Montmorillonite-aminocaproic acid complexes (monomer complexes) were prepared by the intercalation of 6-aminocaproic acid to various homoionic (Na+, Ca2+, Mg2+, Co2+, and Cu2+) montmorillonites. Infrared spectra of the monomer complexes indicated that the interaction between the exchangeable cations and the 6-aminocaproic acid increased in the following order: Na-, Ca-, and Mg- < Co- < Cu-montmorillonite-aminocaproic acid complex. Montmorillonite-nylon complexes (polymer complexes) were prepared by thermal treatment of the monomer complexes, which was confirmed by X-ray powder diffraction and infrared spectroscopy the results of which indicated the condensation of 6-aminocaproic acid in the interlayer space.

Thermal degradation of montmorillonite-nylon complexes was studied by thermogravimetry. It was found that the thermal stability of the polymer complexes increased in the following order: Cu- < Co- < Na- < Mg- < Ca-montmorillonite-nylon complex.

It was suggested that the difference in thermal stability depended upon the length of the polymer chain which might be influenced by the interaction between the exchangeable cations and the 6-aminocaproic acid. The activation energy for the thermal degradation of each montmorillonite-nylon complex was obtained, and the value for Cu-montmorillonite-nylon complex was smaller than that for the other cation-exchanged montmorillonite-nylon complexes.

The adsorption of uncharged polymers by clays is largely “entropy-driven.” Polymer conformation changes from a random coil in solution to an extended form at the surface in which adsorbed polymer segments or trains alternate with loops and tails extending away from the surface. Although the net interaction energy, ε, per segment-surface contact is small (~1 kT unit), the total energy of adsorption is large because the fraction of train segments, p, is commonly between 0.3 and 0.5. The adsorption isotherms are typically of the high-affinity type, and there is an apparent lack of desorption on dilution. Positively charged polymers (polycations) are adsorbed largely through electrostatic interactions between the cationic groups of the polymer and the negatively charged sites at the clay surface. Here ε ≫ 1 kT unit and p > 0.7, leading to an almost complete collapse of the polymer chain onto the surface. Indeed, beyond a given level of adsorption charge reversal can occur in that the clay-polycation system effectively behaves as an anion exchanger. Little adsorption occurs with negatively charged polymers (polyanions) due to initial charge repulsion between the polymer and the clay surface. Acid pH, a high ionic strength, and the presence of polyvalent cations in the system enhance and promote polyanion adsorption. Uncharged polymers and polycations can enter the interlayer space of expanding 2:1 type layer silicates but polyanions generally fail to intercalate.

The interactions of clays with biopolymers, such as proteins, nucleic acids, and polysaccharides, can be rationalized in similar terms. When intercalation occurs, the interlayer biopolymer is further stabilized against microbial (enzymatic) degradation giving rise to practical applications of clay-polymer complexes as flocculants and soil conditioners. Polyanions are effective as flocculants because of their large “grappling distance,” whereas uncharged polymers are better suited as soil conditioners because they can spread over adjacent clay/soil particle surfaces like a coat of paint.

To control a vast spectrum of applications and processes, an understanding of the morphologies of clay mineral assemblies dispersed in aqueous or non-aqueous media is important. As such, the objective of this study was to verify the relationship between dispersion medium type and the size and morphology of the clay aggregates that are formed, which can increase knowledge on the assembly formation process. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) spectroscopy were used in an attempt to describe kaolinite platelet organization in non-aqueous media and to compare it to the organization in aqueous media or in media with or without a selection of dissolved organic polymers. The SEM images indicated that the kaolinite platelet assembly process occurs during slow evaporation of the solvent. Because the experimental procedure was rigorously identical for all cases in this study, the SEM images compared how the effects of various media and environments on kaolinite platelet interactions can lead to different morphologies. Quite spectacular morphological differences were indeed observed between samples dispersed in aqueous and non-aqueous media, particularly when the kaolinite platelets were dispersed in an organic solvent with dissolved organic polymers. For kaolinite dispersed in water, only small aggregates were observed after slow evaporation. In contrast, large kaolinite booklets or vermiform aggregates were formed by slow solvent evaporation when kaolinite was first dispersed into some organic solvents. The aggregates were particularly large when an organic polymer was dissolved in the organic solvent. For example, kaolinite aggregates dispersed in a binary cyclohexane/toluene mixture with dissolved ethyl cellulose (EC) had top apparent surface areas (i.e. stacking length × width) of more than 3,000 µm2. Other dissolved polymers, such as polystyrene or the polysaccharide, guar gum, gave similar results. Kaolinite platelet aggregation resulted from face-to-face interactions as well as edge-to-face and edge-to-edge interactions. The XRD results showed that ethyl cellulose led to the formation of smaller kaolinite platelets with an increased tendency to form larger aggregates, which is due to the ability of EC to chemically interact with silanol and/or the aluminol groups of kaolinite.

