Surface structure of thin asymmetric PS-b-PMMA diblock copolymers investigated by atomic force microscopy

Asymmetric poly(styrene-b-methyl methacrylate) (PS-b-PMMA) diblock copolymers of molecular weight M_n = 29,700 g mol⁻¹ (M_PS = 9300 g mol⁻¹M_PMMA = 20,100 g mol⁻¹, PD = 1.15, χ_PS = 0.323, χ_PMMA = 0.677) and M_n = 63,900 g mol⁻¹ (M_PS = 50,500 g mol⁻¹, M_PMMA = 13,400 g mol⁻¹, PD = 1.18, χ_PS = 0.790, χ_PMMA = 0.210) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Atomic force microscopy (AFM) was used to investigate the surface structure of thin films, prepared by spin-coating the diblock copolymers on a silicon substrate. We show that the nanostructure of the diblock copolymer depends on the molecular weight and volume fraction of the diblock copolymers. We observed a perpendicular lamellar structure for the high molar mass sample and a hexagonal-packed cylindrical patterning for the lower molar mass one. Small-angle X-ray scattering investigation of these samples without annealing did not reveal any ordered structure. Annealing of PS-b-PMMA samples at 160 °C for 24 h led to a change in surface structure.     

Nanocomposites of polystyrene-b-polyisoprene copolymer with layered silicates and carbon nanotubes

Nanocomposites of polystyrene-b-polyisoprene (PS-b-PI) copolymer with layered-smectite clays (organically modified montmorillonite) and nanostructured clay-carbon nanotube hybrids were prepared. The diblock copolymer was synthesized by anionic polymerization using high-vacuum techniques and was molecularly characterized by size exclusion chromatography. Carbon nanotubes were developed on clay-supported nickel nanoparticles by the CCVD method. Nanotubes attached on the clay platelets were then chemically modified to create ester groups on their surfaces. PS-b-PI nanocomposites at various polymer to reinforcement loadings were prepared by solution intercalation. The final nanocomposites were characterized by powder X-ray diffraction, FT-IR spectroscopy, thermal analysis, and scanning electron microscopy. The experiments complemented with viscometry measurements reveal the successful incorporation of the reinforcements in the polymer mass.     

From self-assembled monolayers to chemically patterned brushes: Controlling the orientation of block copolymer domains in films by substrate modification

Block copolymer lithography is emerging as one of the leading technologies for patterning nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical and lamellar domains is required for pattern transfer from the block copolymer film. This review highlights the state-of-art development of brushes to modify the substrates to control the assembly behaviors of block copolymers in films. Selected important contributions to the development of self-assembled monolayers, polymer brushes and mats, and chemically patterned brushes are discussed.     

Thermosensitive aggregates self-assembled by an asymmetric block copolymer of dendritic polyether and poly(N-isopropylacrylamide)

An asymmetric linear-dendritic block copolymer of polyether dendrimer and poly(N-isopropylacrylamide) was prepared by an atom transfer radical polymerization method. The self-assembly behavior and thermosensitive property of this copolymer in water were studied by dynamic light scattering (DLS), transmission electron microscopy (TEM) and fluorescence probe spectroscopy. It was found that the thermosensitive phase transition takes place at the temperature of 37.5 °C; simultaneously the spherical aggregates grow into larger entangled nanotubules. The unique temperature-sensitive supramolecular aggregates may make them especially useful as intelligent capsules for drug delivery systems and as chemical sensors.     

Synthesis, post-modification and self-assembled thin films of pentafluorostyrene containing block copolymers

Block copolymers consisting of a pentafluorostyrene (PFS) block and a hydrophilic block were synthesized by RAFT polymerisation. The hydrophilic blocks consist of methacrylate derivatives, 4-hydroxystyrene or 4-vinylpyridine monomers. The block copolymers were obtained with narrow molecular weight distributions and the molecular weights were in good agreement with the theoretical values. In addition, a model thiol was reacted with the PFS moieties of the block copolymers. This polymer–analogous reaction was performed under ambient conditions in high yields resulting quantitatively in para-substitution of the pentafluorophenyl rings. Finally, thin films consisting of block copolymers that showed strong phase-segregation behaviour and ordered nanostructured surfaces consisting of both blocks were obtained.     

