Synthesis and characterization of chlorine‐containing flame‐retardant polyurethane nanocomposites via in situ polymerization

We have developed flame‐retardant polyurethanes (FRPUs) and polyurethane (PU) nanocomposites via in situ polymerization. Three series of thermoplastic elastomeric PUs were synthesized to investigate the effect of incorporating 3‐chloro‐1,2‐propanediol (CPD) and nanoclay on mechanical, thermal properties, and also resistance to burning. PU soft segments were based on poly(propylene glycol). Hard segments were based on either CPD or 1,4‐buthane diol (BDO) in combination with methyl phenyl di‐isocyanate named PU or FRPU, respectively. In the third series, CPD was used as chain extender also nanoclay (1% wt) and incorporated and named as flame‐retardant polyurethane nanocomposites (FRPUN). Mechanical properties and LOI of PUs and nanocomposites have been evaluated. Results showed that increasing the hard segment (chlorine content) leads to the increase in flame retardancy and burning time. Addition of nanoclay to CPD‐containing PUs leads to obtain self‐extinguish PUs using lower CPD contents, higher Young's modulus, and strength without any noticeable decrease in elongation at break. Investigation of the TGA results showed that copresence of nanoclay and chlorine structure in the PU backbone can change thermal degradation pattern and improve nanocomposite thermal stability. X‐ray diffraction and transmission electron microscopy studies confirmed that exfoliation and intercalation have been well done. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterisation of novel flame retardant polyurethanes containing designed phosphorus units

In this study, 2-carboxyethyl(phenyl)phosphinic acid (CEPPA) and trimethylolpropane (TMP) are used to synthesise a novel flame retardant containing phosphorus units: 5-hydroxy-3-(2-hydroxyethyl)-3-methylpentyl-3-[2-carboxyethylphenylphosphine]propanoate (HMCPP). Then, 4,4′-diphenylmethane diisocyanate (MDI) is taken as a hard segment, with HMCPP and polycaprolactone diol (PCL) as soft segments, and 1,4-butanediol (BD) is used as a chain extender to prepare a novel polyurethane (HMCPP/PUs). The results of ¹H NMR and FT-IR reveal the successful synthesis of the HMCPP flame retardant. The gel permeation chromatography analysis demonstrates that an increase in the HMCPP content is accompanied by a decrease in the molecular weight of PU. The FT-IR analysis reveals the complete NCO group exhaustion of PU and HMCPP/PUs. The thermal analysis shows that the initial decomposition temperature of PU is higher than that of HMCPP/PUs by 19 °C. Both DMA and DSC analyses show that the Tg and the dynamic Tg of PU are higher than those of HMCPP/PU. Stress-strain tests indicate that the HMCPP content is increased, the maximum stress and Young’s modulus of HMCPP/PUs are decreased, and the elongation at break is increased. All of the HMCPP/PUs exhibit excellent flame retardancy, obtaining higher than 27.7 in limiting oxygen indices and a V-0 rating in the UL-94 test.     

Synthesis and characterization of polyurethane/bentonite nanoclay based nanocomposites using toluene diisocyanate

Polyurethanes (PUs) prepolymers blended with bentonite nanoclay and without bentonite nanoclay were prepared by the reaction of toluene-2,4-diisocyanate (TDI) and hydroxyl terminated polybutadiene (HTPB), and the chain was further extended with 1,4-butane diol (1,4-BDO) to get final polyurethane nanocomposites (PUNC). A mixture of polymer and bentonite clay enriched in montmorillonite (MMT) was formed in solution polymerization, in which MMT dispersed depending on interaction of MMT with polymer chains. The molecular structure of the monomers and the prepared PU nanocomposites was confirmed by FTIR. A series of PUNCs were prepared by varying the percent compositions of bentonite nanoclay into the PU matrix. The existence of the clay in to the PU was confirmed by scanning electron microscope (SEM). SEM images verified the good dispersion of the bentonite nanoclay in PU matrix.     