Enhancement of the physico-chemical properties of elastomers can be achieved by the addition of fillers, such as silica, but the search for less expensive alternative materials continues. The objective of this study was to investigate natural or organically modified clay minerals as such an alternative. Organo-clays modified by quaternary ammonium cations with three methyl groups and longest alkyl chains of different lengths were prepared by ion-exchange reaction of the commercial product JP A030 (Envigeo, Slovakia) based on Jelšový Potok bentonite with organic salts: tetramethylammonium (TMA) chloride, octyltrimethylammonium (OTMA) bromide, and octadecyltrimethylammonium (ODTMA) bromide. Physico-chemical characterizations of the organo-clays used as fillers in rubber nanocomposites and their mechanical properties were measured using Fourier transform infrared (IR) spectroscopy, which provided information on the chemical composition of the mineral and on the amount of organic moieties adsorbed. X-ray diffraction analysis (XRD) was used to monitor the arrangement of organic chains in galleries of montmorillonite and showed that the longest-chain alkylammonium ODTMA+ ions were intercalated between layers, adopting a pseudotrimolecular conformation, while OTMA+ and TMA+ were in monomolecular arrangement. Surface areas were measured by sorption of N2 and ethylene glycol monoethyl ether. Natural rubber-clay nanocomposites were prepared by melt intercalation, in some cases also with addition of silica, a conventional reinforcing filler. The microstructure of montmorillonite in these composites was characterized by XRD analysis. The effect of clay and organo-clays loading from 1 to 10 phr (parts by weight per hundred parts of rubber) on stress at break, strain at break, and Modulus 100 (M100) was investigated by tensile tests. Filler ODTMA-JP A030 appears to be the most effective among the organoclays; surprisingly similar values of composite elongation and strength were obtained with unmodified bentonite JP A030.

Polymers maintain colloidal stability by adsorbing onto the surface of sepiolite particles, and changes in temperature and salinity can affect this process. We chose three typical polymers to investigate their interactions with sepiolite under high-salinity (15 wt.% NaCl) conditions at >180°C. Sepiolite samples were characterized using infrared testing, X-ray diffraction testing, contact angle testing, thermogravimetric testing, filtration loss testing and rheological testing. The experimental results showed that the desorption of the polymers under high-temperature and high-salinity conditions reduces the stability and filtration control of the suspension significantly. Adding polymers to sepiolite suspensions can maintain good stability even after thermal ageing at 240°C. In terms of drilling fluid regulation, sepiolite can play a role in regulating rheological properties, and the interactions between various polymers and sepiolite can be utilized to maintain the stable colloidal state of the drilling fluid. Studying the adsorption behaviour of various types of polymers on the surface of sepiolite under high-temperature and high-salinity conditions has important implications for the design and selection of sepiolite drilling fluid treatment agents.

Recent work in structure–processing relationships of polymer semiconductors have demonstrated the versatility and control of thin-film microstructure offered by meniscus-guided coating (MGC) techniques. Here, we analyze the qualitative and quantitative aspects of solution shearing, a model MGC method, using coating blades augmented with arrays of pillars. The pillars induce local regions of high strain rates—both shear and extensional—not otherwise possible with unmodified blades, and we use fluid mechanical simulations to model and study a variety of pillar spacings and densities. We then perform a statistical analysis of 130 simulation variables to find correlations with three dependent variables of interest: thin-film degree of crystallinity and transistor field-effect mobilities for charge-transport parallel (μpara) and perpendicular (μperp) to the coating direction. Our study suggests that simple fluid mechanical models can reproduce substantive correlations between the induced fluid flow and important performance metrics, providing a methodology for optimizing blade design.

Additive manufacturing (AM) has made long strides in the recent past and rapidly evolved into a promising alternative in specific applications. The aircraft industry is not an exception to this. The true just-intime production possibility is critical for the aircraft maintenance industries, though the lack of material freedom is a major hurdle. Several fire-retardant materials were investigated for AM in the aerospace context, but mainly for fused deposition modeling (FDM). The material consolidation constraints in FDM led to the expansion to the use of selective laser sintering (SLS) to some extent. Nevertheless, the material options are still limited, proprietary, and lack scientific insights into the material consolidation mechanics. Attempts are made in this paper to fill this gap, evaluating a new fire-retardant material for processing by SLS. Experiments conducted to ascertain the material, process, structure, and consolidation relationships indicated energy density levels 0.062–0.070 J/mm2 with laser power 13 W and scan speed varied slightly around 390 mm/s to give the best laser sintering and mechanical property results in polyetherimide powders.

