Spherulite Growth Rate Research Articles

Change in Concentration of Amorphous Region Due to Crystallization in PTT/PET Miscible Blends.

In a miscible crystalline/crystalline blend of poly(trimethylene terephthalate) (PTT) and poly(ethylene terephthalate) (PET), the PET spherulites grew at 240 °C when the PTT content was 30 wt% or less. The growth rate of PET spherulites decreased with time due to the exclusion of PTT from the growth front of PET spherulites into the amorphous region, resulting in a three-stage crystallization process. Due to the exclusion, the spherulite growth stopped before the volume filling of the PET spherulites, causing the formation of an excluded PTT amorphous region. When the temperature was lowered from 240 °C to 210 °C, the PTT spherulites grew in the excluded PTT amorphous region. The spherulite growth rate of PTT in the excluded PTT amorphous region was equivalent to that of a blend of 60-70 wt% PTT in 30/70 PTT/PET. These results suggest a significant change in the PTT concentration in the amorphous region, from the initial PTT content of 30 wt% to 60-70 wt%, due to the exclusion of PTT during the melt crystallization of PET at 240 °C.

How surface modification of cellulose nanocrystals affects the crystallization process of poly (β-hydroxybutyrate)

Hydroxyl groups on the surface of cellulose nanocrystals (CNC) are modified by chemical methods, CNC and the modified CNC are used as fillers to prepare PHB/cellulose nanocomposites. The absorption peak of carbonyl group of the modified CNC (CNC-CL and CNC-LA) appears in the FT-IR spectra, which proves that the modifications are successful. Thermal stability of CNC-CL and CNC-LA is better than that of pure CNC. Pure CNC is beneficial to the nucleation of PHB, while CNC-CL and CNC-LA inhibit the nucleation of PHB. The spherulite size of PHB and its nanocomposites increases linearly over time, and the maximum growth rate of PHB spherulite exists at 90 °C. Rheological analysis shows that viscous deformation plays the dominant role in PHB, PHBC and PHBC-CL samples, while the elastic deformation is dominant in PHBC-LA. According to the rheological data, the dispersion of CNC-CL and CNC-LA in PHB is better than that of CNC. This work demonstrates the impact of modified CNC on the crystallization and viscoelastic properties of PHB. Moreover, the interface enhancement effect of modified CNC on PHB/CNC nanomaterials is revealed from the crystallization and rheology perspectives.

Crystallization of the β-Form of Polypropylene from the Melt with Reduced Entanglement of Macromolecules.

The influence of decreasing the entanglement density of macromolecules on the crystallization of the β-form of polypropylene was investigated. Polypropylene with seven times less entanglement was obtained from a solution in xylene, and its properties were compared with those of fully entangled polypropylene. To obtain a high β-phase content, the polymer was nucleated using calcium pimelate. In non-isothermal crystallization studies, accelerated growth of β-crystals was found, increasing the crystallization temperature. Also, the isothermal crystallization was fastest in the nucleated, partially disentangled polypropylene. Increased growth rate of spherulites and enhanced nucleation activity in the presence of more mobile macromolecules were responsible for the high rate of melt conversion to crystals in the disentangled polypropylene. It was also observed that the equilibrium melting temperature of β-crystals is lower after disentangling macromolecules. Better conditions for crystal building after reduction of entanglements resulted in enhanced crystallization according to regime II.

Origin and Nucleation Kinetics of Transcrystalline Layer in Bamboo fiber@nano‐TiO2/Polypropylene Composite

AbstractHerein origin and nucleation kinetics of transcrystalline layer (TCL) in bamboo fiber deposited with nano‐TiO2 (BF@TiO2)/polypropylene (PP) composite is studied. Firstly, the surface morphology, roughness, and energy, as well as crystalline structure (e. g., crystal face indices (hkl)) of BF@TiO2 are analyzed to clarify the origin of TCL in the composite. Subsequently, the nucleation kinetics of TCL in BF@TiO2/PP composite at different crystallization temperatures (Tc) are investigated through polarized optical microscopy. The results find that the surface roughness and energy of BF@TiO2 increase by 47.55 % and 2.41 % compared with untreated BF, respectively. Interestingly, the mismatch rates (MRs) of hkl(BF) vs. hkl(PP) are >320 %. In comparison, the MRs of (101)(BF@TiO2)TiO2 vs. (hkl)(PP) are dramatically decreased to <25 %, suggesting a similar crystal plane between BF@TiO2 and PP matrix. These results indicate that the TCL formation in the composite is more facile in BF@TiO2 than in the untreated BF. During isothermal crystallization, the nucleation and spherulite growth rates decrease as the Tc increases. The interface free energy difference (▵σ) between BF@TiO2 and PP is calculated based on the heterogeneous nucleation theory. The ▵σ is 1.54±0.11 J cm−2, highlighting that the BF@TiO2 strongly induces the PP nucleation.

