Phase transitions and dielectric properties in a symmetric liquid crystalline compound with central triaromatic group

Phase transitions and dielectric properties of a symmetric liquid crystalline compound with central triaromatic group are studied and compared with a similar epoxy compound (which has additional strong dipole moments in the tails). The base molecule consists of a central triaromatic group and two symmetric eight-segment aliphatic chains terminated with vinyl groups. The phase transition temperatures are determined through differential scanning calorimetry (DSC), optical data, wide-angle X-ray scattering (WAXS) technique and dielectric measurements. Complex dielectric permittivity is shown for the investigated compound with a sequence of phase transitions in a wide range of frequencies and temperature. In all the cases, phase transitions are clearly visible as the dielectric constant significantly changes near the transition. Physical properties of the material are compared to a closely related compound having polar groups as chain terminators. The impact of this modification of the molecular structure on phase transitions is demonstrated

Maize (Zea mays) reaction in response to rubber rag additive into the soil

The amount of used and worn out tires around the world reaches about 10 million tons. Rubber introduction to the environment in this shape is connected with its pollution, caused by tires’ chemical composition, which, apart from synthetic and natural rubber, contain soot as a filler, plasticizers having some amounts of polycyclic aromatic hydrocarbons and helping substances: activators, accelerator of vulcanization, cross-link means and homogenizers. The most important activator is zinc oxide. The aim of the conducted studies was to determine the influence of rubber rag added to the subsoil on the amount of yield, physiological state and the amount of taken zinc by maize (Zea mays). It was found that the rubber rag introduced into the soil caused an increase in the yield of maize and the plants growing on the soil with the highest amount of rubber rag showing higher efficiency photosynthetic apparatus than others. The zinc content in the aboveground parts of maize increased with the increase of rubber rag in the soil

Proces sieciowania i produkt reakcji nematycznego materiału epoksydowego zawierającego grupy estrowe

Curing process and the product of curing of one liquid crystalline epoxy monomer with a standard omine were examined. The reactions were monitored by DSC measurement and dielectric spectroscopy. Progress of curing of the examined mixture at different temperatures was shown. Influence of curing conditions on the final product was discussed and compared with other similar systems. DSC thermograms of the curing product were also analysed.Badano proces sieciowania i produkt reakcji ciekłokrystalicznego materiału epoksydowego z typową aminą aromatyczną. Reakcje monitorowano za pomocą pomiarów DSC i spektroskopii dielektrycznej. Pokazano przebieg sieciowania badanej mieszaniny w różnych temperaturach. Przedyskutowano wpływ warunków sieciowania na produkt końcowy i dokonano porównania z innymi podobnymi układami. Przeanalizowano także termogramy DSC usieciowanego produktu

Przewodnictwo usieciowanych żywic epoksydowych zawierających grupę bifenylową

Conductivity of two epoxy matrices based on the same monomer was compared. The epoxy monomer had symmetric structure and contained the biphenyl group which induced additional phase transitions in the pure material. Two amines responsible for different curing mechanisms were used to prepare the matrices. Wide ohmic regions were observed in both materials but quite high activation energy results in quick drop of conductivity at low temperatures and the materials can be treated as good isolators below 100°C. The obtained results are comparable with traditional epoxy resins.Porównano przewodnictwo dwóch matryc epoksydowych, opartych na tym samym monomerze. Monomer epoksydowy miał budowę symetryczną i zawierał grupę bifenylową, która wpłynęła na powstanie dodatkowych przejść fazowych w czystym materiale. Do wytworzenia matryc użyto dwóch amin odpowiedzialnych za różne mechanizmy sieciowania. W obu materiałach zaobserwowano szerokie przedziały przewodnictwa omowego, ale duża energia aktywacji powoduje szybki spadek przewodnictwa w niskich temperaturach i poniżej 100°C materiały te mogą być traktowane jak dobre izolatory. Otrzymane wyniki są porównywalne z tradycyjnymi żywicami epoksydowymi

Low-Temperature-Meltable Elastomers Based on Linear Polydimethylsiloxane Chains Alpha, Omega-Terminated with Mesogenic Groups as Physical Crosslinker: A Passive Smart Material with Potential as Viscoelastic Coupling. Part II—Viscoelastic and Rheological Properties

