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Three‐dimensional polymeric nanonetworks combine high surface area, interconnected porosity, and tunable mechanics to enable advanced functions in catalysis, sensing, energy storage, and biomedicine. While existing reviews focus on individual fabrication techniques, this work provides the first systematic cross‐method comparison and practical decision framework for method selection. We evaluate five fundamentally different fabrication strategies—block copolymer self‐assembly, hyper‐crosslinking, template‐assisted methods, 3D printing, and nanolithography—across four critical metrics: resolution, throughput, scalability, and material compatibility. Unlike method‐specific reviews, this work presents a quantitative decision matrix that operationalizes these metrics for application‐driven method selection, bridging the gap between laboratory capabilities and industrial requirements. We showcase hybrid approaches that integrate multiple techniques (e.g., polymerization‐induced phase separation with vat photopolymerization) to achieve hierarchical structures combining nanoscale precision with manufacturability. The review includes a concise primer on block copolymer self‐assembly fundamentals (χN, segregation strength; ƒ, volume fraction), updated polymer topology terminology, and quantified performance envelopes for photopolymerization and two‐photon techniques. Critically, we address real‐world translation challenges—scalability bottlenecks, defect control, device integration, and material limitations—that are often overlooked in technique‐focused reviews. Finally, we discuss future trends in eco‐friendly, scalable fabrication and AI‐driven design tools to accelerate the translation of 3D polymeric nanonetworks into practical applications. By providing integrated cross‐method guidance rather than isolated technique descriptions, this review enables researchers to navigate the complex fabrication landscape and select optimal strategies for their specific performance targets. This review provides the first systematic cross‐method comparison of fabrication techniques for 3D polymeric nanonetworks. It evaluates five key strategies—block copolymer self‐assembly, hyper‐crosslinking, template‐assisted methods, 3D printing, and nanolithography—across critical metrics including resolution, throughput, scalability, and material compatibility. The work presents a quantitative decision matrix to bridge the gap between laboratory capabilities and industrial requirements, addresses real‐world translation challenges like scalability bottlenecks, and discusses future trends in AI‐driven design tools.

The polyethylene oxide‐polypropylene oxide (PEO‐PPO) based triblock copolymers are notable amphiphilic copolymers with a diverse range of applications. The presence of homo‐, and/or diblock impurities in copolymers with PEO‐PPO‐PEO triblock has been demonstrated. This finding suggests that the samples are blends rather than pure triblock copolymers. Furthermore, copolymers with triblock copolymer content of 0 or less than 20% by molar percentage have been identified. The hydrophilic‐lipophilic balance (HLB) is also calculated based on the exact composition of the blends. The effect of HLB values and compositional data on the initial foam height (in casein solution), the surface tension, and the contact angle are investigated. The correlation coefficients for the PPO‐PEO‐PPO copolymers versus HLB values are found to be high, while those obtained for the PEO‐PPO‐PEO copolymers versus values of HLB are significantly lower. The lower correlation coefficients for the PEO‐PPO‐PEO samples can be attributed to the presence of homo‐ and diblock (co)polymer contaminants. In addition, a linear regression model has been constructed to find a mathematical relationship between the percentage of ethylene oxide, the average number of propylene oxide units, and the properties of the copolymer. It is found that polyethylene oxide – polypropylene oxide (PEO‐PPO) triblock copolymers contain homopolymer and diblock copolymers, the tested samples are copolymer blends. This sheds new light on the structure‐physical property relationship. To map this relationship, HLB values are used, calculated from the determined composition. A good correlation is found between composition‐physical properties as determined by detailed analysis.

A laboratory-synthesized triblock copolymer poly(ethylene oxide-b-acrylic acid-b-styrene) (PEG-PAA-PS) was used as a template to synthesize hollow BaCO3 nanoparticles (BC-NPs). The triblock copolymer was synthesized using reversible addition–fragmentation chain transfer radical polymerization. The triblock copolymer has a molecular weight of 1.88 × 104 g/mol. Transmission electron microscopy measurements confirm the formation of spherical micelles with a PEG corona, PAA shell, and PS core in an aqueous solution. Furthermore, the dynamic light scattering experiment revealed the electrostatic interaction of Ba2+ ions with an anionic poly(acrylic acid) block of the micelles. The controlled precipitation of BaCO3 around spherical polymeric micelles followed by calcination allows for the synthesis of hollow BC-NPs with cavity diameters of 15 nm and a shell thickness of 5 nm. The encapsulation and release of methotrexate from hollow BC-NPs at pH 7.4 was studied. The cell viability experiments indicate the possibility of BC-NPs maintaining biocompatibility for a prolonged time.