Synthesis and characterization of elastomeric polyurethane and PU/clay nanocomposites based on an aliphatic diisocyanate

This investigation reports preparation of polyurethane and polyurethane/clay nanocomposites based on polyethylene glycol, isophorone diisocyanate (IPDI), an aliphatic diisocyanate and 1,4‐ Butanediol as chain extender by solution polymerization. In this case PU/clay nanocomposites were prepared via ex‐situ method using 1, 3, and 5 wt % of Cloisite 30B. Thermogravimetric analysis showed that the maximum decomposition temperature (T_max) of the PU/clay nanocomposite is much higher than the pristine PU. The tensile properties improved upon increasing the organoclay (Cloisite 30B) content upto 3 wt %, and then decreased to some extent upon further increasing the nanoparticle loading to 5 wt %. Optical properties of the nanocomposites were studied by UV‐vis spectrophotometer. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) were used to study the morphology of the nanocomposites. It was observed that with the incorporation of 3 wt % nanoclay the crystallinity in PU nanocomposite increases, then diminishes with further loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3328–3334, 2013     

Diffusion and sorption of benzene vapor through polybutadiene‐, polybutadiene/styrene‐, and polybutadiene/acrylonitrile‐based polyurethanes

A series of polyurethane (PU) films made from toluene diisocyanate (TDI), 1,4‐butanediol (BDO), and hydroxyl‐terminated polybutadiene (HTPB), hydroxyl terminated polybutadiene/styrene (HTBS), or hydroxyl terminated polybutadiene/acrylonitrile (HTBN) was synthesized by solution polymerization. The absorption of benzene vapor was found mainly in the soft phase. The equilibrium adsorption (M_∞) was reduced with increasing hard segment content for all the PUs. The values of M_∞ were in the sequence of HTBN‐PUs > HTBS‐PUs > HTPB‐PUs, which could be explained by the different interaction parameters between soft segments and benzene. The HTBN‐PU film showed the lowest degree of phase segregation and had more hard segments intermixed in the soft phase, restricting the movement of soft segments, and therefore resulted to non‐Fickian behavior, while the HTPB‐PU is antithetical. FTIR and atomic force microscopy were utilized to identify the hydrogen bonding behavior and morphology change of the PU films before and after the absorption of benzene vapor. The tensile strength of the HTBN‐PUs showed a greater decrease than that of HTBS‐PUs and HTPB‐PUs after absorbing benzene vapor. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2984–2991, 2004     

TiO2 nanofibers assembled on graphene-silver platform as a visible-light photo and bio-active nanostructure

The heterogeneous titanium oxide-reduced graphene oxide-silver (TiO₂/RGO/Ag) nanocomposites were successfully prepared by incorporation of two dimensional (2D) RGO nanosheets and spherical silver nanoparticles (NPs) into the 1D TiO₂ nanofibers. The novel TiO₂/RGO/Ag nanocomposites were synthesized by loading TiO₂ nanofibers, prepared via electrospinning technique, on the RGO/Ag platform. The resulting nanocomposites have been characterized using various techniques containing transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and ultra-violet-visible (UV–vis) spectroscopy. Microscopic studies clearly verified the existence of TiO₂ nanofibers with Ag NPs on the surface of RGO sheet and formation of TiO₂/RGO/Ag nanocomposites. Moreover, the results of UV–vis spectroscopy demonstrated that TiO₂/RGO/Ag nanocomposites extended the light absorption spectrum toward the visible region and significantly enhanced the visible-light photocatalytic performance of the prepared samples on degradation of rhodamine B (Rh. B) as a model dye. It was found that, incorporation of 50 µl RGO/Ag into the TiO₂ nanofibers lead to a maximum photocatalytic performance. Also, the improvement of the inactivation of Escherichia coli (E. coli) bacteria under visible-light irradiation was revealed by introduction of RGO/Ag into the TiO₂ matrix. The significant enhancement in the photo and bio-activity of TiO₂/RGO/Ag nanocomposites under visible-light irradiation can be ascribed to the RGO/Ag content by acting as electron traps in TiO₂ band gap.     

