Improved PVC/ZnO Nanocomposite Insulation for High Voltage and High Temperature Applications.

Nanosized inorganic oxides have the trends to improve many characteristics of solid polymer insulation. In this work, the characteristics of improved poly (vinyl chloride) (PVC)/ZnO are evaluated using 0, 2, 4 and 6 phr of ZnO nanoparticles dispersed in polymer matrix using internal mixer and finally compressed into circular disk with 80 mm diameter using compression molding technique. Dispersion properties are studied by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), and optical microscopy (OM). The effect of filler on the electrical, optical, thermal, and dielectric properties of the PVC are also analyzed. Hydrophobicity of nano-composites is evaluated by measuring contact angle and recording hydrophobicity class using Swedish transmission research institute (STRI) classification method. Hydrophobic behavior decreases with the increase in filler content; contact angle increases up to 86°, and STRI class of HC3 for PZ4 is observed. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) are employed to evaluate the thermal properties of the samples. Also, continuous decrease of optical band gap energy from 4.04 eV for PZ0 to 2.57 eV for PZ6 is observed. In the meantime, an enhancement in the melting temperature, Tm, is observed from 172 to 215 °C. To check the stability of materials against hydrothermal stresses, all the fabricated materials are then subjected to a hydrothermal aging process for 1000 h and their structural stability is analyzed using optical microscopy and FTIR analyses.

Investigation into the crystal structure-dielectric property correlation in barium titanate nanocrystals of different sizes.

For high capacitance multilayer ceramic capacitors, high dielectric constant and lead-free ceramic nanoparticles are highly desired. However, as the particle size decreases to a few tens of nanometers, their dielectric constant significantly decreases, and the underlying mechanism has yet to be fully elucidated. Herein, we report a systematic investigation into the crystal structure-dielectric property relationship of combustion-made BaTiO3 (BTO) nanocrystals. When the nanocrystal size was 100 nm and below, a metastable paraelectric cubic phase was found in the as-received BTO (denoted as arBTO) nanocrystals based on an X-ray diffraction (XRD) study. A stable ferroelectric tetragonal phase was present when the nanocrystal size was above 200 nm. Notably, the cubic arBTO (particle size ≤100 nm) exhibited tetragonal fluctuations as revealed by Raman spectroscopy, whereas the tetragonal arBTO (particle size ≥200 nm) contained ∼10% cubic fraction according to the Rietveld fitting of the XRD profiles. Thermal annealing of the multi-grain tetragonal arBTO at 950 °C yielded single crystals of annealed BTO (denoted as anBTO), whose dielectric constants were higher than those of arBTO. However, the single crystalline anBTO prevented the formation of 90° domains; therefore, they exhibited a low dielectric constant of ∼300. Although X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy could not identify the exact structural defects, our study revealed that surface and bulk defects formed during synthesis affect the final crystal structures and thus the dielectric properties of BTO nanocrystals with different sizes. The understanding obtained from this study will help us design high dielectric constant perovskite nanocrystals for next-generation multilayer ceramic capacitor applications.

Development of an Atomic-Oxygen-Erosion-Resistant, Alumina-Fiber-Reinforced, Fluorinated Polybenzoxazine Composite for Low-Earth Orbital Applications.

An atomic-oxygen-erosion-resistant fluorinated benzoxazine resin and composite were developed. The benzoxazine resin, abbreviated as "BAF-oda-fu," consists of four benzoxazine rings, and was synthesized from bisphenol AF (BAF), 4,4'-oxydianiline (oda), furfurylamine (fu), and paraformaldehyde. The resin was characterized by infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (1H NMR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). An analysis of the solvent-washed product showed a technical grade purity (>95%) and a yield of approximately 85%. Subsequent polymerization of the resin was successfully performed by heating step-wise and opening the benzoxazine rings to form a crosslinked network. Thermal analyses showed a melting temperature of 115 °C and polymerization temperature of 238 °C, both being characteristic values of benzoxazine monomers. The benzoxazine resin was also blended with polyoctahedral sisesquoxane (POSS) and reinforced with alumina fibers. The Tg of the resin, as determined by DMA of the composite, could reach as high as 308 °C when post-curing and the POSS additive were utilized. The low-Earth orbit atomic-oxygen erosion rate was simulated by an RF plasma asher/etcher. The atomic-oxygen resistance of poly(BAF-oda-fu) fell along an established trend line based on its fluorine content.