Influence of poly(methyl methacrylate) on the structure and phase transition behavior of poly(vinylidene fluoride)

The structure and organization of poly(vinylidene fluoride) (PVDF) spherulites in blends with poly(methyl methacrylate) of high (PMMA-H) and low (PMMA-L) molecular weights, respectively, have been studied in details. It is confirmed that the addition of PMMA-H and PMMA-L have different influence on the morphologies of PVDF spherulites in several aspects, such as the spacing of ring-band α-PVDF spherulites, the kinetics of both α-PVDF crystallization and α−γ′ solid phase transition, as well as the formation of Wagon-Wheel spherulites. First, incorporation of PMMA-L enlarges the band spacing, which is associated to the increased chain mobility of crystallizable PVDF that helps to release the surface stresses of lamellae. In contrast, the low mobility of PMMA-H chains enhances the congestion at fold surfaces, which results in a vigorous twisting and thus the formation of tightened ring-band α-PVDF structure. Second, the PMMA-H reduces the crystallization rate of PVDF more severely than the PMMA-L, resulting in an extremely slow growth rate of α-PVDF spherulites in PVDF/PMMA-H sample at 160 °C, only about one-twenty-third compared to the neat PVDF. Third, the remarkably reduced α-PVDF spherulite growth rate and enhanced α−γ′ transition rate at 160 °C lead to the formation of Wagon-Wheel PVDF spherulites with inner γ′-PVDF crystals and outer γ crystals. It originates from the synchronization of slow α-PVDF growth and accelerated α−γ′ transition rate through homoepitaxy. That is, when the α−γ′ transition with exceeded rate reaches the growth front of the original α-PVDF spherulite, the transformed γ′-PVDF crystals trigger the growth of γ-PVDF crystals directly from melt with non-band feature. These results help to unravel the formation mechanism of Wagon-Wheel PVDF spherulites to be the competition of α-γ′ crystal transformation and α-spherulite radial growth rates.

Tailoring the Nucleation and Crystallization Rate of Polyhydroxybutyrate by Copolymerization.

In the polyester family, the biopolymer with the greatest industrial potential could be poly(3-hydroxybutyrate) (PHB), which can be produced nowadays biologically or chemically. The scarce commercial use of PHB derives from its poor mechanical properties, which can be improved by incorporating a flexible aliphatic polyester with good mechanical performance, such as poly(ε-caprolactone) (PCL), while retaining its biodegradability. This work studies the structural, thermal, and morphological properties of block and random copolymers of PHB and PCL. The presence of a comonomer influences the thermal parameters following nonisothermal crystallization and the kinetics of isothermal crystallization. Specifically, the copolymers exhibit lower melting and crystallization temperatures and present lower overall crystallization kinetics than neat homopolymers. The nucleation rates of the PHB components are greatly enhanced in the copolymers, reducing spherulitic sizes and promoting transparency with respect to neat PHB. However, their spherulitic growth rates are depressed so much that superstructural growth becomes the dominating factor that reduces the overall crystallization kinetics of the PHB component in the copolymers. The block and random copolymers analyzed here also display important differences in the structure, morphology, and crystallization that were examined in detail. Our results show that copolymerization can tailor the thermal properties, morphology (spherulitic size), and crystallization kinetics of PHB, potentially improving the processing, optical, and mechanical properties of PHB.

