Copolymer Solutions Research Articles

Self-assembly of gradient copolymers in a selective solvent. New structures and comparison with diblock and statistical copolymers

We perform comparative studies of self-assembly of equivalent statistical, diblock and gradient AB copolymers in a selective solvent using dissipative particle dynamics simulations. Both effects of the fraction of soluble and insoluble groups, selectivity of the solvent and degree of immiscibility of A and B groups on self-assembled structures are studied. With a simplified model of the statistical copolymer we predict macroscopic phase segregation, when non-aggregated chains coexist with precipitate. The later can be dense or swollen (physical gel) depending on degree of immiscibility of the A and B groups. For the case of diblock copolymer solutions, we predict thermodynamic stability of few structures: spherical and worm-like micelles, rings, vesicles and precipitate. We develop a simple theory, which allows calculating free energies of worms and rings (closed worms) and explaining transition between the structures. A number of diagrams of states is constructed. In case of gradient copolymers, two scenarios of self-assembly are predicted. The spherical micelles of gradient copolymer can aggregate with each other forming worms, rings and vesicles through aggregation of coronae (so-called sticky corona), which contain insoluble groups, if the fraction of insoluble groups per chain is not high. Herewith, the core of the assembled structures remains multidomain despite a high interfacial tension. The second (“diblock-like”) scenario is realized when the fraction of insoluble groups is high enough. In this case the core of worms, rings and vesicles is practically a monodomain, however, solvophilic groups can be intercalated into the core due to the primary structure of the copolymer. A new structure of a multi-compartment vesicle on the basis of gradient copolymers is predicted.

Instantaneous Degelling Thermoresponsive Hydrogel.

Responsive polymeric hydrogels have found wide application in the clinic as injectable, biocompatible, and biodegradable materials capable of controlled release of therapeutics. In this article, we introduce a thermoresponsive polymer hydrogel bearing covalent disulfide bonds. The cold aqueous polymer solution forms a hydrogel upon heating to physiological temperatures and undergoes slow degradation by hydrolytic cleavage of ester bonds. The disulfide functionality allows for immediate reductive cleavage of the redox-sensitive bond embedded within the polymer structure, affording the option of instantaneous hydrogel collapse. Poly(ethylene glycol)-b-poly(lactic acid)-S-S-poly(lactic acid)-b-poly(ethylene glycol) (PEG-PLA-SS-PLA-PEG) copolymer was synthesized by grafting PEG to PLA-SS-PLA via urethane linkages. The aqueous solution of the resultant copolymer was a free-flowing solution at ambient temperatures and formed a hydrogel above 32 °C. The immediate collapsibility of the hydrogel was displayed via reaction with NaBH4 as a relatively strong reducing agent, yet stability was displayed even in glutathione solution, in which the polymer degraded slowly by hydrolytic degradation. The polymeric hydrogel is capable of either long-term or immediate degradation and thus represents an attractive candidate as a biocompatible material for the controlled release of drugs.

Novel Polyimide-block-poly(dimethyl siloxane) copolymers: Effect of time on the synthesis and thermal properties

Polyimide-block-poly(dimethyl siloxane) copolymer was synthesized by a two-step process, initiated by coupling anhydride terminated poly(amic acid), AT-PAA with amino terminated poly(dimethyl siloxane), (NH2)2-PDMS to form poly(amic acid)-block-poly(dimethyl siloxane). The resulting copolymer is then thermally treated to produce polyimide-block-poly(dimethyl siloxane), PI-PDMS. Because of the high glass transition temperature, Tg of polyimide, it is usually cured at a high temperature of about 300°C for over 2.5 h. Copolymerization of polyimide with polysiloxane, reduces the imidization temperature while maintaining high thermomechanical properties. A series of instruments were used to monitor the progress of copolymerization. The time-based analysis of the product of copolymerization enables the optimization of the structure and properties of the copolymers. The chemical structure and composition of the copolymer were studied by Fourier Transform Infrared Spectroscopy, (FT-IR). The incorporation of PDMS blocks into the copolymer and the degree of imidization of the polyimide block increased with increasing reaction time. The change in the viscosity of the copolymerizing solution was monitored by simple shear viscometry conducted with the Brookfield Viscometer. The reported increase in solution viscosity with increasing copolymerization time is associated with increasing molecular weight of the copolymer. The intrinsic viscosity of the copolymer solution was measured as a function of copolymerization time and it was found that the intrinsic viscosity of the copolymer solution increased with increasing reaction time. The glass transition temperature (Tg) and the thermal stability of the copolymer were determined by differential scanning calorimetry, DSC and thermogravimetric analysis, and TGA, respectively. Between 25°C and 420°C, the copolymers synthesized in this study show two glass transition temperatures due to the polyimide, PI block at around 380°C and another peak associated with PDMS plasticized polyimide at about 290–300°C. The two Tg peaks observed in the DSC thermogram are believed to be indicative of the structure of a block copolymer. TGA analysis shows that the thermoxidative stability of the copolymers increased with increasing reaction time, due to the incorporation of increased amount of PDMS unit into the copolymer. The combination of increasing molecular weight of copolymer, higher degree of imidization of polyimide blocks and enhanced thermoxidative stability may translate into improved flame retardancy of copolymers. This suggested enhancement in flame retardancy in air atmosphere, is believed to be due the incorporated PDMS blocks, which can be converted into silica, SiO2, a recognized thermally stable material.