Advanced Carbon Materials Derived from Polybenzoxazines: A Review.

This comprehensive review article summarizes the key properties and applications of advanced carbonaceous materials obtained from polybenzoxazines. Identification of several thermal degradation products that arose during carbonization allowed for several different mechanisms (both competitive ones and independent ones) of carbonization, while also confirming the thermal stability of benzoxazines. Electrochemical properties of polybenzoxazine-derived carbon materials were also examined, noting particularly high pseudocapacitance and charge stability that would make benzoxazines suitable as electrodes. Carbon materials from benzoxazines are also highly versatile and can be synthesized and prepared in a number of ways including as films, foams, nanofibers, nanospheres, and aerogels/xerogels, some of which provide unique properties. One example of the special properties is that materials can be porous not only as aerogels and xerogels, but as nanofibers with highly tailorable porosity, controlled through various preparation techniques including, but not limited to, the use of surfactants and silica nanoparticles. In addition to the high and tailorable porosity, benzoxazines have several properties that make them good for numerous applications of the carbonized forms, including electrodes, batteries, gas adsorbents, catalysts, shielding materials, and intumescent coatings, among others. Extreme thermal and electrical stability also allows benzoxazines to be used in harsher conditions, such as in aerospace applications.

Review on the Accelerated and Low-Temperature Polymerization of Benzoxazine Resins: Addition Polymerizable Sustainable Polymers.

Due to their outstanding and versatile properties, polybenzoxazines have quickly occupied a great niche of applications. Developing the ability to polymerize benzoxazine resin at lower temperatures than the current capability is essential in taking advantage of these exceptional properties and remains to be most challenging subject in the field. The current review is classified into several parts to achieve this goal. In this review, fundamentals on the synthesis and evolution of structure, which led to classification of PBz in different generations, are discussed. Classifications of PBzs are defined depending on building block as well as how structure is evolved and property obtained. Progress on the utility of biobased feedstocks from various bio-/waste-mass is also discussed and compared, wherever possible. The second part of review discusses the probable polymerization mechanism proposed for the ring-opening reactions. This is complementary to the third section, where the effect of catalysts/initiators has on triggering polymerization at low temperature is discussed extensively. The role of additional functionalities in influencing the temperature of polymerization is also discussed. There has been a shift in paradigm beyond the lowering of ring-opening polymerization (ROP) temperature and other areas of interest, such as adaptation of molecular functionality with simultaneous improvement of properties.

Nacre-Mimetic Green Flame Retardant: Ultra-High Nanofiller Content, Thin Nanocomposite as an Effective Flame Retardant.

A nacre-mimetic brick-and-mortar structure was used to develop a new flame-retardant technology. A second biomimetic approach was utilized to develop a non-flammable elastomeric benzoxazine for use as a polymer matrix that effectively adheres to the hydrophilic laponite nanofiller. A combination of laponite and benzoxazine is used to apply an ultra-high nanofiller content, thin nanocomposite coating on a polyurethane foam. The technology used is made environmentally friendly by eliminating the need to add any undesirable flame retardants, such as phosphorus additives or halogenated compounds. The very-thin coating on the polyurethane foam (PUF) is obtained through a single dip-coating. The structure of the polymer has been confirmed by proton nuclear magnetic resonance spectroscopy (1H NMR) and Fourier transform infrared spectroscopy (FTIR). The flammability of the polymer and nanocomposite was evaluated by heat release capacity using microscale combustion calorimetry (MCC). A material with heat release capacity (HRC) lower than 100 J/Kg is considered non-ignitable. The nanocomposite developed exhibits HRC of 22 J/Kg, which is well within the classification of a non-ignitable material. The cone calorimeter test was also used to investigate the flame retardancy of the nanocomposite's thin film on polyurethane foam. This test confirms that the second peak of the heat release rate (HRR) decreased 62% or completely disappeared for the coated PUF with different loadings. Compression tests show an increase in the modulus of the PUF by 88% for the 4 wt% coating concentration. Upon repeated modulus tests, the rigidity decreases, approaching the modulus of the uncoated PUF. However, the effect of this repeated mechanical loading does not significantly affect the flame retarding performance.

Structure and Performance of Benzoxazine Composites for Space Radiation Shielding.