Sphere-to-rod transition of short-chain PEO-b-PDMS-b-PEO in aqueous solution induced by copolymer concentration

A short-chain triblock copolymer EO9-DMS7-EO9 was synthesized by coupling reaction of allyl-terminated poly（ethylene oxide） and Si-H-terminated poly（dimethylsiloxane）. The structure and purity of synthesized copolymer was carefully characterized. Self-assembly behavior of EO9-DMST-EO9 triblock copolymer in water was investigated. And it was found that along with the increase of copolymer concentration, morphology of self-assembled aggregates transits from sphere to rod. A plausible understanding of the morphology transition for the investigated triblock copolymer was proposed.     

Reaction-induced microphase separation in epoxy resin containing polystyrene-block-poly(ethylene oxide) alternating multiblock copolymer

Polystyrene-block-poly(ethylene oxide) alternating multiblock copolymer (PS-alt-PEO) was synthesized with the combination of atom transfer radical polymerization (ATRP) and Huisgen 1,3-dipolar cycloaddition (i.e., click chemistry). The copolymer has been characterized by means of Fourier transform infrared spectroscopy (FTIR), ¹H nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The PS-alt-PEO alternating multiblock copolymer was incorporated into epoxy resin to investigate the behavior of reaction-induced microphase separation, which has been compared to the case of the thermosets containing PS-b-PEO diblock copolymer. The morphology of epoxy thermosets containing PS-alt-PEO alternating multiblock copolymer were investigated by means of atomic force microscopy (AFM), and small-angle X-ray scattering (SAXS) and the nanostructures were detected in all the thermosetting blends investigated. In marked contrast to the case of the thermosets containing PS-b-PEO diblock copolymer, the thermosets containing PS-alt-PEO multiblock copolymer displayed disordered nanostructures, which have been interpreted on the basis of the restriction of the alternating multiblock topology of the block on the formation of the nanostructures via reaction-induced microphase separation.     

Polybutadiene-graft-polystyrene copolymer: Grafting quantification by liquid chromatography at critical conditions using single UV detection

We propose a fast, reliable chromatographic method to determine the grafting yield of a Polybutadiene-graft-Polystyrene (PB-g-PS) copolymer synthesized in our laboratory for High Impact Polystyrene applications. We used Liquid Chromatography at Critical Conditions of PS to separate non-grafted PS from graft product and ungrafted PB. Separation between grafted copolymer and non-grafted PS was very efficient and thanks to linearity of UV-detector response, we could quantify the amount of grafted PS in the copolymer, as well as calculate the grafting yield. Results shown here are for DOW BR1202D high-cis PB and BASF CB529T low-cis PB, Luperox TBIC M75 initiator at 8 × 10⁻⁴ mol L⁻¹ and 125 °C reaction temperature.     

Dependence of size and morphology on shear flow for PS-based amphiphilic block copolymer micelles in aqueous solution

This contribution focuses on the impact of shear flow on size and nanostructure of PS-based amphiphilic block copolymer (BC) micelles by varying the stirring rate and copolymer composition.The results show that the vesicles formed from diblock copolymer (di-BC) of PS-b-PAA remain with vesicular morphology,although the average size decreases,with the increase of stirring rate.However,the multi-compartment micelles (MCMs) formed from tri-block copolymer (tri-BC) of PS-b-P2VP-b-PEO are quite intricate,in which the copolymer first self-assembles into spheres,then to clusters,to large compound micelles (LCMs),and finally back to spheres,as stirring rate increases from 100 r/min to 2200 r/min.Formation mechanism studies manifest that vesicles form simultaneously as water is added to the di-BC solution,termed as direct-assembly,and remain with vesicular structure in the flowing process.While for the PS-b-P2VP-b-PEO copolymer,spherical micelles at initial stage can further assemble into clusters and LCMs,termed as second-assembly,due to the speeding-up-aggregation of the favorable stirring.As a result,an invert V-relationship between tri-BC micelle dimension and stirring rate is observed in contrast to the non-linear decreasing curve of di-BC vesicles.It is by investigating these various amphiphilic BCs that the understanding of shear dependence of size and morphology of micelles is improved from self-assembly to second-assembly process.     

