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Sulfonated cellulose (SC) was successfully derived from microcrystalline cellulose (MCC) extracted from sugarcane bagasse, which is a type of agricultural waste. The obtained MCC was first modified by oxidation using sodium periodate in order to cleave the carbon-carbon bonds at the C2 and C3 of the pyranose ring to form 2,3-dialdehyde cellulose. These activated aldehyde groups significantly facilitated the sulfonation carried out using potassium metabisulfite. The sulfonic acid group contents, surface morphology, and water solubility of the obtained products were characterized by titration, field-emission scanning electron microscopy, UV–vis spectroscopy, and zeta potential. High sulfonic acid group content was achieved for the obtained SC samples (i.e., 305–689 μmol/g). The increase in the sulfonic acid group content resulted in the gradual change in the surface morphology and water solubility of the SC samples. The obtained results imply that sugarcane bagasse is a promising raw material for the production of SC with good water solubility.

Recent observations of the high-velocity impact response in poly (urethane urea), PUU, elastomers has inspired a new inquiry on whether enabling molecular mechanisms could benefit dynamic impedance optimization at the interface of a glass/polymer bilayer, particularly at the moment of impulse interaction. In this work, we investigate the molecular influence on dynamic impedance using microballistic measurements on two bulk elastomers, a PUU and a polyurea, PU. Upon impact at strain rates ∼108/s, PUU exhibits a moderate improvement in resistance against penetration than PU, that is more pronounced at higher speeds. The variation in dynamic stiffening corroborates well with the corresponding segmental dynamics data determined via broadband dielectric relaxation. Meanwhile, we calculate the shock impedance from the shock velocity data derived from the respective shock Hugoniot to discern the efficacy of dynamic impedance optimization between PUU and glass. New insight on molecular attributes will guide glass/polymer interface designs.

In the present investigation, we explore the influence of uniaxial orientation and subsequent thermal annealing on semi-crystalline poly(ethylene-tetrafluoroethylene) (ETFE) microstructure and dynamics, and the connection to dielectric breakdown strength. Understanding the influence of crystalline microstructure on dynamics and breakdown, and in turn how processing influences microstructure, is critical for establishing rational design of polymer dielectrics. When drawn below the glass transition temperature (Tg), the Weibull breakdown strength decreases compared to that of the undrawn precursor film, but increases on thermal annealing near or above Tg. This behavior is associated with the formation and elimination of drawing-induced microvoids, respectively. When drawn above Tg, the breakdown strength increases to ∼870 MV/cm, dominated by orientation of amorphous segments, and decreases on thermal annealing above Tg to near that of the undrawn film.

It is a great challenge in dielectric polymers to achieve a high dielectric constant while maintaining low dielectric loss and high operating temperatures. Here we report that by blending two glassy state dipolar polymers i.e., poly(arylene ether urea) (PEEU, K=4.7) and an aromatic polythiourea (ArPTU, K=4.4) to form a nanomixture, the resulting blend exhibits a very high dielectric constant, K=7.5, while maintaining low dielectric loss (

This paper presents an investigation of semi-crystalline poly[tetrafluoroethylene -co-(perfluoropropylvinylether)] (PFA) films uniaxially drawn at two temperatures. The extent of crystal unit cell orientation increased significantly with drawing at both draw temperatures as expected, but crystallinity was found to increase with draw ratio only at the lower draw temperature, remaining unchanged at the higher temperature. Considering the evolution of small-angle X-ray scattering patterns as a function of deformation, a model for the changes in PFA lamellar microstructure on drawing was developed. The observed mechanical α and γ relaxations of PFA were assigned to relaxation of rigid and mobile amorphous segments, respectively. Drawing at 200 °C to a draw ratio of 7 leads to a ∼40 °C increase in the α transition temperature compared to the unoriented film, and the findings support the key role of molecular orientation in suppressing the cooperative motions of non-crystalline segments in drawn polymers.

