Solid-state relaxations in linear low-density (1-octene comonomer), low-density,and high-density polyethylene blends

Extensive thermal and relaxational behavior in the blends of linear low-density polyethylene (LLDPE) (1-octene comonomer) with low-density polyethylene (LDPE) and high-density polyethylene (HDPE) have been investigated to elucidate miscibility and molecular relaxations in the crystalline and amorphous phases by using a differential scanning calorimeter (DSC) and a dynamic mechanical thermal analyzer (DMTA). In the LLDPE/LDPE blends, two distinct endotherms during melting and crystallization by DSC were observed supporting the belief that LLDPE and LDPE exclude one another during crystallization. However, the dynamic mechanical β and γ relaxations of the blends indicate that the two constituents are miscible in the amorphous phase, while LLDPE dominates α relaxation. In the LLDPE/HDPE system, there was a single composition-dependent peak during melting and crystallization, and the heat of fusion varied linearly with composition supporting the incorporation of HDPE into the LLDPE crystals. The dynamic mechanical α, β, and γ relaxations of the blends display an intermediate behavior that indicates miscibility in both the crystalline and amorphous phases. In the LDPE/HDPE blend, the melting or crystallization peaks of LDPE were strongly influenced by HDPE. The behavior of the α relaxation was dominated by HDPE, while those of β and γ relaxations were intermediate of the constituents, which were similar to those of the LLDPE/HDPE blends. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1633–1642, 1997     

Multivariable structural characterization of semicrystalline polymer blends by small‐angle light scattering

A new multi‐variable‐measurement approach for characterizing and correlating the nanoscale and microscale morphology of crystal‐amorphous polymer blends with melt‐phase behavior is described. A vertical small‐angle light scattering (SALS) instrument optimized for examining the scattering and light transmitted from structures ranging from 0.5 to 50 μm, thereby spanning the size range characteristic of the initial‐to‐late stages of thermal‐phase transitions (e.g., melt‐phase separation and crystallization) in crystal‐amorphous polymer blends, was constructed. The SALS instrument was interfaced with differential scanning calorimetry (DSC), and simultaneous SALS/DSC/transmission measurements were performed. We show that the measurement of transmitted light and SALS under H_V (cross‐polarized) optical alignments during melting can be used to reliably measure the thermodynamic (e.g., crystal melting and melt‐phase separation temperatures) and structural variables (e.g., crystalline fraction within the superstructures and volume fraction of superstructures) necessary for describing the multiphase behavior of crystal‐amorphous blends in one combined measurement. We also evaluate the orientation correlations of crystalline volume elements within the superstructures. Our results indicate that simultaneous measurement of transmitted light can provide a reliable estimate of the total scattering from density and orientation fluctuations and the melt‐phase separation temperature of polymer blends. For solution‐cast poly(?‐caprolactone)/poly(D,L‐lactic acid) blends, our multivariable measurements during melting provide the parameters necessary to generate a crystal–liquid and liquid–liquid phase diagram and characterize the solid‐state morphology. This opens up the challenge to explore use of our vertical SALS instrument as a rapid and convenient method for developing structure–property relationships for crystal‐amorphous polymer blends. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2714–2727, 2002     

Crystallization and thermal properties of PLLA comb polymer

Poly(L ‐lactide) (PLLA) on poly(2‐hydroxyethyl methacrylate) (PHEMA) backbone was prepared by a combination of atom transfer radical polymerization (ATRP) and ring‐opening polymerization (ROP). The structure of the comb polymer was analyzed by wide angle X‐ray diffraction (WAXD), small angle X‐ray scattering (SAXS), and differential scanning calorimetry (DSC). WAXD result indicates that the comb polymer has α crystalline modification with a 10₃ helical conformation. Lamellar parameters of the crystalline structure were obtained by one‐dimension correlation function (1DCF) calculated from SAXS results. The calculations show that the thickness of crystalline layer is controlled by annealing temperature and comb structure. DSC was applied to study kinetics of the crystallization and melting behavior. Two melting peaks on melting curves of the comb polymer at different crystallization temperature were detected, and the peak at higher temperature is attributed to the melt‐recrystallization. The equilibrium melting temperature is found to be influenced by the comb structure. In this article the effects of the comb structure on Avrami exponent, equilibrium melting point and melting peak of the comb polymer were discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 589–598, 2008     