Rheological and viscoelastic properties of physically crosslinked low-temperature elastomers were studied. The supramolecularly assembling copolymers consist of linear polydimethylsiloxane (PDMS) elastic chains terminated on both ends with mesogenic building blocks (LC) of azobenzene type. They are generally and also structurally highly different from the well-studied LC polymer networks or LC elastomers: The LC units make up only a small volume fraction in our materials and act as fairly efficient physical crosslinkers with thermotropic properties. The aggregation (nano-phase separation) of the relatively rare, small and spatially separated terminal LC units generates temperature-switched viscoelasticity in the molten copolymers. Their rheological behavior was found to be controlled by an interplay of nano-phase separation of the LC units (growth and splitting of their aggregates) and of the thermotropic transitions in these aggregates (which change their stiffness). As a consequence, multiple gel points (up to three) are observed in temperature scans of the copolymers. The physical crosslinks also can be reversibly disconnected by large mechanical strain in the ‘warm’ rubbery state, as well as in melt (thixotropy). The kinetics of crosslink formation was found to be fast if induced by temperature and extremely fast in case of internal self-healing after strain damage. Thixotropic loop tests hence display only very small hysteresis in the LC-melt-state, although the melts show very distinct shear thinning. Our study evaluates structure-property relationships in three homologous systems with elastic PDMS segments of different length (8.6, 16.3 and 64.4 repeat units). The studied copolymers might be of interest as passive smart materials, especially as temperature-controlled elastic/viscoelastic mechanical coupling

Self-Healing and Super-Elastomeric PolyMEA-co-SMA Nanocomposites Crosslinked by Clay Platelets

Novel solvent-free ultra-extensible, tough, and self-healing nanocomposite elastomers were synthesized. The self-assembled materials were based on the copolymer matrix poly(methoxyethyl acrylate-co-sodium methacrylate) physically crosslinked by clay nano-platelets (‘poly[MEA-co-SMA]/clay’). Depending on the content of SMA, the super-elastomers were predominantly hydrophobic, water-swelling, or fully water-soluble, and hence repeatedly processible. The SMA co-monomer introduces a tremendous increase in tensile strength, an increase in toughness, while ultra-extensibility is preserved. By tuning the contents of nano-clay and SMA co-monomer, a very wide range of product properties was achieved, including extreme ultra-extensibility, or high stiffness combined with more moderate super-extensibility, or very different values of tensile strength. There was very attractive, great improvement in autonomous self-healing ability induced by SMA, combined with tremendously enhanced self-recovery of internal mechanical damage: even complete self-recovery could be achieved. The ionic SMA repeat units were found to assemble to multiplets, which are phase-separated in the hydrophobic polyMEA matrix. The dynamics of SMA-units-hopping between these aggregates was of key importance for the mechanical, visco-elastic, tensile, and self-healing properties. The studied super-elastomers are attractive as advanced self-healing materials in engineering, soft robotics, and in medical or implant applications

Liquid crystal epoxide network based on azoxy mesogen – electrical properties

In this work, electric properties of two matrices based on nematic epoxy monomers with azoxy groups are compared. The process of curing the monomers with DDM amine was monitored by means of dielectric spectroscopy at temperatures of 110 °C and 120 °C. In the next step, measurements of direct current conductivity were performed for the epoxy matrices cured at the temperature of 120 °C. The conductivity in the studied matrices was of the order of 10−9–10−7 S/m at temperatures between 150 °C and 170 °C. The conductivity of both the samples was of activation nature and their resistance grew rapidly below the temperature of 140 °C. Dielectric studies were also carried out for both the materials in a broad range of frequency and temperature. A relaxation process with similar activation energy was observed in both the cases. This process can be connected with the motion of polar azoxy groups present in the mesogen. An additional relaxation process appeared at higher temperatures in one of the cases, it was probably related to some structural change in the material

Novel Tough and Transparent Ultra-Extensible Nanocomposite Elastomers Based on Poly(2-methoxyethylacrylate) and Their Switching between Plasto-Elasticity and Viscoelasticity