Fluorinated semi-crystalline polymers are attractive for dielectric film applications due to their chemical inertness and high thermal stability. In the present investigation we explore the influence of orientation induced by uniaxial drawing on the crystalline microstructure and relaxation processes of poly(ethylene-tetrafluoroethylene) (ETFE), in order to ascertain how morphological control can benefit polymer dielectric design. When drawn below or near the Tg, the crystallinity of the drawn films is unchanged, and oriented amorphous structures and crystalline microfibrils form at high draw ratios. This orientation slows segmental relaxation, reflected by an increase in the dynamic Tg. When drawing above Tg, the films undergo strain-induced crystallization at high draw ratios. For these films, an increase in dynamic Tg is also observed, in addition to a second segmental relaxation process, appearing as a shoulder on the primary process. We propose that this represents a contribution from a rigid amorphous fraction, having slowed chain dynamics.

This paper represents the first report of polyvinyl alcohol (PVA) modified TPS resins (scCO2TPSxPVA05y), gelatinized and/or modified with the aid of supercritical carbon dioxide (scCO2). The melt flow rate, initial and retention values of tensile strength (σf) of scCO2TPSxPVA05y prepared with the aid of both scCO2 and PVA05 were considerably higher than those of the corresponding scCO2TPS prepared using scCO2 fluid and/or TPSxPVA05y materials prepared in the conventional way. The moisture contents of conditioned scCO2TPSxPVA05y were considerably lower than those of the corresponding scCO2TPS and TPSxPVA05y aged for the same amounts of time. Conditioned scCO2TPSxPVA05y exhibited only Vh-type crystals with melting temperatures ∼ 40 °C and ∼ 20 °C lower than those of corresponding conditioned TPS and TPSxPVA05y, respectively. In comparison to TPS and TPSxPVA05y, more dissociated amylopectin chains with loosely hydrogen-bonded −OH groups and significantly less retrogradation was obtained for conditioned scCO2TPS and scCO2TPSxPVA05y, respectively.

The dependences of the glass transition temperature and the dielectric constant on molecular volume of the repeat unit for polymerized ionic liquids, the monomers they were polymerized from and simple ionic liquids, are reviewed and compared. The ionic conductivities of these materials and the frequencies at which ionic rearrangements occur are shown to be controlled by their glass transition temperatures. The ionic conductivity is proportional to the product of dielectric constant and ionic rearrangement frequency, with the proportionality constant determined by the molecular volume of the repeat unit.

Poly(ethylene glycol) plasticizer is blended with a PEO-based single-ion conductor to lower the glass transition temperature of the ionomer and solvate the lithium counterions. With increasing plasticizer content at room temperature, FTIR spectra indicate that the fraction of ions in isolated ion pairs increases relative to those in ionic aggregates, and X-ray scattering data indicate that the ionic aggregates are further apart than expected by dilution alone. Together these data show that the average size of ionic aggregates decreases as PEG plasticizer is added. The dissolution of aggregates into ion pairs promotes ion conduction. Coupled with faster segmental dynamics and ion mobility from the depressed Tg, the ionic conductivity of plasticized ionomers improved by two orders of magnitude at room temperature. Resolving the alpha relaxation of these ionomer blends reveals that the mechanism for ion transport is segmentally-assisted ion motion.

This paper describes the influence of mixed poly(tetramethylene oxide) (PTMO) soft segments on microphase separation and morphology, hydrogen bonding, and polymer transitions for a series of alternating polyurea copolymers prepared from a single modified diphenylmethane diisocyanate. The fraction of two PTMO soft segments [with molecular weight = 1000 and 250 g/mol] was systematically varied and incorporated during bulk polymerization. ATR-FTIR spectroscopy confirmed that the intended polymers were synthesized and was used to determine the state of the local hydrogen bonding in these copolymers. Systematic changes in hard domain microstructure as a function of soft segment composition were clearly observed in AFM tapping mode phase images: the polyureas become progressively disordered with increasing content of the shorter PTMO. This was confirmed in a quantitative fashion using small-angle X-ray scattering. Results from dynamic mechanical analysis experiments reveal rather significant changes in dynamic segmental relaxations and storage moduli at 25 °C for this series of polyureas, which are in keeping with the findings from other experiments.

