pewi7x9XV1TJ0h35Kmp2MyY+Dg4PSZ54CP5u+vb1dTE5OljH38dx4HMjp3bt3xezsbBlTFC3DUnz58qUMdWd5ebloGbbGU1V2ci8NVqISNCVx58FOBjlpR4KfnY12L9Gxw1Ee7cibdinaYZr7ILtRQ52MBS6OK2Ge0oHquGtHy5iTR+OpPDy1Cx4F1JkT1R38S50bzy1XdCuentArwrFd6BkuxpEPB6RpPDQOcSzgueUe2+4TVRfYccRvU8fHx0VrYIuZmZni8vIy+d+8eVO8ffs2nbpaMk35eLJzJA9+djDcI+/u7qadJXfE8R54bGyscXdjRgc7yNYELebn54tPnz6lnWVrsqY4xq410VM+xpRxPzs7S37S2dEyhh8/fiy2trbap4Pr6+u2XsRd8N+O50Z/ILe6Uym6ifzgx48ftbq2ubmZ5Ds3N1fs7++nOI0DOnx+fp7iICe521D1AQvR0dFRWtQWFhaSv0kxBMd1Fi/4+vVrUozT01NPwMxgDFdWVpL7+fNnGXsfrl3g9va2ODk5SROf/IwnCwjjy0KATsDExETKQ7x5iOfGYFhaWuqqYxgz5IuL6xUbBXQ4V2youqBTUYTTEzvp379/p10z/m6wU+lkyCir6e7ejBZNZO04m+BEtbi42M4vPdEOlZMUiy2nMpWnHa/5F8+N3uCGp86IIyM2zhgdjNZjYRPFRoETVSQrubcmUJtK0JRwT1v9toCsWgOb/Nzxyg+6843fLCLcE5Me73/r6jCj10nGkTpxfAuAOF5K01gpTfmJV1jjLn3AjXKMqS8nkFWcJ/AS58ZzyxUZIieI+sd6g5ykt4rHbW5utv1RtqB46anG6LnlTlvEP/zTikhgWUPQBIYpG64+2FVyR2/uY53snxxlx2lAV6SPIce5kYNcOTVxCup0En0KOcg9ytlXf48EgcU/qhgUfOeykTJ/C1yLcj31GDw3muGPuvhT/2F8x8tR7j5RmayxTvaPZTccLNfR4BOVMcaYF4MNlTHGmKyxoTLGGJM1NlTGGGOyxobKGGNM1thQGWOMyRobKmOMMVljQ2WMMSZrbKiMMcZkjQ2VMcaYrLGhMsYYkzU2VMYYY7LGhsoYY0zW2FAZY4zJGhsqY4wxWWNDZUyAH6Lj11P5kUx+D4dfOq3y+fPnlEY+ntGtr6+XuR5CGj9KZ4zpDf9wosmaUeokRopfn+VXaAFjhePXVCPEkU+/gBrbSBq/vLq8vJzCVUjf398f2k+IRzyfh4PlOhqinH2iMqaEE8/p6WkZKto/mR5PQfg7/ZT6x48f0894N4ER/PDhQxkyxjwGGypjWnCagsnJyfQUGJWDg4MyVBQ/fvwo5ufny9BDzs7OUjoGjR2hXIRTla8AjXk8NlTGtLi9vX1gpIArPE5ZMmRNRIPEO1ztcW2BW1xcvGeYqOf3799lyBjTDRsqY7rAdd7R0VH6w4qlpaUy9j4ySvF7FsYN43VyclLGGGP6wYbKmBZv3rxpPDVtbGwUm5ubxc3NTe2pqw6MGt+ydKKKUM/Y2FgZMsZ0w4bKmBYyQDJWfEfa29tLf4IOa2trxfj4eDJAKysr7TRd9/GsGrqrq6sUzx9QzM3NlbF3f1Axir/6M+a14D9PN1kzSp3E0MQ/Tx8GGLetrS3/efoLxnIdDVHOPlEZU8Kpij+c0Clq0PDn76MyUsa8JnyiMlljnewfy244WK6jwScqY4wxLwYbKmOMMVljQ2WMMSZrbKiMMcZkjQ2VMcaYrLGhMsYYkzU2VMYYY7LGhsoYY0zW2FAZY4zJGhsqY4wxWWNDZYwxJmtsqIwxxmSNDZUxxpisefB/TzfGGGNyQObJP/NhssY62T+W3XCwXEdDlLOv/owxxmTNsxgqfvIbaxnd58+fU1qMI18TpH///r0M3Udl8UutKltxgl9bVT2UQ1gQVhplfPv27UFdlKd3q/BOU9tyg77FvhtjTHa0jlZtKsGhcnV19WdqaqoM3dV9cXHR9nfi8PDwz9raWnJVKJd05YGdnZ17dRG/uLhYhv4kv9JpA/VTTgxTXhXeU5tfA/Slrp/PySh18rVh2Q0Hy3U0RDlnc/XXMh7Fjx8/ylBnbm5uik+fPhV7e3tlzL/8/PmzWF5eTn6dyDY2NoqFhYXkJ473dnd3UxiOj4/b6dvb20XLsBWTk5MpPDs7i7TaZb5mDg4OSp8xxuRDNobq9PS0ePv2bRnqzPX1dTIkrRPNgys2jBhgWC4vL9vXczJMGLLW6altiITST05OHt0OwLhSx/T0dArrSlBGMl4xcs0G8epTV5IxTmXpXd7jSTj6AT9XjbrmVB30mbDShd7FqU5djWLAV1ZWkr+ujTwVfilXm8aYV8DdweqOSnCocLVGfXLxGq9TO7ie0nVbvN4DXftFdHWnqz7S4zVgFfLG6zzKVxu5QoxQpsoln9Ipn7ZQjtqn/vJUuuKAcggD7+g98qoO8sZ4UP94xvJiH3mftpGH/uNUF/FqN2VLfrE9KlN1V+UwTFS36R3LbjhYrqMhyvlZT1StxZSWJBev4jrBCWZubi7t7Nn9x+u/eO3HyYJdv67ugPDY2FjRWoBTuA7aFK/AaFdrYU6OK8QqW1tb6Tk/P5+eEdo6MTGR/DoB3t7etsM4tY2TnE55q6ur7RMZRNnIH/tAufST92l/fBc+fPiQTqHkQWY4ZNUJTqOUhZwB2dEXwl+/fk1xxhgzCl7En6fHqyuQccOxSOsaStd+gu9NVViseadaphbk/f39ZPx0hfZYeG98fLwM3UF4c3OzDN0t/tQP1aszjIKu2H7//l28e/cu+XtBBgqDhSFTH5CLDKnkRns7wfUjZSg/7cZQ61211Rhjhk5r4WlTCQ4NrpSoSy4S4+V0DaWwruZ07YX7z3/+c+/aT1dcSte1laBMpeEisVw56q8S2xSvzwi3DM+9MK6u3TjKiWXRNohlqb08CctfLauuDvU9yqP6Ln76gJ9nbA+OsOrFqZ5hQ12mPyy74WC5joYoZ/+fKV44nMw4OfKXi68R62T/WHbDwXIdDVHONlQvHMYMmr6hvXSsk/1j2Q0Hy3U0RDnbUJmssU72j2U3HCzX0RDl/CL+mMIYY8zfiw2VMcaYrLGhMsYYkzU2VMYYY7LGhsoYY0zW2FAZY4zJGhsqY4wxWWNDZYwxJmtsqIwxxmSNDZUxxpissaEyxhiTNTZUxhhjssaGyhhjTNbYUBljjMkaGyrzV8HP9fPzAfzUvsBPnH66vwppuPX19TKmdyhb5TTBz/srDz+I+RKQ7N6/f1/G3AeZqU9P6ZfKaRqDlyi7XlDfRJ3cpds4/P2iMqrzQfFNYz1MbKjMXwML2NTUVHFxcVFcXl6mOBY+fiGZ373Z2tpKcRHSScPt7e01LoIsDCyWTZyfn6cyDg8PG/ONj4+365qdnS1j84V+nJ6epvYizzpDPz8/3+7T2tpaY7+aDBCoXMqAujHY3NxM6Ywt4/lakPFBb9T/qLOTk5Nt+SwsLBRXV1fJdZJntzTKxcX5QB2Kf45fE7ehMn8Nc3NzacLHxZKFdnl5Ofk/fvz4YLHd3d0tfXe/ovz79+8y9HhYbFQOBmtpaSn5I9S7srLyLLvVfuEXpVkogYXz5uYm+QX9lmyfAjJbXV1Nfp4HBwfJX0WnCLXpNYDxQe+iHOnnzMxM8iOP/f39FMcpi76r/5JHL3z69Ck92QwwHwRGC4P5XKdVGyrzV4Ah4DSlCVc1SKK62FYZGxsrfY9HCwf1YhjrFlIWHu2QX5KxinAijMR+ssBxuuoHFtw3b96UofoFmA0I44vBjJuLlwwy43R0dnaWdCeexI+OjkrfHbe3tw/0irheoQxOVWzq3r59W8bebehoC/HPYaxsqMxfAQaI3SkTjuuhumu+blxfXz+4usKosIiwSHL9hB9Xt5hiiNil1l29aJHRItvPbvg54dTT6fT048eP9ilAsOBJXlyryt/paqoJNhCcPE5OTp5t1z9oOL1zXYquYiTQL0BHpGsYjqqBqoONWZ2s666hKV9GSVAHjrnTdKIdJjZUA4YFRkrwUnfGr5WJiYk02TA2TMQqGKLqqUCweNbt1LmvxwBRHgul7vGbFg+uy7oZoXfv3pW+lwGLna6MmkC2VZkwDpIXC7L8VTnznk4HLN51suUkhWwZhw8fPpSxrwPkRJ/ZDKE7+CUr4rj+48QZ9YpvhvEUyiZC70RZI7M6qIN8VV2tbtRGhQ3VgIlK9BwfHU09fBf6+vVr8jP5FhcXk59Tlq4B4/eqCEZK11ZNfwjxWNjtdzNEdYt6rkgetLdJNsibTUK/IHvt4uP3KkH5nKSAdtRtQl4i6CKnn0jUCzbCnNBlyDBOyAKn71VPgXKqZTBXqvIfCa0FtU0laMyzM0idbJ14UnnVMhV3eHiYwq2FLoV5tgxaOx1HGZFquhzviouLi3Y8+QVlKRzLie8+BcoaJq0dd7vNOMKKlx/oZ12folzqyolIPjGNMGUA8Xpf4zgsqGNU0Bf1SzJUX6v9jPKsyjuWE11Vn1sntHaayojl1o3NsKA+8Q//tCISXFeFoDHPjnWyfyy74WC5joYoZ1/9GWOMyRobKmOMMVljQ2WMMSZrbKiMMcZkjQ2VMcaYrLGhMsYYkzU2VMYYY7LGhsoYY0zW2FAZY4zJGhsqY4wxWWNDZYwxJmtsqIwxxmSNDZUxxpissaEyxhiTNTZUxhhjssaGyhhjTNbYUBljjMkaG6on8v379/RLlLjPnz+nuPX19RTmGXn//n3pM8+BxiWOw69fvx6MXySmV9/tB95HZ6pEPfr27VsZmz/T09Md5RL7hSz7pWlORVTPa5tndf2S3KPOojfKW6djj6FJD6nnqWU/iT+BStA8gsPDw9J3x9XV1Z+pqank1xN2dnZSmumNQenkxcVFe6zW1tZSGBgjjUv0izi+pDGOdXRKE5RFf1R3hDYBaYPq87Dnc9RpZFedCxD7JX8dndIoV+k86+RXV/ewGOU6WdevqtyBcJ2/jseMQ1UP5Sd+cXEx+YdNrN8nqifADnFlZSXtMjqhneTk5GR6mtHz5s2bYnl5OfkZj9nZ2eQHjcvHjx+Lo6Oj5BczMzOlryh+/vxZvH37tgz1zvn5edGa5GXoPru7u+lJu8jzlNPHqNjY2GjLbnt7u7i5uUn+yKdPn9Lzx48fxerqavL3CnLTuzwPDg6SP7K1tfV8u/0hUtevpaWlJHd0ZGFhIcXd3t62/aRx4upHFp308DnXMRuqJ9Iy9kVr19M2VgwiCkNYivPly5c0qc3zwbjoWiNOtNbus+OEjnlZMKOB6wWurLQIPIbnWAyeyvj4eOn7F/rBorm5udm37Fgg2WiIOiN+enqaxnJubu5VGau6fiFTruJap6Zifn4+xcHe3l7pGxzSQ9Y46mND0oseD4y7g9UdlaDpAY7jTcd0jss6Snc6kpuHDEMnubrQWPGkDrm6MRR1VyaUFd+X4/pFMPYql/yEm4h5nwrtGBWdrpOAPtH3iOZE1VXL4j3Jk3eq5URI79aWp0IbR01Tv2iLZEN6lGPUwaqeyzVdV1f1kDB5eQf/KKAucU/iMcH0RnVgAUWRImiyoUyDWoj+Boahk5p0EcamU12MWacJGse6SnUBwTWVNchFtlN/Bgn9jotiE50MTKd+kyZ5MQ7dZDRIGdYxKrlWqesXsq/qEjLqV9aimkflMc6j2mxHOfvqb0Bwb65vIMJXfnnC95LqtyauNVoTvgw95CnXflyVtOZacq0Jn+qpK4srMn3TqfsLxBxRO3Ud1QTXdf1eZ3K9pe9S8XtVHfylWr/fwnKmqV9nZ2f3dInrQb6bHx8flzG9U9VDxu7k5CSFGcOWsUr+kZLMVUklaLrAbgaZ4aqnJHYkcaeDn3y++uuNQelkHKt48mE8iIsnAvzVuKZdKDtNlRtdfDdCfukF7dBOtfp+1J1+oZxhgkximyUjnjjJEVen95oTVVcna8k5phGmjFhO3buDhnpGQVO/os5JTyTrpvWF9UnvRBfnAlTTVT71K6661g0L6hL/8E8rIsGH5hA05tmxTvaPZTccLNfREOXsqz9jjDFZY0NljDEma2yojDHGZI0NlTHGmKyxoTLGGJM1NlTGGGOyxobKGGNM1thQGWOMyRobKmOMMVljQ2WMMSZrbKiMMcZkjQ2VMcaYrLGhMsYYkzU2VMYYY7LGhsoYY0zW2FAZY4zJGhsqY4wxWWND1QefP39Ovz7JM/L+/fsH8dPT0ynu27dvZUxR/Pr1q1hfXy9DZlRoLBgnwVgQVzeeke/fvz94txcYb9XThNL7reM5qJNp5KlyE5Jft3lDexjT10a1X03y0Hjw7Bfex8U1S+OIew5sqPpgY2Oj2NnZKUN3sMi9e/cu/XTy2dlZUioGemFhobi6uir29/fLnEXx5cuXYnd3twyZUcD4nJ6epvG5vLxsT0KND/Ffv36tXeTIOzc3l/IdHx+XsffhvSZDxySfn59PdaytrdUutryLTumnt3knd5pkGpmdnS0uLi7KUDOdDJDK7SYb2sMYvTaq/WqSB884Hk10kjVpvI/b2toqY4uk/8Qxlp3eHxY2VAMC47S0tJT8Hz58KI6OjpK/Ckq2urpahsyoYHMxOTmZ/Nvb28XNzU3yg+I/fvz4YNwwQCsrK2mCKl+vsFgvLy8n/6dPn2qNIVxfX5e+onjz5k3py5dOMh0k5+fn7TnD8+DgIPkjkunU1FR6vhbq+tUkD8aAfHUbhseCfgJGj/kgPxssQJcxhqPGhmpAsIOJCxmLDosTg4ryYLwAJWOwzfMyPj6enuxUm3bogOFaXFxMO0quPTrlfSx1Bo9FH12hDnay/RrF50QyHTQs1tFw1xl6bimQ4Wujrl9N8uCWhlMPG6t+jRV6x4kJfX/79m2K+/37dzExMZH8om4MhokN1ZDBgKE8GC3u6VEmjvIsSM9xhDZ3mwWdcA4PD9tGaHNz88Fiy4aDycsYkpdda4Qx5V02I7yPH9c0kTtd+7KDxShW63gJRJk+Foy+5LW3t9f29zovXustRa/90uaGzVf81ACUVSdr1qIq6CdlMC9ywYZqQMSPnVyBVHcgKIrufPkWwsLHDnrUO5O/HSamrjeAxZWx0DeAusWW70swMzPz4O6fb1Z6X9+YcHUnIhZmlVWFdrGDpTze7XdH/BxUZfpYuFmQvLhakr9qyJHH7e1t8rO7r8qWRVmbDcaBTcNrmFdN/eomD8LVOOl5VdZNp1DeJx/1jY2N3buWpi3V8oeNDdWA4A8p9H0jfq8SvvJ7frR7ZJJVd5IsAnUf/dnRanfK4sAfX/QDRoqTEgsG/uoVIgvBjx8/kp9NzrC+9wyaTjIdFBh3fYeJ32eENgs4xvE5FtJh0NSvbvLotCHqBRlF1i1OYUDZ+l41UlpCaFMJmgZaO+ckK9zh4WEZ++dPS5lSHOkR4iN6vzXgZYxpYlA6iaw1ZlH2GrPWIpDCgD/G6d3qOMLi4mK