Effect of filler content on the structure‐property behavior of poly(ethylene oxide) based polyurethaneurea‐silica nanocomposites

Poly(ethylene oxide) (PEO) based polyurethaneurea‐silica nanocomposites were prepared by solution blending and characterized by Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, Differential Scanning Calorimetry and tensile testing. The colloidal silica nanoparticles with an average size of 50 nm were synthesized by modified Stöber method in isopropanol. Silica particles were incorporated into three cycloaliphatic polyurethaneurea (PUs) copolymers based on PEO oligomers with molecular weights of 2,000, 4,600, and 8,000 g/mol. Hard segment content of PUs was constant at 30% by weight. Silica content of the PU nanocomposites varied between 1 and 20% by weight. Soft segment (SS) glass transition and melting temperatures slightly increased with increasing filler content for all the copolymers. Degree of SS crystallinity first increased with 1% silica incorporation and subsequently decreased by further silica addition. Elastic modulus and tensile strengths of PU copolymers gradually increased with increasing amount of the silica filler. Elongation at break values gradually decreased in PEO‐2000 based PU copolymer with increasing silica content, whereas no significant change was observed in PUs based on PEO‐4600 and PEO‐8000. Enhancement in tensile properties of the materials was mainly attributed to the homogeneous distribution of silica filler in polymer matrices and strong polymer‐filler interactions. POLYM. ENG. SCI., 58:1097–1107, 2018. © 2017 Society of Plastics Engineers     

High performance epoxy resin nanocomposites containing both organic montmorillonite and castor oil-polyurethane

Summary Epoxy resin/polyurethane interpenetrating polymer network nanocomposites with various contents of organophilic montmorillonite (oM-EP/PU nanocomposites) were prepared by a sequential polymeric technique and an in situ intercalation method. X-ray diffraction(XRD), and transmission electronic microscopy(TEM) analysis showed that organophilic montmorillonite (oMMT) disperses uniformly in epoxy resin/polyurethane interpenetrating networks(IPNs), and the intercalated or exfoliated microstructures of oMMT are formed. Differential scanning calorimetry(DSC) test proved that oMMT promotes the compatibility of EP phase and PU phase, and glass transition temperature(T_g) of oM-EP/PU nanocomposites improves with increasing oMMT content. Mechanical properties tests and thermal gravity analysis (TGA) indicated that oMMT and the IPNs of EP and PU exhibit synergistic effect on improving mechanical and thermal properties of pure EP. The mechanism of toughing and reinforcing of oM-EP/PU nanocomposites was further discussed by scanning electronic microscope(SEM).     

Aliphatic polycarbonate‐based polyurethane elastomers and nanocomposites. II. Mechanical,thermal, and gas transport properties

Thermal, thermomechanical, tensile and gas transport properties of aliphatic polycarbonate‐based polyurethanes (PC‐PUs) and their nanocomposites with bentonite for organic systems were studied. Hard segments are formed from hexamethylene diisocyanate and butane‐1,4‐diol. All PC‐PUs and their nanocomposites feature high degree of the phase separation. Three phase transitions were detected by temperature‐modulated differential scanning calorimetry (TMDSC) and dynamic mechanical thermal analysis. TMDSC revealed the filler affinity both to soft and hard segments, even though the affinity to hard segments is much stronger. Elongation‐at‐break at ambient temperatures is mostly over 700%, which leads together with high tensile strength (in some cases) to very high toughness values (over 200 mJ/mm³). The addition of 1 wt % of bentonite does not practically affect mechanical properties implying its very good incorporation into the PU matrix. Permeabilities and other gas transport properties depend on regularity of PC‐diol and on hard segment content, but the variations are insignificant. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

热塑性聚氨酯／纳米铜复合材料的制备与表征

选择热塑性聚氨酯（PU）为基体材料,用自制纳米铜颗粒代替铜丝或铜管等块体铜,采用机械共混的方法制备了一种全新的宫内节育器（IUD）材料——聚氨酯／纳米铜复合材料,并采用红外光谱（FFIR）分析、X射线衍射（XRD）分析、扫描电镜分析（SEM）、力学性能测试、热重分析等表征方法对自制纳米铜粉和复合材料的结构及性能进行了表征。结果表明,利用液相还原法成功制备了纳米级铜粉,聚氨酯／纳米铜复合材料的拉伸强度、撕裂强度随着纳米铜含量的增加略有增加,热稳定性随着纳米铜含量的增加稍有降低,为下一步复合材料铜离子的可控释放研究工作提供了很好的基础。     

Synthesis and Thermal Characterization of Polyurethane/Clay Nanocomposites Based on Palm Oil Polyol

Polyurethanes (PUs) are very versatile polymeric materials with a wide range of physical and chemical properties. PUs also have desirable properties, such as high abrasion resistance, tear strength, shock absorption, flexibility, and elasticity. Although they have poor thermal stability, it can be improved by using treated clay.

