A random acrylate copolymer with epoxy‐amphiphilic structure as an efficient toughener for an epoxy/anhydride system

Toughening of epoxy resin by block copolymers containing an epoxy‐philic block and an epoxy‐phobic block is usually costly because of their complex preparation procedure. In this work, a novel, random epoxy‐amphiphilic copolymer (PHGEL), which combines an “epoxy‐philic” component and an “epoxy‐phobic” component, has been synthesized and evaluated as a potential toughening agent for a diglycidyl ether of bisphenol A–based epoxy thermoset (EP). The curing behavior of the EP/PHGEL system has been investigated, and the results show that the hydroxyl group on the PHGEL chain can slightly activate the curing reaction. The mechanical testing shows that the toughness of the epoxy resin is improved by 294% when 4 wt % of PHGEL is added. Simultaneously, the tensile strength, elongation at break, and glass‐transition temperature are also improved. In addition, the thermogravimetric analysis shows that PHGEL has no obvious effect on the thermal stability of the epoxy thermosets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44863.     

Controllable design of nanostructure in block copolymer reinforced epoxy composites

The modification of epoxy composites through the construction of nanostructures via the self‐organization of block copolymers in epoxy has become a hot topic. In this research, polystyrene‐b‐poly(?‐caprolactone)‐b‐polydimethylsiloxane‐b‐poly(?‐caprolactone)‐b‐polystyrene (PS‐PCL‐PDMS‐PCL‐PS) block copolymers with different lengths of PS subchains were synthesized and incorporated into epoxy thermoset. Due to the difference in the length of PS subchains, two different sizes of core‐shell nanostructures were obtained. When these two block copolymers were incorporated into epoxy, the tensile strength, elongation at break, damping temperature in range (tan δ > 0.2), and storage modulus of the epoxy thermoset below 105 °C were simultaneously improved. Meanwhile, the effects of the lengths of PS subchains on the size of nanostructures and the relationship between microstructure and macroscopic properties of epoxy composites were systematically investigated. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46362.     

Nanostructured thermosetting epoxy systems modified with poly(isoprene‐b‐methyl metacrylate) diblock copolymer and polyisoprene‐grafted carbon nanotubes

Nanostructured thermosetting composites based on an epoxy matrix modified with poly(isoprene‐b‐methyl methacrylate) (PI‐b‐PMMA) block copolymer were prepared through PI block segregation. Morphological structures were examined by means of atomic microscopy force microscopy. As epoxy/pristine multi‐walled carbon nanotubes (MWCNT) systems were found to present big agglomerations, with a very poor dispersion of the nanofiller, epoxy/PI‐b‐PMMA/MWCNT systems were prepared by using polyisoprene‐grafted carbon nanotubes (PI‐g‐CNT) to enhance compatibility with the matrix and improve dispersion. It was found that the functionalization of MWCNT with grafted polyisoprene was not enough to totally disperse them into the epoxy matrix but an improvement of the dispersion of carbon nanotubes was achieved by nanostructuring epoxy matrix with PI‐b‐PMMA when compared with epoxy/MWCNT composites without nanostructuring. Nevertheless, some agglomerates were still present and the complete dispersion or confinement of nanotubes into desired domains was not achieved. Thermomechanical properties slightly increase with PI‐g‐CNT content for nanostructured samples, whereas for nonnanostructured epoxy/PI‐g‐CNT composites they appeared almost constant and even decreased for the highest nanofiller amount due to the presence of agglomerates. Compression properties slightly decreased with block copolymer content, while remained almost constant with nanofiller amount. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nanostructures and nanoporosity in thermoset epoxy blends with an amphiphilic polyisoprene-block-poly(4-vinyl pyridine) reactive diblock copolymer

Nanostructured thermoset blends were prepared based on a bisphenol A-type epoxy resin and an amphiphilic reactive diblock copolymer, namely polyisoprene-block-poly(4-vinyl pyridine) (PI-P4VP). Infrared spectra revealed that the P4VP block of the diblock copolymer reacted with the epoxy monomer. However, the non-reactive hydrophobic PI block of the diblock copolymer formed a separate microphase on the nanoscale. Ozone treatment was used to create nanoporosity in nanostructured epoxy/PI-P4VP blends via selective removal of the PI microphase and lead to nanoporous epoxy thermosets; disordered nanopores with the average diameter of about 60 nm were uniformly distributed in the blend with 50 wt% PI-P4VP. Multi-scale phase separation with a distinctly different morphology was observed at the air/sample interface due to the interfacial effects, whereas only uniform microphase separated morphology at the nanoscale was found in the bulk of the blend.     