Evaluation of spherulite growth in PHB‐based systems – A DoE approach

AbstractFormulations based on poly(hydroxybutyrate) (PHB) and poly(hydroxybutyrate‐co‐valerate) were studied to statistically assess the importance of process parameters (temperature) and chemistry in filled and/or plasticized PHB‐based formulations on spherulite growth rate (SGR) and nucleation density (ND). It was found that in binary systems, addition of a plasticizer results in shift of the maximum SGR towards lower temperatures, with the value of the shift dependent on polymer‐plasticizer compatibility. The presence of the filler does not significantly influence SGR, instead resulting in ND changes dependent on filler chemistry, with Cloisite Ca++ showing the strongest nucleating action in all formulations among fillers studied. In ternary systems, statistical analysis shows that SGR strongly depends on the crystallization temperature (Tc), plasticizer type and concentration, and hydroxyvalerate content in the polymer chain while being independent of the presence and chemistry of the filler in the system. ND has, however, proven to be dependent on all investigated parameters, including both filler type and its concentration, with Tc being the most important factor. These results expand the understanding of factors controlling crystallization in polymer systems and provide an initial set of design tools that can be used to control mechanical properties in new generations of packaging materials.

Synthesis, Morphology, and Crystallization Kinetics of Polyheptalactone (PHL).

Aliphatic polyesters are widely studied due to their excellent properties and low-cost production and also because, in many cases, they are biodegradable and/or recyclable. Therefore, expanding the range of available aliphatic polyesters is highly desirable. This paper reports the synthesis, morphology, and crystallization kinetics of a scarcely studied polyester, polyheptalactone (PHL). First, we synthesized the η-heptalactone monomer by the Baeyer-Villiger oxidation of cycloheptanone before several polyheptalactones of different molecular weights (in the range between 2 and 12 kDa), and low dispersities were prepared by ring-opening polymerization (ROP). The influence of molecular weight on primary nucleation rate, spherulitic growth rate, and overall crystallization rate was studied for the first time. All of these rates increased with PHL molecular weight, and they approached a plateau for the highest molecular weight samples employed here. Single crystals of PHLs were prepared for the first time, and hexagonal-shaped flat single crystals were obtained. The study of the crystallization and morphology of PHL revealed strong similarities with PCL, making PHLs very promising materials, considering their potential biodegradable character.

Nanoparticle Diffusion in Miscible Polymer Nanocomposite Melts

X-ray photon correlation spectroscopy measurements were used to quantify the dynamics of bare and bimodal grafted silica nanoparticles mixed with PEO melts of different molecular weights. In dilute polymer nanocomposite (PNC) samples, we find diffusive NP behavior as described by the Stokes–Einstein relationship so long as the adsorbed PEO polymer layer is taken into account in determining both the effective NP size and its role on composite viscosity. The size of this bound layer was found to be approximately 2Rg, where Rg is the chain radius of gyration. We also expanded our system to investigate how the dynamics of grafted NPs differ from bare NPs with an adsorbed layer. We showed that the dynamics again can be determined by an effective NP radius at a scale smaller than the effective interparticle spacing; however, at larger length scales, the morphology and grafting parameters play a major role in the system dynamics. These results allow us to quantify NP ordering driven by polymer crystallization. It has previously been speculated that behavior is controlled by the relative ratio of time scale of crystal growth and the diffusive time scale of the NPs, a Peclet number. When the former time scale is longer, then the NPs are expected to be segregated into the interlamellar amorphous zones, while the NPs are too slow to be reorganized in the opposite case. We show here that this conjecture is quantitatively correct and the demarcation in behavior occurs for Pe = 1. Thus, we provide a way to estimate a critical spherulite growth rate for any semicrystalline PNC, at which a given NP can be ordered. Together, the results of this study permit us to tunably design PNCs through directed dispersion of NPs in a polymer matrix.

Mutual influence of the morphology and growth kinetics in binary crystalline blends of poly(butylene terephthalate) and polyarylate

The spherulitic morphology and crystallization behaviors of binary crystalline blends of poly(butylene terephthalate) (PBT) and polyarylate (PAr), based on bisphenol A, (27:73 isophthalic:terephthalic acids), are investigated herein. PBT and PAr crystallize simultaneously or sequentially; various crystallization behaviors and morphologies are observed. In the PBT-rich blends, PAr does not crystallize; the PBT spherulites coarsen as the PAr concentration increases. Non-crystallizable PAr is trapped inside the spherulites. The PBT spherulitic growth rate decreases when PAr is added and remains constant thereafter. For the 50/50 blends, PBT and PAr crystallize simultaneously, and their spherulites co-exist separately. The spherulitic growth rate of PBT increases with time while PAr is crystallizing, but it remains constant if PAr crystallizes prior. At a crystallization temperature of 250 °C, only PAr crystallizes; the non-crystallizable PBT is expelled from the PAr spherulites because the crystallization rate of PAr is low. The spherulites of PAr do not fill the space in the final crystallization stage. The crystallization rate of the binary crystalline PBT/PAr blends was notably influenced by the prior crystallization of the other component, and was due to the change of the amorphous composition in addition to the constraints of the crystals on the chain mobility.

