Unveiling the Potential of Chitosan Nanoparticles and Jojoba Oil for Optimizing Poly(lactic acid) Characteristics: Insights into Physico-chemical Attributes and Crystallization Mechanisms

Unveiling the Potential of Chitosan Nanoparticles and Jojoba Oil for Optimizing Poly(lactic acid) Characteristics: Insights into Physico-chemical Attributes and Crystallization Mechanisms | 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 Unveiling the Potential of Chitosan Nanoparticles and Jojoba Oil for Optimizing Poly(lactic acid) Characteristics: Insights into Physico-chemical Attributes and Crystallization Mechanisms Moataz A. Elsawy, E. S. Ali, Jesper Claville Chritiansen, Gamal. R. Saad This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4009522/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Poly(lactic acid), PLA, loaded with chitosan nanoparticles, CsNP, (3.0%, w/w) and jojoba oil, JO, (3.0%, w/w), as a plasticizer, were prepared by twin screw extrusion. The manufactured PLA/CsNP, PLA/JO and PLA/CsNP/JO compounds were characterized by differential scanning calorimetry (DSC), thermogravemetric analysis (TG), tensile testing, Izod impact test and wide angle X-ray diffraction (WAXD). The PLA/CsNP, PLA/JO and PLA/CsNP/JO compounds exhibited improved elongation and impact strength compared with neat PLA. The presence of JO slightly improved the thermal stability of PLA, while CsNP decreased the thermal stability of the PLA. The incorporation of CNPs and JO accelerated the cold crystallization rate of PLA, which is related to a nucleation effect of the CsNP and increase of the chain mobility as a plasticization effect of the JO. No modification in crystalline structure of PLA was observed as a result of the presence of the CsNP and the JO. Avrami equation was employed to describe the cold and melt isothermal crystallization process of neat PLA and PLA/CNP composite with and without JO. The combination additives of CsNP and JO accelerated the crystallization rate in a less extent than CsNP or JO alone. PLA chitosan nanoparticles Jojoba oil composites mechanical properties isothermal crystallization Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 1. Introduction Biodegradable polymers have received great attention from both ecological and biomedical perspectives [ 1 – 4 ]. Among them, poly(lactic acid) (PLA) is one of the most promising materials, which is used as biomaterials for medical applications and food packaging due to its renewable resources, availability, relative good strength, biocompatibility and biodegradability [ 5 – 9 ]. However, PLA also has some drawbacks, such as its inherent brittleness, low impact resistance and moderate gas barrier properties[ 10 ]. PLA also presents a relatively low crystallization rate and is prone to aging at room temperature, aspects which are important from an industrial point of view [ 11 – 13 ]. Therefore, many approaches have been carried out in order to overcome some of its drawbacks, including blending/compounding with other polymers, plasticizers, reinforcing materials in micro (e.g., natural fibers) and nano size green fillers (cellulose and chitin nanowiskers) to broad its application [ 14 – 17 ]. These fillers have shown to be able to improve the properties of PLA by affecting the crystallinity, mechanical properties and thermal properties. In addition, the prepared composites have the advantage of being lightweight, renewable, and biodegradable. The positive impact of using natural nano-fillers as reinforcement material in nanocomposites provides several benefits, including complete biodegradability, low density, comparatively low cost, and improved mechanical properties [ 18 – 20 ]. On the other hand, various low molecular weight compounds have been investigated as potential plasticizers for PLA [ 21 – 25 ]. The role of the plasticizer is to reduce the modulus of elasticity in PLA, and it is of great importance that the plasticizer be compatible with the polymer in order to be evenly distributed in its matrix [ 26 , 27 ]. The mechanical properties of the PLA plasticized with jojoba oil (JO) was studied by Elsawy et al. [ 28 ] and the results showed an improvement of the elongation and Izod impact strength. Chitosan is a natural polymer derived from chitin which arouses a lot of interest because of its biodegradability, biocompatibility and its bacteriostatic and fungistatic properties [ 29 – 32 ]. Chitosan nanoparticles (CsNP) can be obtained by ionic gelation, where the positively charged amino groups of chitosan form electrostatic interactions with polyanions employed as cross-linkers, such as tripolyphosphate [ 33 – 36 ]. It is well known that the morphology of semi-crystalline polymers, which is in turn determined by the crystallization process, determines the mechanical and physical properties of semi-crystalline polymers. Thus, the crystallization behavior affects the characteristics of semi-crystalline polymers like PLA. In comparison to neat PLA, the addition of nanofillers and plasticizers alter the mechanical and thermal properties via influencing the crystallization behavior [ 37 , 38 ]. Therefore, study on the crystallization behavior and morphology of polymer is useful to understand their effect on the properties. In our previous work [ 25 ], a considerable improvement of the elongation and impact strength of PLA was reported by addition of 3.0 wt% JO, as a plasticizer. Also, the incorporation of the chitosan nanoparticles (CsNP) into PLA matrix have proven to be promising green nano-filler for the improvement of mechanical and thermal properties of PLA [ 28 ]. Thus, the aim of the use of CsNP as a reinforcement agent and JO as a plasticizer for PLA is to create new, effective nano-biocomposites with improved properties while of these additives preserving their environmental attributes. The goal of this work is to investigate the influence of the addition of both CsNP and JO on the thermal, mechanical properties and isothermal cold and melt crystallization behavior of PLA. The PLA/CsNP, PLA/JO and PLA/CsNP/JO were prepared using melt extrusion technique. Next, the kinetics of isothermal crystallization was modeled applying Avrami model. 2. Experimental 2.1. Materials The PLA polymer (Ingeo™3001D) was purchased from NatureWorks® LLC (Minnetonka, USA) and PLA granules were dried in vacuum oven for 2 h at 100°C before use. Chitosan nano-particles (CN001) (≥ 96% deacetylated) of particle size 200 nm were purchased from G.T.C Bio Corporation company (Hongkong, China). The chitosan nano-particles (CsNP) was dried in vacuum oven for 24 h at 60°C. Jojoba oil, a commercial grade, was purchased from Egyptian Natural Oil Company NATOIL (Cairo, Egypt) and used as received. 2.2. Samples preparation PLA compounds containing 3.0 w/w CsNP without and with 3.0 w/w JO were prepared using a Prism Eurolab 16 co-rotating twin-screw extruder from Thermo Scientific with a strong configuration of the screws having 3 mixing zones with 90 degrees spaced mixing disks as part of the zone. First, predetermine weight of CsNP was homogeneously dispersed in dry acetone using ultrasonic homogenizer for 20 minutes, and then the dispersed CsNP were sprayed over PLA pellets. The coated PLA pellets with CsNP were dried at 60 o C in oven for 5 min to remove the residual acetone and then feed with predetermine weight of JO in the extruder with temperature profile ranged from 170 to 180 o C for 3 min in order to prevent the degradation of PLA/ CsNP nanocomposites. Samples of neat PLA and PLA/JO were processed in exactly the same way for comparison purposes. PLA with 3.0 wt% JO designed as PLA-3JO. Nanocomposites with 3.0% CsNP in the absence of Jojoba oil and in the presence of 3.0% Jojoba are deigned here as PLA-3CsNP and PLA-3JO-3CsNP, respectively. All materials were molded into dog bones with dimensions of 50 × 4 × 2 mm using a piston type Haake minijet injection moulding machine from Thermo Scientific. The specimens were obtained using an injection pressure set to 800 bar, a melting temperature of 180°C, a post pressure of 650 bar and the temperature of the mould was set to 25°C. 2.3. Characterization 2.3.1. Differential Scanning Calorimetry Differential scanning calorimetry (DSC) of the all material was performed using DSC Q2000 instrument. The samples were cut into small pieces and the sample's weights were maintained at low levels (5–7 mg) for all measurements in order to minimize any possible thermal lag during the scans. To remove the thermal history, the sample was heated from 25°C to 180 o C and cooled rapidly at a rate of 40 o C to 20°C and then reheated up to 180°C at a heating rate 10°C min − 1 under nitrogen atmosphere (30 mL min − 1 ). The glass transition temperature (T g ), cold crystallization temperature (T cc ), cold crystallization enthalpy (ΔH cc ), melting temperature (T m ) and the melting enthalpy (ΔH m ) of the prepared materials were determined from these heating scans. To study the kinetics of isothermal cold-crystallization behavior (from glassy state) in the different crystallization temperatures, all the specimens were first heated at a heating rate 60 o C min − 1 to 180 o C and held there for 3 min, to erase any thermal history, and cooled at 60 o C min − 1 to 20 o C to obtain wholly amorphous glassy sample and subsequently reheated at the same rate to the desired crystallization temperature (T c ) and held until the crystallization completed. For melt isothermal crystallization, a fresh sample was initially melted at 180 o C for 3 min and then cooled to the predetermined crystallization temperatures and maintained for the time necessary for isothermal crystallization at these temperatures. The exothermal curves of heat flow of both cold and melt crystallization as function of time were recorded. 2.3.2. Thermogravimetric Analysis The thermogravimetric analysis (TG) was performed on a Jupiter STA 449 F1-Netzsch instrument. Samples of 6.5 mg were heated from room temperature up to 600°C, with a heating rate of 10°C min − 1 , in an open platinum crucible, under 50 mL min − 1 nitrogen flow. 2.3.3. Mechanical Analysis The tensile properties were determined using Universal tensile machine –INSTRON 5944 with a load cell of 2 kN. Five specimens from each material were tested according to the ISO-527−2 tensile test procedure. The measurements were done at room temperature with a crosshead speed of 50 mm min −1 and at least five samples were tested. Izod impact tests were performed on an Instron CEAST 9050 impact tester equipped with a DAS 8000 Junior data-acquisition system, with a sample frequency of 1000 kHz and a 50 J instrumented hammer. Specimens with dimensions of 80×10×3 mm were molded on the Haake minijet as described previously. Impact tests were carried out at room temperature and a minimum of 5 specimens were tested for each material. 2.3.4. Wide Angle X-ray Diffractometry (WAXD) WAXD measurements were recorded using a Rikagu diffractometer (Cu radiation, λ = 0.1546 nm) running at 40 kV and 40 mA. The scan angles range of 2θ was from 5 to 40° at scanning rate 3 o min − 1 . 2.3.5. Morphology JEOL (JSM-5200) scanning electron microscope was used to examine the dispersion of chitosan nanoparticles in the PLA matrix. The extrude materials were fractured and their surfaces were sputter coated with gold prior to examination. 