7zOhieehITFM56AHvg+qM6U+FsoZJk0x5yt8y/g/SRUyLrpoPJOeYRpgyIsguyn4YUO+oqfarKo+oP9KpSFUH5erWKqU16fCoiHX9wz+tiARHzBA05tmxTvaPZTccLNfREOXsqz9jjDFZY0NljDEma2yojDHGZI0NlTHGmKyxoTLGGJM1NlTGGGOyxobKGGNM1thQGWOMyRobKmOMMVljQ2WMMSZrbKiMMcZkjQ2VMcaYrLGhMsYYkzU2VMYYY7LGhsoYY0zW2FAZY4zJGhuqPnj//n36Ua/p6eky5g7Fx5/kJg9x3759K2PufuJ5fX29DJlRobFgnARjQRyu05jwE9zVd3uB8Vc9TSg96kruILNObVa6XPUn+B+Lyuk2b1TPa4G1hP5U1xrpcozX+iOHbveK9BxXN6bU10+5T8WGqkcYvK2trfTLkwyajBLPd+/epfizs7M0mORdWFgorq6uiv39/ZQPvnz5Uuzu7pYhMwoYn9PT0zQ+l5eX7UnIWBweHqZ40usmIXnn5ubSOB4fH5ex9+G9uEGpcn5+nuqgrrp8LMCk49CvlwJ6vLa2VoYeMj8/3+4X+WZnZ8uU+3QyQBoryoA6Y4f8WVw1lq8B6SL9+fjxY1sOWleI50mYvFqXcMh6cnIy5a/SSdYHBwfp/YuLi2JlZaWMvQO9ZQ48BzZUPbK8vNyebCjG9fV18mOclpaWkv/Dhw/F0dFR8ldBqVZXV8uQGRUbGxvtibu9vV3c3NwkP0R/dXKzADBhmbhNE78blKGNCQZLehL59OlTerIIsyi9Bug38+WpIDPNGZ4splVYsHd2dgZSX06gt8D6EvsmIwZjY2Pp2bQJ6AXpKWUtLi6269FzamoqPUeNDdUTmZiYSE926XEhw4ChWOzSGVyMFzDpBqFQ5mmMj4+nJxNzc3Mz7cYZqypsOJiwnKjI08/VlfRCddQZPOLY6VLP27dvy9iXTewncuN01Q8skm/evClD9xdpoGx2+izmyLjTyfYlgfzoK32KyGARj0xZT6KsB7kZVrncPMhoPgc2VE+AnV23wcOAcZRGubhDZmFkIqFk3e7bzXBgsxB3p+zE2UwwGauw4WCyMoZcK3Eai+i7AO/L4OGqiylQBqelpnFHN1hwMVavjR8/fhQzMzNl6A4MjOS1t7fX9vc6L37//p2uurjhQH6Mw2tBusczGmA+M6jPVeo2wxivOlk3GXXGRpvrHG6BbKj6pDp48SMjV0k6aQnyS6m+fv2alK/pm4gZHkxMXbMBiyJXcWwoGIu6E5NOAiy05IvwzYqxZIHE4OHXwlIHG5tOY857LECvTS9k8CMsppIXfZZf10+C925vb5Mfo9QkW50s2DS8Nvmhs/rMwFrCjQByYuPzmBMkG7M6WTdttNmEazPH93XdKKDnzyFfG6o+QFG0a8HPoLHD0Xep+L1K+Mrv+dGEZjGTn7H7+fNn8hPPQhhhM6I/hGGx5FvIU8AQoiudoE1Ni/FLhP5UN269wEZB36WYR9XdPQsqp4TIa5IfoKPaMLERRg6AwZIBA/Sr3ytWwaZbmznmiTZjOIwUxmrk8m1V3qYSNDW0ds1JTnKLi4tlyp8/rUFMceSJEB9RGa2dTRljmkBOgwBZa8yi7C8uLtpxGsvWRExhnqB3q+MIvKP3o9O7UFcHoAcKS3eq7z4Fyho2Ua70U3GSL9DPuj5FuUQX3xWSc0wjrDoPDw/b7w9Kfk1QxyiIfarKRPHVttTJDmJZ0VXXqmq65CvQ02HLV1C/+Id/WhEJjnYhaMyzY53sH8tuOFiuoyHK2Vd/xhhjssaGyhhjTNbYUBljjMkaGypjjDFZY0NljDEma2yojDHGZI0NlTHGmKyxoTLGGJM1NlTGGGOyxobKGGNM1thQGWOMyRobKmOMMVljQ2WMMSZrbKiMMcZkjQ2VMcaYrLGhMsYYkzU2VMYYY7LGhqoPPn/+nH59cnp6uoy54/379ymedEEe4r59+1bGFMWvX7+K9fX1MmRGBTKvGwvicN+/fy9j76P0p4yZ6sZ1gra9JN2ok2kEmZLO3HgKqqebbJhvjOlrQWtNXFOgkzy05vQrB97FVVH8U8eyH2yoekSDz08kf/z4sT1BUaR3796l+LOzs5SPtIWFheLq6qrY399P+eDLly/F7u5uGTKjApmvra2VoTsYC8aMMdre3i5j/4WFgHTc3t5eozFjvKuLieCd+fn5VAb1d1psV1ZWSt/LoE6mkdnZ2eLi4qIMNdNJJppjyA+axgD5M46viY2NjWJnZ6cM3dFJHhgS1iXSJicny9j7dJI1qNwIdRKPOz4+LmNHhw1VH6A8gEFaXl5u+5eWlpL/w4cPxdHRUfJXYcBXV1fLkHluPn36lJ4/f/5M41YlbihYMH7//l2GHg+LtfSE+pp2uiwgh4eHZciI8/Pz9pzheXBwkPwRyXRqaio9XzNN8uCkw6ZB69Mg2draSkawaZMwbGyoeoRdCpOiejS+vLy8t4O5vr5Oi9Pp6WmaPFoEUTIWLpMHjBkTnJPMzMxMGdvM2NhY6eufup2uTl3mIcy3N2/elKF/jVKEk/EwFugcqZMH7uTkJD1Zm7qdmnqFdYzT6tzc3LMYKxuqPmCh0dG66bpHYMDIi9FiQWSHzjvDUCbTH1xlcD3FNW0n2HxUNxmMKWPJZmRzczP5cXWLKTRd+7Ir1qnrb4EFT/LiWlX+XueFbymK4vb2tlhcXEwnH9Yb5Bl1EBnVybrb+iVY63DMk7oT7bCxoXoCXOOweEH8iHtzc1NMTEwkv0BRUCL4+vVrUiZ2KU0LmhktGKDqH8dEWDzrDAxGjrFkt8nVIH5cL6cm4rV4cLLD/zdsYpC55MWVlfxVOSNLFmLg6rUqW77/stNHfowDm4bXPK86yUMbKYyW8gCboDpZ93oKfa7bIBuqJ8B3DS08/CGFvkvF71XCV34vF4yGxvmxO9AqGCP+WIMFAz9OxAWbb1QsJHVG8W8F2WsXH7/PCG0WcBgpjFXdRuG1UCcPdIjbGxlo/MNYb57t9Noa3DaVoKmhtZAkOeFaC0oZe0drkqT41s66jLmD+Ajpde+bhwxSJ5G3xu7i4iLFKRzraS10KcyztTO9l6c6ttV0Od4VUWdw0gfK4v0IeQelF9Q1bOpkSpz6QJzSq/2KadHV9V9yjmmEVadAtlH2w4B6R4XWChy6IerkEeVZlUtVB+Wq+gxKk552GsNhQn3iH/5pRSQ4OoegMc+OdbJ/LLvhYLmOhihnX/0ZY4zJGhsqY4wxWWNDZYwxJmtsqIwxxmSNDZUxxpissaEyxhiTNTZUxhhjssaGyhhjTNbYUBljjMkaGypjjDFZY0NljDEma2yojDHGZI0NlTHGmKyxoTLGGJM1NlTGGGOyxobKGGNM1thQGWOMyZpsDRW/zc8vPEb3/fv34tevX/fimlA+nk18/vz5XlnKX1c3jngR86yvr6ey6up6//79vTKmp6dTfKyb95sgH2XUgTzkVJbaLyQHHOWQRn4R20d8p7YYY8yz8CdQCT47/M6/fqNfv9sPV1dX7d/zb2JnZye9y7MTpCsP9ancWDdQP3HAM8pKYfLUsbi42E6jTJUb626CvLSJPlfRuzGddqidxMV2SYZKp12xj4S7yXXURDmb3rDshoPlOhqinF/M1d/s7GzRWkTvnQa6sbq6Wnz9+rUMdWd5ebloLe4PTkaEf/z4kdJha2uraC32yQ/Et2SZ2tgN2nR6elqGOkO