Isothermal crystallization kinetics of poly(lactic acid)/synthetic mica nanocomposites

The isothermal crystallization kinetics of PLA/fluoromica nanocomposites was studied. Three types of synthetic mica at three concentrations (2.5, 5.0, and 7.5 wt % mica) were used and the effect of these micas on the crystallization and thermal properties of PLA was investigated by differential scanning calorimetry (DSC). The Avrami and Hoffman‐Weeks equations were used to describe the isothermal crystallization kinetics and melting behavior. Addition of these micas to the PLA matrix increased the crystallization rate, and this effect depended on the mica type and concentration. While the nonmodified Somasif ME‐100 exerted the smallest effect, the effect observed for the organically modified Somasif MPE was the most pronounced. The lower half‐time of crystallization t_1/2 was around 3 min for the PLA/Somasif MPE nanocomposites containing 7.5 wt % of filler at 90°C, which is about 16 min below that found for neat PLA. The equilibrium melting temperature ( ) of PLA were estimated for these systems, showing an increase in the composites and an increase with increasing loading, except for PLA/Somasif MPE, in which the increase of the mica content decreased about 5°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40322.     

Crystallization behavior of poly(lactide)/poly(β‐hydroxybutyrate)/talc composites

The morphology and miscibility of commercial poly(lactide) (PLA)/poly(β‐hydroxybutyrate) (PHB, from 5 to 20 wt %) blends prepared by melt extrusion method, were investigated using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) observations. The results show that for all the studied blend contents, PLA/PHB blends are immiscible. The effects of PHB and talc on the nonisothermal cold crystallization kinetics of PLA were examined using a differential scanning calorimetry (DSC) at different heating rates. PHB acted as a nucleating agent on PLA and the addition of talc to the blend yielded further improvement, since significant increase in the enthalpy peak was observed for samples containing 10 wt % PHB and talc (from 0.5 to 5 phr). The crystallization kinetics were then examined using the Avrami–Jeziorny and Liu–Mo approach. The simultaneous presence of PHB and talc induced a decrease of the crystallization half time. The evolution of activation energies determined with Kissinger's equation suggests that blending with PHB and incorporating talc promote nonisothermal cold crystallization of PLA. The synergistic nucleating effect of PHB and talc was also observed on isothermal crystallization of PLA from the melt. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal degradation of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) in drying treatment

This study examines the isothermal treatment of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) powders and films. The PHB and PHBV crystallinities were determined using X‐ray diffractometry, and shown to increase with temperature (130–150°C) and then decreased from 55% to 45% at 180°C. The crystal morphology of crystal planes (101) and (111) became sharp at a high temperature. The weight average molecular weight (M_w) of PHB decreased from 1,028,000 to 41,800 g/mol when heated at 180°C for 30 min. The molecular weight of PHB decreased more rapidly than that of PHBV with time. No peak signal was observed in gel permeation chromatography after heating at 150°C because the solubility of PHB changed with crystallinity. The thermal behaviors of PHB and PHBV were analyzed by differential scanning calorimetry and thermogravimetric analysis. The roughness, contact angle, and surface morphology of PHB and PHBV films were also measured to determine the surface properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3659–3667, 2013     

Environmental degradation of biodegradable polyesters. IV. The effects of pores and surface hydrophilicity on the biodegradation of poly(ϵ‐caprolactone) and poly[(R)‐3‐hydroxybutyrate] films in controlled seawater

Poly(?‐caprolactone) (PCL) and poly[(R)‐3‐hydroxybutyrate] (R‐PHB) films with pores and hydrophilic surfaces were prepared by the water extraction of poly(ethylene oxide) from as‐cast blend films (1:1) and by the alkali treatment of as‐cast nonporous films, respectively. These films, as well as as‐cast nonporous PCL and R‐PHB films, were biodegraded in static seawater kept at 25°C, and their biodegradation was monitored with gravimetry, gel permeation chromatography (GPC), and scanning electron microscopy. The pores or highly hydrophilic surfaces of the PCL and R‐PHB films enhanced their biodegradation in seawater. Moreover, GPC measurements could be used to trace the biodegradation in seawater when the biodegradation proceeded to a great extent. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 587–593, 2003     