3. Results and discussion 3.1. Physicochemical characterization of the tested samples The micrographs obtained by SEM for the tested samples are given in the supplementary information (S1). The plasticized PLA (PLA-3JO) showed smooth surface with almost no distinct interface, indicating a good adhesion between PLA and JO. PLA/CsNP composite showed that CsNP particles are relatively well dispersed in the PLA matrix and the dispersion of CsNP was slightly improved by the presence of JO. The XRD of the neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP films (S2) displayed that the diffraction peaks characteristics of PLA insignificantly changed by the presence of Jojoba and/or CsNT, suggesting that CsNP and/or JO did not change the crystal structure of PLA [ 39 ]. The stress–strain curves of the processed neat PLA, PLA-3CsNP, PLA-3JO, and PLA-3JO-3CsNP are shown in S3 and the reported results derived from these curves are summarized in Table 1 . It was found that the elongation and tensile strength (stress) at break of neat PLA were 3.3%±0.2% and 74.1±2.9 MPa, respectively, which was in accordance with literature reported previously [ 40 ]. The incorporation of 3.0% JO into PLA matrix caused a reduction in the tensile strength and an increase of elongation at break, which were found to be 35.5±0.7 MPa and 42.2±2.1%, respectively. Incorporation of 3.0% CsNP into PLA leads to an increase in the modulus and elongation and a reduction of the tensile strength of PLA[ 41 ]. Blending PLA with and 3.0% CsNP and 3.0% JO increased the tensile modulus, while lowered the tensile strength compared with PLA loaded with JO or CsNP alone. On the other hand, the elongation is comparable to PLA loaded with 3.0 JO and greater than PLA loaded with 3.0% CsNP. The impact strength increases in the following order: PLA-3JO > PLA-3CsNP > PLA-3JO-3CsNP > PLA. Therefore, it can be concluded that the tested samples exhibited somewhat good mechanical properties, particularly, tensile modulus, elongation and impact strength compared with neat PLA. Table 1 Mechanical properties of neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP. Sample code Tensile modulus (GPa) Tensile strength at break (MPa) Elongation at break (%) Impact strength (kJm − 2 ) PLA 3.51±0.10 74.1±2.9 3.3±0.2 13.1±0.6 PLA-3JO 3.49±0.81 35.2±0.6 42.2±0.8 21.3±0.8 PLA-3CsNP 3.66±0.07 53.5±1.0 7.76±.0.2 17.1±1.5 PLA-3JO-3CsNP 3.84±0.21 28.8±1.1 39.9±0.7 16.7±1.4 The effect of blending PLA with 3.0% JO and 3.0% CsNP on the thermal transitions of PLA matrix (Fig. 1 and Table 2 ) can be compared with the results from our previous study [ 42 , 43 ], where PLA was blended with 3.0% JO and 3.0% CsNP alone. It can be seen that the presence of JO slightly reduced T g value of PLA, reflecting an enhancement of segmental mobility of the PLA chains promoted by plasticization effect of JO. This T g reduction enables crystallization to start at an earlier temperature upon heating, where the cold crystallization transition (T cc ) of the plasticized PLA was declined by 6.0 o C compared with neat PLA. On the other hand, presence of CsNP has no pronounced effect on T g and cold crystallization temperature of PLA matrix, indicating a limit nucleating effect of CsNP on the non-isothermal cold crystallization of PLA matrix. The T cc value of the PLA modified by the combination of JO and CsNP slightly shifts toward lower temperature compared with neat PLA. The T cc was decreased with about 3.6 o C which lies between PLA blended with 3.0% JO and 3.0% CsNP, suggesting that the combination of the Jojoba and CsNP has no significant synergistic effect on the promotion of the cold crystallization ability of PLA. A double melting is observed in all tested samples that could be related to the formation of different crystal structures or to lamellar populations with different perfection degrees. A similar thermal behavior can be observed for other PLA systems [ 44 , 45 ]. From the determined enthalpy of melting (ΔH m ), the degree of crystallinity (χ c ) was calculated by considering the melting enthalpy of 100% crystalline PLA as 93 J/g [ 46 – 48 ]. The data of the χ c of the tested samples are summarized in Table 2 showed that the extent of crystallinity of the PLA is not significantly affected by the presence of JO or/and CsNP. Table 2 The DSC and TG data for neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP. Sample code T g ( o C) T cc ( o C) ΔH cc (Jg − 1 ) T m ( o C) ΔH m (Jg − 1 ) χ c (%) T onset o C T max ( o C) PLA 61.5 108.7 32.6 170.0 38.8 41.7 337 371 PLA-3JO 57.1 102.7 30.0 168.7 40.8 45.2 342 372 PLA-3CsNP 62.3 110.7 32.1 169.5 38.6 42.4 330 372 PLA-3JO-3CsNP 62.1 105.1 28.2 168.6 34.8 40.2 331 365 The temperature for the onset of thermal decomposition (T onset ), the temperature at which decomposition rate is maximum (T m ) and were determined from TGA thermograms (Fig. 2 ) of the tested samples, and the data included in Table 2 . Comparison of the investigated samples indicated that the T onset of PLA-3JO is higher than that of neat PLA, reflecting somewhat improvement of the thermal stability of PLA by incorporation of JO. On the other hand, PLA loaded with CsNP showed slightly lower thermal stability compared to neat PLA. This is possibly related to the worse thermal stability of CsNP which adds to the thermal degradation of PLA. The results also indicated that all samples are thermally stable up to 220 o C, above about 40 o C of the temperature where the materials are processed. 3.2. Cold and melt isothermal crystallization Depending on the initial state of the occurrence of crystallization, polymer crystallization may involve mainly two types, including melt crystallization from the crystal-free melt and cold crystallization from the completely amorphous state. In this section, we compare the isothermal cold and melt crystallization of the PLA in the presence of JO and/or CsNP. The isothermal cold and melt crystallization kinetics studies of the tested samples were analyzed in the temperature range between 80 o C and 100 o C. Figures 3 a and 4 a show typical DSC traces of the neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP isothermally cold and melt crystallized at T c = 90 o C, as representative examples, respectively. These results indicated that the completion of crystallization of PLA loaded with JO or CsNP takes a short time as compared to that of neat PLA, which reflects an increment of crystallization rate of PLA matrix as the result of the presence of JO as well as CsNP. Similar Tc-dependent crystallization behavior was also observed at various crystallization temperatures and the time required for each sample to complete crystallization became shorter with increasing T c (Table 3). Compared to the cold crystallization, the melt crystallization completion takes longer time. The plots of relative crystallinity versus crystallization time for the tested samples during isothermal cold and melt crystallization processes at 90 o C are illustrated in Figs. 3 b and 4 b, respectively. $$\left(1-{X}_{t}\right)=\text{e}\text{x}\text{p}(-K{t}^{n})$$ 1 To analyze the isothermal crystallization kinetics, the Avrami equation was used following the procedure reported previously[ 46 ][ 49 , 50 ]. The Avrami equation can be written as the following: where X t is the relative degree of crystallinity, K is the crystallization rate constant depending on nucleation and growth rate, and n is the Avrami exponent depending on the nature of nucleation and growth geometry of the crystals [ 51 ]. Figure 5 presents the plots of log [-ln (1-X t )] vs. log t. The Avrami parameters of n and K were obtained by fitting the X t data between 0.05 and 0.80 and listed in Table 4 . Most correlation coefficient values are larger than 0.994, indicating good fits of the experimental data. As seen from Table 4 , the range of n values of the cold crystallization were found to be 2.02–3.52 for neat PLA, 2.21–2.75 for PLA-3JO, 2.46–3.37 for PLA-3CsNP and 2.65–3.05 for PLA-3JO-3CsNP, while the range of n values of the melt crystallization were 2.05–3.49 for neat PLA, 1.86–2.55 for PLA-3JO, 2.23–3.50 for PLA-3CsNP and 2.42–3.58 for PLA-3JO-3CsNP. For neat PLA, the n of the cold crystallization increased with increasing crystallization temperature, while decreased for melt crystallization. For PLA samples loaded with JO or/and CsNP, the n of both cold and melt crystallization decreased with increasing crystallization temperature. These values for the Avrami exponent are in accordance with that reported in the literature [ 52 – 54 ], indicating that the crystallization mechanism is a three-dimensional growth process with possibly some thermal and athermal nucleation (i.e. instantaneous and sporadic nucleation mechanisms) [ 55 ]. Considering the unit consistency, the K 1/n rather than K is adopted to compare the overall crystallization rate in the samples with different Avrami exponent n values. As shown in Table 4 , the K 1/n values of cold and melt crystallization are found to be increased in the following order: PLA-3JO > PLA-3CsNP > PLA-3JO-3Cs > PLA. An important bulk or overall crystallization kinetic parameter which can be determined directly from the experimental X t versus t data (Figs. 3 b and 4 b) is the half-time of crystallization t 1/2 , defined as the elapsed time from the onset of crystallization to the point where the crystallization is half-completed. The obtained t 1/2 values are included in Table 4 . It is apparent for each tested sample, the t 1/2 of both the cold and melt crystallization decreased with increasing T c (within the T c range studied). At a given T c , the t 1/2 values of both cold and melt crystallization are found to be decreased in the following order: PLA-3JO < PLA-3CsNP < PLA-3JO-3Cs < PLA. These results revealed that the addition of JO and/or CsNP to the neat PLA accelerated the crystallization rate. For example, at the crystallization temperature of 90 o C, the crystallization rate, which is taken as reciprocal of t 1/2 (1/t 1/2 ), are found to be 0.315, 0.532, 0.719 and 0.341 min − 1 , whereas the values are 0.059, 0.116, 0.117 and 0.082 min − 1 for the neat PLA, PLA-3CsNP, PLA-3JO and PLA-3JO-3Cs, respectively. The cold crystallization rate is approximately 5.3, 4.6, 6.2 and 4.2 times faster than of melt crystallization for neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP, respectively, suggesting that the presence of CsNP or JO has a greater impact on the crystallization ability of PLA than two components together. The faster crystallization rate of cold crystallization compared with melt crystallization may be probably due to the existing of more nuclei, which results the enhancement of crystallization rate. These results are consistent with the previous findings for other semicrystalline polymers such as poly(ethylene/trimethylene terepthalate) copolyesters [ 56 ], polypropylene [ 57 ], PLA homopolymer [ 58 , 59 ] and PLA-based polymers [ 58 ]. Table 4 Summary of the Avrami parameters and t 1/2 of cold and melt isothermal crystallization data of neat PLA and PLA-3JO, PLA-3CsNP, PLA-3JO-3CsNP. Sample Code Cold crystallization Melt crystallization PLA Tc/ o C K/min − n K 1/n /min n t 1/2 /min Tc/ o C K/min − n K 1/n /min n t 1/2 /min 80 3.39 x10 − 3 0.060 2.02 14.49 85 4.20 x10 − 6 0.029 3.49 31.08 85 2.37 x10 − 3 0.133 3.00 6.52 90 4.61 x10 − 5 0.053 3.39 16.95 90 0.0116 0.282 3.52 3.18 95 6.18 x 10 − 3 0.097 2.18 8.83 - -- -- - 100 0.015 0.127 2.05 6.67 PLA-3JO 80 0.014 0.212 2.75 3.93 85 7.50 x10 − 4 0.060 2.55 14.42 85 0.025 0.239 2.57 3.45 90 5.902 x − 3 0.095 2.18 8.64 90 0.149 0.442 2.33 1.88 95 0.033 0.155 1.83 5.15 95 0.940 0.973 2.21 0.87 100 0.044 0.187 1.86 4.20 PLA-3CsNP 80 0.013 0.172 2.46 11.90 85 1.39 x 10 − 5 0.041 3.50 21.64 85 0.011 0.175 2.60 4.85 90 2.63 x10 − 3 0.078 2.33 10.94 90 4.76 x 10 − 3 0.224 3.57 2.97 95 7.91 x 10 − 3 0.118 2.26 7.29 - -- -- - 100 0.043 0.243 2.23 3.94 PLA-3JO-3CsNP 80 2.44 x 10 − 4 0.063 3.00 14.43 85 7.69 x10 − 6 0.037 3.58 23.14 85 3.01 x 10 − 3 0.149 3.05 5.96 90 1.31 x − 3 0.072 2.52 12.27 90 0.040 0.297 2.65 2.94 95 5.42 x 10 − 3 0.126 2.52 6.90 - - 100 0.0188 0.194 2.42 4.48 Conclusion In this work PLA/CsNP composite containing 3.0% CsNP without or with 3.0% JO were prepared and characterized with their respect to mechanical tensile and thermal properties. Further, the impact of JO and CsNP on the cold and melt crystallization behavior of PLA matrix was studied. It was found that incorporation of CsNP with and without JO into PLA matrix increased the elongation at break and impact strength, while decreased the tensile strength compared with that of neat PLA. The thermal stability of the PLA/CsNP composite was less than neat PLA but thermally stable above the processing temperature. The plasticization effect of JO and nucleation effect of CsNP on the crystallization of PLA was investigated with DSC. The results showed that crystallization of PLA was enhanced in the presence of JO as well as CsNP. Both cold and melt isothermal crystallization data were analyzed by the Avrami model. The resultant Avrami exponent indicated that the cold and melt crystallization mechanism of PLA corresponded to three-dimensional spherulitic growth, and the addition of the JO as well as CsNP was not significantly influence crystallization mechanism. Therefore, JO and CsNP may be considered as a green plasticizer and CsNP an effective green nucleating agent for expanding the applications of PLA. Declarations Author Contributions All authors have read and agreed to the published version of the manuscript. All authors contributed equally in Data curation; formal analysis; investigation; methodology; validation; visualization; writing – original draft; writing – review and editing. Conflicts of Interest The authors declare no conflict of interest. References T.M. Madkour, S. Fadl, M.M. Dardir, M.A. Mekewi, High performance nature of biodegradable polymeric nanocomposites for oil-well drilling fluids, Egypt. J. Pet. 25 (2016) 281–291. https://doi.org/10.1016/j.ejpe.2015.09.004. T.P. Haider, C. Vçlker, J. Kramm, K. Landfester, F.R. Wurm, Plastics of the Future ? The Impact of Biodegradable Polymers on the Environment and on Society, Angew.Chem. Int.Ed. 58 (2019) 50–62. https://doi.org/10.1002/anie.201805766. D. Puppi, F. Chiellini, Biodegradable Polymers for Biomedical Additive Manufacturing, Appl. Mater. Today J. 20 (2020) 100700. https://doi.org/10.1016/j.apmt.2020.100700. M.C.M.C. Nandhini, L. Benny, L. George, A road map on synthetic strategies and applications of biodegradable polymers, Springer Berlin Heidelberg, 2023. https://doi.org/10.1007/s00289-022-04565-9. E.M. Elmowafy, M. Tiboni, M.E. Soliman, Biocompatibility , biodegradation and biomedical applications of poly ( lactic acid )/ poly ( lactic ‑ co ‑ glycolic acid ) micro and nanoparticles, Springer Singapore, 2019. https://doi.org/10.1007/s40005-019-00439-x. R. Zulkifli, I.N. Beas, Environmental Impact of Food Packaging Materials : A Review of Contemporary Development from Conventional Plastics to Polylactic Acid Based Materials, Materials (Basel). 