Innovative multifunctional materials that combine structural functionality with other spacecraft subsystem functions have been identified as a key enabling technology for future deep space missions. In this work, we report the structure and performance of multifunctional polymer matrix composites developed for aerospace applications that require both structural functionality and space radiation shielding. Composites comprised of ultra-high molecular weight polyethylene (UHMWPE) fiber reinforcement and a hydrogen-rich polybenzoxazine matrix are prepared using a low-pressure vacuum bagging process. The polybenzoxazine matrix is derived from a novel benzoxazine resin that possesses a unique combination of attributes: high hydrogen concentration for shielding against galactic cosmic rays (GCR), low polymerization temperature to prevent damage to UHMWPE fibers during composite fabrication, long shelf-life, and low viscosity to improve flow during molding. Dynamic mechanical analysis (DMA) is used to study rheological and thermomechanical properties. Composite mechanical properties, obtained using several standardized tests, are reported. Improvement in composite stiffness, through the addition of carbon fiber skin layers, is investigated. Radiation shielding performance is evaluated using computer-based simulations. The composites demonstrate clear advantages over benchmark materials in terms of combined structural and radiation shielding performance.

Developing Further Versatility in Benzoxazine Synthesis via Hydrolytic Ring-Opening.

In this study, 2-(aminomethyl)phenol and its derivatives, the reactants for 2-substituted 1,3-benzoxazines, are synthesized by HCl hydrolysis from the typical benzoxazines. The phenol/aniline-based mono-oxazine benzoxazine, PH-a, and the bisphenol A/aniline-based bis-oxazine benzoxazine, BA-a, are used as examples to demonstrate the feasibility of this new approach. Their chemical structures are characterized by nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) and Raman spectroscopies, and are further verified by elementary analysis. Their thermal properties are studied by differential scanning calorimetry (DSC). These two 2-(aminomethyl) phenolic derivatives are reacted with paraformaldehyde to close the oxazine rings. A benzoxazine with a phenyl substituent at the 2-position of the oxazine ring is obtained from the 2-((phenylamino)methyl)phenol (hPH-a) and benzaldehyde. All these results highlight the success of the HCl hydrolysis and the formation of stable intermediates, namely 2-(aminomethyl) phenolic derivatives, from readily available benzoxazine monomers. This further demonstrates the feasibility of using these intermediates as reactants for a novel benzoxazine synthesis.

Poly(benzoxazine-f-chitosan) films: The role of aldehyde neighboring groups on chemical interaction of benzoxazine precursors with chitosan.

This study reports the preparation and characterizations of chitosan-azomethine derivatives containing oxazine ring as new crosslinked polymers. The novel chitosan derivatives have been prepared by functionalization with reactive benzoxazine precursors. Two types of aldehyde-terminated benzoxazine precursors have been synthesized using two different polyetheramines (Jeffamines), 4-hydroxybenzaldehyde, and paraformaldehyde. The benzoxazine precursors are covalently attached to chitosan via Schiff's base formation. Benzoxazine structure is confirmed by proton nuclear magnetic resonance spectroscopy (1H-NMR) and Fourier transform infrared spectroscopy (FT-IR), whereas the imine-linkage formation is confirmed by FT-IR. The benzoxazine-f-chitosan films are crosslinked by cationic ring-opening polymerization of benzoxazine. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) are used to study the thermal behavior of the obtained films. Wettability behavior of the resulting films was studied by contact angle measurements and compared with wettability of the neat chitosan film.

Synthesis and thermally induced structural transformation of phthalimide and nitrile-functionalized benzoxazine: toward smart ortho-benzoxazine chemistry for low flammability thermosets.

A novel ortho-phthalimide-functionalized benzoxazine monomer containing an ortho-nitrile group has been synthesized in order to further systematically evaluate the thermally induced structural transformation from benzoxazine resin to cross-linked polybenzoxazole. The chemical structure of the synthesized monomer has been confirmed by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared (FT-IR) spectroscopy. Also supporting the detailed structure is 1H-13C heteronuclear multiple quantum coherence (HMQC), which identifies the local proton-carbon proximities. The polymerization behaviors, including the ring-opening polymerization of the oxazine rings and the cyclotrimerization of the nitrile functionalities, are studied by differential scanning calorimetry (DSC) and in situ FT-IR. In addition, the subsequent benzoxazole formation after polymerization has also been analyzed using thermogravimetric analysis (TGA) and magic-angle spinning (MAS) solid-state 13C NMR. The resulting cross-linked polybenzoxazole derived from the benzoxazine monomer exhibits exceptionally high thermal stability and low flammability, with an extremely high T d5 temperature (550 °C), a high char yield value (70%) and an extraordinarily low total heat release (THR of 7.6 kJ g-1).