Three diisocyanates with different symmetry and planarity (2,6-TDI, 2,4-TDI and MDI) were used to synthesize polyureas with the same oligomeric polyetheramine having a molecular weight of ∼1000 g/mol. The influence of diisocyanate symmetry on the phase separated morphology, hydrogen bonding behavior, and molecular dynamics were investigated. Symmetric diisocyanate structures facilitated self-assembly of hard segments into ribbon-like domains, driven by strong bidentate hydrogen bonding. The hard domains for the 2,6-TDI polymer appear to be continuous in AFM images, while the persistence length of the hard domains in the 2,4-TDI and MDI polymers gradually decrease, and fewer hard domains are apparent with decreasing hard segment symmetry. The extent of hard/soft segment demixing, assessed from small-angle X-ray scattering, was very incomplete for all of the polyureas and is significantly influenced by hard segment structure. For the 2,4- and 2,6-TDI polyureas, two segmental relaxations were observed using dielectric relaxation spectroscopy; one arising from relatively unrestricted motion in the soft segment rich phase, and a slower process associated with segments in the soft phase constrained by their attachment to hard domains.

Segmented polyurethane (PU) block copolymers were synthesized using 4,4′-methylenediphenyl diisocyanate and 1,4-butanediol as hard segments and oligomeric ethoxypropyl polydimethylsiloxane (PDMS) as the soft segments, with hard segment contents ranging from 26 to 52 wt%. The microphase separated morphology, phase transitions, and degrees of phase separation of these novel copolymers were investigated using a variety of experimental methods. Like similar copolymers with mixed ethoxypropyl PDMS/poly(hexamethylene oxide) soft segments, PU copolymers containing only ethoxypropyl PDMS soft segments were found to consist of three microphases: a PDMS matrix phase, hard domains, and a mixed phase containing ethoxypropyl end group segments and dissolved short hard segments. Analysis of unlike segment demixing using small-angle X-ray scattering demonstrates that degrees of phase separation increase significantly as copolymer hard segment content increases, in keeping with findings from Fourier transform infrared spectroscopy measurements.

Microphase separation is a central feature of segmented polyurethane biomaterials and contributes to the biological response to these materials. In this study we utilized atomic force microscopy (AFM) to study the dynamic restructuring of three polyurethanes having soft segment chemistries of interest in biomedical applications. For each of the materials we followed the changes in near surface mechanical properties during hydration, as well as fibrinogen activity and platelet adhesion on these surfaces. Both AFM phase imaging and force mode analysis demonstrated that these polyurethane biomaterials underwent reorientation and rearrangement resulting in a net enrichment of hard domains at the surface. Fibrinogen activity and platelet adhesion on the polyurethane surfaces were found to decrease with increasing hydration time. The findings suggest that water-induced enrichment of hydrophilic hard domains at the surface changes the local surface physical and chemical properties in a way that influences the conformation of fibrinogen, changing the availability of the platelet-binding sites in the protein. This work demonstrates that the hydrated polyurethane biomaterial interface is a complex and dynamic environment where the surface chemistry is changing, altering the activity of fibrinogen and affecting blood platelet adhesion.

The dynamics of three main-chain liquid crystalline polysiloxanes were investigated using broadband dielectric relaxation spectroscopy. The liquid crystalline polymers (LCP) differ regarding the substituents on the rigid mesogens, and the nature of the substituents is found to influence the relaxation behavior. Within the temperature and frequency range examined, five relaxations are observed; two glassy state processes are associated with motions of the spacer segments (γ relaxation) and the substituted phenyl rings (β relaxation). The segmental (α) relaxation time changes with the nature of the mesogen substituent. A relaxation assigned to interfacial polarization between domain boundaries was observed, which disappears at the LCPs clearing temperature.