13 (2020) 4994. https://doi.org/10.3390/ma13214994. H.M.H. Zakaly, E.S. Ali, Polylactic acid tungsten trioxide reinforced composites : A study of their thermal , optical , and gamma radiation attenuation performance, Radiat. Phys. Chem. 205 (2023) 110705. https://doi.org/10.1016/j.radphyschem.2022.110705. H.N.Y. Kamal, Graphene modifications in polylactic acid nanocomposites : a review, Polym. Bull. 72 (2015) 931–961. https://doi.org/10.1007/s00289-015-1308-5. M. Heydari, M. Babak, Poly ( lactic acid )‑ based bionanocomposites : effects of ZnO nanoparticles and essential oils on physicochemical properties, Polym. Bull. 79 (2022) 97–119. https://doi.org/10.1007/s00289-020-03490-z. A.A. Seraji, F. Goharpey, J.K. Yeganeh, Highly crystallized and tough polylactic acid through addition of surface modified cellulose nanocrystals, J Appl Polym Sci. 139 (2022) 52871. https://doi.org/10.1002/app.52871. L.-T. Lim, R. Auras, M. Rubino, Processing technologies for poly (lactic acid), Prog. Polym. Sci. 33 (2008) 820–852. https://doi.org/10.1016/j.progpolymsci.2008.05.004. K.M. Nampoothiri, N.R. Nair, R.P. John, An overview of the recent developments in polylactide (PLA) research, Bioresour. Technol. 101 (2010) 8493–8501. https://doi.org/10.1016/j.biortech.2010.05.092. C. Zhou, H. Li, Y. Zhang, F. Xue, S. Huang, H. Wen, J. Li, J. de Claville Christiansen, D. Yu, Z. Wu, Deformation and structure evolution of glassy poly (lactic acid) below the glass transition temperature, CrystEngComm. 17 (2015) 5651–5663. https://doi.org/10.1039/C5CE00669D. R. Csizmadia, G. Faludi, K. Renner, J. Móczó, B. Pukánszky, PLA/wood biocomposites: Improving composite strength by chemical treatment of the fibers, Compos. Part A Appl. Sci. Manuf. 53 (2013) 46–53. https://doi.org/10.1007/s10924-009-0124-0. Y. Altun, M. Doğan, E. Bayramlı, Effect of alkaline treatment and pre-impregnation on mechanical and water absorbtion properties of pine wood flour containing poly (lactic acid) based green-composites, J. Polym. Environ. 21 (2013) 850–856. https://doi.org/10.1007/s10924-012-0563-x. R. Patwa, M. Singh, A. Kumar, V. Katiyar, Kinetic modelling of thermal degradation and non-isothermal crystallization of silk nano-discs reinforced poly (lactic acid) bionanocomposites, Springer Berlin Heidelberg, 2019. https://doi.org/10.1007/s00289-018-2434-7. O. Paper, Thermal and mechanical properties of poly ( lactic acid ) filled with modified silicon dioxide : importance of the surface area, Polmer Bull. 79 (2022) 1409–1435. https://doi.org/10.1007/s00289-021-03571-7. Y. Ren, L. Huang, Y. Wang, L. Mei, R. Fan, M. He, C. Wang, A. Tong, H. Chen, G. Guo, Stereocomplexed electrospun nanofibers containing poly ( lactic acid ) modified quaternized chitosan for wound healing, Carbohydr. Polym. 247 (2020) 116754. https://doi.org/10.1016/j.carbpol.2020.116754. S.A.M. Issa, A.W. Alrowaily, D.E. Abulyazied, E.S. Ali, H.M.H. Zakaly, Effects of WO 3 reinforcement on the properties of poly ( lactic acid ) composites for radiation shielding, Radiat. Phys. Chem. 212 (2023) 111121. https://doi.org/10.1016/j.radphyschem.2023.111121. M. Reza, K. Chantara, T. Ratnam, Mechanical properties of polylactic acid / synthetic rubber blend reinforced with cellulose nanoparticles isolated from kenaf fibres, Polym. Bull. 75 (2018) 809–827. https://doi.org/10.1007/s00289-017-2061-8. E. Piorkowska, Z. Kulinski, A. Galeski, R. Masirek, Plasticization of semicrystalline poly (L-lactide) with poly (propylene glycol), Polymer (Guildf). 47 (2006) 7178–7188. https://doi.org/10.1016/j.polymer.2006.03.115. M. Murariu, A. Da Silva Ferreira, M. Alexandre, P. Dubois, Polylactide (PLA) designed with desired end‐use properties: 1. PLA compositions with low molecular weight ester‐like plasticizers and related performances, Polym. Adv. Technol. 19 (2008) 636–646. https://doi.org/10.1002/pat.1131. F. Hassouna, J.-M. Raquez, F. Addiego, P. Dubois, V. Toniazzo, D. Ruch, New approach on the development of plasticized polylactide (PLA): Grafting of poly (ethylene glycol)(PEG) via reactive extrusion, Eur. Polym. J. 47 (2011) 2134–2144. https://doi.org/10.1016/j.eurpolymj.2011.08.001. M.G.A. Vieira, M.A. da Silva, L.O. dos Santos, M.M. Beppu, Natural-based plasticizers and biopolymer films: A review, Eur. Polym. J. 47 (2011) 254–263. https://doi.org/10.1016/j.eurpolymj.2010.12.011. F. Ali, Y.-W. Chang, S.C. Kang, J.Y. Yoon, Thermal, mechanical and rheological properties of poly (lactic acid)/epoxidized soybean oil blends, Polym. Bull. 62 (2009) 91–98. https://doi.org/10.1007/s00289-008-1012-9. D. Li, Y. Jiang, S. Lv, X. Liu, J. Gu, Q. Chen, Y. Zhang, Preparation of plasticized poly (lactic acid) and its influence on the properties of composite materials, PLoS One. 13 (2018) 1–15. https://doi.org/10.1371/journal.pone.0193520. M.P. Arrieta, Influence of plasticizers on the compostability of polylactic acid, J. Appl. Res. Technol. Eng. 2 (2021) 1–9. https://doi.org/10.4995/jarte.2021.14772. M.A. Elsawy, J. Declaville, C. Sanporean, Investigation of Jojoba Oil-wax as a Plasticizer for Poly (lactic acid), J. Optoelectron. Adv. Mater. 8 (2014) 109–114. A.M. Motawie, K.F. Mahmoud, A.A. El-Sawy, H.M. Kamal, H. Hefni, H.A. Ibrahiem, Preparation of chitosan from the shrimp shells and its application for pre-concentration of uranium after cross-linking with epichlorohydrin, Egypt. J. Pet. 23 (2014) 221–228. https://doi.org/10.1016/j.ejpe.2014.05.009. C. Ke, F. Deng, C. Chuang, C. Lin, Antimicrobial Actions and Applications of Chitosan, Polymers (Basel). 13 (2021) 904. https://doi.org/10.3390/polym13060904. Y. Qin, P. Li, Z. Guo, Cationic chitosan derivatives as potential antifungals : A review of structural optimization and applications, Carbohydr. Polym. 236 (2020) 116002. https://doi.org/10.1016/j.carbpol.2020.116002. M.F. Abou, T. Abdullah, Radiation synthesis and characterization of sodium alginate/chitosan/hydroxyapatite nanocomposite hydrogels: a drug delivery system for liver cancer, Polym. Bull. 72 (2015) 725–742. https://doi.org/10.1007/s00289-015-1301-z. T. López-León, E.L.S. Carvalho, B. Seijo, J.L. Ortega-Vinuesa, D. Bastos-González, Physicochemical characterization of chitosan nanoparticles: electrokinetic and stability behavior, J. Colloid Interface Sci. 283 (2005) 344–351. https://doi.org/10.1016/j.jcis.2004.08.186. N. Sawtarie, Y. Cai, Y. Lapitsky, Colloids and Surfaces B : Biointerfaces Preparation of chitosan / tripolyphosphate nanoparticles with highly tunable size and low polydispersity, Colloids Surfaces B Biointerfaces. 157 (2017) 110–117. https://doi.org/10.1016/j.colsurfb.2017.05.055. M. Carolina, D. Santo, C. Luciana, D. Antoni, A. Paula, D. Rubio, A. Alaimo, O.E. P, Biomedicine & Pharmacotherapy Chitosan-tripolyphosphate nanoparticles designed to encapsulate polyphenolic compounds for biomedical and pharmaceutical applications − A review, Biomed. Pharmacother. 142 (2021) 111970. https://doi.org/10.1016/j.biopha.2021.111970. S. Mahtab, H. Saeedeh, M. Majid, Designing chitosan nanoparticles embedded into graphene oxide as a drug delivery system, Polym. Bull. 79 (2022) 541–554. https://doi.org/10.1007/s00289-020-03506-8. M.L.I. Montes, D.A.D.L.B. Manfredi, Effect of Natural Glyceryl Tributyrate as Plasticizer and Compatibilizer on the Performance of Bio-Based Polylactic Acid / poly ( 3- hydroxybutyrate ) Blends, J. Polym. Environ. 27 (2019) 1429–1438. https://doi.org/10.1007/s10924-019-01425-y. N.D. Bikiaris, I. Koumentakou, C. Samiotaki, D. Meimaroglou, D. Varytimidou, A. Karatza, Z. Kalantzis, M. Roussou, R.D. Bikiaris, G.Z. Papageorgiou, Recent Advances in the Investigation of Poly ( lactic acid ) ( PLA ) Nanocomposites : Incorporation of Various Nanofillers and their Properties and Applications, Polymers (Basel). 15 (2023) 1196. https://doi.org/10.3390/polym15051196. M.A. Elsawy, M. Fekry, A.M. Sayed, N.A. Maziad, G.R. Saad, Physico-chemical Characteristics of Biodegradable Poly(lactic acid) and Poly(lactic acid)/Chitosan Nano-Composites Under the Influence of Gamma Irradiation, J. Polym. Environ. 31 (2023) 2705–2714. https://doi.org/10.1007/s10924-022-02693-x. M.A. Elsawy, G.R. Saad, A.M. Sayed, Mechanical, thermal, and dielectric properties of poly(lactic acid)/chitosan nanocomposites, Polym. Eng. Sci. 56 (2016) 987–994. https://doi.org/10.1002/pen.24328. J.M.Q.D.E. Rodríguez-félix, J.C. Encinas-encinas, L.L. Lizárraga-laborín, Extrusion of polypropylene / chitosan / poly ( lactic-acid ) films : Chemical , mechanical , and thermal properties, J Appl Polym Sci. 138 (2021) 49850. https://doi.org/10.1002/app.49850. G.R. Saad, M.A. Elsawy, M.S.A. Aziz, Nonisothermal crystallization behavior and molecular dynamics of poly(lactic acid) plasticized with jojoba oil, J. Therm. Anal. Calorim. 128 (2017). https://doi.org/10.1007/s10973-016-5910-z. M.A. Elsawy, G.R. Saad, A.M. Sayed, N. City, Mechanical , Thermal , and Dielectric Properties of Poly (lactic acid)/ Chitosan Nanocomposites, Polym. Eng. Sci. 56 (2016) 987–994. https://doi.org/10.1002/pen. N. Helya, I. Kamaludin, H. Ismail, A. Rusli, S. Sung, Thermal behavior and water absorption kinetics of polylactic acid / chitosan biocomposites, Iran. Polym. J. 30 (2021) 135–147. https://doi.org/10.1007/s13726-020-00879-5. E. Altuntas, D. Aydemir, Effects Of Wood Flour On The Mechanical , Thermal And Morfphological Properties Of Poly (L-Lactic Acid) -Chitosan Biopolymer Composites, Maderas. Cienc. Y Tecnol. 21 (2019) 611–618. https://doi.org/10.4067/S0718-221X2019005000416. D. Grenier, P. Homme, Avrami analysis: three experimental limiting factors, J. Polym. Sci. Polym. Phys. Ed. 18 (1980) 1655–1657. G.R. Saad, M.A. Elsawy, M.S. Abdel, Nonisothermal crystallization behavior and molecular dynamics of poly (lactic acid) plasticized with jojoba oil, J. Therm. Anal. Calorim. 128 (2017) 211–223. https://doi.org/10.1007/s10973-016-5910-z. A.M. Harris, E.C. Lee, Improving mechanical performance of injection molded PLA by controlling crystallinity, J. Appl. Polym. Sci. 107 (2008) 2246–2255. M. Avrami, Transformation-time relations for random distribution of nuclei, J. Chem. Phys. 8 (1940) 212–224. https://doi.org/10.1002/pol.1980.180180715. M. Avrami, Kinetics of phase change. III. Granulation, phase change, and microstructure, J. Chem. Phys. 9 (1941) 117–184. G.P. Balamurugan, S.N. Maiti, Nonisothermal crystallization kinetics of polyamide 6 and ethylene‐co‐butyl acrylate blends, J. Appl. Polym. Sci. 107 (2008) 2414–2435. https://doi.org/10.1002/app.27377. J.F. Mano, Y. Wang, J.C. Viana, Z. Denchev, M.J. Oliveira, Cold crystallization of PLLA studied by simultaneous SAXS and WAXS, Macromol. Mater. Eng. 289 (2004) 910–915. https://doi.org/10.1002/mame.200400097. S. Iannace, L. Nicolais, Isothermal crystallization and chain mobility of poly (L‐lactide), J. Appl. Polym. Sci. 64 (1997) 911–919. https://doi.org/10.1002/(SICI)1097-4628(19970502)64:53.0.CO;2-W. Y. Xu, W. Zhang, Y. Qiu, M. Xu, B. Li, L. Liu, Preparation and mechanism study of a high efficiency bio-based flame retardant for simultaneously enhancing flame retardancy, toughness and crystallization rate of poly (lactic acid), Compos. Part B Eng. 238 (2022) 109913. https://doi.org/10.1016/j.compositesb.2022.109913. B. Wunderlich, Thermal characterization of polymeric materials, New York: Academic Press, 1997. T.-W. Shyr, C.-H. Tung, W.-S. Cheng, C.-C. Yang, The crystallization rate and morphological structure of poly (ethylene/trimethylene terephthlate) copolyesters under isothermal melt-crystallization and cold-crystallization, J. Polym. Res. 20 (2013) 1–10. https://doi.org/10.1007/s10965-013-0186-5. P. Supaphol, J.E. Spruiell, Isothermal melt-and cold-crystallization kinetics and subsequent melting behavior in syndiotactic polypropylene: a differential scanning calorimetry study, Polymer (Guildf). 42 (2001) 699–712. https://doi.org/10.1016/S0032-3861(00)00399-2. T. Tábi, I.E. Sajó, F. Szabó, A.S. Luyt, J.G. Kovács, Crystalline structure of annealed polylactic acid and its relation to processing, Express Polym. Lett. 4 (2010) 659–668. https://doi.org/10.3144/expresspolymlett.2010.80. P. Badrinarayanan, K.B. Dowdy, M.R. Kessler, A comparison of crystallization behavior for melt and cold crystallized poly (l-Lactide) using rapid scanning rate calorimetry, Polymer (Guildf). 51 (2010) 4611–4618. https://doi.org/10.1016/j.polymer.2010.08.014. Table 3 Table 3 is not available with this version Additional Declarations No competing interests reported. Supplementary Files Supplementaryinformation.docx Cite Share Download PDF Status: Posted Version 1 posted 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. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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-4009522","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":276158861,"identity":"3931b5f7-bbf6-45e5-8799-5f62db829c4d","order_by":0,"name":"Moataz A. Elsawy","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA00lEQVRIiWNgGAWjYPACGyBmbAASEkQpBylNI13LYRJcpNve/PzBjz/n5cylDzcw/qixYODnX4Bfi9mZY4aNPTy3jS37EhuYeY5JMEjOeEBAy40EwwYeiduJG84wNjAzNkgwGNw4QEhL+sfGPwbn6kFaGH8CtdgT1pJj2MyTcCDBAKiFgRdkC38DIb+cKZwtcyDZcGcPY8NhoF94JG7g18Fgdrx9w8c3f+zkzXnYHz78UVMnx99PwGFwYADEILU8DBIJJGiBAH5ibRkFo2AUjIKRAgBnAkUQIKFN/AAAAABJRU5ErkJggg==","orcid":"","institution":"Egyptian Petroleum Research Institute","correspondingAuthor":true,"prefix":"","firstName":"Moataz","middleName":"A.","lastName":"Elsawy","suffix":""},{"id":276158862,"identity":"ea677d91-0bf7-415f-aba9-379810e38401","order_by":1,"name":"E. S. Ali","email":"","orcid":"","institution":"Egyptian Petroleum Research Institute","correspondingAuthor":false,"prefix":"","firstName":"E.","middleName":"S.","lastName":"Ali","suffix":""},{"id":276158863,"identity":"4478463c-93e2-4418-b950-87be2a57a6c1","order_by":2,"name":"Jesper Claville Chritiansen","email":"","orcid":"","institution":"Aalborg University","correspondingAuthor":false,"prefix":"","firstName":"Jesper","middleName":"Claville","lastName":"Chritiansen","suffix":""},{"id":276158864,"identity":"7d7b10f0-8781-4e0c-8363-03808e3a9ef0","order_by":3,"name":"Gamal. R. Saad","email":"","orcid":"","institution":"Cairo University","correspondingAuthor":false,"prefix":"","firstName":"Gamal.","middleName":"R.","lastName":"Saad","suffix":""}],"badges":[],"createdAt":"2024-03-03 19:18:10","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4009522/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4009522/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":52043732,"identity":"06bbbfec-9402-4d19-85be-a407afc45019","added_by":"auto","created_at":"2024-03-05 19:02:47","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":9321,"visible":true,"origin":"","legend":"\u003cp\u003eHeating DSC thermograms of neat PLA and PLA-3JO and PLA-3CsNP and PLA-3JO-3CsNP.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4009522/v1/510c6572e2f7022fe74ad5bb.png"},{"id":52043730,"identity":"67a6fbc6-3f62-43d6-b0e2-0d03efe9c432","added_by":"auto","created_at":"2024-03-05 19:02:47","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":9102,"visible":true,"origin":"","legend":"\u003cp\u003eTGA curves of neat PLA, PLA-3JO, and PLA-3CsNP and PLA-3JO-3CsNP at a heating rate 10\u003csup\u003eo\u003c/sup\u003eC min\u003csup\u003e-1\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4009522/v1/4cc7743fb582324080eab921.png"},{"id":52043733,"identity":"25be1ff9-be3b-4345-85ca-f5369cc54800","added_by":"auto","created_at":"2024-03-05 19:02:48","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":21316,"visible":true,"origin":"","legend":"\u003cp\u003eIsothermal cold crystallization (a) and the relative crystallinity (b) for neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP at T\u003csub\u003ec\u003c/sub\u003e=90 \u003csup\u003eo\u003c/sup\u003eC.\u0026nbsp;\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4009522/v1/712a3582c0a168b2241f1cd6.png"},{"id":52043734,"identity":"d67549e4-899b-400f-9957-720ca23f781b","added_by":"auto","created_at":"2024-03-05 19:02:48","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":20855,"visible":true,"origin":"","legend":"\u003cp\u003eIsothermal melt crystallization (a) and the relative crystallinity (b) for neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP at T\u003csub\u003ec\u003c/sub\u003e=90 \u003csup\u003eo\u003c/sup\u003eC.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4009522/v1/b382ae76004376cfa708c78e.png"},{"id":52043731,"identity":"ab391935-2f8f-4dec-b5d8-2f9139d4bf5a","added_by":"auto","created_at":"2024-03-05 19:02:47","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":17253,"visible":true,"origin":"","legend":"\u003cp\u003eAvrami plots for cold crystallization (a) and melt crystallization (b) for neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-4009522/v1/38635c545f6716b847269c2f.png"},{"id":52412983,"identity":"dbd460cd-b46e-45c5-9c22-d847910794b1","added_by":"auto","created_at":"2024-03-11 10:27:30","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":447236,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4009522/v1/c0b7f6da-16a9-4a9a-9c07-c6dbceb0ad63.pdf"},{"id":52043737,"identity":"dac1a02d-110d-4809-95fa-839d286e8fd4","added_by":"auto","created_at":"2024-03-05 19:02:49","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":132003,"visible":true,"origin":"","legend":"","description":"","filename":"Supplementaryinformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-4009522/v1/1c0d9ad2d05ad956328f14f2.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Unveiling the Potential of Chitosan Nanoparticles and Jojoba Oil for Optimizing Poly(lactic acid) Characteristics: Insights into Physico-chemical Attributes and Crystallization Mechanisms","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eBiodegradable polymers have received great attention from both ecological and biomedical perspectives [\u003cspan additionalcitationids=\"CR2 CR3\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. Among them, poly(lactic acid) (PLA) is one of the most promising materials, which is used as biomaterials for medical applications and food packaging due to its renewable resources, availability, relative good strength, biocompatibility and biodegradability [\u003cspan additionalcitationids=\"CR6 CR7 CR8\" citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. However, PLA also has some drawbacks, such as its inherent brittleness, low impact resistance and moderate gas barrier properties[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. PLA also presents a relatively low crystallization rate and is prone to aging at room temperature, aspects which are important from an industrial point of view [\u003cspan additionalcitationids=\"CR12\" citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. Therefore, many approaches have been carried out in order to overcome some of its drawbacks, including blending/compounding with other polymers, plasticizers, reinforcing materials in micro (e.g., natural fibers) and nano size green fillers (cellulose and chitin nanowiskers) to broad its application [\u003cspan additionalcitationids=\"CR15 CR16\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. These fillers have shown to be able to improve the properties of PLA by affecting the crystallinity, mechanical properties and thermal properties. In addition, the prepared composites have the advantage of being lightweight, renewable, and biodegradable. The positive impact of using natural nano-fillers as reinforcement material in nanocomposites provides several benefits, including complete biodegradability, low density, comparatively low cost, and improved mechanical properties [\u003cspan additionalcitationids=\"CR19\" citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eOn the other hand, various low molecular weight compounds have been investigated as potential plasticizers for PLA [\u003cspan additionalcitationids=\"CR22 CR23 CR24\" citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. The role of the plasticizer is to reduce the modulus of elasticity in PLA, and it is of great importance that the plasticizer be compatible with the polymer in order to be evenly distributed in its matrix [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. The mechanical properties of the PLA plasticized with jojoba oil (JO) was studied by Elsawy et al. [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e] and the results showed an improvement of the elongation and Izod impact strength.\u003c/p\u003e \u003cp\u003eChitosan is a natural polymer derived from chitin which arouses a lot of interest because of its biodegradability, biocompatibility and its bacteriostatic and fungistatic properties [\u003cspan additionalcitationids=\"CR30 CR31\" citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. Chitosan nanoparticles (CsNP) can be obtained by ionic gelation, where the positively charged amino groups of chitosan form electrostatic interactions with polyanions employed as cross-linkers, such as tripolyphosphate [\u003cspan additionalcitationids=\"CR34 CR35\" citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIt is well known that the morphology of semi-crystalline polymers, which is in turn determined by the crystallization process, determines the mechanical and physical properties of semi-crystalline polymers. Thus, the crystallization behavior affects the characteristics of semi-crystalline polymers like PLA. In comparison to neat PLA, the addition of nanofillers and plasticizers alter the mechanical and thermal properties via influencing the crystallization behavior [\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e, \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]. Therefore, study on the crystallization behavior and morphology of polymer is useful to understand their effect on the properties.\u003c/p\u003e \u003cp\u003eIn our previous work [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e], a considerable improvement of the elongation and impact strength of PLA was reported by addition of 3.0 wt% JO, as a plasticizer. Also, the incorporation of the chitosan nanoparticles (CsNP) into PLA matrix have proven to be promising green nano-filler for the improvement of mechanical and thermal properties of PLA [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. Thus, the aim of the use of CsNP as a reinforcement agent and JO as a plasticizer for PLA is to create new, effective nano-biocomposites with improved properties while of these additives preserving their environmental attributes. The goal of this work is to investigate the influence of the addition of both CsNP and JO on the thermal, mechanical properties and isothermal cold and melt crystallization behavior of PLA. The PLA/CsNP, PLA/JO and PLA/CsNP/JO were prepared using melt extrusion technique. Next, the kinetics of isothermal crystallization was modeled applying Avrami model.\u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Materials\u003c/h2\u003e \u003cp\u003eThe PLA polymer (Ingeo\u0026trade;3001D) was purchased from NatureWorks\u0026reg; LLC (Minnetonka, USA) and PLA granules were dried in vacuum oven for 2 h at 100\u0026deg;C before use. Chitosan nano-particles (CN001) (\u0026ge;\u0026thinsp;96% deacetylated) of particle size 200 nm were purchased from G.T.C Bio Corporation company (Hongkong, China). The chitosan nano-particles (CsNP) was dried in vacuum oven for 24 h at 60\u0026deg;C. Jojoba oil, a commercial grade, was purchased from Egyptian Natural Oil Company NATOIL (Cairo, Egypt) and used as received.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Samples preparation\u003c/h2\u003e \u003cp\u003ePLA compounds containing 3.0 w/w CsNP without and with 3.0 w/w JO were prepared using a Prism Eurolab 16 co-rotating twin-screw extruder from Thermo Scientific with a strong configuration of the screws having 3 mixing zones with 90 degrees spaced mixing disks as part of the zone. First, predetermine weight of CsNP was homogeneously dispersed in dry acetone using ultrasonic homogenizer for 20 minutes, and then the dispersed CsNP were sprayed over PLA pellets. The coated PLA pellets with CsNP were dried at 60\u003csup\u003eo\u003c/sup\u003eC in oven for 5 min to remove the residual acetone and then feed with predetermine weight of JO in the extruder with temperature profile ranged from 170 to 180\u003csup\u003eo\u003c/sup\u003eC for 3 min in order to prevent the degradation of PLA/ CsNP nanocomposites. Samples of neat PLA and PLA/JO were processed in exactly the same way for comparison purposes. PLA with 3.0 wt% JO designed as PLA-3JO. Nanocomposites with 3.0% CsNP in the absence of Jojoba oil and in the presence of 3.0% Jojoba are deigned here as PLA-3CsNP and PLA-3JO-3CsNP, respectively.\u003c/p\u003e \u003cp\u003eAll materials were molded into dog bones with dimensions of 50 \u0026times; 4 \u0026times; 2 mm using a piston type Haake minijet injection moulding machine from Thermo Scientific. The specimens were obtained using an injection pressure set to 800 bar, a melting temperature of 180\u0026deg;C, a post pressure of 650 bar and the temperature of the mould was set to 25\u0026deg;C.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Characterization\u003c/h2\u003e \u003cdiv id=\"Sec6\" class=\"Section3\"\u003e \u003ch2\u003e2.3.1. Differential Scanning Calorimetry\u003c/h2\u003e \u003cp\u003eDifferential scanning calorimetry (DSC) of the all material was performed using DSC Q2000 instrument. The samples were cut into small pieces and the sample's weights were maintained at low levels (5\u0026ndash;7 mg) for all measurements in order to minimize any possible thermal lag during the scans. To remove the thermal history, the sample was heated from 25\u0026deg;C to 180\u003csup\u003eo\u003c/sup\u003eC and cooled rapidly at a rate of 40\u003csup\u003eo\u003c/sup\u003eC to 20\u0026deg;C and then reheated up to 180\u0026deg;C at a heating rate 10\u0026deg;C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e under nitrogen atmosphere (30 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). The glass transition temperature (T\u003csub\u003eg\u003c/sub\u003e), cold crystallization temperature (T\u003csub\u003ecc\u003c/sub\u003e), cold crystallization enthalpy (ΔH\u003csub\u003ecc\u003c/sub\u003e), melting temperature (T\u003csub\u003em\u003c/sub\u003e) and the melting enthalpy (ΔH\u003csub\u003em\u003c/sub\u003e) of the prepared materials were determined from these heating scans.