98/PzxcLCQnF0dFTG/sv4+HjpK4rb29v0bBmj9IQvX74ULUPUbhdPpSPHk5OTYnd3N4Xh+Pi4uLy8LEPGGJMHL8ZQsWhjRB5jDGRolLdqeJpg8cYYTk5OpvDe3l66EiNOqB0zMzNlTG9g8DA8jwHjRD0Yt7OzszL2Dto6NjaW/Nvb28Xc3Fy6xqPPMqgYRAxdROm0o3WCKmONMSZfsjdU0VjEU0wnfv78WSwtLSX/x48fa08jkc3NzVQHi/3+/n4ZW6TTCCclDFMn4nee+H0oQtmkU1c8xXQDo4lx4aQTDS6GRoZYJzqgjl5OnYKy1QecMcbkQvaGSsYCp5NCN87Pz5Nhk2GI139aiPVHDbCzs9OuQ4t/BGOxsbHR9kM0flyZ0U4MKScg1RH/CIIrN9XxWGRAcRjLWGe89tMfQNAO6uGEBfTx5uYm+avwPld/Mn70S23rpY3GGDNsXszVXzeiUZiYmGgbBS26WpAV18+3GNWBQcKI1J1ctODjMBy9QHn8lR9wMsM4qSwMkK7/4rUfcMVX1xa+pVXbSfk4jD5Xf4+9hjTGmGejtQi2qQSfFf4yjfbg+Gs00Vq82/HR8ddrrcW8HSYfxHKqf2FHWGm8L+I70cX36/LUQduVzjsi1h0dfaAt+GO/Yzkt41PG3kFZMV19hygTXFUG8T1clEMO0CbTH5bdcLBcR0OU8z/804pIcMUUgsY8O9bJ/rHshoPlOhqinF/N1Z8xxpjXiQ2VMcaYrLGhMsYYkzU2VMYYY7LGhsoYY0zW2FAZY4zJGhsqY4wxWWNDZYwxJmtsqIwxxmSNDZUxxpissaEyxhiTNTZUxhhjssaGyhhjTNbYUBljjMkaGypjjDFZY0NljDEma16toZqenk6uCj9JXxefK/z8fd3PzBtjzN/Cq/2FXwzSwsJCcXl5Wca8fNbX14vd3d0y9HfgX1PtH8tuOFiuo8G/8PtC2dvbK33GGPP38OoNFacQLPPnz59TmGs/rtMEaXLi27dv7Thdu/G+4lQWfspSHeQlLL/Kie8KvYMjH8T8+PVevK5UOJZJGNQ3yjbGmFdD62jVphJ80VxdXaX+HB4epjB+4i4uLv4sLi6muLW1tRSGnZ2dFE+eqampFMe7itM7QFm8h1MdOMXjpzygDpVHnOrkCWonT8XpXeBd0oB8ENtDXbxHHO+pXa8F9dn0jmU3HCzX0RDl/KpPVK1FvlheXk7+1sKenpHT09PizZs3yb+0tJS+Z93e3qZvW8C7x8fHxc+fP4vJyckUBy3DUPz+/Tv5KVd1ED87O5v819fX6Qnb29vp+fbt2/T88eNHMTExkfyUSxnUOz8/n05Im5ubKa0J8p6cnKS8KysrqR+U8/Xr12Jubi6Vb4wxr4W/4hsVV2Ms7NHYAFdlX758SX4ZKAxX9VvQ2NhYitMVG8+ZmZnk7wUZqPHx8XvGCAOJgcPgtTYPRet01PH6jjZi3MiL0x+M8CSMkVRbjTHmxdNa2NpUgi8ersLoEy5en+F0vaawrucgvhev7RTHdRsozNVbnV/XcgrHOmK8ruq4zlNcfFfv8SSsaz7l5T3KUDjW89KhP6Y/LLvhYLmOhijnV/vn6bnAyYgrPV0Pmt6wTvaPZTccLNfREOVsQzVE+Ms9viEB13nVq0fTHetk/1h2w8FyHQ02VObFYJ3sH8tuOFiuoyHK2f/BrzHGmKyxoTLGGJM1NlTGGGOyxobKGGNM1thQGWOMyRobKmOMMVljQ2WMMSZrbKiMMcZkjQ2VMcaYrLGhMsYYkzU2VMYYY7LGhsoYY0zW2FAZY4zJGhsqY4wxWWNDZYwxJmtsqMxfw/T0dPqNm/fv35cxdyieH7qsg/yk4/qFX3ruVMb379/b6U3tyIUoD9yvX79SvML0tQnJmme/RFmq7iqSZ3WsXxqfP3+ulZfkWNf/TmndaNJDjflTxu1J/AlUgsY8O4PSyZ2dnT9XV1fJPzU19efw8DD519bW2n7iq1xcXPxZXFxMfsrA1UHZTWmUEevDVVEceQfV52HMZ/pJG4XaHftEvTGPIE5j0Ik6+UQkyyZIpw2PqasfhiHXOqJO8az2G32t9pG2Nemh6CTfOj2kXo0nc6Fb+YMiyvmexEc1AMY8lmHoJBNPky0ap7rFgAmqPHXpIi4qnSCfDF8TpA9ikR2G7Krtqlv0muREv2hTkwxFp4WUsimjKQ/tI73OUA6KYci1jijrOp2pGirydJKdeEweqNND5PrY959KlLOv/sxfyfj4eOm7z83NTem7Y3Z2tlhYWEjXHrC8vJyeT2FycrL0NfOYPM9BbBdXQ6urq2XoPmNjY6XvX3Z3d1l5ipWVlb6vN5eWllIZXGvVXTEeHR0VrQW2mJubS2PGVdZLBVnTT+leJ8h3cnLSzt/p+rUX6vRwYmKi9I2QZK5KKkFjnp1h6GTcEVZPVHWnIsXXtUWnhKqr7kRFt90oO9ZuJ47HQjuGSVNfuvUR2VRPCPS5KkNc3XiIOHaCulU/ZVbrGQS0a9TQp6os4okKvaGvOknSxqiDvcq3SQ+7je0goX3CJ6oBox0N7qV/yH2N8HH606dPZeg+19fXD05a2pFvbGwUrYn7YKd6fHzMbCpai0LRmvTJj6vbiVLW/Px8Garn4OBgIKe25wL5cHLqBLKpyoc+S3atxbDtR+5NcNKtQzKemZkpLi8vk/+lg86in93gBgA4Vd7e3iY/9CrfOj3sdIIeNjZUA4YJKCVgETP5gJECxkh+FjtdQ52enj6YnL9//y7Ozs6Sn+ssNiL9gJHa3t5O5eOvu5LiL6pkRNW+XKkzuhgpxXVq/2MMdr+wkO7v7yc/C3WTMXtp/Pz5s6PMMFAYZeknfhmtXqnTQ+bI+fl5KhN/v/Ogb1oLaptK0JhnZ1A6yZUFZcnFKwzF6aqDKxPCujrhikV54nUKPObqr3rtoisrrl10NRXTcbrCeQqUMyyqV0BVOehKib7Sf8kUpz5HqjKSq7vuUpqojpfGWnIeNLHuYRJlUpV3nRzQGcVV9eex8q2mUw55Ylzd+A0D6hL/8E8rIsF1VQga8+xYJ/vHshsOlutoiHL21Z8xxpissaEyxhiTNTZUxhhjssaGyhhjTNbYUBljjMkaGypjjDFZY0NljDEma2yojDHGZI0NlTHGmKyxoTLGGJM1NlTGGGOyxobKGGNM1thQGWOMyRobKmOMMVljQ2WMMSZrbKiMMcZkjQ2VMcaYrLGheiLfv39Pv0SJ+/z5c4pbX19PYZ6R9+/flz7zHGhcvn37VsYUacw0ftU0wbjVjWcvUG63MmJb0KtckRxxEcmpGi8kA1ydnB9DLKOTjH79+lVMT0+XoZeLZFrtC+Fe4ntB8q2jU9owsaF6Ir9//04/l4zb2NhIE+T09DSFeQoWod3d3TJkngPkv7a2VobuGB8fb4/fzs5OMTMzU6bcwcK4tbWV0hlbXB3Ea6NSx/LycnF4eFiG6oltmZ2dLWPzAuMwPz+f2ogsZXhlNCTHOlkgx6urq+TwN9HJmJ+fn6c6kOWHDx/K2Ic8ZVORC1H3MDySKfELCwspnqeMPmOgtefy8jLF1dFNNrxfBf3GQCH3uvRhY0P1BBi8lZWVrjsMLW6Tk5PpafIhGqbr6+sHY0R6NBrDGkMWG3Qp91M3ssDowqdPn+4Z7rg4YnTruL29Tc9+d/za7KkNdSDLTkbspUAfpXsYLPRTRLmPjY2l5/b2djE1NdU2XIMEg8gGpJPch4kN1RNhd8EuQ8aKhYxBJcwTvnz5kk5bJj9keJj4ExMTyR8hnYnPeL57966MHTwYRHSJ+l7SFbHkx4IqvYe6BW1/f7+Ym5tL+Y6Pj8vY/mkydpy6qifj14D0U7JF1pxuZcww4ugQG55BGitOapyCz87OUp2dbg6GRqtjbSpB0wOt3caflsEqQ/9C/MXFRXLIt7XjKVPMYxi0Tq6trdWOE3GMUScYu2qexcXF1Maqa03sMse/UAf1d4My697vFdoxTKp9QddxTfXSJ6VXx4CwZBcd+etoGi+1ibqGNddo16ipkzVxdX2k7+hQpFf5kiakt8ibsmPaMIn1+EQ1IN6+fVv6/kXHc3Y8HMtbg5x2k8M4mpunwS5cO9MmGEO+SUY4GbTmURrb1qRPfpxOGv0wzJPboNC3KqFvVNwctBa22u8gxJGOfNj1RzglSHatRbHtb7qJaBqvvb29tOvnCowxecofFeQC68Xq6moZugtztcoJ6uPHjw9OOOheVf96lW8dyJtykW28ehwFNlQD4uDg4MF1h6/8XhejulKq+1aWExgljDb6jh+HAedqCPhmUreQnZyctOOfsthhiPStqrpIawHGSFFHpz8qeAlglGSU8SOzm5ubFAcYrPjtCqqbiKfCOLMBiIxcP1uD2qYSNF3QNQaO43FER2WBn3x1R3XTzCB1kjHReMWxqV4j6XqDZ3ynOsbw2Ks/3lWarlt46oomllN9t18oa9DEfuCiPuNXvPpAnOQW54tkIKrl1uXTuERHnOKj3PAPa65R1yiI8sLF67wYD1E21Ws/eIx8hdKi/OL7Uc7DhLrEP/zTikiwUwlBY54d62T/WHbDwXIdDVHOvvozxhiTNTZUxhhjssaGyhhjTNbYUBljjMkaGypjjDFZY0NljDEma2yojDHGZI0NlTHGmKyxoTLGGJM1NlTGGGOyxobKGGNM1thQGWOMyRobKmOMMVljQ2WMMSZrbKiMMcZkjQ2VMcaYrLGh6gN+/pof9ar+DPb79+8fxE9PT6c4fkZa8HPS6+vrZciMCmReHQtQPK7u59E1rrh+iXU0ofRq+3KD9tHOqg4/Vk7k4+fS+4HxUR1NZSj9NcwxyZR1JKJ1pboGgdKe8lP/uEhTO0aFDVUfbGxsFDs7O2XoDhTm3bt36Rcpz87OkpIwoRcWFoqrq6tif3+/zFkUX758KXZ3d8uQGRXIfG1trQz9y/z8fBo33OTkZBl7hxZD0hjzuoUBGO+mNMpQHdRft4ASpzZsbW2VsXmyvLxcHB4elqE7Hisn5sTJyUkZqqeTgWHuUAdzant7u4z9lyjHvb29vg1iDiArdIG+YCAkU56np6cp/uvXrylOYEw+fvyY0qq6LLoZcN6NNLVjlNhQDQiM09LSUvJ/+PChODo6Sv4qDPrq6moZMs8Nk25lZaXj5L28vCx9RTE+Pl76Hs/s7Gxa3OHTp0+1O13igYWVheYl8hg5nZ+fF4uLi2WodySnnz9/pnlWJW4AMZi/f/8uQy8PdAbdAQzF9fV18rPOYITQIzbCglMPGyE20oOkqR2jxIZqQDBJ4w6GwWSA2flMTU21JxUTVYNunh8mPTtFJn2dsWKsWAx0FSKD8xTqdrrEUf/c3Fzx9u3bMvbl8Bg50b+n3iQgJxZkNhczMzNlbDNjY2Ol7+UzMTGRnsiADRbrCid1QH85qfJkDLqdmp6C2jFSWpO0TSVoOtDarSUnWkpT+v78OTw8/NPa2ZShf2ntJNOT95B1XR5zn0HrJDJnfOqIYxjRWNe1hTElvuqurq7KHPfpNua8x/uDYFDl1FGn453kdHFx0ZY7MiMcIU2yi47y6uD9pvESw5pftGvUNPWFtqAzyCPKVfGiV/mSVsewZFpHbINPVAOCu1td6dzc3DzYdeieF7hXbsk+nbb0jnl+4jWK0DcOrlNak/3BTvX4+DiNJd9MWpM++XF1pyZ9q+oE77UWgxenF93kdHBwkE5B7PbZ+XNyjN+POIFJdvRf/qZrLE5wnT7sD+L0lgudPhegc7e3t2XoTi7A9WqM71W+dTznZwsbqgHBH1Lou1T8XiV85fcy4RsH4wlcI/VrQFiU+fjPgoE/LtJVqKPO0OVMNzlhNLQ4soi2dv5Dmw8YKW0InuPD/yDBOGjtwF+VKzInDcfnB6XjH6R8u7Vj6LQUp00laBrQ9QZO1xnAVQRx1eN09YpC74/yGP1SGaROIm+Nm65INGaxHl2/6eok5onXKfCYq7/qtYv0AT3gfehUR79Q1jCI/Ym6XtcH4uIcgXhFJaoykqvOpZgmqIswz+p4VN8fBLHuYaJ1Qk66EvsY5Yi/Lh4eK19QWtTT+I7aMWyoS/zDP62IBMfyEDTm2bFO9o9lNxws19EQ5eyrP2OMMVljQ2WMMSZrbKiMMcZkjQ2VMcaYrLGhMsYYkzU2VMYYY7LGhsoYY0zW2FAZY4zJGhsqY4wxWWNDZYwxJmtsqIwxxmSNDZUxxpissaEyxhiTNTZUxhhjssaGyhhjTNbYUBljjMkaGypjjDFZY0PVB+/fv0+/Pjk9PV3G3KH4z58/lzFFykPct2/fypii+PXrV7G+vl6GzKhA5tWxEIxZHDfBWPGOHGPcD9TJ+03jrnS5urbkDG3uBP2uk/tj0TxiPOpAXi9Rbt1o6pfkEfUx6mqTnB6Dyqii+H7nwFOwoeoRJtvW1lb6iWSURQrE8927dyn+7OwsKQp5FxYWiqurq2J/fz/lgy9fvhS7u7tlyIwKZL62tlaG/oWx2tzcLEP3+fnzZxpTHOPIGNdBGZ0WyeXl5eLw8LAM1aN6yPf27dsyNn+6bbq+f/9e7O3tlaF6upVxeXlZTE1NlaGHbGxsFDs7O2Xo9VDXL2S1vb2ddGVycrK9AdBag+skz26yptwq1CH9PD4+LmNHhw1Vj7DgzM7OJj8G6/r6OvkxTktLS8n/4cOH4ujoKPmrMOCrq6tlyOQAG4emRW5mZqb03RmtYRmQWM/5+Xlbx3IHIzQ/P1+G6jk4OKjdIJj+YFMkfWEtYRNMHBtnDBcOiBsUrHWcphjv58CG6olMTEykJzs+KQhgwDBqp6enaSeI8YKXtAj9DXTbOMQxHebYxXpeEhgh9LwJTpmfPn0qQ2ZQVDfCt7e3D3SIuEHBOsZJbW5u7lmMlQ3VE2CScjTvBAaM4zKTmbtdrp+YvOxOuh3BzfB5qvHRd0k2I1wf6h6/393sY04oudDNCEkGTUaYvkpeXA3K73nRGdYQ6RqG4zGbHDZkdbLudF0doQ7cxcVFWvdGjQ1Vn1R34hy7NTFvbm7aJy1Bfo7P8PXr12S82KUM8nhueoMx0aRl4uOaJm7TyYv7esaS3SbXh7rHf8ziUUe3E0pOoMcYaOQHegp2/VpQkfPKykqSo2CDIHlxNSi/v992Bt2SrJA/evnmzZt7awkbZOIEOqV3oqy7bbSrPNdtkA1VHzDZtBPHj4LwkV3H8fi9SvjKLz/i5MXI4JomrsfvIbotwIGeAlkqncWRPxJ5KUb4JcBp/uPHj0kvMV6MB2sRTt+rBk3Thm3otJSoTSVoamgtZklOcouLi2XKnz+t3U2KI0+E+IjKaE3eMsY0gZwGBfLWuF1cXJSxdzAmGrfW6Sjl4SmaxorxV5nRxXehtUi301QPz6g/tIl8g4K6RkWsC1lV5UW42jf6K5lEVydrzS2cwK9x1JzCDVKGdcQ2DJu6fiGfun5GeXbSv+ikixGlad2K5daNzbCgPvEP/7QiEhzRQ9CYZ8c62T+W3XCwXEdDlLOv/owxxmSNDZUxxpissaEyxhiTNTZUxhhjssaGyhhjTNbYUBljjMkaGypjjDFZY0NljDEma2yojDHGZI0NlTHGmKyxoTLGGJM1NlTGGGOyxobKGGNM1thQGWOMyRobKmOMMVljQ2WMMSZrbKiMMcZkjQ1VH3z+/Dn9+uT09HQZc8f79+9TPOmCPMR9+/atjCmKX79+Fevr62XIjApkXjcWxOG+f/9ext5H48349gt1UkancVc7nlLPqJF+N7VZMpdrknE3VE6T/DRGT6kjR9SvuKaA5F5dg0Bp6HY/SI6R55avDVWPaPD5ieSPHz+2Fz0G8t27dyn+7Ows5SNtYWGhuLq6Kvb391M++PLlS7G7u1uGzKhA5mtra2XoDsaCMWOMtre3y9h/YVIynuRhfKORizDe1cUksry8XBweHpahh/Duzs5O+6e3X8JiS5tPT09Tmy8vL2tlMz8/n9JxyH52drZMuU8nA65yO8lmc3MzpV9cXNSO40tlY2Mj6UVE6wr95RnljiFhXSJtcnKyjL1PJ1mD5Bx5bvnaUPUBygMsYCxA8i8tLSX/hw8fiqOjo+SvglKtrq6WIfPcfPr0KT1//vyZxq3Kjx8/2vGMb9xwDJrr6+vSVxRv3rwpffnCPNBiyOJ1c3OT/ALjrfnxFM7Pz9tzhufBwUHyV9EmsmmBfk2orzA2NpaenGrZDGh9GjTPKV8bqh5hkBiw6tGYHWUcQBYdJik7zqmpqfZix6Rr2lWa0cOYMcFXVlaKmZmZMvZfGEctBMA4DwMWF3QFvdra2nqRi+34+HjpuyP2gVMQp6t+YL5Fwx0XacFplXmGwXzttxUy/ugKMmU9QSYnJyfttanbqalXnlu+NlR9wATU0brTdQ+wsJEX5WJBZJB5ZxjKZPrj+Pg4XWlwjdIrjCljySTmegQ/rm4x7QZXNouLiy/y6ooNWKfTEyfT6kYA4yV57e3ttf39zAs2E1yRsVi/hGvTp8I1NKcnNjVwe3ubdIcw6w3yjDrITU6drLutX+K55WtD9QS4NtJ1DR8wpRhcgUxMTCS/QFGkVF+/fk3KxA66nwXNDB52pXUfphnH379/Jz+LQTUPRo6x5BuXvjHhej0RsWC8ffs2lce78btD7tB2XaE2wTypygSZS14suvJXd+y8h+yBsaiTLcadUynjUHeF+5pANzi9Iic2N9HY6LYGoyWZAZuIOlk/9prwueVrQ/UE+K6h6wx2OPouFb9XCV/5vUwwHvouFb9XDRoWcsoHjGP1e0+uaJHEeDTtztmMVTduvcAc03ep+L1KUD47faAdLKavGXQDOQAGC91hbeH2Rhtf/INab7KQb8uqtqkETQ2Hh4dJTrjWzqSMvWNqairFt3bWZcwdxEdIr3vfPGSQOom8NXYXFxcpTuFYT2sipjBP0HutXWoKR4iLZcjpXRH1RvrBU2WqTlxVX/qFsoZJlCdO+sxTfqCfVXkAYxDfr5YTkZxjGmGNI/F6H1kPE+oYFVorqv1SXGxLlKfkIqL+RSddjCgt6uEo5SuoS/zDP62IBHeWIWjMs2Od7B/LbjhYrqMhytlXf8YYY7LGhsoYY0zW2FAZY4zJGhsqY4wxWWNDZYwxJmtsqIwxxmSNDZUxxpissaEyxhiTNTZUxhhjssaGyhhjTNbYUBljjMkaGypjjDFZY0NljDEmax7839ONMcaYHJB5umeojDHGmNzw1Z8xxpissaEyxhiTMUXx/wOKC/vCodz3LwAAAABJRU5ErkJggg==\"\u003e\u003c/div\u003e\n \u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec23\"\u003e\n \u003ch2\u003e3.8 Biodegradation study\u003c/h2\u003e\n \u003cp\u003eFigure 13 shows photographs of biodegraded biocomposite films with different soil burial times for biodegradation test. The pure PLA film did not change after a 6-month biodegradation time in soil, whereas the pure PLA-PEG-PLA film exhibited many voids in film matrices from bulk erosion and easily broken. This is due to the higher hydrophilicity of PLA-PEG-PLA [36, 43, 47]. The PLA/SCG films displayed some voids in film matrices from bulk erosion and some cavity on film surfaces from surface erosion, particularly for the higher SCG content. The PLA-PEG-PLA/SCG films showed faster degradation than the PLA/SCG films, including the larger void number and the faster film shape loss for higher SCG content.\u003c/p\u003e\n \u003cp\u003eFigure 14 shows the weight loss of sample films after burial in soil for 6 months. The weight loss increased with the increase of biodegradation time indicating that these films were biodegradable. The pure PLA and PLA-PEG-PLA films had weight losses at 6-month biodegradation time of 0.32% and 6.70%, respectively. The hydrophilic PEG blocks induced faster biodegradation of PLA-PEG-PLA [36, 43]. The weight loss of both biocomposite series increased as the SCG content increased. The weight losses at 6-month biodegradation time of PLA/30%SCG and PLA-PEG-PLA/30%SCG biocomposites were 17.08% and 35.55%, respectively. This may be explained by the hydrophilic SCG accelerated the biodegradation of film matrices [18]. The hydrophilicity of film matrices increased by the addition of SCG as supported from the above results of water contact angle and water uptake.