Morphological Studies of Solution-Crystallized Thermoplastic Elastomers with Polyethylene Endblocks and a Random-Copolymer Midblock.

Styrenic thermoplastic elastomers (TPEs) in the form of triblock copolymers possessing glassy endblocks and a rubbery midblock account for the largest global market of TPEs worldwide, and typically rely on microphase separation of the endblocks and the subsequent formation of rigid microdomains to ensure satisfactory network stabilization. In this study, the morphological characteristics of a relatively new family of crystallizable TPEs that instead consist of polyethylene endblocks and a random-copolymer midblock composed of styrene and (ethylene-co-butylene) moieties are investigated. Copolymer solutions prepared at logarithmic concentrations in a slightly endblock-selective solvent are subjected to crystallization under different time and temperature conditions to ascertain if copolymer self-assembly is directed by endblock crystallization or vice versa. According to transmission electron microscopy, semicrystalline aggregates develop at the lowest solution concentration examined (0.01 wt%), and the size and population of crystals, which dominate the copolymer morphologies, are observed to increase with increasing aging time. Real-space results are correlated with small- and wide-angle X-ray scattering to elucidate the concurrent roles of endblock crystallization and self-assembly of these unique TPEs in solution.

Sticking Effect of a Tackifier on the Fibrillation of Acrylic Pressure-Sensitive Adhesives.

In this study, the effect of a tackifier on the viscoelastic and adhesion properties of acrylic pressure-sensitive adhesives (PSAs) was investigated. The intermediate products in the process of PSA synthesis, including an acrylate-based copolymer solution, a cross-linked copolymer, and the final product with a tackifier, were prepared and characterized using dynamic mechanical analysis (DMA). A significant increase in storage and loss moduli at high angular velocities was observed for the final product with the tackifier. The adhesion forces of the copolymer solution and the cross-linked copolymer measured by atomic force microscopy (AFM) were found to be almost independent of the release velocity, whereas that of the final product with the tackifier significantly increased at higher release velocities because of viscoelastic effects. Their fibrillations during the release process were also visualized using a charge-coupled device (CCD) camera installed on the cantilever holder. Although the contact area of the copolymer solution and the cross-linked copolymer with the probe surface decreased until detachment, the final product with the tackifier remained constant, with necking just below the probe surface. The increased storage and loss moduli were considered to resist the shrinkage of the contact area because the contact outline was subject to high shearing deformation, which led to localized high strain rates. Overall, the crucial role of the tackifier in maintaining the contact area for sufficient elongation during fibrillation was established.

Cryogel Monoliths for Analyte Enrichment by Capture and Release

A platform based on cryogel monoliths in small capillaries, which allows very strong enrichment of an analyte through a capture and release process, is described. For their preparation, a photoreactive copolymer solution containing capture molecules of interest is filled into a capillary, frozen in, and then photochemically transformed into cryogel monoliths through C,H-insertion cross-linking reactions. As a test example, the platform is used for the preconcentration of dopamine from bovine serum albumin and urine samples through capture and release processes. During capture from a large volume and release into a smaller volume, the platform shows recovery rates up to 97% and allows up to a roughly 630-fold enrichment of the concentration of the analyte. The presented platform could be used as a disposable device for the purification and enrichment of a variety of cis-diol-containing samples.