SAXS/WAXS/DSC studies on crystallization of a polystyrene-b-poly(ethylene oxide)-b-polystyrene triblock copolymer with lamellar morphology and low glass transition temperature

Crystallization of a polystyrene-b-poly(ethylene oxide)-b-polystyrene (S-EO-S) triblock copolymer, S₄₀EO₁₃₆S₄₀, with lamellar morphology in the melt and low glass transition temperature (T_g=47 °C) of the S block was studied. The triblock copolymer was cooled from ordered melt and isothermal crystallization was conducted at crystallization temperatures (T_c) near the T_g of the S block. It is found that crystallization behavior of S₄₀EO₁₃₆S₄₀ strongly depends on T_c. When T_c is far below T_g, an Avrami exponent n=0.5 is observed, which is attributed to diffusion-controlled confined crystallization. As T_c slightly increases, the Avrami exponent is 1.0, indicating that crystallization is confined and crystallization rate is determined by the rate of homogeneous nucleation. When T_c is just below the T_g of the S block, crystallization tends to become breakout and accordingly Avrami exponent changes from 1.0 to 3.2. Crystallinity and melting temperature of the EO block in breakout crystallization are slightly higher than those in confined crystallization. Time-resolved small and wide angle X-ray scattering (SAXS/WAXS) were used to monitor isothermal crystallization of S₄₀EO₁₃₆S₄₀. It shows that the long period is constant in confined crystallization, but it gradually increases during breakout crystallization. WAXS result reveals that confined or breakout crystallization has no effect on the crystal structure of the EO block.     

Reactive μCP on ultrathin block copolymer films: Localized chemistry for micro- and nano-scale biomolecular patterning

Three different, complementary soft lithographic approaches for the fabrication of chemical patterns on ultrathin polystyrene-block-poly(tert-butyl acrylate) (PS₆₉₀-b-PtBA₁₂₁₀) films are discussed. Central to the methodology is the previously introduced reactive PS₆₉₀-b-PtBA₁₂₁₀ platform that allows one to covalently graft (bio)molecules via robust amide linkages in high densities on flat, as well as on structured, surfaces. As shown in this paper, the combination of the polymer-based platform and reactive microcontact printing (μCP) patterning approaches allows one to obtain patterns of (bio)molecules with (sub)micrometer feature sizes. The μCP approaches comprise: (A) the direct transfer of functional (bio)molecules from an oxidized elastomeric stamp to hydrolyzed and N-hydroxysuccinimide (NHS) activated PS₆₉₀-b-PtBA₁₂₁₀; (B) the transfer of a passivating poly(ethylene glycol) layer to hydrolyzed and NHS-activated PS₆₉₀-b-PtBA₁₂₁₀ followed by wet chemical grafting of functional moieties; (C) the local hydrolysis of the PtBA skin layer with trifluoroacetic acid (TFA), followed by NHS activation and wet chemical derivatization. The applicability and the versatility of the combination of the polymer thin film-based platform and soft lithographic methodologies for patterning biologically relevant molecules is demonstrated for polyamidoamine (PAMAM) dendrimers, different proteins, as well as probe DNA. The successful hybridization of target DNA and the immobilization of fibronectin in micropatterns show that ultrahigh density patterns for micro- and nano-arrays, as well as for studies of cell-surface interactions, can be conveniently fabricated based on these approaches and platforms.     

Crystallization and melting behaviors of polystyrene-b-poly(ethylene-co-butene) block copolymers

Non-isothermal and isothermal crystallization behaviors of polystyrene-b-poly(ethylene-co-butene) (PSt-b-PEB) block copolymers with different compositions and chain lengths were investigated by differential scanning calorimetry (DSC). The results show that crystallization of PEB block is strongly dependent on the composition. Crystallization temperature (T_c), melting temperature (T_m) and fusion enthalpy (ΔH_f) increase rapidly with PEB volume fraction (V_E) for block copolymers with V_E below 50%, but there is little change when PEB block becomes the major component. Glass transition temperature (T_g) of the PSt block and order-disorder transition temperature (T_ODT) of block copolymers also have a weak effect. The isothermal crystallization kinetics results show that Avrami exponent (n) was strongly dependent on the composition and crystallization temperature. For the block copolymers with V_E below 38.7 vol%, the values of n vary between 0.9 and 1.3, indicating that crystallization is confined. For the PSt-b-PEB block copolymers with V_E higher than 50%, fractionated crystallization behavior is usually observed. A two-step isothermal crystallization procedure is applied to these block copolymers. It is found that breakout crystallization occurs at higher T_c, but confined at lower T_c. Two overlapped melting peaks are observed for the block copolymers with fractionated crystallization behavior after two-step crystallization, and only the higher melting peak corresponding to breakout crystallization can be used to derive equilibrium melting temperature.     