\u003c/p\u003e \u003cp\u003eTo study the kinetics of isothermal cold-crystallization behavior (from glassy state) in the different crystallization temperatures, all the specimens were first heated at a heating rate 60\u003csup\u003eo\u003c/sup\u003eC min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to 180\u003csup\u003eo\u003c/sup\u003eC and held there for 3 min, to erase any thermal history, and cooled at 60\u003csup\u003eo\u003c/sup\u003eC min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to 20\u003csup\u003eo\u003c/sup\u003eC to obtain wholly amorphous glassy sample and subsequently reheated at the same rate to the desired crystallization temperature (T\u003csub\u003ec\u003c/sub\u003e) and held until the crystallization completed. For melt isothermal crystallization, a fresh sample was initially melted at 180\u003csup\u003eo\u003c/sup\u003eC for 3 min and then cooled to the predetermined crystallization temperatures and maintained for the time necessary for isothermal crystallization at these temperatures. The exothermal curves of heat flow of both cold and melt crystallization as function of time were recorded.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section3\"\u003e \u003ch2\u003e2.3.2. Thermogravimetric Analysis\u003c/h2\u003e \u003cp\u003eThe thermogravimetric analysis (TG) was performed on a Jupiter STA 449 F1-Netzsch instrument. Samples of 6.5 mg were heated from room temperature up to 600\u0026deg;C, with a heating rate of 10\u0026deg;C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, in an open platinum crucible, under 50 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e nitrogen flow.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section3\"\u003e \u003ch2\u003e2.3.3. Mechanical Analysis\u003c/h2\u003e \u003cp\u003eThe tensile properties were determined using Universal tensile machine \u0026ndash;INSTRON 5944 with a load cell of 2 kN. Five specimens from each material were tested according to the ISO-527\u0026minus;2 tensile test procedure. The measurements were done at room temperature with a crosshead speed of 50 mm min\u003csup\u003e\u0026minus;1\u003c/sup\u003e and at least five samples were tested.\u003c/p\u003e \u003cp\u003eIzod impact tests were performed on an Instron CEAST 9050 impact tester equipped with a DAS 8000 Junior data-acquisition system, with a sample frequency of 1000 kHz and a 50 J instrumented hammer. Specimens with dimensions of 80\u0026times;10\u0026times;3 mm were molded on the Haake minijet as described previously. Impact tests were carried out at room temperature and a minimum of 5 specimens were tested for each material.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section3\"\u003e \u003ch2\u003e2.3.4. Wide Angle X-ray Diffractometry (WAXD)\u003c/h2\u003e \u003cp\u003eWAXD measurements were recorded using a Rikagu diffractometer (Cu radiation, λ\u0026thinsp;=\u0026thinsp;0.1546 nm) running at 40 kV and 40 mA. The scan angles range of 2θ was from 5 to 40\u0026deg; at scanning rate 3\u003csup\u003eo\u003c/sup\u003e min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section3\"\u003e \u003ch2\u003e2.3.5. Morphology\u003c/h2\u003e \u003cp\u003eJEOL (JSM-5200) scanning electron microscope was used to examine the dispersion of chitosan nanoparticles in the PLA matrix. The extrude materials were fractured and their surfaces were sputter coated with gold prior to examination.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Physicochemical characterization of the tested samples\u003c/h2\u003e \u003cp\u003eThe micrographs obtained by SEM for the tested samples are given in the supplementary information (S1). The plasticized PLA (PLA-3JO) showed smooth surface with almost no distinct interface, indicating a good adhesion between PLA and JO. PLA/CsNP composite showed that CsNP particles are relatively well dispersed in the PLA matrix and the dispersion of CsNP was slightly improved by the presence of JO.\u003c/p\u003e \u003cp\u003eThe XRD of the neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP films (S2) displayed that the diffraction peaks characteristics of PLA insignificantly changed by the presence of Jojoba and/or CsNT, suggesting that CsNP and/or JO did not change the crystal structure of PLA [\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe stress–strain curves of the processed neat PLA, PLA-3CsNP, PLA-3JO, and PLA-3JO-3CsNP are shown in S3 and the reported results derived from these curves are summarized in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. It was found that the elongation and tensile strength (stress) at break of neat PLA were 3.3%±0.2% and 74.1±2.9 MPa, respectively, which was in accordance with literature reported previously [\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e]. The incorporation of 3.0% JO into PLA matrix caused a reduction in the tensile strength and an increase of elongation at break, which were found to be 35.5±0.7 MPa and 42.2±2.1%, respectively. Incorporation of 3.0% CsNP into PLA leads to an increase in the modulus and elongation and a reduction of the tensile strength of PLA[\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e]. Blending PLA with and 3.0% CsNP and 3.0% JO increased the tensile modulus, while lowered the tensile strength compared with PLA loaded with JO or CsNP alone. On the other hand, the elongation is comparable to PLA loaded with 3.0 JO and greater than PLA loaded with 3.0% CsNP. The impact strength increases in the following order: PLA-3JO \u0026gt; PLA-3CsNP \u0026gt; PLA-3JO-3CsNP \u0026gt; PLA. Therefore, it can be concluded that the tested samples exhibited somewhat good mechanical properties, particularly, tensile modulus, elongation and impact strength compared with neat PLA.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e\u003cdiv class=\"gridtable\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\"±\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\"±\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\"±\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\"±\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eMechanical properties of neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e\u003ccolgroup cols=\"5\"\u003e\u003c/colgroup\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample code\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTensile modulus (GPa)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eTensile strength at break (MPa)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eElongation at break (%)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eImpact strength (kJm\u003csup\u003e− 2\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePLA\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c2\"\u003e \u003cp\u003e3.51±0.10\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c3\"\u003e \u003cp\u003e74.1±2.9\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c4\"\u003e \u003cp\u003e3.3±0.2\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c5\"\u003e \u003cp\u003e13.1±0.6\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePLA-3JO\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c2\"\u003e \u003cp\u003e3.49±0.81\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c3\"\u003e \u003cp\u003e35.2±0.6\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c4\"\u003e \u003cp\u003e42.2±0.8\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c5\"\u003e \u003cp\u003e21.3±0.8\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePLA-3CsNP\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c2\"\u003e \u003cp\u003e3.66±0.07\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c3\"\u003e \u003cp\u003e53.5±1.0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c4\"\u003e \u003cp\u003e7.76±.0.2\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c5\"\u003e \u003cp\u003e17.1±1.5\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePLA-3JO-3CsNP\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c2\"\u003e \u003cp\u003e3.84±0.21\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c3\"\u003e \u003cp\u003e28.8±1.1\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c4\"\u003e \u003cp\u003e39.9±0.7\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\"±\" colname=\"c5\"\u003e \u003cp\u003e16.7±1.4\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\u003c/div\u003e \u003cp\u003e\u003c/p\u003e \u003cp\u003eThe effect of blending PLA with 3.0% JO and 3.0% CsNP on the thermal transitions of PLA matrix (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) can be compared with the results from our previous study [\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e, \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e], where PLA was blended with 3.0% JO and 3.0% CsNP alone. It can be seen that the presence of JO slightly reduced T\u003csub\u003eg\u003c/sub\u003e value of PLA, reflecting an enhancement of segmental mobility of the PLA chains promoted by plasticization effect of JO. This T\u003csub\u003eg\u003c/sub\u003e reduction enables crystallization to start at an earlier temperature upon heating, where the cold crystallization transition (T\u003csub\u003ecc\u003c/sub\u003e) of the plasticized PLA was declined by 6.0\u003csup\u003eo\u003c/sup\u003eC compared with neat PLA. On the other hand, presence of CsNP has no pronounced effect on T\u003csub\u003eg\u003c/sub\u003e and cold crystallization temperature of PLA matrix, indicating a limit nucleating effect of CsNP on the non-isothermal cold crystallization of PLA matrix. The T\u003csub\u003ecc\u003c/sub\u003e value of the PLA modified by the combination of JO and CsNP slightly shifts toward lower temperature compared with neat PLA. The T\u003csub\u003ecc\u003c/sub\u003e was decreased with about 3.6\u003csup\u003eo\u003c/sup\u003eC which lies between PLA blended with 3.0% JO and 3.0% CsNP, suggesting that the combination of the Jojoba and CsNP has no significant synergistic effect on the promotion of the cold crystallization ability of PLA. A double melting is observed in all tested samples that could be related to the formation of different crystal structures or to lamellar populations with different perfection degrees. A similar thermal behavior can be observed for other PLA systems [\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e, \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e]. From the determined enthalpy of melting (ΔH\u003csub\u003em\u003c/sub\u003e), the degree of crystallinity (χ\u003csub\u003ec\u003c/sub\u003e) was calculated by considering the melting enthalpy of 100% crystalline PLA as 93 J/g [\u003cspan additionalcitationids=\"CR47\" citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e–\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e]. The data of the χ\u003csub\u003ec\u003c/sub\u003e of the tested samples are summarized in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e showed that the extent of crystallinity of the PLA is not significantly affected by the presence of JO or/and CsNP.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e\u003cdiv class=\"gridtable\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eThe DSC and TG data for neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e\u003ccolgroup cols=\"9\"\u003e\u003c/colgroup\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample code\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eT\u003csub\u003eg\u003c/sub\u003e (\u003csup\u003eo\u003c/sup\u003eC)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eT\u003csub\u003ecc\u003c/sub\u003e (\u003csup\u003eo\u003c/sup\u003eC)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eΔH\u003csub\u003ecc\u003c/sub\u003e (Jg\u003csup\u003e− 1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eT\u003csub\u003em\u003c/sub\u003e (\u003csup\u003eo\u003c/sup\u003eC)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eΔH\u003csub\u003em\u003c/sub\u003e (Jg\u003csup\u003e− 1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eχ\u003csub\u003ec\u003c/sub\u003e (%)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eT\u003csub\u003eonset\u003c/sub\u003e \u003csup\u003eo\u003c/sup\u003eC\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c9\"\u003e \u003cp\u003eT\u003csub\u003emax\u003c/sub\u003e (\u003csup\u003eo\u003c/sup\u003eC)\u003c/p\u003e \u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePLA\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e61.5\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e108.7\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e32.6\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e170.0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.8\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e41.7\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e337\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e371\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePLA-3JO\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e57.1\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e102.7\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e30.0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e168.7\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e40.8\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e45.2\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e342\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e372\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePLA-3CsNP\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e62.3\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e110.7\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e32.1\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e169.5\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e38.6\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e42.4\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e330\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e372\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePLA-3JO-3CsNP\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e62.1\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e105.1\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e28.2\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e168.6\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e34.8\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e40.2\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c8\"\u003e \u003cp\u003e331\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c9\"\u003e \u003cp\u003e365\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\u003c/div\u003e \u003cp\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe temperature for the onset of thermal decomposition (T\u003csub\u003eonset\u003c/sub\u003e), the temperature at which decomposition rate is maximum (T\u003csub\u003em\u003c/sub\u003e) and were determined from TGA thermograms (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) of the tested samples, and the data included in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Comparison of the investigated samples indicated that the T\u003csub\u003eonset\u003c/sub\u003e of PLA-3JO is higher than that of neat PLA, reflecting somewhat improvement of the thermal stability of PLA by incorporation of JO. On the other hand, PLA loaded with CsNP showed slightly lower thermal stability compared to neat PLA. This is possibly related to the worse thermal stability of CsNP which adds to the thermal degradation of PLA. The results also indicated that all samples are thermally stable up to 220\u003csup\u003eo\u003c/sup\u003eC, above about 40\u003csup\u003eo\u003c/sup\u003eC of the temperature where the materials are processed.