Evaluation of Loco-Regional Skin Toxicity Induced by an In Situ Forming Depot after a Single Subcutaneous Injection at Different Volumes and Flow Rates in Göttingen Minipigs.

The present study aims to investigate the loco-regional tolerability and injection parameters (i.e., flow rate and administration volume) of an in situ forming depot (ISFD) in Göttingen minipigs, to secure both the therapeutic procedure and compliance in chronic medical prescriptions. The ISFD BEPO® technology (MedinCell S.A.) is investigated over 10 days, after a single subcutaneous injection of test item based on a DMSO solution of diblock and triblock polyethylene glycol-polylactic acid copolymers. Injection sites are systematically observed for macroscopic loco-regional skin reactions as well as ultrasound scanning, enabling longitudinal in vivo imaging of the depot. Observations are complemented by histopathological examinations at 72 h and 240 h post-injection. Overall, no treatment-emergent adverse effects are macroscopically or microscopically observed at the subcutaneous injection sites, for the tested injection flow rates of 1 and 8 mL/min and volumes of 0.2 and 1 mL. The histopathology examination confirms an expected foreign body reaction, with an intensity depending on the injected volume. The depot morphology is similar irrespective of the administration flow rates. These results indicate that the ISFD BEPO® technology can be considered safe when administered subcutaneously in Göttingen minipigs, a human-relevant animal model for subcutaneous administrations, in the tested ranges.

Enhancement of Gel Strength of Itaconic Acid-Based Superabsorbent Polymer Composites Using Oxidized Starch.

Herein, core-superabsorbent polymer (CSAP) composites are prepared from oxidized starch (OS) via aqueous solution copolymerization using ammonium persulfate as the initiator, and 1,6-hexanediol diacrylate as the inner-crosslinker. The surface-crosslinking process is performed using various surface-crosslinkers, including bisphenol A diglycidyl ether (BADGE), poly(ethylene glycol) diglycidyl ether (PEGDGE), ethylene glycol diglycidyl ether (EGDGE), and diglycidyl ether (DGE). The structures of the CSAP composites and their surface-crosslinked SAPs (SSAPs) are characterized using Fourier transform infrared (FT-IR) spectroscopy, their absorption properties are measured via centrifuge retention capacity (CRC), absorbency under load (AUL), permeability, and re-swellability tests, and their gel strengths according to surface-crosslinker type and EGDGE content are examined via rheological analysis. The results indicate that an EGDGE content of 0.75 mol provides the optimum surface-crosslinking and SSAP performance, with a CRC of 34.8 g/g, an AUL of 27.2 g/g, and a permeability of 43 s. The surface-crosslinking of the CSAP composites using OS is shown to improve the gel strength, thus enabling the SAP to be used in disposable diapers.

Molecular interaction of poly (acrylamide‐co‐2‐acrylamido‐dodecyl sulfonate) with dual responsiveness and application in oily emulsion wastewater

AbstractStimuli‐sensitive polymers are a class of macromolecular system with “intelligent” behavior. Herein, a copolymer of poly (acrylamide‐co‐2‐acrylamido‐dodecyl sulfonate), which has salt‐sensitive and thermosensitive properties, is synthesized via precipitation polymerization. Its aqueous solution exhibits a clear sol state, while a gel is obtained via salt‐induction by addition a certain amount of NaCl. More interestingly, the gel can transform into clear sol again upon heating, which exhibits a phase transition of upper critical solution temperature in NaCl solution. The dual responsive behaviors of copolymer solutions are studied via rheological measurements. Then fluorescence spectrum, zeta potential test, and dynamic light scattering are employed to investigate molecular interaction in aqueous solution under varying conditions. It is found that dual responsive behaviors are caused by electrostatic interaction and hydrophobic association. At last, oily emulsion wastewater treatment indicates that this polymer shows characteristics of “smart flocculant” and has potential application prospect.

3D bicontinuous diamond-like morphologies in thin films of soluted block copolymers.

