Advanced chemically induced phase separation in thermosets: Polybenzoxazines toughened with multifunctional thermoplastic main-chain benzoxazine prepolymers

Multifunctional thermoplastic main-chain benzoxazine prepolymers were synthesized and systematically varied in their structure in order to function as high-performance toughener additives. Their unique chemical composition allows multiple covalent crosslinking with many thermoset network systems including benzoxazines and epoxides in conjunction with a defined chemical induced phase separation (CIPS) upon curing. This was successfully shown using a benzoxazine-based thermoset resin matrix as an example. The corresponding morphologies were addressable in a predictable manner and brought into context with the obtained macroscopic mechanical and thermal properties. In this relationship the CIPS process was classified and compared with the literature in more general means for advanced morphology control by differentiating between covalently attached and so-called gradient domain structures. The prepolymers were characterized by ¹H NMR, FT-IR, DSC and TGA. The thermoset morphologies were investigated by TEM and AFM. The fracture toughness (K_Ic) and the elastic modulus (E) were measured by fracture and three point bending experiments. Thermal properties of the resulting films have been tested by DMA.     

Sustainable phenolic thermosets coatings derived from urushiol

The over-exploitation of finite fossil resources and/or the increased environmental and sustainable awareness inspire scientists and technologists to search for inexpensive alternatives from renewable chemicals. Phenol formaldehyde (PF) resins, the oldest type of synthetic polymers with good mechanical properties and heat resistance, are widely used in the production of coatings, laminates, molding compositions, and glues. Here, biobased urushiol-derived PF resins were synthesized from the alkali-catalyzed reaction between urushiol and formaldehyde. The chemical compositions and molecular structures of resole resins were characterized by carbon-13 nuclear magnetic resonance and Fourier transform infrared spectroscopy, and their curing behaviors were studied by differential scanning calorimetry. The as-prepared urushiol-derived resole resins had methylol (Ph−CH₂OH), ortho- and para-hemiformal groups (Ph−CH₂OCH₂OH), and the para−para/ortho−para/ortho−ortho links of methylene groups (Ph−CH₂−Ph), whereas the resole resins had low curing temperatures at about 100–113°C. Additionally, given the long side alkyl group moiety on the aromatic rings of urushiol, the films of cured urushiol-derived resole resins had low glass transition temperatures of 132 ± 2°C. Furthermore, the as-prepared urushiol-derived coatings exhibited excellent physical and mechanical properties.     

Aromatic copolyester thermosets: High temperature adhesive properties

The adhesive properties of a new family of crosslinkable aromatic copolyester resins are described in this paper. A unique method for forming an adhesive bond in the solid state through high temperature interchain transesterification reactions (ITR) between cured thin films of these copolyester thermosets is indicated. Bonds formed via this procedure yield average lap shear strengths of roughly 13 MPa to titanium adherends and invariably exhibit failure at the polymer-metal interface and not within the polymer. Various procedures to increase the strength of the bond at the interface between the polymer and the metal were tested such as the effect of surface pretreatments, primers, fillers, and the role of bondline thickness on the lap shear strength of the joints. Of these, the use of surface pretreatments and thinner bondlines has the greatest effect, raising the observed average lap shear strength of the joints to 16.5 and 20.7 Mpa, respectively. Some of the adhesive properties pertaining to the use of this new thermoset as a matrix in a graphite fiber composite are also presented.     

Side-chain phenol-functionalized poly(ether sulfone) and its contribution to high-performance and flexible epoxy thermosets

We prepared a side-chain phenol-functionalized poly(ether sulfone) (P1) from a one-pot reaction of a 4,4′-dihydroxybenzophenone (DHBP)-based poly(ether sulfone), poly(oxy-1,4-phenylenecarbonyl-1,4-phenyleneoxy-1,4-phenylene-sulfonyl-1,4-phenylene (DHBP-PES)), with 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and phenol in the presence of sulphuric acid. The phenol linkages of P1 act as reacting sites for epoxy resins. Subsequently, flexible and light-yellow transparent films of epoxy thermosets can be achieved from the curing of P1 with cresol novolac epoxy (CNE) and diglycidyl ether of bisphenol A (DGEBA). The thermoset based on P1 and CNE (P1/CNE) shows a high T_g value (241 °C), a low coefficient of thermal expansion (44 ppm/°C), and flame retardancy (VTM-0). The moderate-to-high molecular weight of P1 is responsible for the characteristics high T_g and flexibility, which are rarely seen in epoxy thermosets based on a low-molecular weight curing agent.     