Biopolyester‐based nanocomposites: Structural,thermo‐mechanical and biocompatibility characteristics of poly(3‐hydroxybutyrate)/montmorillonite clay nanohybrids

In this work, the structural, thermal, mechanical, and biocompatibility characteristics of biopolyester‐based nanocomposites with phyllosilicate clays, namely those of poly(3‐hydroxybutyrate) (PHB) with octadecylamine‐modified montmorillonite (C₁₈MMT), are reported. PHB/clay nanocomposites with various loadings were prepared by melt mixing. X‐ray diffraction measurements and transmission electron microscopy images revealed the coexistence of intercalated and exfoliated states in the produced nanocomposites. Atomic force microscopy imaging also shed light to the morphological characteristics of the pure PHB and the prepared nanocomposites. The thermal stability of the nanohybrid materials was improved with the 5 wt % loading nanocomposite to show the best improvement. In addition, the nanohybrids have lower melting point compared to pure PHB and enhanced storage modulus (E′). Finally, the biocompatibility of pristine PHB and the 5 wt % nanocomposite was assessed by studying the morphology and proliferation of osteoblast cells attached on their surfaces. The results after 3 and 7 days of cell culturing indicate the incorporation of nanoclays does not change the cell adhesion and spreading as compared to those on pure PHB. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41628.     

Isothermal degradation of poly(3‐hydroxybutyrate)/organically modified montmorillonite nanocomposites

Polymer nanocomposites consisted of biodegradable poly(3‐hydroxybutyrate) (PHB) and organically modified montmorillonite Cloisite25A (OMMT), prepared by the solution‐casting method, were isothermally degraded for 120 min at 230, 235, 240, and 245°C in the nitrogen atmosphere. The addition of OMMT increases the thermal stability of PHB, and the most pronounced effect has the addition of 7 wt% of OMMT. Kinetic analysis was performed using reduced time plots and model‐free isoconversional methods. The empirical kinetic triplets (E, A, and g(α)) for the isothermal degradation of pure PHB and PHB/OMMT nanocomposites were determined. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

The morphology and degradation behavior of electrospun poly(3‐hydroxybutyrate)/Magnetite and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/Magnetite composites

Electrospinning of biodegradable poly(3‐hydroxybutyrate) (PHB)/magnetite and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV)/magnetite composites in 2,2,2‐trifluoroethanol (TFE) and chloroform are investigated to develop nonwoven nanofibrous structure. Ultrafine PHB/magnetite fibers are obtained and the resulting fiber diameters are in the range of 690–710 nm and 8.0–8.4 µm for the polymer dissolved in TFE and chloroform. The surface of PHB composites fiber fabricated in chloroform contains porous structures, which are not observed for the sample of PHB composites fiber dissolved in TFE. The fiber diameters for PHBV5/magnetite composites are in the range of 500–540 nm and 2.3–2.5 µm, depending on the use of TFE and chloroform. The average diameters of PHBV5/magnetite composite fibers are smaller than those of PHB/magnetite composites fiber. All electrospun PHB/magnetite and composite fibers are superparamagnetic. The degradation behaviors of PHB/magnetite and PHBV5/magnetite composite fibers were investigated using Caldimonas manganoxidans. For the fabricated composite fibers, it is found that the degradation rate increased with the increasing loading of magnetite nanoparticles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41070.     