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003e3.2. Cold and melt isothermal crystallization\u003c/h2\u003e \u003cp\u003eDepending on the initial state of the occurrence of crystallization, polymer crystallization may involve mainly two types, including melt crystallization from the crystal-free melt and cold crystallization from the completely amorphous state. In this section, we compare the isothermal cold and melt crystallization of the PLA in the presence of JO and/or CsNP. The isothermal cold and melt crystallization kinetics studies of the tested samples were analyzed in the temperature range between 80\u003csup\u003eo\u003c/sup\u003eC and 100\u003csup\u003eo\u003c/sup\u003eC. Figures\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea and \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea show typical DSC traces of the neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP isothermally cold and melt crystallized at T\u003csub\u003ec\u003c/sub\u003e = 90\u003csup\u003eo\u003c/sup\u003eC, as representative examples, respectively. These results indicated that the completion of crystallization of PLA loaded with JO or CsNP takes a short time as compared to that of neat PLA, which reflects an increment of crystallization rate of PLA matrix as the result of the presence of JO as well as CsNP. Similar Tc-dependent crystallization behavior was also observed at various crystallization temperatures and the time required for each sample to complete crystallization became shorter with increasing T\u003csub\u003ec\u003c/sub\u003e (Table\u0026nbsp;3). Compared to the cold crystallization, the melt crystallization completion takes longer time. The plots of relative crystallinity versus crystallization time for the tested samples during isothermal cold and melt crystallization processes at 90\u003csup\u003eo\u003c/sup\u003eC are illustrated in Figs.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb and \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb, respectively.\u003c/p\u003e\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$$\\left(1-{X}_{t}\\right)=\\text{e}\\text{x}\\text{p}(-K{t}^{n})$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003cp\u003e\u003c/p\u003e \u003cp\u003eTo analyze the isothermal crystallization kinetics, the Avrami equation was used following the procedure reported previously[\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e][\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e, \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e]. The Avrami equation can be written as the following:\u003c/p\u003e \u003cp\u003ewhere \u003cem\u003eX\u003c/em\u003e\u003csub\u003e\u003cem\u003et\u003c/em\u003e\u003c/sub\u003e is the relative degree of crystallinity, \u003cem\u003eK\u003c/em\u003e is the crystallization rate constant depending on nucleation and growth rate, and \u003cem\u003en\u003c/em\u003e is the Avrami exponent depending on the nature of nucleation and growth geometry of the crystals [\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e]. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e presents the plots of log [-ln (1-X\u003csub\u003et\u003c/sub\u003e)] vs. log t. The Avrami parameters of n and K were obtained by fitting the X\u003csub\u003et\u003c/sub\u003e data between 0.05 and 0.80 and listed in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e4\u003c/span\u003e. Most correlation coefficient values are larger than 0.994, indicating good fits of the experimental data. As seen from Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e4\u003c/span\u003e, the range of n values of the cold crystallization were found to be 2.02–3.52 for neat PLA, 2.21–2.75 for PLA-3JO, 2.46–3.37 for PLA-3CsNP and 2.65–3.05 for PLA-3JO-3CsNP, while the range of n values of the melt crystallization were 2.05–3.49 for neat PLA, 1.86–2.55 for PLA-3JO, 2.23–3.50 for PLA-3CsNP and 2.42–3.58 for PLA-3JO-3CsNP. For neat PLA, the n of the cold crystallization increased with increasing crystallization temperature, while decreased for melt crystallization. For PLA samples loaded with JO or/and CsNP, the n of both cold and melt crystallization decreased with increasing crystallization temperature. These values for the Avrami exponent are in accordance with that reported in the literature [\u003cspan additionalcitationids=\"CR53\" citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e–\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e], indicating that the crystallization mechanism is a three-dimensional growth process with possibly some thermal and athermal nucleation (i.e. instantaneous and sporadic nucleation mechanisms) [\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e]. Considering the unit consistency, the K\u003csup\u003e1/n\u003c/sup\u003e rather than K is adopted to compare the overall crystallization rate in the samples with different Avrami exponent n values. As shown in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e4\u003c/span\u003e, the K\u003csup\u003e1/n\u003c/sup\u003e values of cold and melt crystallization are found to be increased in the following order: PLA-3JO \u0026gt; PLA-3CsNP \u0026gt; PLA-3JO-3Cs \u0026gt; PLA. An important bulk or overall crystallization kinetic parameter which can be determined directly from the experimental X\u003csub\u003et\u003c/sub\u003e versus t data (Figs.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb and \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb) is the half-time of crystallization t\u003csub\u003e1/2\u003c/sub\u003e, defined as the elapsed time from the onset of crystallization to the point where the crystallization is half-completed. The obtained t\u003csub\u003e1/2\u003c/sub\u003e values are included in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e4\u003c/span\u003e. It is apparent for each tested sample, the t\u003csub\u003e1/2\u003c/sub\u003e of both the cold and melt crystallization decreased with increasing T\u003csub\u003ec\u003c/sub\u003e (within the T\u003csub\u003ec\u003c/sub\u003e range studied). At a given T\u003csub\u003ec\u003c/sub\u003e, the t\u003csub\u003e1/2\u003c/sub\u003e values of both cold and melt crystallization are found to be decreased in the following order: PLA-3JO \u0026lt; PLA-3CsNP \u0026lt; PLA-3JO-3Cs \u0026lt; PLA. These results revealed that the addition of JO and/or CsNP to the neat PLA accelerated the crystallization rate. For example, at the crystallization temperature of 90\u003csup\u003eo\u003c/sup\u003eC, the crystallization rate, which is taken as reciprocal of t\u003csub\u003e1/2\u003c/sub\u003e (1/t\u003csub\u003e1/2\u003c/sub\u003e), are found to be 0.315, 0.532, 0.719 and 0.341 min\u003csup\u003e− 1\u003c/sup\u003e, whereas the values are 0.059, 0.116, 0.117 and 0.082 min\u003csup\u003e− 1\u003c/sup\u003e for the neat PLA, PLA-3CsNP, PLA-3JO and PLA-3JO-3Cs, respectively. The cold crystallization rate is approximately 5.3, 4.6, 6.2 and 4.2 times faster than of melt crystallization for neat PLA, PLA-3JO, PLA-3CsNP and PLA-3JO-3CsNP, respectively, suggesting that the presence of CsNP or JO has a greater impact on the crystallization ability of PLA than two components together. The faster crystallization rate of cold crystallization compared with melt crystallization may be probably due to the existing of more nuclei, which results the enhancement of crystallization rate. These results are consistent with the previous findings for other semicrystalline polymers such as poly(ethylene/trimethylene terepthalate) copolyesters [\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e], polypropylene [\u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e57\u003c/span\u003e], PLA homopolymer [\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e, \u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e] and PLA-based polymers [\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e\u003cdiv class=\"gridtable\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c11\" colnum=\"11\"\u003e\u003c/div\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eSummary of the Avrami parameters and t\u003csub\u003e1/2\u003c/sub\u003e of cold and melt isothermal crystallization data of neat PLA and PLA-3JO, PLA-3CsNP, PLA-3JO-3CsNP.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e\u003ccolgroup cols=\"11\"\u003e\u003c/colgroup\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample Code\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colspan=\"5\" nameend=\"c6\" namest=\"c2\"\u003e \u003cp\u003eCold crystallization\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colspan=\"4\" nameend=\"c10\" namest=\"c7\"\u003e \u003cp\u003eMelt crystallization\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePLA\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTc/\u003csup\u003eo\u003c/sup\u003eC\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eK/min\u003csup\u003e− n\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eK\u003csup\u003e1/n\u003c/sup\u003e/min\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003en\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003et\u003csub\u003e1/2\u003c/sub\u003e/min\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eTc/\u003csup\u003eo\u003c/sup\u003eC\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003eK/min\u003csup\u003e− n\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003eK\u003csup\u003e1/n\u003c/sup\u003e/min\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003en\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003et\u003csub\u003e1/2\u003c/sub\u003e /min\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.39 x10\u003csup\u003e− 3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.060\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.02\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e14.49\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e85\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e4.20 x10\u003csup\u003e− 6\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.029\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e3.49\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e31.08\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e85\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.37 x10\u003csup\u003e− 3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.133\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e6.52\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e4.61 x10\u003csup\u003e− 5\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.053\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e3.39\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e16.95\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.0116\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.282\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3.52\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.18\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e6.18 x 10\u003csup\u003e− 3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.097\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2.18\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e8.83\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003e-\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e--\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e--\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u003cb\u003e-\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.015\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.127\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2.05\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e6.67\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePLA-3JO\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.014\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.212\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.75\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.93\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e85\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e7.50 