Regime transition temperature of poly(ethylene oxide) in thin films: Effect of film thickness and molecular weight

In thin films of poly(ethylene oxide), the regime transition temperature between regimes II and III, TIII→II, was found to increase with decrease in the film thickness D below 1 μm and increase in the molecular weight (Mw). When D was 1 μm or greater, TIII→II was found to be highly dependent on Mw and independent of D. As D decreased, the dependence of TIII→II on Mw decreased. The spherulitic growth rate, on the other hand, was almost independent of D for D ≥ 100 nm. These results were discussed based on the suppression of chain mobility in the cases of small D and high Mw. The reduced mobility slowed down the lateral growth rate of secondary nuclei and relatively enhanced the secondary nucleation frequency. The results also implied that the surface free energy of the folded surface decreases with lowering D and that the chain folds are disordered.

Polyethylene Oxide/Sodium Sulfonamide Polymethacrylate Blends as Highly Conducting Single-Ion Solid Polymer Electrolytes

In this work, blends of polyethylene oxide (PEO) and poly(sodium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethanesulfonyl) imide) (PNaMTFSI) in different compositions were investigated for their application as solid electrolytes for sodium batteries. PNaMTFSI and PEO are miscible, exhibiting only one Tg in the whole range of compositions. PNaMTFSI was shown to reduce the crystal growth rate of PEO crystals but increase PEO nucleation, making the overall crystallization rate higher in blends with 15 and 30 wt % PNaMTFSI. The ionic conductivity is also affected by the blend composition. The highest values of ionic conductivity were observed with 15 and 30 wt % PNaMTFSI at high temperatures equal to 5.84 × 10–5 and 7.74 × 10–5 S cm–1 at 85 °C, respectively, with values of sodium-ion transference numbers of higher than 0.83 and electrochemical stability between 3.5 and 4.5 V versus Na+/Na0 depending on the composition, which opens the possibility of its use in sodium batteries. Finally, a comparison was made between the effect of sodium and lithium on these types of electrolytes, showing that sodium electrolytes have a lower ionic conductivity due to the larger size of the Na cation. The differences in the spherulitic growth rate and overall crystallization rate between Li and Na-containing electrolytes were compared and rationalized in terms of the blends’ intermolecular interactions and the relative contribution of primary nucleation and growth.

Radial growth rate of near-critical crystal nuclei in poly(l-lactic acid) (PLLA) in Tammann's two-stage development method.

The specific features of crystal nucleation widely determine the morphology of the evolving crystalline material. Crystal nucleation is, as a rule, not accessible by direct observation of the nuclei, which develop with time. This limitation is caused by the small size (nanometer scale) of the critical nuclei and the stochastic nature of their formation. We describe an experimental approach to the determination of specific features of the cluster size distribution employing fast scanning calorimetry at scanning rates up to 10 000Ks-1. The surviving cluster fraction is determined by selectively melting/dissolving clusters smaller than the critical size corresponding to the highest temperature of a short spike positioned between the nucleation and the development stage in Tammann's two-stage method. This approach allows for estimating the time evolution of the radius of the largest detectable clusters in the distribution. Knowing this radius as a function of nucleation time allows for determining a radial growth rate. In the example of poly(l-lactic acid) (PLLA), the order of magnitude estimate of radial growth rates of clusters of about 2-5nm yields values between 10-5 and 10-3nms-1. The radial growth rate of micrometer-sized spherulites is available from optical microscopy. The corresponding values are about three orders of magnitude higher than the values for the nanometer-sized clusters. This difference is explainable by stochastic effects, transient features, and the size dependence of the growth processes on the nanometer scale. The experimental and (order of magnitude) classical nucleation theory estimates agree well.