Morphological Changes of Linear,Branched Polyethylenes and their Blends during Crystallization and Subsequent Melting by Synchrotron SAXS and DSC

Summary: The crystalline structure and phase morphology of linear, branched polyethylenes and their blends during crystallization and subsequent melting were investigated, using a combination of differential scanning calorimetry (DSC), and synchrotron small angle X-ray scattering (SAXS). A linear polyethylene (PE1) with weight-average molecular weight (M_w) of 114 000 g/mol, and two branched polyethylene copolymers, containing 4.8 mol% (PE4) and 15.3 mol% (PE10) hexane, with molecular weights of 93 000 g/mol and 46 000 g/mol were used as pure samples. Two blends, PE1-4 and PE1-10, each with a weight ratio of 50/50, were prepared by solution blending. Our results indicate that in PE4 a phase separation within the branched component itself occurred, forming a broad distribution of lamellar thicknesses during the crystallization process. PE10 on the other hand did hardly crystallize because of the high degree of branching. Co-crystallization of both components took place in blend PE1-4 and liquid-liquid phase separation occurred in the melt of PE1-10. Morphological parameters were determined by using Bragg's law and the correlation function, respectively. The detected semicrystalline morphology can be well described by the lamellar insertion mode where thin lamellae develop between thicker primary lamellae. During subsequent heating, lamellae melted in the reversed sequence of their formation. The evolution of the structural parameters as a function of temperature revealed that surface melting began at first, and then the complete melting of stacks occurred until the final melting temperature was reached.     

Preferential formation of electroactive crystalline phases in poly(vinylidene fluoride)/organically modified silicate nanocomposites

The role of organically modified silicate (OMS), Lucentite STN on the formation of β‐crystalline phase of poly(vinylidene fluoride) (PVDF) is investigated in the present study. The OMS was solution blended with PVDF and cast on glass slide to form PVDF‐OMS nanocomposites. Solution cast samples were subjected to various thermal treatments including annealing (AC‐AN), melt‐quenching followed by annealing (MQ‐AN), and melt‐slow cooling (MSC). Fourier‐transform infrared spectroscopy (FT‐IR), wide angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC) were used to investigate the crystalline structure of thermally treated samples. As a special effort, the combination of in situ thermal FT‐IR, WAXD, and DSC studies was utilized to clearly assess the thermal properties. FT‐IR and WAXD results of MQ‐AN samples revealed the presence of β‐phase of PVDF. Ion‐dipole interaction between the exfoliated clay nanolayers and PVDF was considered as a main factor for the formation of β‐phase. Melt‐crystallization temperature and subsequent melting point were enhanced by the addition of OMS. Solid β‐ to γ‐crystal phase transition was observed from in situ FT‐IR and WAXD curves when the representative MQ‐AN sample was subjected to thermal scanning. Upon heating, β‐phase was found to disappear through transformation to the thermodynamically stable γ‐phase rather than melting directly. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2173–2187, 2008     

Phase behavior of crystalline blends of poly(tetrafluoroethylene) and of random fluorinated copolymers of tetrafluoroethylene

In the present article, we investigate by differential scanning calorimetry (DSC) the thermal behavior (melting, crystallization, and crystal–crystal transitions) far from equilibrium of blends constituted of two crystalline polymers. In particular, the following blends are examined: PTFE–PFMVE, PTFE–FEP, and FEP–PFMVE where PTFE is poly(tetrafluoroethylene), PFMVE is poly(tetrafluoroethylene‐co‐perfluoromethylvinylether), and FEP is poly(tetrafluoroethylene‐co‐hexafluoropropylene). The two last ones are random tetrafluoroethylene copolymers with small amounts of comonomer. Our results indicate that, under the experimental investigated conditions, the blends containing PTFE do not give cocrystallization on cooling from the melt, although under very rapid crystallization conditions, quenching, the presence of the copolymer would seem to slightly influence PTFE crystallization (lower peak temperatures are observed for the crystalline transitions and the melting with respect to those of the neat homopolymer). The behavior of the FEP–PFMVE blend is completely different; in fact, our results indicate the occurrence of cocrystallization, then miscibility in the crystalline phase, for almost all compositions and all investigated experimental conditions. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 679–689, 1999     