New epoxy thermosets modified with amphiphilic multiarm star polymers as toughness enhancer

The synthesis and characterization of two novel amphiphilic multiarm star polymers with linear polyethylene glycol (PEG) and poly(ε-caprolactone) (PCL) arms and their use as toughening modifiers of epoxy anhydride thermosets are reported. The new star polymers were obtained by partial pegylation of a hyperbranched polyester and subsequent growth of PCL arms. The curing process was studied by calorimetry and thermomechanical analysis, demonstrating the accelerating effect and the influence on gelation of the hydroxyl terminal groups. The curing kinetics was analyzed by model-free and model-fitting methods. The final properties of the resulting materials were determined by thermal and mechanical tests. The addition of the star-like modifiers led only to notable improvement on impact strength in the material containing a 10% of the star with PCL and PEG arms, without compromising glass transition temperature and thermal stability. The morphology of the resulting materials depended on the structure of the toughness modifier used, as demonstrated by electron microscopy, but all modified thermosets obtained showed phase-separated morphologies with nanosized particles.     

Effect of hydroxyl ended and end-capped multiarm star polymers on the curing process and mechanical characteristics of epoxy/anhydride thermosets

Multiarm star polymers have been synthesized by cationic ring-opening polymerization of ?-caprolactone from a hyperbranched poly(ethyleneimine) core and end-capped with acetic anhydride. These star polymers have been used as modifiers in diglycidylether of bisphenol A/methyl tetrahydrophthalic anhydride/benzyl dimethylamine formulations. The curing process is studied by dynamic scanning calorimetry and rheometry and the resulting thermosets are characterized by dynamic mechanical thermal analysis and thermogravimetry.     

High temperature mullite dissolution in ceramic bodies derived from Al-rich sludge

Mullite-based refractory ceramic materials were produced from an industrial Al-rich sludge derived from wastewater treatment of aluminium anodising or surface coating industrial processes, and other low cost raw materials (ball clay, kaolin and diatomite). Cylindrical samples processed by uniaxial dry pressing (32 MPa) were sintered at various temperatures (1250–1650 °C) to study the mullitisation process. The performance of the materials at high temperature (1650 °C) was evaluated through different techniques (XRD, SEM/EDS, optical microscopy, and impedance spectroscopy) to access the microstructural changes occurring under prolonged tests (dwell times up to 100 h). For dwell times <80 h, a preferential dissolution of the smaller mullite grains in the glassy phase and its partial re-precipitation onto the coarser ones, leading to an overall coarsening of the mullite crystals. For dwell times >80 h, coarse α-alumina and Cr-doped alumina developed at the surface of the specimens, being accompanied by the formation of pores in the vicinity of alumina grains. Near alumina grains, additional relevant features include the increase of surface roughness, the appearance of concentration gradients within the glassy phase, which became almost depleted in Al and enriched in alkalines. The continuity of the glassy phase and its enrichment in alkaline species enhanced the electrical conductivity of the material, enabling the use of impedance spectroscopy to access the microstructural changes occurring during prolonged heat treatment.     

Preparation and properties of some thermosets derived from allyl‐functional naphthoxazines

A series of novel naphthoxazine monomers containing allyl functionalities were synthesized from the reaction of 1‐naphthol, 2‐naphthol, and 1,5‐dihdroxynaphthalene with allylamine and formalin. Another series of naphthoxazines were similarly prepared by using aniline instead of allylamine for comparison. The chemical structures of these novel monomers were confirmed by IR, ¹H NMR, and elemental analysis. DSC of the aniline‐ based naphthoxazines showed an exotherm due to the ring‐opening polymerization of oxazine. For allylamine‐based naphthoxazines, two exotherms were observed. The first exotherm is attributed to the thermal crosslinking of the allyl group and the second is due to the ring‐ opening polymerization of oxazine. The thermal cure of the allylamine‐based naphthoxazine monomers gave thermoset resins with novel structure comprising of polynaphthoxazine with extended network via the polymerization of allyl functionalities. Dynamic mechanical analyses and thermogravimetric analyses showed that the thermosets derived from allyl‐ functional naphthoxazines have high T_g's and stable storage moduli to higher temperature as well as better thermal stability than that of aniline‐based naphthoxazines. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3769–3777, 2006     