Nowadays, theranostics drug delivery systems (DDSs) with imaging and therapy bi-functions have been regarded as a future orientation for imaging-guided cancer therapy. To achieve high imaging quality, a donor–acceptor (D–A)/Förster resonance energy transfer (FRET) bi-adjustment strategy is carried out for designing dual-colored DDSs with amplified aggregation-induced emission (AIE) behavior for imaging-guided cocktail cancer therapy in this study. In detail, four AIE-active conjugated polymers P-1 to P-4 are synthesized via the Suzuki reaction. Noteworthily, the D–A-type structure is applied in tuning the fluorescence color from orange (P-1) to far-red/near-infrared (P-2), while the intramolecular FRET process further enhanced the fluorescence signal for six times (P-3). Afterwards, P-3-based amphipathic polymer P-4 further acts as a drug carrier in preparing doxorubicin (Dox)- and curcumin (Cur)-loaded polymer dots (Pdots) (Dox-loaded Pdots as PDox and Cur-loaded Pdots as PCur). PDox + PCur DDS is successfully applied in imaging-guided cocktail cancer therapy to give obviously higher in vivo anticancer efficacy compared with single PDox or PCur. In addition, the drug-loaded Pdots also exhibit higher biocompatibility compared with free drugs. This work provides a novel D–A/FRET bi-adjustment strategy for developing high efficiency imaging-guided cocktail DDSs in cancer therapy.

Poly(phthalaldehyde) (pPHA) and copolymers with aliphatic aldehydes were investigated as dry-develop, positive-tone photoresist. Exposure of the films loaded with a photoacid generator to 248 nm radiation creates an acid that depolymerizes the polymer into volatile monomers, allowing the development of features by vaporization rather than solution-based processes. By controlling the acid content, the vaporization rate of the reaction products, and the degree of liquid formation of the decomposed polymer, control of spatial resolution and the quality of polyaldehyde dry-develop photoresist was achieved. Heat, vacuum, and forced convection were evaluated as development techniques in determining the resist sensitivity, contrast, and resolution. Forced convection of heated nitrogen was the most controllable development method for pPHA films. Five-micron lines and spaces were printed. Poly(aldehyde) copolymer resins had slightly lower spatial resolution but were able to be developed faster due to higher vapor pressure of the depolymerized monomers. Cold photo-exposures and development were used to prevent detrimental liquid formation of the decomposed copolymers. In addition to exploring new dry-development methods that have not been tested before, these findings offer insights into designing better material systems and optimizing processes for dry-develop photoresists.

Boronic ester bonds can be reversibly formed between phenylboronic acid (PBA) and triol moieties. Here, we aim at a glucose-induced shape-memory effect by implementing such bonds as temporary netpoints, which are cleavable by glucose and by minimizing the volume change upon stimulation by a porous cryogel structure. The polymer system consisted of a semi-interpenetrating network (semi-IPN) architecture, in which the triol moieties were part of the permanent network and the PBA moieties were located in the linear polymer diffused into the semi-IPN. In an alkaline medium (pH = 10), the swelling ratio was approximately 35, independent of Cglu varied between 0 and 300 mg/dL. In bending experiments, shape fixity Rf ≈ 80% and shape recovery Rr ≈ 100% from five programming/recovery cycles could be determined. Rr was a function of Cglu in the range from 0 to 300 mg/dL, which accords with the fluctuation range of Cglu in human blood. In this way, the shape-memory hydrogels could play a role in future diabetes treatment options.

In this paper, we use finite element analysis (FEA) to study the linear viscoelastic response of polyurea, a type of hard–soft block copolymer. A Niblack's algorithm-based technique employed on atomic force microscopy images provides geometry inputs for the FEA model, while the viscoelastic master curves of the soft matrix are obtained via a combination of dynamic mechanical analysis data and molecular dynamic (MD) estimations. In this microstructural image-based FEA framework, we introduce an interphase area of altered properties between the hard and soft domains. Both spatial and property distributions of this interphase area affect the viscoelastic response of the copolymer system. To quantitatively investigate the impact of structural and property features of the interphase on the energy storage and dissipation of a system during linear perturbation, we develop a statistical descriptor representation of the interphase region related to physical parameters. Utilizing decision-tree and random forest concepts from machine learning, we apply a ranking algorithm to identify the most significant features for four different mechanical response descriptors. Results show that the total interphase volume fraction and shifting factor distributions in the interphase area dominate the magnitude of the tan δ peak, whereas the magnitudes of the shifting factors primarily affect the tan δ peak location in frequency space. This method allows us to readily identify the dominant features impacting individual properties and paves the way for material design of hard–soft block copolymer systems.