Micro‐phase‐separation behavior of amphiphilic polyurethanes involving poly(ethylene oxide) and poly(tetramethylene oxide)

The temperature dependence of thermal, morphological, and rheological properties of amphiphilic polyurethanes was examined with differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXS), small‐angle X‐ray scattering (SAXS), rheological measurements, and Fourier transform infrared spectroscopy. Multiblock (MPU) and triblock (TPU) polyurethanes were synthesized with two crystallizable segments—poly(ethylene oxide) (PEO) as a hydrophilic block and poly(tetramethylene oxide) (PTMO) as a hydrophobic block. DSC and WAXS measurements demonstrated that the microphase of MPUs in the solid state is dominantly affected by the PEO crystalline phase. However, high‐order peaks were not observed in the SAXS measurements because the crystallization of the PEO segments in MPUs was retarded by poor sequence regularity. The microphase in the melt state was induced by the hydrogen bonding between the N? H group of hexamethylene diisocyanate linkers and the ether oxygen of PEO or PTMO blocks. As the temperature increased, the smaller micro‐phase‐separated domains were merged into the larger domains, and the liquidlike ordering was eventually disrupted because of the weakening hydrogen bonding. However, the fully homogeneous state of an MPU with a molar ratio of 5/5 PEO/PTMO (MPU55) was not confirmed even at much higher temperatures with both SAXS and rheological measurements. However, the SAXS patterns of TPU showed weak but broad second‐order peaks below the melting temperature of the PEO block. Compared with MPU55, the ordering of the TPU crystalline lamellar stacks was enhanced because of the high sequence regularity and the low hydrogen‐bonding density. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2365–2374, 2003     

Use of SAXS and linear correlation functions for the determination of the crystallinity and morphology of semi‐crystalline polymers. Application to linear polyethylene

The use of correlation functions to obtain the morphological parameters of crystalline‐amorphous two‐phase lamellar systems is critically reviewed and extended. It is shown that processing of the experimental SAXS‐patterns only significantly affects the curvature of the autocorrelation triangle and that the parameters of the corresponding ideal two‐phase structure can be determined independently of the data processing procedure. The methods to be used depend on the normalization of the correlation function. The validity of the formulation is illustrated for a sample of linear polyethylene, cooled and heated at 10°C per min. Crystallite thickening during crystallization and surface melting during heating are observed. The overall crystallinity and the fraction of semi‐crystalline stacks during crystallization and melting are determined quantitatively as a function of temperature using the total scattering power of the corresponding ideal two‐phase structure, correlation functions, and a scaling procedure. Absolute intensities are not required. The SAXS results are confirmed by independent techniques (DSC, WAXD, and SALLS). During crystallization, amorphous regions are present outside the semi‐crystalline regions because growing spherulites do not fill space completely. During melting, larger amorphous regions develop in the spherulites because of the complete melting of stacks. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1715–1738, 1999     

The double melting behavior of a liquid crystalline polyimide derived from PMDA and 1,3‐bis[4‐(4′‐aminophenoxyl) cumyl] benzene

The double melting behavior of a thermotropic liquid crystalline polyimide was studied by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), transmission electron microscopy (TEM), wide‐angle X‐ray diffraction (WAXD), and small‐angle X‐ray scattering (SAXS). This liquid crystalline polyimide exhibited a normal melting peak around 278 °C and transformed into a smectic A phase. The smectic A phase changed to nematic phase upon heating to 298 °C, then became isotropic melt around 345 °C. The samples annealed or isothermally crystallized at lower temperature showed double melting endotherms during heating scan. The annealing‐induced melting endotherm was highly dependent on annealing conditions, whereas the normal melting endotherm was almost not influenced by annealing when the annealing temperature was low. Various possibilities for the lower melting endotherm are discussed. The equilibrium melting points of both melting peaks were extrapolated to be 283.2 °C. Combined analytical results showed that the double melting peaks were from the melting of the two types of crystallites generated from two crystallization processes: a slow and a fast one. Fast crystallization may start from the well‐aligned liquid crystal domains, whereas the slow one may be from the fringed or amorphous regions. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3018–3031, 2000     