High temperature thermosets based on the cocuring of a novel spirodilactam bisallylether and bismaleimide

Spirodilactam bisallylether is a new high temperature performance monomer. It melts at 154°C, and is thermally inactive in forming a homopolymer. However, it reacts readily with a bismaleimide via “ene” reaction. Therefore, it could be used as a comonomer and an effective toughening modifier for bismaleimide. The properties of the blends of spirodilactam bisallylether and 4,4'-bismaleimidodiphenyl-methane were studied. The cocured resins have high glass transition temperature, > 300°C. By adding 30 to 40 mole % of the bisallylether, the compact tension toughness of the bismaleimide was improved to 0.7 MPa-m^1/2. Therefore, the resins have a combination of high glass transition temperature and toughness. They also showed good flexural properties. Despite the high water absorption, 5 to 7%, the resins retained high hot/wet flexural properties because of the high glass transition.     

High-performance thermosets with tailored properties derived from multi-arm stared vanillin and carbon fiber composites

Vanillin, a rigid compound can be separated from lignin, is a promising sustainable candidate for industrial and high performance polymers, while synthesis of hexa-epoxies is challenging. Meanwhile, carbon fiber reinforced bio-based polymers combining high performance are more difficult to be achieved because of the contradictions of liquidity and high rigidity in the polymer structure and performance. In this paper, a novel hexa-epoxy functionalized bio-based epoxy resin (HPVIGEP) with a multi-arm star structure, which simultaneously reduced the viscosity and improved thermo-mechanical properties. The rheological behavior analysis results of HPVIGEP indicated that the viscosity was 3406.9 mPa·s at 25°C, which dramatically decreased by 75.8% compared to DGEBA (14,096 mPa·s), leading to excellent processability and adaptability. At the same time, the study on mechanical properties revealed that the cured HPVIGEP manifested 30.6%, 33.7% and 49.0% in higher tensile strength, tensile modulus and storage modulus (30°C) than of cured commercial epoxy, respectively. The tensile strength and flexural strength of carbon fiber composites which were applied HPVIGEP were increased by 9.3% and 10.9%, respectively. In a word, this work provides the promise for the application of environmentally friendly bio-based composite materials.     

Gas permeation properties of silica membranes with uniform pore sizes derived from polyhedral oligomeric silsesquioxane

The sol‐gel method was applied in the fabrication of homogenous polyhedral oligomeric silsesquioxane (HOMO‐POSS)‐derived silica membranes. Single gas permeation characteristics in a temperature range of 100–500^°C were examined to discuss the effect of silica precursor on amorphous silica networks. HOMO‐POSS‐derived membranes showed a CO₂ permeance of 1.1 × 10^?7 mol m^?2 s^?1 Pa^?1 with a CO₂/CH₄ permeance ratio of 131 at 100^°C, which is a superior CO₂/CH₄ separation performance by comparison with tetraethoxysilane (TEOS)‐derived silica membranes. Normalized Knudsen‐based permeance (NKP) was applied for quantitative evaluation of pore size. HOMO‐POSS‐derived membranes had loose amorphous silica structures compared to TEOS‐derived membranes and pore size was successfully tuned by changing the calcination temperatures. The activation energy for a HOMO‐POSS‐derived membrane fired at 550^°C with a uniform pore size of ～ 0.42 nm increased linearly with the ratio of the kinetic diameter of the gas molecule to the pore diameter, λ (=d_k/d_p), and showed a trend similar to that of DDR‐type zeolite membranes. © 2011 American Institute of Chemical Engineers AIChE J, 58: 1733–1743, 2012     

The Journey of Phenolics from the First Spark to Advanced Materials

The emergence, historical and recent developments of phenolic resins are reviewed. The history of the invention of the first man made plastics and a short bibliography of the inventor Leo H. Baekeland is provided. Moreover, the basic chemistry of phenol-formaldehyde resins, as synthesis of resol and novolak, their structures, variations, and curing are discussed. Modification of these resins and molecular designs for specific applications in retro perspective are highlighted. This review also provides a comprehensive account on the development of benzoxazine resins as an alternative to classical phenolics. In addition to the benzoxazine synthesis and their curing mechanism, special monomers and polybenzoxazine precursors as curable thermoplastics are reviewed. Besides classical chemicals, the potential of renewables for phenolic resin production is also highlighted. Finally, the relative advantages and disadvantages of these systems are discussed and their future potentials are presented.     