In this paper we explore the temperature dependence of segregation of hard and soft segments of selected segmented polyurethane copolymers using synchrotron small-angle X-ray scattering (SAXS). The copolymers are composed of the same hard segments but three different soft segment chemistries

The molecular dynamics of solutions of poly(2-vinylpyridine) (P2VPy) and a series of low molecular weight phenols containing from one to six hydroxyl groups were investigated using broadband dielectric spectroscopy (DRS). Dynamic mechanical analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, small-angle X-ray scattering and wide-angle X-ray diffraction were employed in a complementary role. Segmental relaxation times for the α processes of all solutions follow expectations from T g s derived from DSC experiments. For three of the model mixtures at 30 and 50 mol% [i.e., those containing bis (4-hydroxyphenyl) methane, 2,6 dihydroxynaphthalene, and 2,2-methylenebis[6-(2-hydroxy-5-methylbenzyl)- p -cresol] significantly broadened dielectric α relaxation time distributions were observed, indicating dynamic heterogeneity. On the other hand, 4-ethyphenol–P2VPy solutions display dynamic homogeneity. P2VPy with 10 mol% 2,3,3,4,4,5-hexahydroxybenzophenone behaved differently than all mixtures investigated in this study: it displayed a T g (and T α ) significantly higher than that of the neat components, a small SAXS scattering peak, and an additional dielectric relaxation that we propose originates from Maxwell–Wagner–Sillars interfacial polarization. We propose that this behavior is a result of a phase separation of different types of hydrogen-bonded complexes, one rich in P2VPy and the other involving the type of 2,3,3,4,4,5-hexahydroxybenzophenone hydrogen-bonded structures found in the neat state. Intermolecular hydrogen bonding in all of the P2VPy–phenol mixtures suppresses, in some cases completely, the local P2VPy β relaxation by decreasing the mobility of the pyridine side groups.

Segmented polyurethane block copolymers were synthesized using 4,4′-methylenediphenyl diisocyanate (MDI) and 1,4-butanediol (BDO) as hard segments and various soft segments derived from poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS)-based macrodiols and mixtures thereof. The microstructure and degrees of phase separation were characterized using a variety of experimental methods. Copolymers synthesized with the PDMS macrodiol and from PDMS/PHMO macrodiol mixtures were found to consist of three phases: a PDMS phase; hard domains; and a mixed phase of PHMO, PDMS ether end group segments and some dissolved hard segments. Two models were used to characterize the small-angle X-ray scattering from these copolymers: pseudo two-phase and core–shell models. Analysis using both methods demonstrates that as the PDMS content in the soft segment mixture increases, the greater the fraction of hard segments involved in hard domains than are dissolved in the mixed phase. Findings from analysis of the carbonyl region of FTIR spectra are also in agreement with greater hard/soft segment demixing in copolymers containing higher PDMS contents.

The l -α-lysophosphatidylcholine calorimetric method for determining amylose content of starches was used to characterize an amylose fraction derived from common maize starch using an aqueous leaching process. The enthalpy of amylose-LPC complexation and dissolution was significantly greater for the leached maize starch fraction compared with that for potato amylose, leading to erroneously high values for amylose content when potato amylose was used as the reference standard. This was not likely caused by a difference in molecular weight as previously proposed, but possibly to differences in degree of branching. A spherulitic morphology was observed after rapid cooling from 180 °C at low LPC concentrations, but its formation was inhibited at concentrations of lipid typically used in the LPC test. The mechanism of spherulite formation during rapid cooling in the absence of lipid appears to be different than that observed on slow cooling in the presence of lipid.

The relationship between ionic conduction and matrix glass transition was investigated in selected plasticized and doped poly((ethylene glycol)n-co-5-sulfoisophthalate lithium) ionomers. Plasticization with a poly(ethylene glycol) oligomer significantly increases the ionic conductivity, despite a decrease in lithium concentration. Doping with LiClO4 leads to much lower conductivity, despite the increase in Li+ content. These observations were reconciled by considering the corresponding change in ionomer glass transition temperature (Tg), and it was found that ionomers with different plasticizer/dopant levels exhibit similar conductivity at constant T − Tg. The fact that Tg plays such a strong role suggests that Li+ ion mobility is controlled by segmental motion of PEO.