As shown theoretically earlier via both weak segregation and self-consistent field theories, ordering of confined molten di- and tri-block copolymer morphologies in the presence of a proper 1D patterned substrate could induce the formation of 3D bicontinuous (in particular, diamond-like) morphologies (DLMs). The purpose of the present paper is to study, unlike the previous studies, how the stable DLMs are formed not in a melt but in a solution of symmetric diblock copolymers with a nonselective solvent that wets the thin film on the patterned substrate. It is shown, via a straightforward self-consistent field calculation of the total solution free energy for various competing phases, that the DLM could be formed in the solutions (with the solvent volume fraction of 0.5), which provides much faster thermodynamic equilibration of the solution as compared to the melt. The last circumstance can ease the production of stable DLMs in thin films of copolymers. The phase diagram describing the stable phases on the plane "the pattern period-the film thickness" is built.

Preparation and properties of polyurethane film with photothermal conversion and energy storage capability

Purpose This paper aims to provide a flexible polyurethane (PU) film with visible light trapping ability, photothermal conversion and energy storage performance by covalently bonded a visible light absorbing dye into the polymer through copolymerization. Design/methodology/approach For this target solution copolymerization of diphenyl-methane-diisocyanate (MDI), poly(1,4-butylene adipate) (PBA2000), polyethylene glycol (PEG) of different molecular weight, self-made dye, 1,4-butanediol (BuOH) was carried out in a flame-dried flask under an inert nitrogen (N2) atmosphere. First, an isocyanate-terminated prepolymer of dried PEG, MDI and PBA2000 was prepared in dimethylformamide and stirred for 1 h at 35°C. Then, self-made dye and 1, 4-butanediol (BuOH) were added and heated at 85°C for 3 h to get photothermal conversion polyurethane (PTPU) solution. Allowed the solution to dry at room temperature for seven days and then at 65°C for 12 h to get PTPU films. Findings The flexible PU films with photothermal conversion and energy storage performances were successfully synthesized and the functional films presented both excellent energy storage and mechanical property when the molecular weight of PEG was in the range of 6,000∼10,000. Research limitations/implications The materials that were used in this research paper had a reasonably low cost. Also, the procedures for the synthesis of dye and polymers were extremely easy because there was no need for high pressure or temperature and no dangerous solvents were used. Practical implications The photothermal conversion property and mechanical performance of the synthesized flexible PU films were characterized. The results have proved that these films were soft and elastic, and have certain photothermal conversion and energy storage ability, thus can be used in the surface finishing of special fabric and leather. Originality/value Visible light trapping photothermal conversion PU flexible film with energy storage capability was prepared for the first time.

Block copolymer solution self‐assembly: Recent advances, emerging trends, and applications

AbstractThe self‐assembly process of block copolymers (BCPs) in solution has been at the focus of extended scientific research over the past several decades owing to the astonishing morphological diversity and attainable complexity of the resulting nanoassemblies, including spheres, cylinders, lamellae, vesicles, and many other complex, bicontinuous or even hierarchical structures. The ever‐increasing sophistication in the development of synthetic chemistry methods and techniques has led to a myriad of available macromolecules with varying chemical compositions, architectures, features, and properties. This assortment of characteristics has led in turn to a plethora of intriguing self‐organized polymeric nanostructures, with countless possible applications in several nanotechnological fields relevant to physics, chemistry, material science, nanomedicine, and biomaterials. The present review aims to illuminate the importance and fascinating potential of BCPs solution self‐assembly by highlighting recent advances and emerging trends in the field, as well as significant application‐oriented progress, through characteristic contemporary examples.

Enhancing the application of mechanochemistry in the synthesis of high-concentration polycarboxylate superplasticizer: is aqueous copolymerization needed?

Mechanochemical synthesis, a rapid and efficient method, was utilized in the synthesis of polycarboxylate superplasticizers (PCEs) for the first time. For comparison, traditional polycarboxylate superplasticizer (TPCE) was also synthesized by the aqueous solution copolymerization method. The molecular structure of PCEs synthesized by mechanochemistry (MPCEs) and TPCE were confirmed by gel permeation chromatography, Fourier transform infrared spectroscopy, and 1H-nuclear magnetic resonance spectroscopy. The molecular weight of the synthesized MPCEs decreases with increasing reaction time in mechanochemical synthesis. Additionally, the concentrations of MPCEs and TPCE and the fluidity of the cement paste with MPCEs and TPCE were also investigated. MPCEs were found to have a much higher concentration than TPCE. When PCEs are added at 0.30 wt% of the cement dosage, the fluidities of the cement slurry with MPCE-A3 or MPCE-B3 are comparable to those of TPCE.