Morphology and mechanical properties of nanostructured acrylic tri‐block‐copolymer modified epoxy

In this study, acrylic tri‐block‐copolymers of different compositions and constituents were used to modify an epoxy resin. In epoxy the block‐copolymers self‐assembled to generate different nanostructured phases. Spherical micelles and vesicles were formed due to preferential interactions among constituents of the blends. The effect of modifier concentration and morphology on the resulting mechanical properties was investigated. At a modifier content of 5 wt% a more than threefold increase in strain energy release rate was observed relative to the unfilled epoxy for the block‐copolymer/epoxy systems studied. This improvement was accompanied by slight reductions in tensile stiffness, strength and glass transition temperature of developed epoxy blends. Microstructural studies revealed that during crack propagation, vesicle and micelle structures respectively underwent debonding and cavitation followed by shear yielding of the substrate matrix. POLYM. ENG. SCI., 54:1047–1055, 2014. © 2013 Society of Plastics Engineers     

Comparison of morphologies and mechanical properties of crosslinked epoxies modified by polystyrene and poly(methyl methacrylate)) or by the corresponding block copolymer polystyrene-b-poly(methyl methacrylate)

Polystyrene (PS, M_n=28,400, PI=1.07), poly(methyl methacrylate) (PMMA, M_n=88,600, PI=1.03), and PS (50,000)-b-PMMA (54,000) (PI=1.04), were used as modifiers of an epoxy formulation based on diglycidyl ether of bisphenol A (DGEBA) and m-xylylene diamine (MXDA). Both PS and PMMA were initially miscible in the stoichiometric mixture of DGEBA and MXDA at 80 °C, but were phase separated in the course of polymerization. Solutions containing 5 wt% of each one of both linear polymers exhibited a double phase separation. A PS-rich phase was segregated at a conversion close to 0.02 and a PMMA rich phase was phase separated at a conversion close to 0.2. Final morphologies, observed by scanning electron microscopy (SEM), consisted on a separate dispersion of PS and PMMA domains. A completely different morphology was observed when employing 10 wt% of PS-b-PMMA as modifier. PS blocks with M_n=50,000 were not soluble in the initial formulation. However, they were dispersed as micelles stabilized by the miscible PMMA blocks, leading to a transparent solution up to the conversion where PMMA blocks began to phase separate. A coalescence of the micellar structure into a continuous thermoplastic phase percolating the epoxy matrix was observed. The elastic modulus and yield stress of the cured blend modified by both PS and PMMA were 2.64 GPa and 97.2 MPa, respectively. For the blend modified by an equivalent amount of block copolymer these values were reduced to 2.14 GPa and 90.0 MPa. Therefore, using a block copolymer instead of the mixture of individual homopolymers and selecting an appropriate epoxy-amine formulation to provoke phase separation of the miscible block well before gelation, enables to transform a micellar structure into a bicontinuous thermoplastic/thermoset structure that exhibits the desired decrease in yield stress necessary for toughening purposes.     

Compatibilizing efficiency of copolymer precursors for immiscible polymer blends

An anhydride‐terminated polystyrene (PS‐b‐Anh) as a block copolymer precursor and a copolymer (PS‐co‐TMI) of styrene (St) and 3‐isopropenyl‐α,α‐dimethylbenzene isocyanate (TMI) as a graft copolymer precursor are chosen to investigate the effect of the type of the copolymer precursor on its compatibilizing and stabilizing efficiency for polymer blends. Results show that during the melt blending of the PS and PA6, the addition of PS‐b‐Anh dramatically decreases the size of the dispersed phase domains, irrespective of its molecular weight. This indicates that a diblock copolymer PS‐block‐PA6 (PS‐b‐PA6) is formed by a reaction between the terminal anhydride moiety of the PS‐b‐Anh and the terminal amine group of the PA6. When PS/PA6 (30/70) blends are annealed at 230°C for 15 min, their morphologies are much more stable in the presence of the PS‐b‐Anh block copolymer precursor than in the presence of the PS‐co‐TMI graft copolymer precursor. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphological and mechanical study of nanostructured epoxy systems modified with amphiphilic poly(ethylene oxide-b-propylene oxide-b-ethylene oxide)triblock copolymer