Novel stiff, tough, highly transparent and ultra-extensible self-assembled nanocomposite elastomers based on poly(2-methoxyethylacrylate) (polyMEA) were synthesized. The materials are physically crosslinked by small in-situ-formed silica nanospheres, sized 3–5 nm, which proved to be a very efficient macro-crosslinker in the self-assembled network architecture. Very high values of yield stress (2.3 MPa), tensile strength (3.0 MPa), and modulus (typically 10 MPa), were achieved in combination with ultra-extensibility: the stiffest sample was breaking at 1610% of elongation. Related nanocomposites doubly filled with nano-silica and clay nano-platelets were also prepared, which displayed interesting synergy effects of the fillers at some compositions. All the nanocomposites exhibit ‘plasto-elastic’ tensile behaviour in the ‘as prepared’ state: they display considerable energy absorption (and also ‘necking’ like plastics), but at the same time a large but not complete (50%) retraction of deformation. However, after the first large tensile deformation, the materials irreversibly switch to ‘real elastomeric’ tensile behaviour (with some creep). The initial ‘plasto-elastic’ stretching thus causes an internal rearrangement. The studied materials, which additionally are valuable due to their high transparency, could be of application interest as advanced structural materials in soft robotics, in implant technology, or in regenerative medicine. The presented study focuses on structure-property relationships, and on their effects on physical properties, especially on the complex tensile, elastic and viscoelastic behaviour of the polyMEA nanocomposites

Synthesis and Morphology Characteristics of New Highly Branched Polycaprolactone PCL

A simple and efficient method for the synthesis of biodegradable, highly branched polycaprolactone (PCL) is presented. The solvent-free (bulk) reaction was carried out via ring opening polymerization (ROP), catalyzed by tin octanoate Sn(Oct)2, and it employed hyperbranched polyamide (HPPA) as a macro-initiator. The core–shell structure of the obtained products (PCL-HPPA), with the hyperbranched HPPA core and linear PCL chains as shell, was in the focus of the product characterization. 1H nuclear magnetic resonance (1H NMR) and elemental analysis confirmed the covalent incorporation of the HPPA in the products, as well as a high degree of grafting conversion of its amino functional groups. Confocal Raman Micro spectroscopy, and especially Time-of-Flight Secondary Ion Mass Spectrometry, further supported the existence of a core–shell structure in the products. Direct observation of macromolecules by means of cryogenic transmission electron microscopy, as well as gel permeation chromatography (GPC), suggested the existence of a minor ‘aggregated’ product fraction with multiple HPPA cores, which was attributed to transesterification reactions. Differential scanning calorimetry, as well as X-ray diffraction, demonstrated that the PCL-HPPA polymers displayed a similar degree of crystallinity to linear neat PCL, but that the branched products possessed smaller and less regular crystallites

Przewodnictwo elektryczne w matrycach epoksydowych z nanocząsteczkami

This work presents results of DC conductivity measurements obtained for epoxy matrices with different concentration of the nanofiller. In the first step, optimal curing conditions were determined - which turned out to be similar to those established for a plain epoxy matrix. In order to confirm stability of the matrix, measurements of the current-time dependency were made, which clearly show both the chemical and electric stabilization at the given temperature. All the obtained materials appeared to be good insulators with high activation energy. It was observed that the activation energy decreases slightly with increasing concentration of the nanofiller.W pracy zaprezentowano wyniki pomiarów przewodnictwa stałoprądowego uzyskane dla matryc epoksydowych z różnym stężeniem nanonapełniacza. Początkowo ustalono optymalne warunki sieciowania, które były podobne do tych ustalonych dla samej matrycy. W celu potwierdzenia stabilności matrycy przeprowadzono pomiary zależności prądu od czasu, które dobrze obrazują zarówno stabilizację chemiczną, jak i elektryczną w danej temperaturze. Wszystkie uzyskane materiały okazały się dobrymi izolatorami z dużą energią aktywacji. Zauważono, że wraz ze wzrostem stężenia nanocząstek energia aktywacji nieznacznie maleje