Development of Hydrogen-Rich Benzoxazine Resins with Low Polymerization Temperature for Space Radiation Shielding.

A systematic study has been carried out to develop a material with significant protection properties from galactic cosmic radiation and solar energetic particles. The research focused on the development of hydrogen-rich benzoxazines, which are particularly effective for shielding against such radiation. Newly developed benzoxazine resin can be polymerized at 120 °C, which meets the low-temperature processing requirements for use with ultrahigh molecular weight polyethylene (UHMWPE) fiber, a hydrogen-rich composite reinforcement. This highly reactive benzoxazine resin also exhibits low viscosity and good shelf-life. The structure of the benzoxazine monomer is confirmed by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. Polymerization behavior and thermal properties are evaluated by differential scanning calorimetry and thermogravimetric analysis. Dynamic mechanical analysis is used to study chemorheological properties of the benzoxazine monomer, rheological properties of the cross-linked polybenzoxazine, and rheological properties of UHMWPE-reinforced polybenzoxazine composites. The theoretical radiation shielding capability of the composite is also evaluated using computer-based simulations.

Examining the effect of hydroxyl groups on the thermal properties of polybenzoxazines: using molecular design and Monte Carlo simulation.

The influence of methylol and phenolic hydroxyl on the thermal properties of polybenzoxazines has been studied using two monofunctional benzoxazine monomers synthesized from para methylol-/ethyl- phenol, aniline and paraformaldehyde. The chemical structures of the synthesized monomers are confirmed by 1H nuclear magnetic resonance (NMR), 13C NMR and Fourier transform infrared spectroscopy (FT-IR). Polymerizations are monitored by differential scanning calorimetry (DSC). The glass transition temperature (T g) of each polybenzoxazine is measured by DSC as well as dynamic mechanical analysis (DMA), indicating the greatly increased T g via incorporation of methylol functionality into benzoxazine moiety. Monte Carlo simulations are also applied to further investigate the underlying structure-property relationship between intermolecular hydrogen-bonding network originating from different types of hydroxyl groups and thermal properties of polybenzoxazines. The agreement between the experimental and simulation results provide us with a fundamental understanding of the designing roles in highly thermally stable polybenzoxazines.

Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations.

Polymerization of benzoxazine resins is indicated by the disappearance of a 960-900 cm-1 band in infrared spectroscopy (IR). Historically, this band was assigned to the C-H out-of-plane bending of the benzene to which the oxazine ring is attached. This study shows that this band is a mixture of the O-C2 stretching of the oxazine ring and the phenolic ring vibrational modes. Vibrational frequencies of 3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-a) and 3-(tert-butyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-t) are compared with isotope-exchanged and all-substituted compounds. Deuterated benzoxazine monomers, 15N-isotope exchanged benzoxazine monomers, and all-substituted benzoxazine monomers without aromatic C-H groups are synthesized and studied meticulously. The various isotopic-exchanges involved deuteration around the benzene ring of phenol, selective deuteration of each CH2 in the O-CH2-N (2) and N-CH2-Ar (4) positions on the oxazine ring, or simultaneous deuteration of both positions. The chemical structures were confirmed by 1H nuclear magnetic resonance spectroscopy (1H NMR). The IR and Raman spectra of each compound are compared. Further analysis of 15N isotope-exchanged PH-a indicates the influence of the nitrogen isotope on the band position, both experimentally and theoretically. This finding is important for polymerization studies of benzoxazines that utilize vibrational spectroscopy.

Smart, Sustainable, and Ecofriendly Chemical Design of Fully Bio-Based Thermally Stable Thermosets Based on Benzoxazine Chemistry.