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eThis study was carried out the use of SCG as a bio-filler in the PLA-PEG-PLA compared to the PLA. The biocomposites with different SCG contents (0, 5, 10, 20, and 30 wt%) were successfully prepared via melt mixing and compression molding. The position shifting of \u0026minus;OH bands from FTIR spectra and the increasing of decomposition temperatures from TG/DTG thermograms of PLA-PEG-PLA/SCG biocomposites suggested chemical interactions between the PLA-PEG-PLA matrix and the dispersed SCG phases, which may due to good phase compatibility between the phases as observed from SEM. However, the no chemical interactions and poor phase compatibility between the PLA matrix and the SCG were found. The crystallization properties obtained from DSC analysis and hydrophilicity resulted from water contact angle and water uptake determinations decreased as the SCG content increased for both the biocomposite series. Tensile properties such as maximum stress, strain at break, and Young\u0026rsquo;s modulus of both the biocomposite series decreased with increasing SCG content. However, the PLA-PEG-PLA/SCG biocomposites displayed higher flexibility than those of the PLA/SCG biocomposites. From soil burial test for 6 months, the PLA-PEG-PLA/SCG biocomposites showed faster biodegradation than the PLA/SCG biocomposites. Addition of SCG has increased the biodegradation properties of both the biocomposite series. It can be concluded that the physicochemical and biodegradation properties of PLA-PEG-PLA can be controlled by adjusting the content of SCG filler. Thus, the SCG shows potential for use as a low cost, renewable and sustainable filler for flexible and biodegradable PLA-PEG-PLA. In the future, the improvement of interfacial adhesion between the PLA-PEG-PLA matrix and dispersed SCG could be proposed through treatment of SCG.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u0026nbsp;\u003c/strong\u003eThis work was financially supported by Thailand Science Research and Innovation (TSRI). YB is also grateful to the partially support provided by the Centre of Excellence for Innovation in Chemistry (PERCH-CIC), Office of the Higher Education Commission, Ministry of Education, Thailand.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor Contributions\u0026nbsp;\u003c/strong\u003eY.S. and Y.B. performed most of the experimental part, A.M. performed some characterizations and formal analysis,\u0026nbsp;All authors contributed to writing-original draft, and revising of the paper.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData Availability\u0026nbsp;\u003c/strong\u003eNo datasets were generated or analysed during the current study.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of competing interest\u0026nbsp;\u003c/strong\u003eThe authors declare that they have no competing interests.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eTripathi N, Misra M, Mohanty AK (2021) Durable polylactic acid (PLA)-based sustainable engineered blends and biocomposites: Recent developments, challenges, and opportunities. 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Prog Polym Sci 37:1657-1677\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"polymer-bulletin","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"pobu","sideBox":"Learn more about [Polymer Bulletin](http://link.springer.com/journal/289)","snPcode":"289","submissionUrl":"https://submission.nature.com/new-submission/289/3","title":"Polymer Bulletin","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Polylactide, Block copolymer, Spent coffee grounds, Biocomposites, Biodegradation","lastPublishedDoi":"10.21203/rs.3.rs-6230035/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6230035/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThis study is aimed to prepare and characterize the poly(L-lactide)-\u003cem\u003eb\u003c/em\u003e-poly(ethylene