Crystallization behavior and secondary nucleation model of PP/GN nanocomposites under supercritical N2

Supercritical N2, as a physical blowing agent, is commonly used in microcellular foam injection molding to improve the crystallization kinetics and foaming performance of polymer-based composites. Herein, the crystal morphology and growth behavior of polypropylene/graphite nanosheet (PP/GN) nanocomposites under supercritical N2 were investigated using a self made in-situ high pressure microscope system. Due to the heterogeneous nucleation effect of GN, more irregular lamellar crystals inside the spherulites were generated and the stacking of lamellar crystals was more disordered. The intrinsic mechanisms of GN content on the growth rate of spherulites were investigated on the basis of the interfacial free energy induced by GN. The calculated results of the secondary nucleation model are in line with the results obtained from the isothermal crystallization experiments, indicating that the model can effectively predict the grain growth rate of PP/GN nanocomposites under supercritical N2. In addition, based on the crystallization kinetics of PP/GN composites, the action mechanism of GN on the foaming behavior of PP was explored. As expected, more cell nuclei were induced due to the refinement of grains and the increased of GN content.

Crystallization studies on heterogeneous melts of polybutene-1

The heterogeneous melts of isotactic polybutene-1 (iPB-1) containing Form I or Form II seeds with uniform size and random distribution were prepared by selective melting of melt crystallized and transformed samples, respectively. Compared with a reference blank melt, the remnant Form I or II seeds are able to significantly reduce the half-time of crystallization under isothermal conditions. Besides, the nucleation efficiency of Form II seeds is much higher than that of Form I seeds because of the lower lateral surface energy and highly lattice match. Furthermore, a great number of tiny spherulites with submicrometer radius nucleate and grow simultaneously, offers an opportunity to follow the development of spherulites at the very early stage. The analysis of the differential scanning calorimetry (DSC) curves confirms that the mass fraction for faster primary crystallization of heterogeneous melts is lower than that of blank melt, which clearly indicates that growth rate of spherulites is decreasing before impingement. The radius of spherulites was not much larger than the diffusion length provides the foundation for the observed non-linear growth of spherulites. This quantitative comparison of the crystallization kinetics of blank melt and heterogeneous melts can therefore be applied as a method to improve our understanding of nucleation and the diffusion-controlled growth of polymer.

Study on in situ visualization crystallization behavior and secondary nucleation model of polypropylene under supercritical N2

The crystal morphology and crystallization kinetics of polymers under supercritical N2 have an important impact on the polymers’ melt strength as well as the microstructure and properties of microcellular plastic parts. Herein, the self-made in-situ high pressure microscopy system was employed to study the spherulite morphology and crystal growth behavior in high pressure N2. It was found that PP spherulites were significantly refined under supercritical N2. As the N2 pressure was augmented to 20.69 MPa at 130 °C, the spherulite size was reduced to 48.41 μm, refined by 35.84%, indicating that the crystallization behavior of PP can be controlled by pressure regulation. The new growth pattern for spherulite under supercritical N2 was discovered by atomic force microscope (AFM) for the first time. In addition, the spherulite growth rate exhibited a phenomenon that was inhibited first and then promoted. To explore the re-promoting effect of supercritical N2, a secondary nucleation model that considered the effect of additional free energy induced by high-pressure N2, was established. The re-promotion of spherulite growth rate at elevated N2 pressure is attributed to the augment in translational free energy induced by N2, i.e., entropy-driven crystallization. The calculated results of secondary nucleation model achieved a good agreement with the experimental results, and the variation trend of PP spherulite growth rate could be well predicted under supercritical N2.

Effect of the TrFE Content on the Crystallization and SSA Thermal Fractionation of P(VDF-co-TrFE) Copolymers.

In this contribution, we study the effect of trifluoro ethylene (TrFE) comonomer content (samples with 80/20, 75/25, and 70/30 VDF/TrFE molar ratios were used) on the crystallization in P(VDF-co-TrFE) in comparison with a PVDF (Poly(vinylidene fluoride)) homopolymer. Employing Polarized Light Optical Microscopy (PLOM), the growth rates of spherulites or axialites were determined. Differential Scanning Calorimetry (DSC) was used to determine overall crystallization rates, self-nucleation, and Successive Self-nucleation and Annealing (SSA) thermal fractionation. The ferroelectric character of the samples was explored by polarization measurements. The results indicate that TrFE inclusion can limit the overall crystallization of the copolymer samples, especially for the ones with 20 and 25% TrFE. Self-nucleation measurements in PVDF indicate that the homopolymer can be self-nucleated, exhibiting the classic three Domains. However, the increased nucleation capacity in the copolymers provokes the absence of the self-nucleation Domain II. The PVDF displays a monomodal distribution of thermal fractions after SSA, but the P(VDF-co-TrFE) copolymers do not experience thermal fractionation, apparently due to TrFE incorporation in the PVDF crystals. Finally, the maximum and remnant polarization increases with increasing TrFE content up to a maximum of 25% TrFE content, after which it starts to decrease due to the lower dipole moment of the TrFE defect inclusion within the PVDF crystals.