A smart synthetic chemical design incorporating furfurylamine, a natural renewable amine, into a partially bio-based coumarin-containing benzoxazine is presented. The versatility of the synthetic approach is shown to be flexible and robust enough to be successful under more ecofriendly reaction conditions by replacing toluene with ethanol as the reaction solvent and even under solventless conditions. The chemical structure of this coumarin-furfurylamine-containing benzoxazine is characterized by FTIR, (1) H NMR spectroscopy and two-dimensional (1) H-(1) H nuclear Overhauser effect spectroscopy (2D (1) H-(1) H NOESY). The thermal properties of the resin toward polymerization are characterized by differential scanning calorimetry (DSC) and the thermal stability of the resulting polymers by thermogravimetric analysis (TGA). The results reveal that the furanic moiety induces a co-operative activating effect, thus lowering the polymerization temperature and also contributes to a better thermal stability of the resulting polymers. These results, in addition to those of natural renewable benzoxazine resins reviewed herein, highlight the positive and beneficial implication of designing novel bio-based polybenzoxazine and possibly other thermosets with desirable and competitive properties.

Intramolecular Hydrogen Bonding in Benzoxazines: When Structural Design Becomes Functional.

The future evolution of benzoxazines and polybenzoxazines as advanced molecular, structural, functional, engineering, and newly commercial materials depends to a great extent on a deeper and more fundamental understanding at the molecular level. In this contribution, the field of benzoxazines is briefly introduced along with a more detailed review of ortho-amide-functional benzoxazines, which are the main subjects of this article. Provided in this article are the detailed and solid scientific evidences of intramolecular five-membered-ring hydrogen bonding, which is supposed to be responsible for the unique and characteristic features exhibited by this ever-growing family of ortho-functionalized benzoxazines. One-dimensional (1D) (1)H NMR spectroscopy was used to study various concentrations of benzoxazines in various solvents with different hydrogen-bonding capability and at various temperatures to investigate in detail the nature of hydrogen bonding in both ortho-amide-functionalized benzoxazine and its para counterpart. These materials were further investigated by two-dimensional (2D) (1)H-(1)H nuclear Overhauser effect spectroscopy (NOESY) to verify and support the conclusions derived during the 1D (1)H NMR experiments. Only highly purified single-crystal benzoxazine samples have been used for this study to avoid additional interactions caused by any impurities.

Advanced and economical ambient drying method for controlled mesopore polybenzoxazine-based carbon xerogels: Effects of non-ionic and cationic surfactant on porous structure.

Polybenzoxazine has been successfully synthesized by a facile quasi-solventless method and used as a precursor for producing carbon xerogels via an ambient drying method, rather than usually used CO2 critical or freeze drying. In this work, we aim to study the effect of non-ionic (Synperonic NP30) and cationic (CTAB) surfactants on porous structure of polybenzoxazine-based carbon xerogels. Of particular interest is the formation of inter-connected structure of mesoporous carbon xerogels with mesopore diameters in the range of 15-36 nm by using different concentrations of the cationic surfactant. In addition, carbon xerogel nanospheres with the size of 50-200 nm are also obtained through the emulsion process. The mesopore diameters start to decrease when the carbon xerogel nanospheres are formed at the cationic surfactant concentration of equal to or exceeding 0.030 M. By using the non-ionic surfactant, the properties of the obtained carbon xerogels are shifted from mesoporous materials for the reference carbon xerogel (no surfactant added) to microporous materials at higher concentrations of the non-ionic surfactant (0.009-0.180 M). The carbon xerogel microspheres with the diameter size of about 2.5 µm are also obtained through the emulsion process when the concentration of the non-ionic surfactant is at 0.180 M.

Molecular dynamic simulations of self-assembly of amphiphilic comb-like anionic polybenzoxazines.

Fully atomistic molecular dynamic simulations were performed to address the self-assembly of amphiphilic and comb-like polybenzoxazines (iBnXz) in water, with i = 3 (trimer), i = 4 (tetramer); i = 6 (hexamer), i = 8 (octamer), and i = 10 (decamer). Spontaneous aggregation of these comb-like polybenzoxazine molecules into a single micelle occurs in the simulations. The simulations show that molecular size and concentration play important roles in micellar morphology. At an iBnXz concentration of 50 mM, the 3BnXz and 4BnXz molecules aggregate into spherical micelles, whereas the 6BnXz, 8BnXz, and 10BnXz molecules aggregate into cylindrical micelles. The micellar morphology is spherical at low concentrations, but undergoes a transition to cylindrical shape as concentration increases. The transition point depends on the molecular size-both the true size as indicated by molecular weight, as well as an additional effective size dependent on molecular flexibility.

Synthesis and evaluation of novel anionic polymeric surfactants based on polybenzoxazines.