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

A renewable chemical, eugenol, is methacrylated to produce methacrylated eugenol (ME) employing the Steglich esterification reaction without any solvent. The resulting ME is used as a low‐viscosity co‐monomer to replace styrene in a commercial epoxy‐based vinyl ester resin (VE). The volatility and viscosity of ME and styrene are compared. The effect of ME loading and temperature on the viscosity of the VE–ME resin is investigated. Moreover, the thermomechanical properties, curing extent and thermal stability of the fully cured VE–ME thermosets are systematically examined. The results indicate that ME is a monomer with low volatility and low viscosity, and therefore the incorporation of ME monomer in VE resins allows significant reduction of viscosity. Moreover, the viscosity of the VE–ME resin can be tailored by adjusting the ME loadings and processing temperature to meet commercial liquid molding technology requirements. The glass transition temperatures of VE–ME thermosets range from 139 to 199 °C. In addition, more than 95% of the monomer is incorporated and fixed in the crosslinked network structure of VE–ME thermosets. Overall, the developed ME monomer exhibits promising potential for replacing styrene as an effective low‐viscosity co‐monomer. The VE–ME resins show great advantages for use in polymer matrices for high‐performance fiber‐reinforced composites. This work is of great significance to the vinyl ester industry by providing detailed experimental support. © 2018 Society of Chemical Industry     

Improving glass transition temperature of unsaturated polyester thermosets: Conventional unsaturated polyester resins

Highly crosslinkable unsaturated polyester resins (UPR) have attracted many interests in the application as reinforced matrix materials. Here, we present a systematical study of the influence of different curing conditions and styrene concentrations on resin viscosity and dynamic-mechanical properties of the thermoset. The pure maleic Palapreg® P18-03 was selected as model UPR because of its broad industrial use. By applying newly developed thermal curing profiles (without thermal initiators) and by raising the styrene content, the T_g of the network could be increased up to 206/215°C (1/10 Hz). For the first time, a fast curable UPR based on propylene glycol and neopentyl glycol with a T_g of up to 215°C is described. A partial substitution of problematic styrene with methylmethacrylate, tert-butylacrylate, and maleic anhydride (MA) was studied as well. MA leads to significantly improved resin reactivity. A resin containing 42 wt% styrene and 8 wt% MA yields thermosets with remarkably improved mechanical properties and with a narrower glass transition range compared to the original P18-03.     

Microwave processing of thermosets: non-contact cure monitoring and fibre optic temperature sensors

Abstract

Conventionally, curing thermosetting resins involves heating the sample in an autoclave or an oven where heat is transferred to the sample through conduction and convection involving long processing time. Microwave curing offers an efficient alternative to thermal processing as heating occurs directly inside the sample resulting in lower energy consumption and faster curing. However, it requires non-metallic cure monitoring systems. In this study, a non-contact fibre optic probe was constructed and deployed inside a custom-modified microwave oven to record near-infrared (NIR) spectra, in real-time, of a thermoset undergoing cure. Simultaneous spectroscopic and temperature data on the sample during cure have been obtained for a range of microwave power levels. Comparison is also made between a sample cured in the microwave oven with one cured conventionally. In the final part, two optical fibre temperature sensors were designed and evaluated with an aim to use them in the microwave oven for temperature metrology. The sensors were based on the Fabry-Perot interferometer. The first sensor was evaluated from ambient to 400°C with an accuracy of ± 1·0°C, while the second sensor was tested from ambient to 300°C. The accuracy of the second sensor was ± 0·5°C.     