Investigation of the degradation behaviour of poly(ethylene glycol-co-d,l-lactide) copolymer

The aim was to investigate the degradation behaviour of poly(ethylene glycol-co-d,l-lactide) (PEG-d,l-PLA) multiblock copolymer, in bulk and as microspheres, in aqueous medium. The degradation behaviour of PLA homopolymers in bulk and microspheres was evaluated as comparison.Microsphere preparation was performed by the double emulsion solvent evaporation method. Physical-chemical characterization of the raw polymers and the microspheres was performed by nuclear magnetic resonance (NMR) and modulated differential scanning calorimetry (MDSC). Polymer molecular weight, before and after incubation in aqueous environment, was evaluated by GPC; water uptake and mass loss were determined gravimetrically.The presence of PEG segments inside PLA chains gave a characteristic spongy structure to the microspheres. A significant increase in polymer T_g values was found for the microsphere formulations compared to polymer in bulk. After 63 days of incubation in the aqueous environment, the PEG-d,l-PLA microspheres achieved an average M_w reduction of 47% compared to 20% for PLA microspheres. The corresponding M_w decrease of the polymers in bulk was significantly higher: 72% and 41% for PEG-d,l-PLA and PLA, respectively.The data show how the degradation behaviour of polymer in bulk in an aqueous environment is significantly different from the behaviour of the corresponding microspheres. These results highlight the importance of performing a thorough physical-chemical characterization on microsphere formulations.     

Control of morphology orientation in thin films of PS-b-PEO diblock copolymers and PS-b-PEO/resorcinol molecular complexes

One of the main limits in the use of block copolymers for nanotechnological applications lies in the poor control over the alignment of the nanoscopic domains. The self-assembling behavior of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) has been modified by stoichiometric complexation of the ethylene oxide units with resorcinol and a simple procedure to prepare nanostructured films with normally oriented cylinders is reported. By direct spin coating of a series of complexated PS-b-PEO samples with different molecular weight and composition, films with the same morphology and orientation (i.e., normally oriented packed cylinders) have been obtained, also when different nanostructures and alignments were expected on the basis of the volume fraction composition and self-assembling behavior of pure copolymers. Tuning of the cylinder diameters in the range from 20 to 50 nm was possible by varying the length of the PEO block. The effects of resorcinol complexation have been studied by differential scanning calorimetry and X-ray diffraction and the morphologies of PS-b-PEO and PS-b-PEO/resorcinol films have been monitored by atomic force microscopy and electron microscopies. DSC and XRD analyses demonstrate that resorcinol significantly influences the crystallization behavior of the PEO block. The varied interfacial and surface energies of the PEO domains and the overall reduction of the crystalline phase in PS-b-PEO/resorcinol films appear to be strictly related to the morphological changes occurring by complexation.     

在平行板受限条件下AB两嵌段共聚物/纳米粒子复合物自组装行为的Monte Carlo模拟

采用Monte Carlo模拟方法研究了在平行板受限条件下A_(15)B_5非对称两嵌段共聚物与纳米粒子复合物的自组装行为,其中平行板对多组分嵌段A具有吸引相互作用.模拟结果表明,纳米粒子在两嵌段共聚物/纳米粒子复合物中的体积分数、嵌段共聚物不同嵌段与纳米粒子间的相互作用均对体系在平行板受限条件下的形貌结构及纳米粒子在体系中的分布有重要影响.当平行板间距一定时,未添加纳米粒子的A_(15)B_5非对称两嵌段共聚物中的A嵌段被吸附在平行板上形成层状相,而B嵌段则在平行板中形成六角堆积穿孔层状结构.加入与A嵌段不相容而与B嵌段相容的纳米粒子后,增加了纳米粒子与B嵌段的相容性,有利于保持B嵌段所形成的穿孔结构及孔洞尺寸,同时纳米粒子能够均匀地分散在B相区中.当引入的纳米粒子与A和B两嵌段均不相容时,降低纳米粒子与嵌段共聚物的不相容性同样有利于维持体系的穿孔结构.当纳米粒子与AB两嵌段共聚物间的排斥作用微弱时,即使含量较高,纳米粒子也不聚集,并且均匀分布在A相区与B相区的交界处.     