Thermosetting systems based on DGEBA epoxy resin and poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (EPE) triblock copolymer were prepared and investigated. Different mixtures were obtained by using different contents of EPE block copolymer in order to study the influence of the modifier on the properties of the final materials. All thermosetting systems were prepared without using any solvent and were cured at ambient temperature, taking into account the lower critical solution temperature (LCST) behavior of the block copolymer. DSC results indicated that the addition of block copolymer affected to the curing reaction time and to the glass transition temperature of the mixtures and also the miscibility of EPE triblock copolymer in the epoxy resin was proved. The morphologies studied by AFM and TEM showed clear nanostructuration up to 25 wt % EPE content. The addition of 5 and 15 wt % of EPE block copolymer led to a considerable improvement in the toughness of the materials. When EPE block copolymer was added to the epoxy resin, the surface became more hydrophilic and the UV–vis transmittance decreased slightly maintaining a high level of transparency.     

Effect of crosslink density on fracture behavior of model epoxies containing block copolymer nanoparticles

Model diglycidyl ether of bisphenol-A based epoxy resins containing well-dispersed 15 nm block copolymer (BCP) nanoparticles were prepared to study the effect of matrix crosslink density on their fracture behavior. The crosslink density of the model epoxies was varied via the controlled epoxy thermoset technology and estimated experimentally. As expected, it was found that the fracture toughness of the BCP-toughened epoxy is strongly influenced by the crosslink density of the epoxy matrix, with higher toughenability for lower crosslink density epoxies. Key operative toughening mechanisms of the above model BCP-toughened epoxies were found to be nanoparticle cavitation-induced matrix shear banding for the low crosslink density epoxies. The toughening effect from BCP nanoparticles was also compared with core-shell rubber-toughened epoxies having different levels of crosslink density. The usefulness of the present findings for designing toughened thermosetting materials with desirable properties is discussed.     

Nanophase morphology and crystallization in poly(vinylidene fluoride)/polydimethylsiloxane‐block‐poly(methyl methacrylate)‐block‐polystyrene blends

An approach to achieve confined crystallization of ferroelectric semicrystalline poly(vinylidene fluoride) (PVDF) was investigated. A novel polydimethylsiloxane‐block‐poly(methyl methacrylate)‐block‐polystyrene (PDMS‐b‐PMMA‐b‐PS) triblock copolymer was synthesized by the atom‐transfer radical polymerization method and blended with PVDF. Miscibility, crystallization and morphology of the PVDF/PDMS‐b‐PMMA‐b‐PS blends were studied within the whole range of concentration. In this A‐b‐B‐b‐C/D type of triblock copolymer/homopolymer system, crystallizable PVDF (D) and PMMA (B) middle block are miscible because of specific intermolecular interactions while A block (PDMS) and C block (PS) are immiscible with PVDF. Nanostructured morphology is formed via self‐assembly, displaying a variety of phase structures and semicrystalline morphologies. Crystallization at 145 °C reveals that both α and β crystalline phases of PVDF are present in PVDF/PDMS‐b‐PMMA‐b‐PS blends. Incorporation of the triblock copolymer decreases the degree of crystallization and enhances the proportion of β to α phase of semicrystalline PVDF. Introduction of PDMS‐b‐PMMA‐b‐PS triblock copolymer to PVDF makes the crystalline structures compact and confines the crystal size. Moreover, small‐angle X‐ray scattering results indicate that the immiscible PDMS as a soft block and PS as a hard block are localized in PVDF crystalline structures. © 2019 Society of Chemical Industry     

Long-tailed spherical aggregates formed from ABA triblock copolymer by changing the properties of selective solvent