x10\u003csup\u003e− 4\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.060\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2.55\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e14.42\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e85\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.025\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.239\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.57\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.45\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e5.902 x\u003csup\u003e− 3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.095\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2.18\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e8.64\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.149\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.442\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.33\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.88\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.033\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.155\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.83\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e5.15\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.940\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.973\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.21\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.87\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.044\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.187\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.86\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e4.20\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePLA-3CsNP\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.013\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.172\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.46\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e11.90\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e85\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.39 x 10\u003csup\u003e− 5\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.041\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e3.50\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e21.64\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e85\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.011\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.175\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.60\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e4.85\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e2.63 x10\u003csup\u003e− 3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.078\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2.33\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e10.94\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e4.76 x 10\u003csup\u003e− 3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.224\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3.57\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.97\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e7.91 x 10\u003csup\u003e− 3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.118\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2.26\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e7.29\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003e-\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e--\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e--\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u003cb\u003e-\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.043\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.243\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2.23\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e3.94\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePLA-3JO-3CsNP\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.44 x 10\u003csup\u003e− 4\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.063\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3.00\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e14.43\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e85\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e7.69 x10\u003csup\u003e− 6\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.037\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e3.58\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e23.14\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e85\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.01 x 10\u003csup\u003e− 3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.149\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3.05\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e5.96\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.31 x\u003csup\u003e− 3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.072\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2.52\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e12.27\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.040\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.297\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.65\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.94\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e95\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e5.42 x 10\u003csup\u003e− 3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.126\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2.52\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e6.90\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.0188\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.194\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e2.42\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e \u003cp\u003e4.48\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\u003c/div\u003e \u003cp\u003e\u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn this work PLA/CsNP composite containing 3.0% CsNP without or with 3.0% JO were prepared and characterized with their respect to mechanical tensile and thermal properties. Further, the impact of JO and CsNP on the cold and melt crystallization behavior of PLA matrix was studied. \u0026nbsp;It was found that incorporation of CsNP with and without JO into PLA matrix increased the elongation at break and impact strength, while decreased the tensile strength compared with that of neat PLA. The thermal stability of the PLA/CsNP composite was less than neat PLA but thermally stable above the processing temperature. The plasticization effect of JO and nucleation effect of CsNP on the crystallization of PLA was investigated with DSC. The results showed that crystallization of PLA was enhanced in the presence of JO as well as CsNP. Both cold and melt isothermal crystallization data were analyzed by the Avrami model. The resultant Avrami exponent indicated that the cold and melt crystallization mechanism of PLA corresponded to three-dimensional spherulitic growth, and the addition of the JO as well as CsNP was not significantly influence crystallization mechanism. Therefore, JO and CsNP may be considered as a green plasticizer and CsNP an effective green nucleating agent for expanding the applications of PLA.\u003c/p\u003e\n"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthor Contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll authors have read and agreed to the published version of the manuscript.\u0026nbsp;All authors contributed equally in Data curation; formal analysis; investigation; methodology; validation; visualization; writing \u0026ndash; original draft; writing \u0026ndash; review and editing.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflicts of Interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;The authors declare no conflict of interest.\u0026nbsp;\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eT.M. Madkour, S. Fadl, M.M. Dardir, M.A. Mekewi, High performance nature of biodegradable polymeric nanocomposites for oil-well drilling fluids, Egypt. J. Pet. 25 (2016) 281\u0026ndash;291. https://doi.org/10.1016/j.ejpe.2015.09.004.\u003c/li\u003e\n\u003cli\u003eT.P. Haider, C. V\u0026ccedil;lker, J. Kramm, K. Landfester, F.R. Wurm, Plastics of the Future ? The Impact of Biodegradable Polymers on the Environment and on Society, Angew.Chem. Int.Ed. 58 (2019) 50\u0026ndash;62. https://doi.org/10.1002/anie.201805766.\u003c/li\u003e\n\u003cli\u003eD. Puppi, F. Chiellini, Biodegradable Polymers for Biomedical Additive Manufacturing, Appl. Mater. Today J. 20 (2020) 100700. https://doi.org/10.1016/j.apmt.2020.100700.\u003c/li\u003e\n\u003cli\u003eM.C.M.C. Nandhini, L. Benny, L. George, A road map on synthetic strategies and applications of biodegradable polymers, Springer Berlin Heidelberg, 2023. https://doi.org/10.1007/s00289-022-04565-9.\u003c/li\u003e\n\u003cli\u003eE.M. Elmowafy, M. Tiboni, M.E. Soliman, Biocompatibility , biodegradation and biomedical applications of poly ( lactic acid )/ poly ( lactic ‑ co ‑ glycolic acid ) micro and nanoparticles, Springer Singapore, 2019. https://doi.org/10.1007/s40005-019-00439-x.\u003c/li\u003e\n\u003cli\u003eR. Zulkifli, I.N. Beas, Environmental Impact of Food Packaging Materials : A Review of Contemporary Development from Conventional Plastics to Polylactic Acid Based Materials, Materials (Basel). 13 (2020) 4994. https://doi.org/10.3390/ma13214994.\u003c/li\u003e\n\u003cli\u003eH.M.H. Zakaly, E.S. Ali, Polylactic acid tungsten trioxide reinforced composites : A study of their thermal , optical , and gamma radiation attenuation performance, Radiat. Phys. Chem. 205 (2023) 110705. https://doi.org/10.1016/j.radphyschem.2022.110705.\u003c/li\u003e\n\u003cli\u003eH.N.Y. Kamal, Graphene modifications in polylactic acid nanocomposites : a review, Polym. Bull. 72 (2015) 931\u0026ndash;961. https://doi.org/10.1007/s00289-015-1308-5.\u003c/li\u003e\n\u003cli\u003eM. Heydari, M. Babak, Poly ( lactic acid )‑ based bionanocomposites : effects of ZnO nanoparticles and essential oils on physicochemical properties, Polym. Bull. 79 (2022) 97\u0026ndash;119. https://doi.org/10.1007/s00289-020-03490-z.\u003c/li\u003e\n\u003cli\u003eA.A. Seraji, F. Goharpey, J.K. Yeganeh, Highly crystallized and tough polylactic acid through addition of surface modified cellulose nanocrystals, J Appl Polym Sci. 139 (2022) 52871. https://doi.org/10.1002/app.52871.\u003c/li\u003e\n\u003cli\u003eL.-T. Lim, R. Auras, M. Rubino, Processing technologies for poly (lactic acid), Prog. Polym. Sci. 33 (2008) 820\u0026ndash;852. https://doi.org/10.1016/j.progpolymsci.2008.05.004.\u003c/li\u003e\n\u003cli\u003eK.M. Nampoothiri, N.R. Nair, R.P. John, An overview of the recent developments in polylactide (PLA) research, Bioresour. Technol. 101 (2010) 8493\u0026ndash;8501. https://doi.org/10.1016/j.biortech.2010.05.092.\u003c/li\u003e\n\u003cli\u003eC. Zhou, H. Li, Y. Zhang, F. Xue, S. Huang, H. Wen, J. Li, J. de Claville Christiansen, D. Yu, Z. Wu, Deformation and structure evolution of glassy poly (lactic acid) below the glass transition temperature, CrystEngComm. 17 (2015) 5651\u0026ndash;5663. https://doi.org/10.1039/C5CE00669D.\u003c/li\u003e\n\u003cli\u003eR. Csizmadia, G. Faludi, K. Renner, J. M\u0026oacute;cz\u0026oacute;, B. Puk\u0026aacute;nszky, PLA/wood biocomposites: Improving composite strength by chemical treatment of the fibers, Compos. Part A Appl. Sci. Manuf. 53 (2013) 46\u0026ndash;53. https://doi.org/10.1007/s10924-009-0124-0.\u003c/li\u003e\n\u003cli\u003eY. Altun, M. Doğan, E. Bayramlı, Effect of alkaline treatment and pre-impregnation on mechanical and water absorbtion properties of pine wood flour containing poly (lactic acid) based green-composites, J. Polym. Environ. 21 (2013) 850\u0026ndash;856. https://doi.org/10.1007/s10924-012-0563-x.\u003c/li\u003e\n\u003cli\u003eR. Patwa, M. Singh, A. Kumar, V. Katiyar, Kinetic modelling of thermal degradation and non-isothermal crystallization of silk nano-discs reinforced poly (lactic acid) bionanocomposites, Springer Berlin Heidelberg, 2019. https://doi.org/10.1007/s00289-018-2434-7.\u003c/li\u003e\n\u003cli\u003eO. Paper, Thermal and mechanical properties of poly ( lactic acid ) filled with modified silicon dioxide : importance of the surface area, Polmer Bull. 79 (2022) 1409\u0026ndash;1435. https://doi.org/10.1007/s00289-021-03571-7.\u003c/li\u003e\n\u003cli\u003eY. Ren, L. Huang, Y. Wang, L. Mei, R. Fan, M. He, C. Wang, A. Tong, H. Chen, G. Guo, Stereocomplexed electrospun nanofibers containing poly ( lactic acid ) modified quaternized chitosan for wound healing, Carbohydr. Polym. 247 (2020) 116754. https://doi.org/10.1016/j.carbpol.2020.116754.\u003c/li\u003e\n\u003cli\u003eS.A.M. Issa, A.W. Alrowaily, D.E. Abulyazied, E.S. Ali, H.M.H. Zakaly, Effects of WO 3 reinforcement on the properties of poly ( lactic acid ) composites for radiation shielding, Radiat. Phys. Chem. 212 (2023) 111121. https://doi.org/10.1016/j.radphyschem.2023.111121.