线性低密度聚乙烯在与丁苯橡胶的共混体系中的结晶行为

本工作采用DSC、X-射线衍射、小角激光光散射、偏光显微镜等手段,研究了线性低密度聚乙烯/丁苯橡胶共混体系中聚乙烯的结晶结构、平衡熔点和结晶动力学。     

A new approach to DSC calibration in wax/polymer blending

DSC analysis of wax/polymer blends is carried out between 270 and 420 K. Calibration for melting point and enthalpy is normally carried out using indium (melting point 430 K), which is unsatisfactory for these materials. IUPAC organic standards covering this range tend to sublime and their onset temperatures are variable. Pure alkanes have similar thermal characteristics to wax/polymer blends and some have been well characterised by adiabatic calorimetry. They are being investigated as alternative secondary calibration standards to give more accurate thermal characterisation of wax/polymer blends. Also,n-triacontane can be used to check DSC resolution.     

Phase behavior and crystallization of a poly(ethylene oxide)/cellulose acetate butyrate blend

The phase behavior of a partially miscible blend of poly(ethylene oxide) (PEO) and cellulose acetate butyrate (CAB) and the crystalline microstructure of PEO in the blend were studied with differential scanning calorimetry (DSC), optical microscopy, and synchrotron small‐angle X‐ray scattering (SAXS) methods. PEO/CAB showed a lower critical solution temperature (LCST) of 168 °C at the critical composition of PEO of 60 wt %. All blend compositions showed a single glass‐transition temperature (T_g) when they were prepared at temperatures lower than the LCST. However, with increasing CAB content, T_g of the blend changed abruptly at 70 wt % CAB; that is, a cusp existed. Below 70 wt % CAB, the change in T_g with blend composition was predicted by the Brau–Kovacs equation, whereas this change was predicted by the Fox equation at higher CAB contents. A gradual but small depression of the melting point of PEO in the blend with an increasing amount of CAB suggested that the PEO/CAB blends exhibited a weak intermolecular interaction. From DSC and SAXS experiments, it was found that amorphous CAB was incorporated into the interlamellar region of PEO for blends with less than 20 wt % CAB, whereas it was segregated to exist in the interfibrillar region in PEO for other blends with larger amounts of CAB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1673–1681, 2002     

Novel characterization of the crystalline segment distribution and its effect on the crystallization of branched polyethylene by differential scanning calorimetry

Based on a thermal segregation treatment, a novel semiquantitative method for the characterization of the crystalline segment distribution in branched polyethylene copolymers was established by the results of differential scanning calorimetry being treated with the Gibbs–Thomson equation. The method was used to describe the segment distribution of Ziegler–Natta‐catalyzed linear low‐density polyethylene (Z–N LLDPE), metallocene‐catalyzed linear low‐density polyethylene (m‐LLDPE), and a commercial linear low‐density polyethylene with a wide molecular weight distribution. The isothermal crystallization kinetics of Z–N LLDPE and m‐LLDPE were studied to assess the effect of different segment distributions. According to their molecular characteristics, the crystallization behaviors were analyzed. They indicated that the different segment distributions of the two polymers resulted in different crystallization processes, including the nucleation and growth of crystals under various crystallization conditions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2107–2118, 2002     

Effect of melt temperature on the phase morphology, thermal behavior and mechanical properties of injection-molded PP/LLDPE blends

<正>The phase morphology and thermal behavior of various isotactic polypropylene(PP)/linear low density polyethylene(LLDPE) blends were investigated with aid of scanning electron microscopy(SEM) and differential scanning calorimetry(DSC),respectively.The effect of barrel(melt) temperature on the morphology,thermal behavior and the resultant mechanical properties of the injection molded bars was the research focus,and the influence of LLDPE composition was also taken into account.It was found that the mechanical properties,especially the tensile ductility and the impact strength,were greatly affected by the processing temperature.The samples obtained at low temperatures had the highest elongation at break and impact strength,while those molded at high temperatures had the poorest toughness.Two reasons were responsible for that:first,the phase size in the samples increased with the processing temperature;second, possible orientation existed in the samples obtained at low processing temperatures.     