With the development of nanotechnology, the production and use of the nanocomposites has been increased. Polymer nanocomposites are among the most widely used nanocomposites. In this study, block copolymer and block copolymer-based polymer nanocomposites were synthesized and evaluated. For this purpose; firstly, poly(β-butyrolactone)- b -poly(methyl methacrylate) [P(BL- b -MMA)] block copolymers were prepared simultaneously in one-pot by recycling additive/fragmentation chain transfer (RAFT) and ring-opening (ROP) polymerizations using a novel bifunctional RAFT-ROP agent which synthesized by chemical reaction with 3-bromo-1-propanol and potassium ethyl xanthate. Secondly, for the preparation of polymer nanocomposite, SiO 2 nanoparticles were added to the prepared block copolymer with a rate of 3 wt% both during the polymerization stage and after the polymerization stage. The synthesized RAFT-ROP agent, block copolymer, and polymer nanocomposites were characterized using spectroscopic methods. The effect of copolymerization reaction conditions on molecular weight and molecular weight distribution (dispersity) was investigated. In one-pot copolymerization processes, relatively high weight copolymers were obtained by changing the copolymerization conditions due to the active centers in the copolymerization environment. The thermal characterization showed that the glass transition temperature of the block copolymer decreases with the addition of SiO 2 during the polymerization stage and increases with the addition of SiO 2 after the polymerization stage. SEM surface morphologies showed that block copolymer and polymer nanocomposites morphology is different from each other. The difference can be explained by the good dispersion of the block copolymer and SiO 2 nanoparticles within each other.

Fluorescence correlation spectroscopy (FCS) has been widely used to investigate molecular diffusion behavior in various samples. The use of the maximum entropy method (MEM) for FCS data analysis provides a unique means to determine multiple distinct diffusion coefficients without a priori assumption of their number. Comparison of the MEM-based FCS method (MEM-FCS) with another method will reveal its utility and advantage as an analytical tool to investigate diffusion dynamics. Herein, we measured diffusion of fluorescent probes doped into nanostructured thin films using MEM-FCS, and validated the results with single molecule tracking (SMT) data. The efficacy of the MEM code employed was first demonstrated by analyzing simulated FCS data for systems incorporating one and two diffusion modes with broadly distributed diffusion coefficients. The MEM analysis accurately afforded the number of distinct diffusion modes and their mean diffusion coefficients. These results contrasted with those obtained by fitting the simulated data to conventional two-component and anomalous diffusion models, which yielded inaccurate estimates of the diffusion coefficients. Subsequently, the MEM analysis was applied to FCS data acquired from hydrophilic dye molecules incorporated into microphase-separated polystyrene-block-poly(ethylene oxide) (PS-b-PEO) thin films characterized under a water-saturated N2 atmosphere. The MEM analysis revealed distinct fast and slow diffusion components attributable to molecules diffusing on the film surface and inside the film, respectively. SMT studies of the same materials yielded trajectories for mobile molecules that appear to follow the curved PEO microdomains. Diffusion coefficients obtained from the SMT data were consistent with those obtained for the slow diffusion component detected by MEM-FCS. These results highlight the utility of MEM-FCS and SMT for gaining complementary information on molecular diffusion processes in heterogeneous material systems.Graphical Abstract

We investigated the segregation behavior of a molten diblock copolymer, poly(n-butyl acrylate)-b-poly(methyl methacrylate-r-styrene) (PBA-b-P(MMA-r-S)), wherein styrene (S) is incorporated as a comonomer in the second block to modulate the effective interaction between homopolymer and a random copolymer block. The temperature dependence of the effective interaction parameter χeff between n-butyl acrylate (BA) and the average monomer of the MMA-r-S random block was evaluated from small-angle X-ray scattering (SAXS) analysis using the random phase approximation (RPA) approach. The calculated χeff, as a function of the styrene fraction in the random copolymer block, shows a good agreement with the mean-field binary interaction model. This consistency indicates that the effective interaction between component BA and the average monomer of the random copolymer block is smaller than the interactions between pure components (χBA,MMA,χBA,S). The present study suggests that the introduction of a random copolymer block to a block copolymer can effectively reduce the degree of incompatibility of the block copolymer system without altering the constituent species, which may serve as a viable methodology in designing novel thermoplastic elastomers based on triblock or multiblock copolymers.