Dynamics of the miscible blend of poly(vinyl methyl ether) and poly(4-vinylphenol) [PVME/PVPh] have been studied using broadband dielectric relaxation spectroscopy (DRS). The results are compared with those reported for PVME/polystyrene [PS] and PVME/poly(2-chlorostyrene) [P2CS] blends to examine the effect of intermolecular hydrogen bonding. These blends have similar chemical structures, with the exception that strong intermolecular hydrogen bonds are formed between PVME and PVPh. Whereas PVME and P2CS (or PS) relax individually in their blends due to intrinsic mobility differences and the absence of strong intermolecular interactions, the segmental relaxations of PVPh and PVME are coupled in the blends controlled by intermolecular hydrogen bonding. Dynamic heterogeneity was observed in PVPh/PVME blends with PVPh concentration higher than 50%. This is due to the decoupling arising from the strong intramolecular hydrogen bonding between PVPh segments. Finally, in the blend, the secondary relaxation processes of both components occur at approximately the same temperature-frequency location as those in corresponding neat polymers, but with much lower intensity, suggesting suppression by the intermolecular hydrogen bonding. Our results suggest that the composition-dependent dynamics in PVPh/PVME are even more complicated than that observed in blends without strong intermolecular interactions.

X-ray scattering and thermal analyses were used to investigate the effects of organically modified layered silicates (OMS) on the paraelectric and ferroelectric phase transitions in poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)]/OMS nanocomposites. Nanocomposites comprising a 75/25 P(VDF-TrFE) random co-polymer with either Nanomer I.30TC or Lucentite STN OMS were prepared with compositions ranging from 2 to 25 wt% OMS. Wide-angle X-ray scattering (WAXS) studies show that the silicate gallery spacing increases modestly in the nanocomposites compared to the neat OMS powder, indicating a level of co-polymer intercalation. Thermogravimetric analysis indicates that thermal stability is improved in nanocomposites with higher OMS contents: they have substantial increase in weight remaining, both at 500 °C and at 1000 °C, compared to that predicted from the behavior of the neat co-polymer and OMS. Differential scanning calorimetry (DSC) and WAXS results show that thermal transitions in the nanocomposites depend on OMS content. Nanocomposites with 2% OMS exhibited a crystal nucleating effect, which results in significant increase in the amount of ferroelectric crystals formed during cooling. For greater OMS additions (10–25%), the amounts of para- and ferroelectric crystals are reduced. The larger OMS additions depress the melt-to-paraelectric transition temperature, while an increase in the paraelectric-to-ferroelectric transition temperature is observed for all compositions. Upon reheating, the ferroelectric phase transition shows significant hysteresis. We conclude that the addition of either Lucentite or Nanomer OMS to 75/25 P(VDF-TrFE) causes an increase in the temperature stability range for the ferroelectric phase.

As part of our continuing effort to understand microphase separation of poly(urethane urea) block copolymers, FTIR spectroscopy and thermal techniques (DSC and DMA) were used to investigate the phase behavior of two series of MDI–polytetramethylene oxide soft segment copolymers, chain-extended with ethylene diamine or a diamine mixture. Due to the complex nature and multiple absorbances in the carbonyl and N–H regions of the FTIR spectra, quantitative analysis was not possible. However, qualitative trends could be discerned, and the spectral changes were found to be in excellent agreement with our previous quantitative analysis of the same copolymers using small-angle X-ray scattering. DSC and DMA experiments both indicate that the soft phase Tg decreases with increasing hard segment content. This is contrary to increased hard segment mixing in the soft phase, but can be rationalized by taking into consideration soft segment crystallinity and the concentration of ‘lone’ MDI units in the soft phase.