Polyetherether ketone/polyarylethersulfone blends: Thermal and compatibility aspects

The compatibility behavior of polyetherether ketone (PEEK) with poly(ether sulfone) (PES) has been reexamined using differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and extrudate swell measurements. The blends were prepared by both melt‐blending and solution‐blending techniques. The phase behavior of blends is strongly affected by the blending technique used. Blends prepared by solution‐blending are compatible in the entire composition range on the basis of the single composition‐dependent glass transitions and exhibit lower critical solution temperature (LCST) behavior. LCST was near 340 °C around which the crystalline melting point of PEEK exists. Near LCST melting‐induced movement of molecular chains disturbs the initial homogeneous state of the solution blends and leads to a phase‐separated state that is thermodynamically more stable in the absence of strong specific interactions between the homopolymers. Contrary to the solution‐blended samples, melt‐blended samples were in the phase‐separated state even at a lower processing temperature of 300 °C. Two glass transitions corresponding to a PEEK‐rich and a PES‐rich phase were found for all compositions. From the measured glass transition of phase‐separated blends, weight fractions of PES and PEEK dissolved in each phase were determined using the Fox equation. Compatibility is greater in the PEEK‐rich compositions than in the PES‐rich compositions. PEEK dissolves more in PES‐rich phases than does PES in the PEEK‐rich phase. Variation of the specific heat increment (ΔC_p) at the glass transition with composition also supports these inferences. Solution‐blended samples, quenched from 380 °C, also indicated similar behavior but were slightly more compatible. The aforementioned results are consistent with those inferred from SEM studies and extrudate swell measurements that show a greater compatibility in PEEK‐rich compositions than in PES‐rich compositions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1407–1424, 2002     

Application of SSA thermal fractionation and X‐ray diffraction to elucidate comonomer inclusion or exclusion from the crystalline phases in poly(butylene succinate‐ran‐butylene azelate) random copolymers

Poly(butylene succinate‐ran‐butylene azelate) random copolyesters were thermally fractionated by successive self‐nucleation and annealing (SSA). The samples before and after SSA were analyzed by differential scanning calorimetry (DSC) and X‐ray diffraction (WAXS and SAXS). WAXS results indicate that a small degree of comonomer inclusion is present in the crystalline phases that are formed in the copolymers depending on composition: a PBS‐like unit cell or/and a PBAz‐like unit cell, thus confirming the isodimorphic behavior of the samples. SSA on the other hand demonstrated that the degree of comonomer exclusion during crystallization is far larger than comonomer inclusion, as judged by the increase in fractionation degree with compositions leading to the pseudo‐eutectic point. Furthermore, WAXS, SAXS, and SSA results show that the isodimorphic behavior is not highly dependent on kinetic factors, as the degree of comonomer inclusion or exclusion in the samples was not significantly altered by SSA thermal fractionation, a thermal treatment that promotes annealing and molecular segregation of defects to the amorphous regions of the material. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2346–2358     

Structure of a self-assembled hydrogen-bonded ‘living’ main chain liquid crystalline polymer

A main chain hydrogen-bonded liquid crystalline polymer was formed by melt mixing two complementary components, A and B, which in their individual states do not exhibit liquid crystallinity. The structure of the polymer and the thermal stability of its mesophase were studied using synchrotron radiation SAXS/WAXS/DSC at Daresbury (UK) and by variable temperature Fourier transform infrared. The chain extension, or “polymerization” process, was accelerated at the point when the polymer formed a liquid crystalline phase upon cooling from the isotropic melt. The polymer has an aabb chain structure and forms a smectic layer with a length of the A-B repeating unit. The hydrogen-bonded main chain polymer studied here is a monotropic liquid crystal. Above 150°C, it exhibits kinetic stabilization of its monotropic smectic phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1617–1624, 1998     