A convenient method of tuning aggregate morphologies from amphiphilic block copolymer by adding second selective solvent is introduced in this paper. Some novel aggregate morphologies, i.e. hierarchical vesicles (and compound spherical micelles) with one or more tails, were formed by introducing a second selective solvent for core-forming blocks into the poly(4-vinyl pyridine)-b-polystyrene-b-poly(4-vinyl pyridine) ABA amphiphilic block copolymer/co-solvent/water systems. Addition of selective solvent (toluene) for core-forming blocks (PS blocks) has significant effect on the aggregate morphologies from the amphiphilic triblock copolymer. The aggregate morphologies changed from spheres to rods, long tailed solid large compound spheres, and to long tailed hierarchical vesicles by adding 0.5, 10 and 30 wt% of toluene to the organic solvent, respectively. There exists an aggregate morphological transition of the long tailed hierarchical vesicles to long tailed solid spheres by decreasing the content of toluene in the organic solvent mixture. The tails disappeared, and irregular vesicular and spherical structures were formed when the toluene content was 20 wt%. The toluene addition is expected to increase the stretching of the core-forming blocks (PS), and to modify the interfacial tension of core-corona interface, which are the main reasons for the aggregate morphology transition. To the best of our knowledge, these tailed vesicles and spherical morphologies have not been found in block copolymer aggregates system up to now.     

Epoxy formulation including an acrylic triblock copolymer adapted for use in filament winding

Commercial triblock copolymers with a poly(butyl acrylate) (PBuA) central block joined to two poly(methyl methacrylate) (PMMA) end blocks (denoted as MAM) or to two random copolymers end blocks based on MMA and N,N′‐dimethylacrylamide (DMA) (denoted as MAM‐N), can be employed as toughening agents for thermoset composites. However, their use in epoxy formulations for filament winding, requiring low viscosities during the fiber‐impregnation step associated with an adequate glass transition temperature of the cured product is not trivial. In this study, we show that a blend of diglycidylether of bisphenol A (DGEBA), 4,4′‐diamino‐3,3′‐dimethyldicyclohexylmethane (3DCM) and benzylamine (BA), with 20% of amine hydrogens provided by BA, and containing 5 wt% MAM, can be used for these purposes. The addition of MAM increased the critical stress intensity factor from 0.63 MPa.m^1/2 to 1.0 MPa.m^1/2, the glass transition temperature from 138°C to 145°C, and the glassy modulus at 25°C from 2.95 GPa to 3.15 GPa. MAM was a better choice for the envisaged applications than MAM‐N because it led to solutions of lower viscosity. The higher viscosity produced by MAM‐N was explained by specific interactions between the epoxy‐amine solvent and DMA units present in its terminal blocks. POLYM. ENG. SCI., 56:1153–1159, 2016. © 2016 Society of Plastics Engineers     

Formation of silver nanoparticles created in situ in an amphiphilic block copolymer film

In this work, silver nanoparticles were synthesized with an amphiphilic diblock copolymer, polystyrene‐block‐poly(1‐vinyl‐2‐pyrrolidone) (PS‐b‐PVP), as a template film. First, microphase‐separated amphiphilic PS‐b‐PVP (70 : 30 wt %) was synthesized through atom transfer radical polymerization. The self‐assembled block copolymer film was used to template the growth of silver nanoparticles by the introduction of a silver trifluoromethanesulfonate precursor and an ultraviolet irradiation process. The in situ formation of silver nanoparticles with an average size of 4–6 nm within the block copolymer template film was confirmed with transmission electron microscopy, ultraviolet–visible spectroscopy, and wide‐angle X‐ray scattering. Fourier transform infrared spectroscopy also demonstrated the selective incorporation and in situ formation of silver nanoparticles within the hydrophilic poly(1‐vinyl‐2‐pyrrolidone) domains, which were mostly due to the stronger interaction strength of the silver with the carbonyl oxygens of poly(1‐vinyl‐2‐pyrrolidone) in the block copolymer. This work provides a simple route for the in situ synthesis of silver nanoparticles within a polymer film. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Limitation of the Coalescence of Evolutive Droplets by the Use of Copolymers in a Thermoplastic/Thermoset Blend