Multiblock copolymer synthesis via controlled radical polymerization in aqueous dispersions. Part 1: Synthesis of S-tert-alkyl-N,N-alkoxycarbonylalkyldithiocarbamates

In a novel two- or three-step synthetic route, S-(1,4-phenylenebis(propane-2,2-diyl)) bis(N-methyldithiocarbamate) is reacted at low temperature with various alkyl chloroformates to form various S-tert-alkyl-N,N-alkoxycarbonylmethyl-dithiocarbamate RAFT agents. Also an alternative and novel synthetic route towards S-(1,4-phenylenebis(propane-2,2-diyl)) bis(N-methyldithiocarbamate), is proposed.     

Preparation and characterization of three-dimensionally ordered macroporous styrene/p-methylstyrene syndiotactic copolymer

Three-dimensionally ordered macroporous (3DOM) styrene/p-methylstyrene syndiotactic copolymer (sPMS) with pore size 170 nm were fabricated by means of silica templates using (dbm)₂ Ti(OPh)₂/MAO catalytic system. The resulting materials were characterized by NMR, SEM, GPC and DSC. The results indicated that the 3DOM sPMS were highly syndiotacic, and the pore contraction was approximately 20.6%. Compared with bulk sPMS, 3DOM sPMS possessed the lower number-average molecular weight and broader molecular weight distribution. In terms of DSC results, the bulk sPMS exhibited the lower glass transition temperature than that of 3DOM one.     

Sol-gel luminescence biosensors: Encapsulation of recombinant E. coli reporters in thick silicate films

A class of sensing elements based on the encapsulation of genetically engineered bioluminescent Escherichia coli (E. coli) reporter strains in sol-gel derived silicates is described. We demonstrate the concept by the immobilization of these bacterial cells in thick silicate films. Heat shock, oxidative stress, fatty acids, peroxides, and genotoxicity reporting bacteria were incorporated in the sol-gel silicates and their luminescence response was compared to that of the non-immobilized culture. All the immobilized bacteria maintained viability and luminescence activity for several months. The bacteria-silicate hybrids can be used either as disposable sensors or in multiple use sensing test-kits, and they can be also integrated in early warning devices operated in continuous flow conditions.     

Degradation mechanism of poly(lactic-co-glycolic) acid block copolymer cast films in phosphate buffer solution

We have investigated the degradation of poly(lactic-co-glycolic) acid copolymer with a lactic to glycolic ratio of 50:50. Solvent-cast films were incubated at 37 °C in phosphate buffered saline solution and their degradation was followed using potentiometry, light microscopy, gravimetry, size exclusion chromatography, differential scanning calorimetry and infrared spectroscopy. The degradation process was found to have two main steps. The first step was observed from 0 to 7 days of degradation. During the first few days a soft layer formed at the surface of the film. As degradation time increased this soft surface layer was found to swell and wrinkle. The polymer molecular weight in the bulk was found to decrease as soon as the film was placed in the medium while the polymer present in the surface layer was found to degrade at a much slower rate. The second step of degradation was found to occur after 8 days. At this stage of the degradation process the molecular weight of the polymer in the bulk of the films was so low that the materials became liquid resulting in the detachment of the film from the glass slide. At this stage the mass loss and amount of acid released in the media were found to increase significantly.     

Thermal induced mobility of self-assembled platelets of polyethylene-block-poly(ethylene oxide) in liquid precursors of unsaturated polyester thermoset

We report the variation of the molecular assembly and crystallinity of polyethylene-block-poly(ethylene oxide) (EEO, 1400 g mol⁻¹) in a non initiated liquid resin of unsaturated polyester (UP). We particularly focus on the driving force that governs the variation of the molecular assembly of the block copolymer in the UP resin upon heating. For this purpose, we performed a set of experiments combining time resolved in situ SAXS and WAXS measurements upon heating and cooling. Upon heating, SAXS shows that the inter-distance of the EEO domains decreases dramatically for temperature above 75 °C (between 90 and 30 nm for the initial system at room temperature vs 9 nm at 110 °C) suggesting that the initially homogeneously dispersed EEO domains undergo aggregation. This is consistent with the macroscopic phase separation observed in such temperature range. In situ WAXS shows that the onset of the aggregation coincides with the melting of the PE domains suggesting that the flexibility of the platelets plays an important role in their aggregation. Upon cooling, peculiar behaviour is observed for the systems with higher EEO content, with an irreversible structure formation leading to macroscopic EEO rich domains dispersed in continuous UP rich phase.