Nonisothermal crystallisation, melting behavior and wide angle X-ray scattering investigations on linear low density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends: effects of compatibilisation and dynamic crosslinking

Crystallisation studies on LLDPE/EVA blends and the individual components were performed with wide angle X-ray scattering (WAXS) technique and differential scanning calorimetry (DSC) DSC was used to characterise the quiescent crystallisation behavior. The heat of fusion and crystallinity of the blends were reduced by the addition of EVA. The experimental and theoretical values of crystallinity of the blends were found to be mutually agreeing. Crystallisation of LLDPE remains impeded to some extent due to the presence of amorphous EVA. Compatibilisation does not affect crystallinity whereas crosslinking decreases crystallinity. Crosslinking and compatibilisation make no significant change in the melting temperature of the blends. X-ray diffraction studies were carried out on un-crosslinked and crosslinked LLDPE/EVA blends with a view to study the effect of blend composition and crosslinking on crystallinity and lattice distance. Studies revealed that LLDPE and EVA have orthorhombic unit cell. Blending with EVA did not affect the crystalline structure of LLDPE, but the crystallinity decreases with EVA content. At low concentrations of EVA the lattice parameters remain unchanged. Above 30% EVA content however, a linear increase has been observed. Dicumyl peroxide (DCP) crosslinked samples show considerable shift of (1 1 0), (2 0 0) and (0 2 0) crystalline peaks towards lower 2θ values indicating an increase of unit cell parameters of the orthorhombic unit cell of polyethylene. At lower EVA-concentrations (<50%) the crystalline structure remains unchanged. For EVA-contents of more than 70% however, increasing DCP-content reduces the crystallinity of the blends and increases the lattice distance. This indicates that DCP-crosslinking is more effective in EVA phase than in the LLDPE phase.     

Miscibility,crystallization kinetics,and morphology of poly(β‐hydroxybutyrate) and poly(methyl acrylate) blends

The miscibility, spherulite growth kinetics, and morphology of binary blends of poly(β‐hydroxybutyrate) (PHB) and poly(methyl acrylate) (PMA) were studied with differential scanning calorimetry, optical microscopy, and small‐angle X‐ray scattering (SAXS). As the PMA content increases in the blends, the glass‐transition temperature and cold‐crystallization temperature increase, but the melting point decreases. The interaction parameter between PHB and PMA, obtained from an analysis of the equilibrium‐melting‐point depression, is −0.074. The presence of an amorphous PMA component results in a reduction in the rate of spherulite growth of PHB. The radial growth rates of spherulites were analyzed with the Lauritzen–Hoffman model. The spherulites of PHB were volume‐filled, indicating the inclusion of PMA within the spherulites. The long period obtained from SAXS increases with increased PMA content, implying that the amorphous PMA is entrapped in the interlamellar region of PHB during the crystallization process of PHB. All the results presented show that PHB and PMA are miscible in the melt. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1860–1867, 2000     

Investigation by combined solid‐state NMR and SAXS methods of the morphology and domain size in polystyrene‐b‐polyethylene oxide‐b‐polystyrene triblock copolymers

The microphase structure of a series of polystyrene‐b‐polyethylene oxide‐b‐polystyrene (SEOS) triblock copolymers with different compositions and molecular weights has been studied by solid‐state NMR, DSC, wide and small angle X‐ray scattering (WAXS and SAXS). WAXS and DSC measurements were used to detect the presence of crystalline domains of polyethylene‐oxide (PEO) blocks at room temperature as a function of the copolymer chemical composition. Furthermore, DSC experiments allowed the determination of the melting temperatures of the crystalline part of the PEO blocks. SAXS measurements, performed above and below the melting temperature of the PEO blocks, revealed the formation of periodic structures, but the absence or the weakness of high order reflections peaks did not allow a clear assessment of the morphological structure of the copolymers. This information was inferred by combining the results obtained by SAXS and ¹H NMR spin diffusion experiments, which also provided an estimation of the size of the dispersed phases of the nanostructured copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 55–64, 2010