Summary: Polystyrene (PS)/epoxy‐amine (DGEBA‐MDEA) is a thermoplastic/thermoset precursor blend which is miscible at high temperature (177 °C), and which phase separates under the polymerization of the epoxy‐amine system. Previous studies have shown that the morphology of this blend polymerized under shear is coarse and irregular because the dispersed epoxy‐amine domains coalesce before they gel. Several styrene‐methyl methacrylate and a styrene‐butadiene‐styrene block copolymers have been added to the PS/DGEBA‐MDEA 60/40 blend in order to limit the coalescence and thus obtain a finer morphology. Two of the copolymers used were reactive either with the epoxy or with the amine. It was shown that the addition of 15 wt.‐% of non reactive copolymer had a positive but limited effect on the size of the final epoxy‐amine particles. The copolymer remained at the interface at the early stages of the polymerization. However, it was pulled out by the shear forces around the gel point of the epoxy domains. Most of the non reactive copolymer was present in the shape of micelles at the end of the process. On the other hand, the reactive copolymers were able to establish covalent bonds with the epoxy‐amine drops and hence were not extracted at all. Consequently they allowed the decrease the size of the particles by a factor of 15. Despite this, the observation of the morphology at different stages of the polymerization has revealed that the copolymer moved at the interface of the epoxy domains during the collision of two droplets. The movements of fluids into the epoxy domains pushed the copolymer out of the inter‐droplet zone so that it could not prevent the drainage of the liquid film between the droplets and consequently their coalescence.

TEM showing that the layer of copolymer (in dark grey) has moved along the interface of epoxy‐amine drops during their successful collision in a polystyrene‐rich matrix.     

Role of block copolymer on the coarsening of morphology in polymer blend: Effect of micelles

The reactive compatibilization of polystyrene/ethylene‐α‐octene copolymer (PS/POE) blend via Friedel–Crafts alkylation reaction was investigated by rheology and electron microscope. It was found that the graft copolymer formed from interfacial reaction reduced the domain size and decreased the coarsening rate of morphology. The reduction of the interfacial tension is very limited according to the mean field theory even assuming that all block copolymer stays on the interface. With the help of self‐consistent field theory and rheological constitutive models, the distribution of graft copolymer was successfully estimated. It was found that large amount of copolymer had detached from the interfaces and formed micelles in the matrix. Both the block copolymer micelles in matrix and the block copolymers at the interface contribute to the suppression of coarsening in polymer blend, but play their roles at different stages of droplet coalescence. In droplet morphology, the micelles mainly hinder the approaching of droplets. © 2014 American Institute of Chemical Engineers AIChE J, 61: 285–295, 2015     

Nanostructures and thermomechanical properties of epoxy thermosets containing reactive diblock copolymer

Polystyrene‐block‐poly(glycidyl methacrylate) reactive diblock copolymer (PS‐b‐PGMA) was synthesized via atom transfer radical polymerization (ATRP). The diblock copolymer was characterized using nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC). The cured epoxy thermosets with 10–20 nm PS particles were prepared by blending the diblock copolymer with epoxy resin. The nanostructures were examined by means of transmission electronic microscopy (TEM) and small angle X‐ray scattering (SAXS). The formation of the nanostructures was caused by the reaction‐induced microphase separation mechanism. It is significant that the glass transition temperatures (T_gs) of these epoxy thermosets were increased by the addition of PS‐b‐PGMA reactive block copolymer as revealed by both differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of functional poly(styrene)‐block‐(methyl methacrylate/methacrylic acid) by homogeneous reverse atom transfer radical polymerization: Spherical nanoparticles,thermal behavior,self‐aggregation,and morphological properties

This study investigates the use of homogeneous reverse atom transfer radical polymerization for the synthesis of polystyrene (PS) initiated by conventional radical peroxide with copper bromide in the lower oxidation state and a 2,2′‐bypyridine complex as the catalyst. In a second stage, an amphiphilic block copolymer containing methyl methacrylate (MMA) was synthesized via normal atom transfer radical polymerization in two steps, followed by partial hydrolysis of the methyl ester linkage of the MMA block under acidic conditions. The block copolymer PS₆₉₉‐b‐P(MMA₂₃₂/MAA₅₈) obtained had a narrow molecular weight dispersity (Ð < 1.3). The structure of the precursor, PS‐b‐PMMA, and resultant polymer, was characterized and verified by FTIR and ¹H‐NMR spectroscopy as well as size exclusion chromatography. The self‐aggregation of PS₆₉₉‐b‐P(MMA₂₃₂/MAA₅₈) in organic solvents was monitored by UV spectroscopy, whereas the morphology and size of the formed microaggregates were investigated by transmission electron microscopy and dynamic light scattering. The results indicate that this copolymer formed regular spherical reverse micelles with a core–shell structure. The atomic force micrographs of PS₆₉₉‐b‐P(MMA₂₃₂/MAA₅₈) showed a rough surface morphology owing to microphase separation of the block copolymer. In addition, thermal characterization was performed by differential scanning calorimetry and thermogravimetric analysis. The glass transition temperature of PS₆₉₉‐b‐P(MMA₂₃₂/MAA₅₈) decreased significantly (65°C), when compared to PS and PMMA, suggesting that an enhanced movement of the polymer chains resulted by the segregation of the hydrolyzed P(MMA₂₃₂/MAA₅₈) block. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Toughening of a dicyandiamide-cured epoxy resin: Influence of cure conditions on different rubber modifications