Room temperature magnetic order in an organic magnet derived from polyaniline

We report on the synthesis and characterisation of a new type of polymer, PANiCNQ produced from polyaniline (PANi) and an acceptor molecule, tetracyanoquinodimethane (TCNQ). PANiCNQ combines a fully conjugated nitrogen containing backbone with molecular charge transfer side groups and this combination gives rise to a stable polymer with a high density of localised spins which are expected to give rise to coupling. Magnetic measurements suggest that the polymer is ferri- or ferro-magnetic with a Curie temperature of over 350 K, and a maximum saturation magnetization of 0.1 JT⁻¹ kg⁻¹. Magnetic force microscopy images support this picture of room temperature magnetic order by providing evidence for domain wall formation and motion. The magnetic measurements reveal that the magnetically ordered state develops with time, taking several months to reach completion; X-ray diffraction data demonstrate that there is a concomitant evolution of the polymer chains from an amorphous state to a partially ordered form. Estimates of spin density from integrated electron spin resonance lines are larger than values obtained from the saturation magnetisation by a factor of 7 which leads us to tentatively conclude that PANiCNQ exhibits ferrimagnetic order.     

Low temperature cure of epoxy thermosets attaining high Tg using a uniform microwave field

It is demonstrated for the first time that an epoxy thermoset resin can be cured at temperatures well below its T_g∞. This study compared the use of a uniform variable frequency microwave (VFM) field to standard oven curing at temperatures above and below T_g∞. Using T_g, tan δ, modulus, and FTIR measurements, it is shown that the reaction of BFDGE with MDA to attain a product with T_g∞ of 133 °C is achieved by VFM at temperatures from 100 to 140 °C; in contrast, the thermal cure normally requires 170 °C to attain the same T_g∞ and the same extent of cure. By following the pregel cure reaction with ¹³C‐NMR spectroscopy, it was determined that the lower cure temperatures of VFM cure predominately lead to chain extension and smaller amounts of crosslinking compared to the thermal cure. To explain these results, it is suggested that, after gelation, with VFM cure there is higher mobility from dipole rotations that continues the cure to completion without vitrification. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44222.     

Study of high glass transition temperature thermosets made from the copper(I)-catalyzed azide–alkyne cycloaddition reaction

Thermal properties of polymers made from the copper(I)-catalyzed cycloaddition reaction between azides and alkynes have been investigated. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to measure the glass transition temperatures (T_g) of these materials. The polymers were found to have unusually high T_g values, up to 60 °C higher than the curing temperature. It has been shown that the increase of T_g was time dependant, thus, depending on the state of cure of the material.     

High temperature anti-oxidative and tunable wave absorbing SiC/Fe3Si/CNTs composite ceramic derived from a novel polysilyacetylene

With the rapid development of high power electromagnetic (EM) equipment and high-speed aircraft, the powerful and high oxidation-resistance absorbers are fundamentally desirable for the EM field. Herein, a novel high temperature anti-oxidative SiC/Fe₃Si/CNTs composite is synthesized by a facile polymer derived ceramic (PDC) route from a Fe-containing polysilyacetylene (PSA). The microstructure of as-prepared SiC/Fe₃Si/CNTs composite absorber is featured by micro-sized SiC ceramic grains with spherical Fe₃Si nanoparticles and carbon nanotubes (CNTs) attached to. The vector network analyzer tests show a tunable wave-absorbing performance by adjusting the thickness of layer, and the effective bandwidth (the reflection loss < −10 dB) is 3.3–16.8 GHz for the sample S-1400 (heat treatment at 1400 °C in nitrogen flow). The minimal RL value is −41.2 dB at 10.5 GHz at a thickness of 2 mm and an effective bandwidth is nearly 4 GHz (12.9–16.9 GHz) at the thickness of only 1.5 mm. Moreover, after the oxidation treatment at 800 °C in the air, this absorber maintains the main structure and shows a good high temperature oxidation resistance. This absorber still remains excellent wave absorption property, in view of a minimal RL value of −40 dB at the thickness of 3 mm and a bandwidth of 4.8 GHz (10.4–15.2 GHz) at the thickness of 2.5 mm. The mechanism of high EM wave absorption performance is studied and attributed to the impendence matching, polarization, and the magnetic properties. Thus, the SiC/Fe₃Si/CNTs composite is a promising EM absorber for high-temperature EM wave-absorbing applications.