glycol)-\u003cem\u003eb\u003c/em\u003e-poly(L-lactide)/spent coffee grounds (PLA-PEG-PLA/SCG) biocomposites compared to PLA/SCG biocomposites. The biocomposites were prepared by melt mixing. Fourier transform infrared (FTIR) spectroscopy shows that the PLA-PEG-PLA matrix chemically interacted with SCG but the PLA did not interact. Scanning electron microscopy (SEM) of the biocomposite fractured surfaces indicates that the phase compatibility between PLA-PEG-PLA matrix and SCG dispersed phases was better than between the PLA matrix and SCG dispersed phases. The addition of SCG decreased crystallizability of both the PLA-PEG-PLA and PLA matrices as determined by differential scanning calorimetry (DSC). The thermal stability of PLA fraction in the PLA-PEG-PLA/SCG biocomposites studied from thermo-gravimetric analysis (TGA) largely increased with an increase in the SCG content but this decreased in the PLA/SCG biocomposites. The hydrophilicity of the biocomposite surfaces and water uptake increased by the addition of SCG for both the composite types. Both the PLA/SCG and PLA-PEG-PLA/SCG biocomposites showed lower mechanical properties compared to their pure polymers. However, the PLA-PEG-PLA/SCG biocomposites were still higher flexible than the PLA/SCG biocomposites. The incorporated SCG accelerated the biodegradation in burial soil of both the biocomposite types. The results have shown that PLA-PEG-PLA/SCG biocomposites could be used as a flexible and biodegradable packaging.\u003c/p\u003e","manuscriptTitle":"Physicochemical and biodegradation properties of flexible poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)/spent coffee grounds biocomposites","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-03-27 16:36:53","doi":"10.21203/rs.3.rs-6230035/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-05-09T06:13:47+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-05T18:18:22+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-04-22T02:33:16+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"134195106972732556021040433139050291095","date":"2025-04-15T10:56:16+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"180801660701888017071403719358546757083","date":"2025-04-01T13:21:50+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-03-19T10:28:19+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-03-17T16:01:00+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-03-17T01:06:02+00:00","index":"","fulltext":""},{"type":"submitted","content":"Polymer Bulletin","date":"2025-03-15T02:59:59+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"polymer-bulletin","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"pobu","sideBox":"Learn more about [Polymer Bulletin](http://link.springer.com/journal/289)","snPcode":"289","submissionUrl":"https://submission.nature.com/new-submission/289/3","title":"Polymer Bulletin","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"51a2a410-d5c8-47f0-8931-4517ae1f5374","owner":[],"postedDate":"March 27th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-06-23T16:02:20+00:00","versionOfRecord":{"articleIdentity":"rs-6230035","link":"https://doi.org/10.1007/s00289-025-05869-2","journal":{"identity":"polymer-bulletin","isVorOnly":false,"title":"Polymer Bulletin"},"publishedOn":"2025-06-22 15:57:45","publishedOnDateReadable":"June 22nd, 2025"},"versionCreatedAt":"2025-03-27 16:36:53","video":"","vorDoi":"10.1007/s00289-025-05869-2","vorDoiUrl":"https://doi.org/10.1007/s00289-025-05869-2","workflowStages":[]},"version":"v1","identity":"rs-6230035","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6230035","identity":"rs-6230035","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}