Vast improvements have been made to the capabilities of advanced manufacturing (AM), yet there are still limitations on which materials can effectively be used in the technology. To this end, parts created using AM would benefit from the ability to be developed from feedstock materials incorporating additional functionality. A common three-dimensional (3D) printing polymer, acrylonitrile butadiene styrene, was combined with bismuth and polyvinylidene fluoride via a solvent treatment to fabricate multifunctional composite materials for AM. Composites of varying weight percent loadings were extruded into filaments, which were subsequently 3D printed into blocks via fused filament fabrication. Investigating the material properties demonstrated that in addition to the printed blocks successfully performing as radiation shields, the chemical, thermal, and mechanical properties are suitable for AM. Thus, this work demonstrates that it is possible to enhance AM components with augmented capabilities while not significantly altering the material properties which make AM possible.

Hydrogels have gained recent attention for biomedical applications because of their large water content, which imparts biocompatibility. However, their mechanical properties can be limiting. There has been significant recent interest in the strength and fracture toughness of hydrogel materials in addition to their stiffness and time-dependent behavior. Hydrogels can fail in a brittle manner, although they are extremely compliant. In this work, the failure and fracture of hydrogels are examined using a compression test of spherical hydrogel particles. Spheres of commercially available polyacrylamide–potassium polyacrylate were hydrated and tested to failure in compression as a function of loading rate. The spheres exhibited little relaxation when compressed to small fixed displacements. The distributions of strength values obtained were examined in a particle fracture framework previously used for brittle ceramics. There was loading rate dependence apparent in the measured peak force and calculated peak strength values, but the data fell on a single empirical distribution function of strength for the hydrogels regardless of loading rate. Strength values for these hydrogels were mostly in the range of 0.05–0.3 MPa, illustrating the challenges using hydrogels for mechanically demanding applications such as tissue engineering.

In this work, filament based on ɛ-polycaprolactone (PCL) and containing the bioactive ceramics nanohydroxyapatite (nHap) and Laponite® (Lap) was prepared by the extrusion process. To obtain the material, a mass ratio of 89:10:1 (PCL:nHap:Lap) was used, and structural and morphological characterization was realized. In addition, cytotoxicity (using Allium cepa bulbs) and viability tests on L929 cells also were performed. The results showed that filament (diameter of 1.79 ± 0.17 mm) presented a good dispersion of nHap and Lap into polymeric matrices. Fourier transform infrared spectroscopy identified typical bands at 1720, 1091, and 1045 cm−1 addressed to PCL and nHAp, In addition, Lap was identified through dispersive energy system and X-ray diffraction analyses. All filaments did not exhibit cytotoxic effects.

The quality of the polymer raw material used in plastic processing methods is an important characteristic because it is one of the main factors in producing quality products. Therefore, the characterization of polymeric pellets in the polymer processing industry is very important to avoid using inferior materials. In general, differences in the interiors of polymeric pellets reflect differences in their densities. In this study, a high-sensitivity magnetic levitation method was used to characterize the polymeric pellets in four different occasions. The device used has a high sensitivity that can distinguish minute differences as small as of 0.0041 g/cm3 in density between different samples. In addition, the method can obtain a sample's density without knowing the weight and volume of the sample. This method can be used to characterize materials by testing only a single pellet, which is very useful for polymeric pellet characterization.

Bioactive dressings which can treat any kind of chronic or acute wounds and can fully replace the conventional gauzes and superabsorbent dressings have proven to be a future market of wound care products in recent times. These dressings are multifunctional, which can effectively combat the wound infection, remove the exudate, promote angiogenesis, and protect the wound from external trauma. Proper selection of bioactive and polymer defines its efficiency. Current research unveils the therapeutic efficacy of curcumin–honey-loaded multilayered polyvinyl alcohol/cellulose acetate electrospun nanofibrous mats as an interactive bioactive wound dressing material. Scanning electron microscopy and Fourier transform infrared spectroscopy analysis infers uniform encapsulation and chemical compatibility of herbal actives and polymer, inside the nanofibrous layers. The as-spun mat shows potential resistance towards Escherichia coli and ∼90% antioxidant activity against diphenyl-picrylhydrazyl (DPPH)–free radical. Additionally, water absorbency, water vapor transmission rate, and wettability analysis show quick and excellent absorption with controlled transmission of wound exudate.