A novel platform of anionic polymeric surfactants, poly(4HBA-oca(-)Na(+)), poly(4HBA-dea(-)Na(+)), and poly(4HBA-doa(-)Na(+)), has been synthesized by polymerizing benzoxazine monomers that are synthesized by reacting an aliphatic amine of variable chain length (C8, C10 and C12), with 4-hydroxybenzoic acid and paraformaldehyde. The structures of the monomers and polymeric surfactants are confirmed by NMR and FTIR. The ring-opening polymerization and thermal behavior of the benzoxazine monomers are studied by DSC and TGA. Size exclusion chromatography (SEC) coupled with Viscotek triple detection technique is used to characterize the molecular weight distribution of polybenzoxazine surfactants. The surfactants have low MW, varying from 2200 to 6000, and are fairly polydisperse. The influence of the structure on the surface activity is investigated by measuring the surface tension of aqueous solutions of the polymeric surfactants using the Wilhelmy plate method. The tensiometry results indicate that the adsorption at the air/water interface is similar for the octylamine, decylamine and dodecylamine-based surfactants. Increasing the alkyl chain length from C8 to C12 does not significantly affect the surface tension at the critical micelle concentration (γcmc), while the critical micelle concentration (cmc) gradually increases due to increasing hydrophobic effect. These polymeric surfactants give cmc values ranging from 0.12 g/L to 0.17 g/L, comparable to other polymeric surfactants reported in the literature. The influences of salt addition on the surface tension at the critical micelle concentration (γcmc) for these surfactants are studied. Theminimum values of the γcmc are observed around 1 wt% NaCl for the polybenzoxazine surfactant solution.

Biobased chitosan/polybenzoxazine cross-linked films: preparation in aqueous media and synergistic improvements in thermal and mechanical properties.

A novel class of polymer blends has been prepared from main-chain-type benzoxazine polymer (MCBP) and chitosan (CTS), a modified biomacromolecule. A water-soluble, main-chain-type benzoxazine polymer, MCBP(BA-tepa), was synthesized from the reaction of bisphenol A (BA), tetraethylenepentamine (TEPA) and formalin. The structure of the MCBP(BA-tepa) was confirmed by proton nuclear magnetic resonance spectroscopy ((1)H NMR) and Fourier transform infrared spectroscopy (FT-IR). The polymer blends were prepared by mixing MCBP(BA-tepa) and CTS in aqueous acetic acid solution (1%). The CTS/MCBP(BA-tepa) films are cross-linked by thermal treatment via the ring-opening polymerization of benzoxazine structures in the main chain to produce an AB-cross-linked network. Differential scanning calorimetry (DSC) and FT-IR were used to study the effects of CTS on the polymerization behavior of benzoxazine. Hydrogen bonding between polybenzoxazine and CTS structures was also observed. The mechanical and thermal properties of cross-linked CTS/MCBP(BA-tepa) films were evaluated, and the results showed unusual levels of synergism. In particular, the tensile strength and thermal stability were significantly enhanced in a nonlinear fashion.

Benzoxazine oligomers: evidence for a helical structure from solid-state NMR spectroscopy and DFT-based dynamics and chemical shift calculations.

A combination of molecular modeling, DFT calculations, and advanced solid-state NMR experiments is used to elucidate the supramolecular structure of a series of benzoxazine oligomers. Intramolecular hydrogen bonds are characterized and identified as the driving forces for ring-shape and helical conformations of trimeric and tetrameric units. In fast MAS (1)H NMR spectra, the resonances of the protons forming the hydrogen bonds can be assigned and used for validating and refining the structure by means of DFT-based geometry optimizations and (1)H chemical-shift calculations. Also supporting these proposed structures are homonuclear (1)H[bond](1)H double-quantum NMR spectra, which identify the local proton-proton proximities in each material. Additionally, quantitative (15)N[bond](1)H distance measurements obtained by analysis of dipolar spinning sideband patterns confirm the optimized geometry of the tetramer. These results clearly support the predicted helical geometry of the benzoxazine polymer. This geometry, in which the N...H...O and O...H...O hydrogen bonds are protected on the inside of the helix, can account for many of the exemplary chemical properties of the polybenzoxazine materials. The combination of advanced experimental solid-state NMR spectroscopy with computational geometry optimizations, total energy, and NMR spectra calculations is a powerful tool for structural analysis. Its results provide significantly more confidence than the individual measurements or calculations alone, in particular, because the microscopic structure of many disordered systems cannot be elucidated by means of conventional methods due to lack of long-range order.