Study of Segregation in Non-Dilute Solutions of Linear Diblock Copolymers and Symmetric Miktoarm (or Janus Star) Polymers Using Monte Carlo Simulations with the Bond Fluctuation Model

The bond fluctuation model was employed to characterize the approach to the mesophase separation transition of pure linear AB copolymers and symmetric miktoarms, also called Janus, star polymers, Af/2Bf/2, where f = 6 or 12 is the total number of arms, in a common good solvent. We consider a concentration sufficiently high to mimic the melting behavior and also a lower concentration. The segregation between A and B units is represented by a repulsive interaction parameter, ε. Different total numbers of units are also considered. Results for different properties, such as the molecular size, the asphericity and orientational correlation of blocks, or arms, of different compositions are obtained as a function of the segregation parameter. We also calculate scattering structure factors. The initial effect of segregation on the scattering with opposite contrast factors between the A and B blocks can be explained with a common description based on the random phase approximation for both the linear copolymers and the f = 6 miktoarms, once the numerical form factors of the different molecules in their particular systems are considered. However, the results for f = 12 clearly deviate from this description probably due to some degree of ordering in the position of highly armed molecules.

An emphasis on dynamic mechanical properties of novel stilbene containing copolymer/organo‐MMTnanocomposites fabricated via in situ interlamellar copolymerization

AbstractThe objective of the present study is to synthesis and characterize the novel functional stilbene containing copolymer‐clay nanocomposites, make clear the influence of organo‐clay on peculiarities of the nanocomposites and emphasis on the dynamic mechanical properties. For this purpose, poly(acrylamide‐co‐trans‐stilbene)‐organo‐MMT [poly(AAm‐co‐Stb)‐O‐MMT] nanocomposites were synthesized by in situ interlamellar solution copolymerization with organically modified montmorillonite (O‐MMT) clay due to its superior properties gives to copolymer. The effect of different amounts of O‐MMT clay incorporation to the nanocomposite structure and properties of copolymer/O‐MMT clay nanocomposites were characterized by X‐ray diffraction (XRD), Attenuated Total Reflectance‐Fourier Transform Infrared, Thermogravimetric Analysis, Differential Scanning Calorimeter, Dynamic mechanic analysis (DMA) methods. XRD analysis showed the basal spacing of the O‐MMT increased in nanocomposites and this indicated that the intercalation of the copolymer chain into the O‐MMT interlayer performed and nanocomposites were obtained successfully. Additionally, copolymer/O‐MMT nanocomposites exhibited improved thermal properties at higher temperatures than the pristine copolymer. DMA results enlightened the viscoelastic properties of synthesized materials. DMA results indicated that obtained nanocomposites have higher mechanical strength because of the interaction/compatibility in between copolymer chains and O‐MMT. In the light of these results, this work has introduced new perspectives on design, fabrication and viscoelastic properties of certain organo‐clay copolymer nanocomposites for the synthesis of new materials and potential industrial applications.

Thermodynamically Consistent Algorithms for Models of Diblock Copolymer Solutions Interacting with Electric and Magnetic Fields

We derive thermodynamically consistent models for diblock copolymer solutions coupled with the electric and magnetic field, respectively. These models satisfy the second law of thermodynamics and are therefore thermodynamically consistent. We then design a set of 2nd order, linear, semi-discrete schemes for the models using the energy quadratization method and the supplementary variable method, respectively, which preserve energy dissipation rates of the models. The spatial discretization is carried out subsequently using 2nd order finite difference methods, leading to fully discrete, energy-dissipation-rate preserving algorithms that are thermodynamically consistent. Convergence rates are numerically confirmed through mesh refinement tests and several numerical examples are given to demonstrate the role of mobility in pattern formation, defect removing effect of both electric and magnetic fields as well as the hysteresis effect with respect to applied external fields in copolymer solutions.