The topology effects of cyclization on thermal phase transition behaviors were investigated for a series of amphiphilic Pluronic copolymers of both hydrophilic–hydrophobic–hydrophilic and hydrophobic–hydrophilic–hydrophobic block sequences. The dye solubilization measurements revealed the lowered critical micelle temperatures (TCMT) along with the decreased micellization enthalpy (ΔHmic) and entropy (ΔSmic) for the cyclized species. Furthermore, the transmittance and dynamic light scattering (DLS) measurements indicated a block sequence-dependent effect on the clouding phenomena, where a profound decrease in cloud point (Tc) was only found for the copolymers with a hydrophilic–hydrophobic–hydrophilic block sequence. Thus, the effect of cyclization on these critical temperatures was manifested differently depending on its block sequence. Finally, a comparison of the linear hydroxy-terminated, methoxy-terminated, and cyclized species indicated the effect of cyclization to be unique from a simple elimination of the terminal hydrophilic moieties.

The use of thickening agents in the composition of industrial lubricants remains an important trend associated with the need to develop effective base formulations for rotating machinery lubricants. The use of both individual polymer compounds and block copolymers for thickening of petroleum and synthetic lubricants allows the desired viscosity of lubricating compositions to be promptly achieved. However, the solubility of such polymer structures in different types of oils remains a poorly investigated area. The lack of knowledge leads to an inefficient use of research resources. In this paper, we aim to empirically generalize information on the solubility of styrene-based block copolymers and lower olefin hydrocarbon-based polymers in the base oils of compressor lubricants.

The self-assembly of block polymers into well-ordered nanostructures underpins their utility across fundamental and applied polymer science, yet only a handful of equilibrium morphologies are known with the simplest AB-type materials. Here, we report the discovery of the A15 sphere phase in single-component diblock copolymer melts comprising poly(dodecyl acrylate)−block−poly(lactide). A systematic exploration of phase space revealed that A15 forms across a substantial range of minority lactide block volume fractions (f L = 0.25 − 0.33) situated between the σ-sphere phase and hexagonally close-packed cylinders. Self-consistent field theory rationalizes the thermodynamic stability of A15 as a consequence of extreme conformational asymmetry. The experimentally observed A15−disorder phase transition is not captured using mean-field approximations but instead arises due to composition fluctuations as evidenced by fully fluctuating field-theoretic simulations. This combination of experiments and field-theoretic simulations provides rational design rules that can be used to generate unique, polymer-based mesophases through self-assembly.

Block copolymers (BCPs), through their self-assembly, provide an excellent guiding platform for precise controlled localization of maghemite nanoparticles (MNPs). Diblock copolymers (di/BCP) represent the most applied matrix to host filler components due to their morphological simplicity. A series of nanocomposites based on diblock copolymer or triblock terpolymer matrices and magnetic nanoparticles were prepared to study and compare the influence of an additional block into the BCP matrix. MNPs were grafted with low molecular weight polystyrene (PS) chains in order to be segregated in a specific phase of the matrix to induce selective localization. After the mixing of the BCPs with 10% w/v PS-g-MNPs, nanocomposite thin films were formed by spin coating. Solvent vapor annealing (SVA) enabled the PS-g-MNPs selective placement within the PS domains of the BCPs, as revealed by atomic force microscopy (AFM). The recorded images have proven that high amounts of functionalized MNPs can be controllably localized within the same block (PS), despite the architecture of the BCPs (AB vs. ABC). The adopted lamellar structure of the “neat” BCP thin films was maintained for MNPs loading approximately up to 10% w/v, while, for higher content, the BCP adopted lamellar morphology is partially disrupted, or even disappears for both AB and ABC architectures.