Cure kinetics of modified epoxy resins cured with dicyandiamide are studied. The influence of different heating rates in the curing process, such as curing behavior, morphology, and thermo-mechanical properties, is studied. Additionally, three different post-cure cycles at 180°C are employed. Two butadiene-based toughening agents are used, a carboxyl-terminated polybutadiene-co-acrylonitril (CTBN) prepolymer and a functionalized block copolymer of polytetrahydrofuran and hydroxyl-terminated polybutadiene. The amphiphilic block copolymer enables investigations with a bimodal particle size morphology. All results are contrasted with those of the neat resin and butadiene-free block polymer. Faster curing processes result in smaller average particle sizes and better fracture toughness of the modified epoxy resins. Further improvements are achieved with additional post-cure cycles at 180°C. An increased interfacial adhesion between the particles and the epoxy matrix is considered to be the main mechanism. Optimized lengths of the post-cure process can be determined with the butadiene-based toughening agents indicating a competing thermal degradation. Longer post-cures than 40 min lead to lower fracture toughness in the butadiene-based modified materials. In general, similar influences of the curing and post-curing process on the bimodal and unimodal distributed system can be observed differing in more intense dependencies of the bimodal system.     

Micro- or nanoseparated phases in thermoset blends of an epoxy resin and PEO-PPO-PEO triblock copolymer

Diaminodiphenylmethane (DDM) curing at several temperatures of a diglycidyl ether of bisphenol A (DGEBA) epoxy resin modified with a poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) block copolymer has been investigated in order to characterize the miscibility and morphological features. Two distinct phases are present for every blends studied except for DGEBA/DDM modified with 10 wt% PEO-PPO-PEO and cured at low temperature. Depending on the curing condition, phase separation takes place at micro or nanoscale due to competition among kinetic and thermodynamic factors. The mechanistic approach used for modeling the curing reactions shows that the formation of epoxy-hydroxyl complex and the auto catalytic process are slightly decreased whilst the noncatalytic process is favoured upon copolymer addition. Modifier addition delays curing process as the influence of both formation of epoxy-hydroxyl complex and catalytic process on reaction rate is higher than the influence of noncatalytic process. A thermodynamic model describing a thermoset/block copolymer considered as only one entity system is proposed. The LCST behaviour allows to elucidate nano or micro separated structures obtained at low and high curing temperatures, respectively.     

Nanophase morphology and crystallization in poly(vinylidene fluoride)/polydimethylsiloxane‐block‐poly(methyl methacrylate) blends

A polydimethylsiloxane‐block‐poly(methyl methacrylate) (PDMS‐b‐PMMA) diblock copolymer was synthesized by the atom transfer radical polymerization method and blended with a high‐molecular‐weight poly(vinylidene fluoride) (PVDF). In this A‐b‐B/C type of diblock copolymer/homopolymer system, semi‐crystallizable PVDF (C) and PMMA (B) block are miscible due to favorable intermolecular interactions. However, the A block (PDMS) is immiscible with PVDF and therefore generates nanostructured morphology via self‐assembly. Crystallization study reveals that both α and γ crystalline phases of PVDF are present in the blends with up to 30 wt% of PDMS‐b‐PMMA block copolymer. Adding 10 wt% of PVDF to PDMS‐b‐PMMA diblock copolymer leads to worm‐like micelle morphology of PDMS of 10 nm in diameter and tens of nanometers in length. Moreover, morphological results show that PDMS nanostructures are localized in the inter‐fibrillar region of PVDF with the addition of up to 20 wt% of the block copolymer. Increase of PVDF long period by 45% and decrease of degree of crystallization by 34% confirm the localization of PDMS in the PVDF inter‐fibrillar region. © 2018 Society of Chemical Industry