\u003c/li\u003e\n\u003cli\u003eM. Reza, K. Chantara, T. Ratnam, Mechanical properties of polylactic acid / synthetic rubber blend reinforced with cellulose nanoparticles isolated from kenaf fibres, Polym. Bull. 75 (2018) 809\u0026ndash;827. https://doi.org/10.1007/s00289-017-2061-8.\u003c/li\u003e\n\u003cli\u003eE. Piorkowska, Z. Kulinski, A. Galeski, R. Masirek, Plasticization of semicrystalline poly (L-lactide) with poly (propylene glycol), Polymer (Guildf). 47 (2006) 7178\u0026ndash;7188. https://doi.org/10.1016/j.polymer.2006.03.115.\u003c/li\u003e\n\u003cli\u003eM. Murariu, A. Da Silva Ferreira, M. Alexandre, P. Dubois, Polylactide (PLA) designed with desired end‐use properties: 1. PLA compositions with low molecular weight ester‐like plasticizers and related performances, Polym. Adv. Technol. 19 (2008) 636\u0026ndash;646. https://doi.org/10.1002/pat.1131.\u003c/li\u003e\n\u003cli\u003eF. Hassouna, J.-M. Raquez, F. Addiego, P. Dubois, V. Toniazzo, D. Ruch, New approach on the development of plasticized polylactide (PLA): Grafting of poly (ethylene glycol)(PEG) via reactive extrusion, Eur. Polym. J. 47 (2011) 2134\u0026ndash;2144. https://doi.org/10.1016/j.eurpolymj.2011.08.001.\u003c/li\u003e\n\u003cli\u003eM.G.A. Vieira, M.A. da Silva, L.O. dos Santos, M.M. Beppu, Natural-based plasticizers and biopolymer films: A review, Eur. Polym. J. 47 (2011) 254\u0026ndash;263. https://doi.org/10.1016/j.eurpolymj.2010.12.011.\u003c/li\u003e\n\u003cli\u003eF. Ali, Y.-W. Chang, S.C. Kang, J.Y. Yoon, Thermal, mechanical and rheological properties of poly (lactic acid)/epoxidized soybean oil blends, Polym. Bull. 62 (2009) 91\u0026ndash;98. https://doi.org/10.1007/s00289-008-1012-9.\u003c/li\u003e\n\u003cli\u003eD. Li, Y. Jiang, S. Lv, X. Liu, J. Gu, Q. Chen, Y. Zhang, Preparation of plasticized poly (lactic acid) and its influence on the properties of composite materials, PLoS One. 13 (2018) 1\u0026ndash;15. https://doi.org/10.1371/journal.pone.0193520.\u003c/li\u003e\n\u003cli\u003eM.P. Arrieta, Influence of plasticizers on the compostability of polylactic acid, J. Appl. Res. Technol. Eng. 2 (2021) 1\u0026ndash;9. https://doi.org/10.4995/jarte.2021.14772.\u003c/li\u003e\n\u003cli\u003eM.A. Elsawy, J. Declaville, C. Sanporean, Investigation of Jojoba Oil-wax as a Plasticizer for Poly (lactic acid), J. Optoelectron. Adv. Mater. 8 (2014) 109\u0026ndash;114.\u003c/li\u003e\n\u003cli\u003eA.M. Motawie, K.F. Mahmoud, A.A. El-Sawy, H.M. Kamal, H. Hefni, H.A. Ibrahiem, Preparation of chitosan from the shrimp shells and its application for pre-concentration of uranium after cross-linking with epichlorohydrin, Egypt. J. Pet. 23 (2014) 221\u0026ndash;228. https://doi.org/10.1016/j.ejpe.2014.05.009.\u003c/li\u003e\n\u003cli\u003eC. Ke, F. Deng, C. Chuang, C. Lin, Antimicrobial Actions and Applications of Chitosan, Polymers (Basel). 13 (2021) 904. https://doi.org/10.3390/polym13060904.\u003c/li\u003e\n\u003cli\u003eY. Qin, P. Li, Z. Guo, Cationic chitosan derivatives as potential antifungals : A review of structural optimization and applications, Carbohydr. Polym. 236 (2020) 116002. https://doi.org/10.1016/j.carbpol.2020.116002.\u003c/li\u003e\n\u003cli\u003eM.F. Abou, T. Abdullah, Radiation synthesis and characterization of sodium alginate/chitosan/hydroxyapatite nanocomposite hydrogels: a drug delivery system for liver cancer, Polym. Bull. 72 (2015) 725\u0026ndash;742. https://doi.org/10.1007/s00289-015-1301-z.\u003c/li\u003e\n\u003cli\u003eT. L\u0026oacute;pez-Le\u0026oacute;n, E.L.S. Carvalho, B. Seijo, J.L. Ortega-Vinuesa, D. Bastos-Gonz\u0026aacute;lez, Physicochemical characterization of chitosan nanoparticles: electrokinetic and stability behavior, J. Colloid Interface Sci. 283 (2005) 344\u0026ndash;351. https://doi.org/10.1016/j.jcis.2004.08.186.\u003c/li\u003e\n\u003cli\u003eN. Sawtarie, Y. Cai, Y. Lapitsky, Colloids and Surfaces B : Biointerfaces Preparation of chitosan / tripolyphosphate nanoparticles with highly tunable size and low polydispersity, Colloids Surfaces B Biointerfaces. 157 (2017) 110\u0026ndash;117. https://doi.org/10.1016/j.colsurfb.2017.05.055.\u003c/li\u003e\n\u003cli\u003eM. Carolina, D. Santo, C. Luciana, D. Antoni, A. Paula, D. Rubio, A. Alaimo, O.E. P, Biomedicine \u0026amp; Pharmacotherapy Chitosan-tripolyphosphate nanoparticles designed to encapsulate polyphenolic compounds for biomedical and pharmaceutical applications \u0026minus; A review, Biomed. Pharmacother. 142 (2021) 111970. https://doi.org/10.1016/j.biopha.2021.111970.\u003c/li\u003e\n\u003cli\u003eS. Mahtab, H. Saeedeh, M. Majid, Designing chitosan nanoparticles embedded into graphene oxide as a drug delivery system, Polym. Bull. 79 (2022) 541\u0026ndash;554. https://doi.org/10.1007/s00289-020-03506-8.\u003c/li\u003e\n\u003cli\u003eM.L.I. Montes, D.A.D.L.B. Manfredi, Effect of Natural Glyceryl Tributyrate as Plasticizer and Compatibilizer on the Performance of Bio-Based Polylactic Acid / poly ( 3- hydroxybutyrate ) Blends, J. Polym. Environ. 27 (2019) 1429\u0026ndash;1438. https://doi.org/10.1007/s10924-019-01425-y.\u003c/li\u003e\n\u003cli\u003eN.D. Bikiaris, I. Koumentakou, C. Samiotaki, D. Meimaroglou, D. Varytimidou, A. Karatza, Z. Kalantzis, M. Roussou, R.D. Bikiaris, G.Z. Papageorgiou, Recent Advances in the Investigation of Poly ( lactic acid ) ( PLA ) Nanocomposites : Incorporation of Various Nanofillers and their Properties and Applications, Polymers (Basel). 15 (2023) 1196. https://doi.org/10.3390/polym15051196.\u003c/li\u003e\n\u003cli\u003eM.A. Elsawy, M. Fekry, A.M. Sayed, N.A. Maziad, G.R. Saad, Physico-chemical Characteristics of Biodegradable Poly(lactic acid) and Poly(lactic acid)/Chitosan Nano-Composites Under the Influence of Gamma Irradiation, J. Polym. Environ. 31 (2023) 2705\u0026ndash;2714. https://doi.org/10.1007/s10924-022-02693-x.\u003c/li\u003e\n\u003cli\u003eM.A. Elsawy, G.R. Saad, A.M. Sayed, Mechanical, thermal, and dielectric properties of poly(lactic acid)/chitosan nanocomposites, Polym. Eng. Sci. 56 (2016) 987\u0026ndash;994. https://doi.org/10.1002/pen.24328.\u003c/li\u003e\n\u003cli\u003eJ.M.Q.D.E. Rodr\u0026iacute;guez-f\u0026eacute;lix, J.C. Encinas-encinas, L.L. Liz\u0026aacute;rraga-labor\u0026iacute;n, Extrusion of polypropylene / chitosan / poly ( lactic-acid ) films : Chemical , mechanical , and thermal properties, J Appl Polym Sci. 138 (2021) 49850. https://doi.org/10.1002/app.49850.\u003c/li\u003e\n\u003cli\u003eG.R. Saad, M.A. Elsawy, M.S.A. Aziz, Nonisothermal crystallization behavior and molecular dynamics of poly(lactic acid) plasticized with jojoba oil, J. Therm. Anal. Calorim. 128 (2017). https://doi.org/10.1007/s10973-016-5910-z.\u003c/li\u003e\n\u003cli\u003eM.A. Elsawy, G.R. Saad, A.M. Sayed, N. City, Mechanical , Thermal , and Dielectric Properties of Poly (lactic acid)/ Chitosan Nanocomposites, Polym. Eng. Sci. 56 (2016) 987\u0026ndash;994. https://doi.org/10.1002/pen.\u003c/li\u003e\n\u003cli\u003eN. Helya, I. Kamaludin, H. Ismail, A. Rusli, S. Sung, Thermal behavior and water absorption kinetics of polylactic acid / chitosan biocomposites, Iran. Polym. J. 30 (2021) 135\u0026ndash;147. https://doi.org/10.1007/s13726-020-00879-5.\u003c/li\u003e\n\u003cli\u003eE. Altuntas, D. Aydemir, Effects Of Wood Flour On The Mechanical , Thermal And Morfphological Properties Of Poly (L-Lactic Acid) -Chitosan Biopolymer Composites, Maderas. Cienc. Y Tecnol. 21 (2019) 611\u0026ndash;618. https://doi.org/10.4067/S0718-221X2019005000416.\u003c/li\u003e\n\u003cli\u003eD. Grenier, P. Homme, Avrami analysis: three experimental limiting factors, J. Polym. Sci. Polym. Phys. Ed. 18 (1980) 1655\u0026ndash;1657.\u003c/li\u003e\n\u003cli\u003eG.R. Saad, M.A. Elsawy, M.S. Abdel, Nonisothermal crystallization behavior and molecular dynamics of poly (lactic acid) plasticized with jojoba oil, J. Therm. Anal. Calorim. 128 (2017) 211\u0026ndash;223. https://doi.org/10.1007/s10973-016-5910-z.\u003c/li\u003e\n\u003cli\u003eA.M. Harris, E.C. Lee, Improving mechanical performance of injection molded PLA by controlling crystallinity, J. Appl. Polym. Sci. 107 (2008) 2246\u0026ndash;2255.\u003c/li\u003e\n\u003cli\u003eM. Avrami, Transformation-time relations for random distribution of nuclei, J. Chem. Phys. 8 (1940) 212\u0026ndash;224. https://doi.org/10.1002/pol.1980.180180715.\u003c/li\u003e\n\u003cli\u003eM. Avrami, Kinetics of phase change. III. Granulation, phase change, and microstructure, J. Chem. Phys. 9 (1941) 117\u0026ndash;184.\u003c/li\u003e\n\u003cli\u003eG.P. Balamurugan, S.N. Maiti, Nonisothermal crystallization kinetics of polyamide 6 and ethylene‐co‐butyl acrylate blends, J. Appl. Polym. Sci. 107 (2008) 2414\u0026ndash;2435. https://doi.org/10.1002/app.27377.\u003c/li\u003e\n\u003cli\u003eJ.F. Mano, Y. Wang, J.C. Viana, Z. Denchev, M.J. Oliveira, Cold crystallization of PLLA studied by simultaneous SAXS and WAXS, Macromol. Mater. Eng. 289 (2004) 910\u0026ndash;915. https://doi.org/10.1002/mame.200400097.\u003c/li\u003e\n\u003cli\u003eS. Iannace, L. Nicolais, Isothermal crystallization and chain mobility of poly (L‐lactide), J. Appl. Polym. Sci. 64 (1997) 911\u0026ndash;919. https://doi.org/10.1002/(SICI)1097-4628(19970502)64:5\u0026lt;911::AID-APP11\u0026gt;3.0.CO;2-W.\u003c/li\u003e\n\u003cli\u003eY. Xu, W. Zhang, Y. Qiu, M. Xu, B. Li, L. Liu, Preparation and mechanism study of a high efficiency bio-based flame retardant for simultaneously enhancing flame retardancy, toughness and crystallization rate of poly (lactic acid), Compos. Part B Eng. 238 (2022) 109913. https://doi.org/10.1016/j.compositesb.2022.109913.\u003c/li\u003e\n\u003cli\u003eB. Wunderlich, Thermal characterization of polymeric materials, New York: Academic Press, 1997.\u003c/li\u003e\n\u003cli\u003eT.-W. Shyr, C.-H. Tung, W.-S. Cheng, C.-C. Yang, The crystallization rate and morphological structure of poly (ethylene/trimethylene terephthlate) copolyesters under isothermal melt-crystallization and cold-crystallization, J. Polym. Res. 20 (2013) 1\u0026ndash;10. https://doi.org/10.1007/s10965-013-0186-5.\u003c/li\u003e\n\u003cli\u003eP. Supaphol, J.E. Spruiell, Isothermal melt-and cold-crystallization kinetics and subsequent melting behavior in syndiotactic polypropylene: a differential scanning calorimetry study, Polymer (Guildf). 42 (2001) 699\u0026ndash;712. https://doi.org/10.1016/S0032-3861(00)00399-2.\u003c/li\u003e\n\u003cli\u003eT. T\u0026aacute;bi, I.E. Saj\u0026oacute;, F. Szab\u0026oacute;, A.S. Luyt, J.G. Kov\u0026aacute;cs, Crystalline structure of annealed polylactic acid and its relation to processing, Express Polym. Lett. 4 (2010) 659\u0026ndash;668. https://doi.org/10.3144/expresspolymlett.2010.80.\u003c/li\u003e\n\u003cli\u003eP. Badrinarayanan, K.B. Dowdy, M.R. Kessler, A comparison of crystallization behavior for melt and cold crystallized poly (l-Lactide) using rapid scanning rate calorimetry, Polymer (Guildf). 51 (2010) 4611\u0026ndash;4618. https://doi.org/10.1016/j.polymer.2010.08.014.\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Table 3","content":"\u003cp\u003eTable 3 is not available with this version\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"PLA, chitosan nanoparticles, Jojoba oil, composites, mechanical properties, isothermal crystallization","lastPublishedDoi":"10.21203/rs.3.rs-4009522/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4009522/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003ePoly(lactic acid), PLA, loaded with chitosan nanoparticles, CsNP, (3.0%, w/w) and jojoba oil, JO, (3.0%, w/w), as a plasticizer, were prepared by twin screw extrusion. The manufactured PLA/CsNP, PLA/JO and PLA/CsNP/JO compounds were characterized by differential scanning calorimetry (DSC), thermogravemetric analysis (TG), tensile testing, Izod impact test and wide angle X-ray diffraction (WAXD). The PLA/CsNP, PLA/JO and PLA/CsNP/JO compounds exhibited improved elongation and impact strength compared with neat PLA. The presence of JO slightly improved the thermal stability of PLA, while CsNP decreased the thermal stability of the PLA. The incorporation of CNPs and JO accelerated the cold crystallization rate of PLA, which is related to a nucleation effect of the CsNP and increase of the chain mobility as a plasticization effect of the JO. No modification in crystalline structure of PLA was observed as a result of the presence of the CsNP and the JO. Avrami equation was employed to describe the cold and melt isothermal crystallization process of neat PLA and PLA/CNP composite with and without JO. The combination additives of CsNP and JO accelerated the crystallization rate in a less extent than CsNP or JO alone.\u003c/p\u003e","manuscriptTitle":"Unveiling the Potential of Chitosan Nanoparticles and Jojoba Oil for Optimizing Poly(lactic acid) Characteristics: Insights into Physico-chemical Attributes and Crystallization Mechanisms","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-03-05 19:02:43","doi":"10.21203/rs.3.rs-4009522/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"f123b6e2-897a-402f-adbc-23bdcff69d4c","owner":[],"postedDate":"March 5th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-04-05T03:44:23+00:00","versionOfRecord":[],"versionCreatedAt":"2024-03-05 19:02:43","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4009522","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4009522","identity":"rs-4009522","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}