A General Approach for Modeling Acrylate and Methacrylate Solution Copolymerizations

A General Approach for Modeling Acrylate and Methacrylate Solution Copolymerizations

Rheological signatures of gel–glass transition and a revised phase diagram of an aqueous triblock copolymer solution of Pluronic F127

In this work, we study temperature-induced state change of an aqueous solution of triblock copolymer composed of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide), PEO-PPO-PEO (Pluronic F127), at different concentrations using rheology. While this temperature-dependent state change visually appears like a liquid–soft solid transition, and the soft solid state has been termed as a gel in the literature, there is a debate regarding the precise microstructure of the soft solid state. We observe that over a concentration domain of interest, an aqueous solution of F127 overwhelmingly demonstrates all the characteristic rheological features of not just a sol–gel–glass transition at low temperatures and glass–liquid transition at high temperatures, but also that associated with the individual states, such as sol, post-gel, and glass. The temperature at which the gel–glass transition is observed decreases while the temperature associated with glass–liquid transition increases with an increase in the concentration of F127. Based on the observed behavior, we propose a mechanism that considers the change in micelle volume fraction and alteration of the hydrophilicity of PEO corona as a function of temperature. Finally, we construct a phase diagram and discuss the similarities and differences with respect to various phase diagrams of F127 solution available in the literature.

Multifunctional injectable pluronic-cystamine-alginate-based hydrogel as a novel cellular delivery system towards tissue regeneration

This paper presents a new thermal sensitive hydrogel system based on cystamine-functionalised sodium alginate-g-pluronic F127 (ACP). The introduction of cystamine to the alginate backbone not only creates a covalent bond with pluronic F127 but also provides intrinsic anti-bacterial activity for the resultant hydrogel. The amount of water uptake inside the hydrogel remained ~200% for 6 days and the degradation was completed in 12 days in physiological media. The ACP copolymer solution could form a hydrogel at body temperature (~37 °C) and could return to the solution phase if the temperature decreased below 25o °C. Fibroblast encapsulated in situ in the ACP hydrogel maintained their viability (≥90% based on the live/dead assay) for 7 days, demonstrating the good biocompatibility of the ACP hydrogel for long-term cell cultivation. In addition, three-dimensional (3D) culture showed that fibroblast attached to the hydrogels and successfully mimicked the porous structure of the ACP hydrogel after 5 days of culture. Fibroblast cells could migrate from the cell-ACP clusters and form a confluent cell layer on the surface of the culture dish. Altogether, the obtained results indicate that the thermal-responsive ACP hydrogel synthesised in this study may serve as a cellular delivery platform for diverse tissue engineering applications.

FORMATION OF NICKEL NANOPARTICLES IN SOLUTIONS OF A HYDROPHILIC GRAFT COPOLYMER

A graft copolymer of poly(vinyl alcohol) and polyacrylamide (PVA-g-PAAm) with interacting main and grafted chains was synthesized by radical matrix polymerization of PAAm from the PVA backbone in an aqueous medium. Its basic molecular parameters including the number and length (molecular weight) of grafts were determined using elemental analysis, DTGA and viscometry. The copolymer macromolecules formed special monomolecular micelles of elipsoidal shape and length ~18-64 nm in aqueous solutions due to the formation of intramolecular polycomplexes between the main and grafted chains. This copolymer was used as a hydrophilic matrix for the in situ synthesis of nickel nanoparticles (NiNPs) in aqueous solutions.On the basis of UV-Vis spectroscopy, an original and simple method for monitoring the kinetics of the formation and yield of metal nanoparticles in systems in which a surface plasmon resonance band does not appear has been proposed and implemented. Using this approach, the kinetics of borohydride reduction of Ni-salt to NiNPs in pure water and PVA-g-PAAm solutions was studied depending on the concentrations of Ni-salt and copolymer matrices. An increase in the initial rate of accumulation and yield of NiNPs with an increase in the concentration of Ni-salt and a decrease in both parameters in copolymer solutions in comparison with pure water was established. At the same time, the accumulation rate and NiNP yield in a complex way was depended on the matrix concentration that was determined by the ratio of such factors as a decrease in the diffusion rate of NaBH4 molecules in copolymer solutions and the accumulation of Ni2+-ions in matrix particles due to complexation with active chemical groups at the first stage of reduction process. The morphology and main structural elements of the NiNPs/PVA-g-PAAm composition were revealed using TEM. It was shown that the in situ synthesis of NiNPs in copolymer matrices was accompanied by the “detachment” of PAAm grafts from the main PVA chains and led to the appearance of two new structures, such as “hairy coils” and “hairy rods”, containing small spherical NiNPs (d~0,5–12,0 nm) in isolated and chain states, respectively. The appearance of the latter structures was explained by the formation of coordination complexes of Ni2+-ions with active groups of both PVA and PAAm chains at the first stage of the reduction reaction.