Epoxy‐Modified Pyrophyllite as a Multifunctional Chain Extender for Poly(latic acid)

AbstractPyrophyllite (Prl), an aluminosilicate with a balanced mineral structure and extremely small particle size, appears to be an ideal filler but is rarely used in polymers. Herein, a method for the application of pyrophyllite in polymers is reported. A multifunctional filler is prepared by epoxy‐modified pyrophyllite and incorporated into poly(latic acid) (PLA) to enhance its processability and crystallization properties. Results show the effectiveness of epoxy‐modified Prl in composite film with a significant reduction in glass transition temperature, and noteworthy increment in crystallinity and spherulite growth rate. Water vapor barrier properties of PLA composite films increase over 30% with a range of Prl Loading. Furthermore, an enhancement of the tensile strength is increased by 30% and strain at break by 337.1% for PLA composite films compared to neat PLA. This work provides a new idea to prepare the functionalized pyrophyllite fillers and a theoretical basis to develop the application of pyrophyllite for polymers.

Supernucleation Dominates Lignin/Poly(ethylene oxide) Crystallization Kinetics

The effect of lignin nanoparticles (LNPs) on the crystallization kinetics of poly(ethylene oxide) (PEO) is examined. Lignin from spruce and ionic isolation was used to prepare LNPs with a number-averaged diameter of 85 nm (with a relatively large polydispersity) by an ultrasonication method. PEO-based nanocomposites with four different LNP contents (5, 10, 15, and 20 wt %) were prepared and subject to isothermal and nonisothermal crystallization protocols in a series of experiments. Scanning electron microscopy (SEM) images showed well-dispersed LNPs in the crystallized PEO matrix. The incorporation of LNPs exponentially increases nucleation density at moderate loadings, with this trend apparently saturating at higher loadings. However, the spherulitic growth rate decreases monotonically with LNP loading. This is attributed to the substantial PEO/LNP affinity, which impacts chain diffusion and induces supernucleation effect (with efficiencies in the order of 200%), but leads to slower growth rates. The overall crystallization kinetics, measured by the DSC, shows faster nanocomposite crystallization rates relative to the neat PEO at all LNP contents examined. This indicates that the supernucleation effect of LNPs dominates over the decrease in the growth rates, although its influence slightly decreases as the LNP content increases. The strong hydrogen-bonded interactions between the LNPs and the PEO are thus reminiscent of confinement effects found in polymer-grafted NP nanocomposites (e.g., PEO-g-SiO2/PEO) in the brush-controlled regime.

Inclusion/Exclusion Behaviors of Small Molecules during Crystallization of Polymers in Miscible PLLA/TAIC Blend.

In this work, PLLA/TAIC has been taken as a model system to investigate the inclusion and exclusion of small molecules during the crystallization of polymers in their miscible blend. Our results indicate that it is the growth rate and diameter of PLLA spherulites that dominate the localization of TAIC. On the one hand, crystallization temperature plays an important role. Crystallization at higher temperature corresponds to higher growth rates and a greater diameter of PLLA spherulites. The former improves the ability of PLLA crystals to trap TAIC while the latter leads to a lower volume fraction of space among neighboring PLLA spherulites. The combination of the two contributes to the enhanced inclusion behaviors. On the other hand, when compared to melt crystallization, cold crystallization results in much smaller spherulites (from higher nucleation density) and sufficient space among spherulites, which accounts for the enrichment of TAIC in interspherulitic regions and for its enhanced exclusion. In the adopted polymer–small molecule blend, TAIC can enrich in interspherulitic regions even in its miscible blend with PLLA, which can be attributed to its stronger diffusion ability.