Time-resolved synchrotron simultaneous wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) experiments were used to investigate the crystallization behavior and microstructure development of poly( l -lactide), PLLA, and two random copolymers containing l -lactide (predominately) and randomly placed R stereochemical defects. The general features of crystallization of PLLA and the copolymers are similar except that the copolymers crystallize much more slowly and to a lesser extent than PLLA, as expected. Lamellar thicknesses derived from SAXS experiments are in very good agreement with mean thicknesses determined in a tapping mode AFM study of the same materials. The reduction in lamellar thickness and crystallinity with increasing meso -lactide content supports significant exclusion of the R stereoisomer from crystalline lamellae. In a separate series of time-resolved WAXD/SAXS experiments, each (co)polymer was crystallized for a fixed time, then heated to above its melting point. The observed behavior suggests a model for crystallization of the copolymers in which thinner lamellae form between ‘primary’ lamellar stacks during crystallization, with an average lamellar thickness that decreases with increasing R stereoisomer content.

Our broadband dielectric study has revealed for the first time a relaxation (termed γ′) between the low temperature β and γ-processes of semi-crystalline poly(ethylene oxide) (PEO). The activation energy of the γ′-transition is indicative of a local process, and this relaxation becomes broader with increasing temperature. We propose that this process is due to the motion of PEO segments in the transition region between PEO lamellae and disordered interlamellar amorphous segments. The unusual local character of the γ′-process is explained by analogy to the fast process or primitive α-relaxation in nanoconfined glass forming systems. This mechanism is supported by comparison of the dielectric behavior of samples with different thermal histories.

Triad concentrations obtained by 1H n.m.r. analysis enable the determination of the degree of randomness and average sequence length of poly(butylene terephthalate) (PBT) units for a number of melt processed PBT/polyarylate blends. Transesterification was confirmed by reduced degrees of crystallinity and melting points.

Richardson's empirical equation relating length to measuring scale has been used extensively to assign fractal dimensions to regged curves. The inconsistency in units, length on one side of the equation vs. fractional units of length on the other has led to considerable debate. This letter presents a derivation of Richardson's equation based upon measure theory. In this context, the constant appearing in Richardson's equation is shown to have a precise meaning; it is the Hausdorff measure of the curve.

FT i.r. and thermal analysis studies have been performed on blends of poly(e-caprolactone) (PCL) with vinylidene chloride copolymers containing the comonomers vinyl chloride and acrylonitrile. The results indicate that the blends are compatible over the whole composition range in the amorphous state. Attempts were also made to obtain coherent blends of PCL and the homopolymer of vinylidene chloride. Evidence for the presence of specific intermolecular interactions has been obtained and the origin of these interactions is discussed.

0–3 composites consisting of carbon black and vanadium oxide conductive fillers in polyethylene, a polyurethane, and polyvinyl alcohol have been developed for use as chemical sensors. Polymer matrices loaded with conductive filler near the percolation threshold swell reversibly in the presence of liquid and gaseous solvents, disrupting the conductive pathways and proportionally increasing the resistance. The magnitude of the swelling (which usually dominates the magnitude of Δ R ) depends on the solubility of a given solvent in the polymer. For non-polar materials, the swelling can be predicted by considering the difference in solubility parameters of polymer and solvent, although the overall magnitude of Δ R may also be influenced by particle morphology, the percolation behavior for the system of interest, and other undefined solvent/polymer/filler interactions. The response time of the sensor is determined primarily by the sample thickness and the diffusion of the solvent through the polymer. Response times will play a role in determining the selection of a sensor for a particular application.

Piezoelectric composites of PZT ceramics and several semi-crystalline polymers have been produced by embedding slender PZT rods (4 volume percent) in the polymers. The observed dielectric constants were considerably lower than that of pure PZT. The hydrostatic piezoelectric voltage coefficients of the composites were larger than PZT, even though the composite hydrostatic piezoelectric strain coefficients were lower. Composite figures of merit ranged from one-third to six times that of PZT.