Degradation behavior of hydrogels from poly(vinyl alcohol)‐graft‐[poly(rac‐lactide)/poly(rac‐lactide‐co‐glycolide)]: Influence of the structure and composition on the material's stability

The swellability and mass loss of poly(vinyl alcohol)‐graft‐[poly(rac‐lactide)/poly(rac‐lactide‐co‐glycolide)] hydrogels upon hydrolysis are strongly affected by the composition of the hydrogels. Hydrophobic hydrogels remain at a relatively constant mass for a couple of weeks, and the mass decreases dramatically thereafter, whereas more hydrophilic hydrogels lose mass right from the beginning. All hydrogels display water uptake values between 90 and 280% within 8 weeks. For longer periods of degradation, the water uptake increases up to a maximum of about 900%. Studies of the thermal properties of samples upon degradation and their IR measurements have shown that the degradation rate is related to the physical and chemical structure of the hydrogels and hence to the hydrophobic/hydrophilic balance; that is, the degradation increases with the increasing hydrophilicity of the material. As a result, degradation can be engineered through the variation of the composition and structure of the material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(ethylene terephthalate)/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate)/clay nanocomposites: Effects of biaxial stretching

In this study, we fabricated poly(ethylene terephthalate) (PET)/clay, PET/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate) (PETG), and PET/PETG/clay nanocomposite plates and biaxially stretched them into films by using a biaxial film stretching machine. The tensile properties, cold crystallization behavior, optical properties, and gas and water vapor barrier properties of the resulting films were estimated. The biaxial stretching process improved the dispersion of clay platelets in both the PETG and PET/PETG matrices, increased the aspect ratio of the platelets, and made the platelets more oriented. Thus, the tensile, optical, and gas‐barrier properties of the composite films were greatly enhanced. Moreover, strain‐induced crystallization occurred in the PET/PETG blend and in the amorphous PETG matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42207.     

Melt‐processed biodegradable polyester blends of poly(L‐lactic acid) and poly(ε‐caprolactone): Effects of processing conditions on biodegradation

Biodegradable polyester blends were prepared from poly(L ‐lactic acid) (PLLA) and poly(ε‐caprolactone) (PCL) (50/50) by melt‐blending, and the effects of processing conditions (shear rate, time, and strain) of melt‐blending on proteinase‐K‐ and lipase‐catalyzed enzymatic degradability were investigated using gravimetry, differential scanning calorimetry, and scanning electron microscopy. The proteinase‐K‐catalyzed degradation rate of the blend films increased and leveled off with increasing the shear rate, time, or strain for melt‐blending, except for the shortest shear time of 60 s. The optimal processing conditions of melt‐blending giving the maximum rate of lipase‐catalyzed degradation were 9.6 × 10² s^?1 and 180 s, whereas a deviation from these conditions caused a reduction in lipase‐catalyzed enzymatic degradation rate. At the highest shear rate of 2.2 × 10³ s^?1, PCL‐rich phase was continuous in the blend films, irrespective of the shear time (or shear strain), whereas PLLA‐rich phase changed from dispersed to continuous by increasing the shear time (or shear strain). This study revealed that the biodegradability of PLLA/PCL blend materials can be manipulated by altering the processing conditions of melt‐blending (shear rate, time, or strain) or the sizes and morphology of PLLA‐rich and PCL‐rich domains. The method reported in the present study can be utilized for controlling the biodegradability of other biodegradable polyester blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 831–841, 2007     

Nanocomposites based on poly(ϵ‐caprolactone) and the montmorillonite treated with dibutylamine‐terminated ϵ‐caprolactone oligomer

Dibutylamine‐terminated ε‐caprolactone oligomers (CLOs: CLOL, CLOM, and CLOH) with number–averaged molecular weight (M_n), 500, 1300, and 2200, respectively, were synthesized by the ring‐opening polymerization of ε‐caprolactone initiated by 2‐(dibutylamino)ethanol in the presence of tin(II) 2‐ethylhexanoate. Nanocomposites based on poly(ε‐caploractone) (PCL) and the caprolactone oligomer‐treated montmorillonites (CLO‐Ms: CLOL‐M, CLOM‐M, and CLOH‐M) were prepared by melt intercalation method. The XRD and TEM analyses of the PCL composites revealed that the extent of exfoliation of the clay platelets increased with increasing molecular weight of the used CLOs. Tensile strength and modulus of the PCL/CLO‐M composites increased with increasing molecular weight of the CLO and increasing inorganic content. The tensile modulus of the PCL/CLOH‐M nanocomposite with inorganic content 5.0 wt % was three times higher than that of control PCL. Among the PCL/CLO‐M composites, the PCL/CLOM‐M composite had the highest crystallization temperature and melting temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Flame‐retarding mechanism of organically modified montmorillonite and phosphorous‐Nitrogen flame retardants for the preparation of a halogen‐free,flame‐retarding thermoplastic poly(ester ether) elastomer