The objective of the present work is to study the thermal stability of polyurethane, polyurethane/montmorillonite (PU CTAB-mont 3% wt), and polyurethane/montmorillonite containing moca (PU Moca CTAB-mont 3% wt) nanocomposites based on palm oil polyol.

The interest of investigating the synthesis of polyurethane/clay nanocomposites based on palm oil polyol is to explore the use of palm oil polyol to partially replace petrochemical-based polyol.

Polyurethane/clay nanocomposites were prepared by a pre-polymer method and evaluated by Fourier Transform Infrared Spectra (FTIR) to determine micro-domain structures of segmented PU, PU CTAB-mont 3% wt, and PU Moca CTAB-mont 3% wt. The morphology of the nanocomposites was characterized by X-ray diffraction (X-RD), and flame retardant was investigated with thermogravimetric analysis (TGA). The result showed that in comparison with the virgin polyurethane, adding clay and moca demonstrated better thermal stability.     

Thermal and anticorrosive properties of polyurethane/clay nanocomposites

A montmorillonite clay has been modified with two different quaternary ammonium salts, dilauryldimethylammonium bromide (LD) and 4,4-diaminodiphenylmethane (AP), to form the corresponding organophilic clays, LDM and APM. Two series of PU/clay nanocomposite materials, PU/LDM and PU/APM, were then prepared by the reaction of appropriate amounts of PPG, TDI and 1,4 butandiol, followed by addition of the various amounts of LDM or APM. The X-ray diffraction patterns and transmission electron micrographs of the nanocomposites revealed that the modified clay galleries were exfoliated or intercalated in the polyurethane matrix. In comparison with the corresponding pure PU, the results of the TGA and LOI measurements showed that the thermal stability and the flame retardancy of the PU/clay nanocomposites were significantly enhanced due to the presence of the dispersed nanolayers of the organophilic clay in the PU matrix. Using the Tafel method, the results of the electrochemical measurements, which included the corrosion potential, polarization resistance and corrosion current, showed that all the PU/clay nanocomposites, even with low clay loading, in the form of coating on stainless steel disk (SSD) exhibited better corrosion protection over the pure PU. The SSD coated with the composite containing 2 wt% of APM showed the lowest corrosion rate, which was one order lower than that of the SSD coated with the pure PU.     

Effect of pyridazine content and crosslinker structure on the properties of polyurethane elastomers

This article studies the development of a series of heterocyclic polyurethanes (PUs) with various pyridazine content and different crosslinker structure in their main chains. All of the isocyanate‐terminated PU prepolymers were prepared from poly(tetramethylene oxide) glycol of molecular weight 1400 (Terathane 1400) and 1,6‐hexamethylene diisocyanate. The properties of the obtained linear and crosslinked pyridazine‐based PU were compared with the properties of common PUs obtained by chain extension with 1,4‐butanediol. All the obtained PUs were characterized through spectral and thermal behavior. The pyridazine‐based PU showed improved thermal stability with 10% weight loss at temperatures above 370–400°C. With the increase of pyridazine content the values of Young's modulus are higher and the strain at break decreases. Increasing pyridazine content leads to increased films surface hydrophilicity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

银原位改性HMS材料的结构及抗菌性能

采用溶胶凝胶法,以银氨离子为银源,原位合成了含Ag六方介孔硅（Ag-HMS）无机抗菌材料,探讨了其抗菌性能,并利用XRD、FT-IR、TG-DTA、UV-Vis、ESEM、EDS及N₂的吸附/脱附等方法对材料进行了表征。结果表明,材料保持了良好的介孔结构和热稳定性,具有良好的紫外线吸收性能,银物种以骨架态和非骨架态形式存在并且分散均匀;相对于HMS,Ag-HMS材料脱模时的热化学过程、孔体积、介孔有序度、比表面积及粒子形貌均发生了显著改变。在抑菌实验中,Ag-HMS对枯草杆菌(B.subtilis)、大肠杆菌(E.coil)、芽孢杆菌(G.bacillus)及金黄色葡萄球菌(S.aureus)均显示出良好的抗菌性能,其中对枯草杆菌和大肠杆菌尤为显著,当Ag-HMS用量为1.00 mg·L^-1,12 h后即可将两者彻底杀灭。     

Thermoplastic polyurethanes with controlled morphology based on methylenediphenyldiisocyanate/isosorbide/butanediol hard segments