In this study, thermoplastic poly(ester ether) elastomer (TPEE) nanocomposites with phosphorus–nitrogen (P–N) flame retardants and montmorillonite (MMT) were prepared by melt blending. The fire resistance of the nanocomposites was analyzed by limiting oxygen index (LOI) and vertical burning (UL 94) tests. The results show that the addition of the P–N flame retardants increased the LOI of the material from 17.3 to 27%. However, TPEE containing P–N flame retardants only obtained a UL 94 V‐2 ranking; this resulted in a flame dripping phenomenon. On the other hand, TPEE containing the P–N flame retardant and organically modified montmorillonite (o‐MMT) achieved better thermal stability and good flame retardancy; this was ascribed to its partially intercalated structure. The synergistic effect and synergism were investigated by Fourier transform infrared spectroscopy and thermogravimetry. The introduction of o‐MMT decreased the inhibition action of the P–N flame retardant and increased the amount of residues. The catalytic decomposition effect of MMT and the barrier effect of the layer silicates are discussed in this article. The residues after heating in the muffle furnace were analyzed by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and laser Raman spectroscopy. It was shown that the intercalated layer silicate structure facilitated the crosslinking interaction and promoted the formation of additional carbonaceous char residues in the formation of the compact, dense, folded‐structure surface char. The combination of the P–N flame retardant and o‐MMT in TPEE resulted in a better thermal stability and fire resistance because of the synergistic effect of the mixture. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41094.     

Compatibilization of polypropylene/ poly(3‐hydroxybutyrate) blends

Blending polypropylene (PP) with biodegradable poly(3‐hydroxybutyrate) (PHB) can be a nice alternative to minimize the disposal problem of PP and the intrinsic brittleness that restricts PHB applications. However, to achieve acceptable engineering properties, the blend needs to be compatibilized because of the immiscibility between PP and PHB. In this work, PP/PHB blends were prepared with different types of copolymers as possible compatibilizers: poly(propylene‐g‐maleic anhydride) (PP–MAH), poly (ethylene‐co‐methyl acrylate) [P(E–MA)], poly(ethylene‐co‐glycidyl methacrylate) [P(E–GMA)], and poly(ethylene‐co‐methyl acrylate‐co‐glycidyl methacrylate) [P(E–MA–GMA)]. The effect of each copolymer on the morphology and mechanical properties of the blends was investigated. The results show that the compatibilizers efficiency decreased in this order: P(E–MA–GMA) > P(E–MA) > P(E–GMA) > PP–MAH; we explained this by taking into consideration the affinity degree of the compatibilizers with the PP matrix, the compatibilizers properties, and their ability to provide physical and/or reactive compatibilization with PHB. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Viscoelastic properties of poly(ε‐caprolactone)/clay nanocomposites in solid and in melt state

Viscoelastic properties in solid and in melt state of poly(ε‐caprolactone), PCL, nanocomposites with organomodified clays (Cloisite30B and Cloisite15A) are thoroughly investigated. Although WAXD is insensitive to the difference in the nanocomposites structure, the melt rheology reveals pronounced differences between the two series. Melt yield stress values, obtained from fittings by the Carreau–Yasuda model, are used as a measure of partial exfoliation of the clay. Temperature dependence of the shift factors, used for time–temperature superposition of the modulus curves, yields similar values of the flow activation energies for all the samples. Temperature dependences of the dynamic modulus and loss factor of solid nanocomposites were correlated to the structural differences deduced from the melt rheology. The increase in the storage modulus is compared to the theoretical predictions from the Halpin–Tsai model. The effective aspect ratio obtained from this comparison agrees reasonably with the value estimated from the melt rheology. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42896.     

Synthesis,characterization, and properties of degradable poly(l‐lactic acid)/poly(butylene terephthalate) copolyesters containing 1,4‐cyclohexanedimethanol

High‐molecular‐weight copolyesters based on poly(butylene terephthalate) as rigid aromatic segments and poly(l‐lactic acid) (PLLA) as degradable aliphatic segments were synthesized via the polycondensation of terephthalic acid, 1,4‐butanediol (BDO), 1,4‐cyclohexanedimethanol (CHDM), and PLLA oligomer. By tailoring the molar ratio of diols (BDO and CHDM), we investigated in detail the effects of the CHDM rigid hexacyclic ring on the synthesis, mechanical properties, thermal stabilities, and degradation behaviors of the copolyesters. With increasing CHDM content, the initial decomposition temperature increased from 282.5 to 322.2°C, and the tensile strength improved by nearly four times, from 5.4 to 19 MPa. When the molar ratio of BDO/CHDM was 95/5, the weight‐average molecular weight of the copolyester was 89,400 g/mol with a polydispersity of 1.96. In addition, hydrolytic degradation results in phosphate buffer solution indicate that the degradation rate of the copolyesters displayed a strong dependency on the temperature and CHDM composition. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Nanocomposites based on poly(butylene adipate‐co‐terephthalate) and montmorillonite

Nanocomposites based on biodegradable poly(butylene adipate‐co‐terephthalate) (PBAT) and layered silicates were prepared by the melt intercalation method. Nonmodified montmorillonite (MMT) and organo‐modified MMTs (DA‐M, ODA‐M, and LEA‐M) by the protonated ammonium cations of dodecylamine, octadecylamine, and N‐lauryldiethanolamine, respectively, were used as the layered silicates. The comparison of interlayer spacing between clay and PBAT composites with inorganic content 3 wt % measured by X‐ray diffraction (XRD) revealed the formation of intercalated nanocomposites in DA‐M and LEA‐M. In case of PBAT/ODA‐M (3 wt %), no clear peak related to interlayer spacing was observed. From morphological studies using transmission electron microscopy, the ODA‐M was found to be finely and homogeneously dispersed in the matrix polymer, indicating the formation of exfoliated nanocomposite. When ODA‐M content was increased, the XRD peak related to intercalated clay increased. Although the exfoliated ODA‐M (3 wt %) nanocomposite showed a lower tensile modulus than the intercalated DA‐M and LEA‐M (3 wt %) composites, the PBAT/ODA‐M composite with inorganic content 5 wt % showed the highest tensile modulus, strength, and elongation at break among the PBAT composites with inorganic content 5 wt %. Their tensile properties are discussed in relation to the degree of crystallinity of the injection molded samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 386–392, 2005     

The Effect of γ‐Irradiation on the Structure and Properties of Poly(propylene)/Clay Nanocomposites

The oxidative degradation of PP/OMMT nanocomposites under γ‐irradiation was studied. Changes in structure and properties resulting from γ‐exposure in the range 0–100 kGy were investigated. The results were analyzed by comparing the influence of PP‐g‐MA and pristine OMMT on the oxidation kinetics of neat PP. γ‐Irradiation in the presence of air strongly degraded the properties of PP materials, particularly for radiation doses above 20 kGy. The rate of oxidative degradation of PP/OMMT/PP‐g‐MA nanocomposites was much faster than that of neat PP. This suggests that PP‐g‐MA and pristine OMMT components behave as oxidation catalysts, leading to the formation of free radicals in the polymer matrix.

     

Tough hyperbranched epoxy/poly(amido‐amine) modified bentonite thermosetting nanocomposites

A tough and highly flexible hyperbranched epoxy and poly(amido‐amine) modified bentonite based thermosetting nanocomposite was demonstrated. The FTIR, XRD, and TGA analyses confirmed the modification of bentonite. The formation of partially exfoliated structure of the nanocomposite with good physicochemical interactions among the hyperbranched epoxy, poly(amido‐amine) hardener and modified clay was investigated by the FTIR, XRD, SEM, and TEM analyses. Significant improvements of 750% toughness, 300% elongation at break, 50% tensile strength, 300% modulus, and 250% adhesive strength of the pristine epoxy were achieved by the formation of nanocomposites with 3 wt % of modified clay. The experimental modulus values of the nanocomposites were compared with three theoretical models to account the interactions between filler and matrix. Thus, the studied epoxy nanocomposite has great potential to be used as an advanced epoxy thermoset. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40327.     

Effect of additives on the melt rheology and thermal degradation of poly[(R)‐3‐hydroxybutyric acid]

Thermal degradation of poly[(R)−3‐hydroxybutyric acid] (PHB) during melt mixing results in random chain scission that produces shorter polymer chains containing crotonic and carboxyl end groups. One way of preventing this serious reduction of molar mass is to add agents that react with at least two of the newly generated end groups. Different types of commercially available additives known to react with carboxyl group, namely bis(3,4‐epoxycyclohexylmethyl) adipate (BECMA), 2,2'‐bis(2‐oxazoline) (BOX), trimethylolpropane tris(2‐methyl‐1‐aziridinepropionate) (PETAP), triphenyl phosphate (TPP), tris(nonylphenyl) phosphate (TNPP), polycarbodiimide (PCDI), and poly(methyl metharylate‐co‐glycidyl methacrylate) (GMA.MMA) were mixed with PHB by cocasting from solution in chloroform. Dynamic rheology as well as measurements of molar masses before and after dynamic analysis was used to evaluate the effect of the additives on the melt stability of PHB. Measurements of the dynamic shear modulus and the molar mass of molten PHB with the additives PCDI and GMA.MMA showed a minor improvement on the thermal stability. Furthermore, TPP and TNPP did not affect the thermal stability of PHB, whereas the presence of BECMA, BOX, and PETAP gave a strong decrease of the dynamic modulus compared with neat PHB. © 2014 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41836.     

Crystallization and melting behavior of poly(ε‐caprolactone‐co‐δ‐valerolactone) and poly(ε‐caprolactone‐co‐L‐lactide) copolymers with novel chain microstructures

Nuclear magnetic resonance spectroscopy (NMR) characterization of the statistical copolymers of this study showed that the poly(ε‐caprolactone‐co‐L‐lactide)s, with ε‐caprolactone (ε‐CL) molar contents ranging from 70 to 94% and ε‐CL average sequence length (l_CL) between 2.20–9.52, and the poly(ε‐caprolactone‐co‐δ‐valerolactone)s, with 60 to 85% of ε‐CL and l_CL between 2.65–6.08, present semi‐alternating (R→2) and random (R～1) distribution of sequences, respectively. These syntheses were carried out with the aim of reducing the crystallinity of poly(ε‐caprolactone) (PCL), needed to provide mechanical strength to the material but also responsible for its slow degradation rate. However, this was not achieved in the case of the ε‐caprolactone‐co‐δ‐valerolactone (ε‐CL‐co‐δ‐VAL). Non‐isothermal cooling treatments at different rates and isothermal crystallizations (at 5, 10, 21 and 37°C) were conducted by differential scanning calorimetry (DSC), and demonstrated that ε‐CL copolymers containing δ‐valerolactone (δ‐VAL) exhibited a larger crystallization capability than those of L‐lactide (L‐LA) and also arranged into crystalline structures over shorter times. The crystallization enthalpies of the ε‐CL‐co‐δ‐VAL copolymers during the cooling treatments and their heat of fusion (ΔH_m) at the different isothermal temperatures were very large (i.e. ΔH_c > 53 Jg^?1) and in some cases, unrelated to the copolymer composition. In some compositions, such as the 60 : 40, Wide Angle X‐ray Scattering (WAXS) proved that that these two lactones undergo isomorphism and co‐crystallize in a single cell. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42534.