Isosorbide, a cyclic, rigid and renewable diol, was used as a chain extender in two series of thermoplastic polyurethanes (PUs). Isosorbide was used alone or in combination with butanediol to examine the effects on the morphology of PU. Two series of materials were prepared – one with dispersed hard domains in a matrix of polytetramethylene ether glycol soft segments of molecular weight 1400 g mol^?1 (at 70 wt% soft segment concentration, SSC) and the other with co‐continuous soft and hard phases at 50 wt% SSC. We investigated the detailed morphology of these materials with optical and atomic force microscopy, as well as ultra‐small‐angle X‐ray scattering. The atomic force microscopy measurements confirmed the different morphologies in PUs with 50 wt% SSC and with 70 wt% SSC. Small‐angle X‐ray scattering data showed that in PU with 70 wt% SSC, the hard domain size varied between 2.4 and 2.9 nm, and decreased with increasing isosorbide content. In PU with 70 wt% SSC, we found that the correlation length and average repeat distances became smaller with increasing isosorbide content. We estimated the thickness of the diffuse phase boundary for PU with 70 wt% SSC to be ca 0.5 nm, decreasing slightly with increasing isosorbide content. © 2015 Society of Chemical Industry     

Synthesis,properties, and dyeing application of nonionic waterborne polyurethanes with different chain length of ethyldiamines as the chain extender

This study deals with the synthesis of some nonionic waterborne polyurethanes (PUs), using ethyldiamines of different chain length, such as ethylenediamine (EDA) and diethyltriamine (DETA), as the chain extender in the reaction, and examines the thermal properties, mechanical properties, and dyeing properties of the PU products and their blends. As far as each PU by itself is concerned, we found that the T_g of the one made with DETA is the highest, followed by that with EDA, and the one with 1,4‐butanediol (1,4‐BD) is the lowest. The PU made with 1,4‐BD as the chain extender has no T_m, while the two others, using diamines as chain extenders, have a clear T_m, the one with DETA being higher than that with EDA. However, the enthalpy data are just the opposite. The tensile strengths of the two PUs, made with diamines as the chain extender, are larger than that made with 1,4‐BD, but their respective elongation properties are just the opposite. A comparison within PUs made with diamines showed that the one made with EDA is greater in both strength and elongation categories than that made with DETA. However, the one made with DETA is far superior to both of those made with 1,4‐BD and EDA in their dye‐exhaustion ratio, color yield (K/S), fixation rate, and color fastness. In respect to the various PU mixtures that we examined, we found that both PUs synthesized with EDA or DETA as the chain extender would have their T_g's greatly increased by blending in some PU made using 1,4‐BD as the chain extender. Among them, in particular, a blend of PU, made separately with DETA and 1, 4‐BD as the chain extender, showed great improvements in both tensile strength and elongation and also demonstrated better dyeability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2824–2833, 2003     

Novel polyether polyurethane/clay nanocomposites synthesized with organicly modified montmorillonite as chain extenders

A kind of novel polyether polyurethane (PU)/clay nanocomposite was synthesized using poly(tetramethylene glycol), 4,4′‐diphenylmethane diisocyanate (MDI), 1,6‐hexamethylenediamine, and modified Na⁺‐montmorillonite (MMT). Here, organicly modified MMT (O‐MMT) was formed by applying 1,6‐hexamethylenediamine as a swelling agent to treat the Na⁺‐MMT. The X‐ray analysis showed that exfoliation occurred for the higher O‐MMT content (40 wt %) in the polymer matrix. The mechanical analysis indicated that, when the O‐MMT was used as a chain extender to replace a part of the 1,2‐diaminopropane to form PU/clay nanocomposites, the strength and strain at break of the polymer was enhanced when increasing the content of O‐MMT in the matrix. When the O‐MMT content reached about 5%, the tensile strength and elongation at break were over 2 times that of the pure PU. The thermal stability and the glass transition of the O‐MMT/PU nanocomposites also increased with increasing O‐MMT content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 6–13, 2006     

Relationship between carbon dioxide transport,free volume and morphology of polyolefin‐based polyurethanes

A series of polyurethane (PU) films, produced from toluene diisocyanate, 1,4‐butane diol and either hydroxyl‐terminated polybutadiene (HTPB), hydroxyl‐terminated polybutadiene/acrylonitrile (HTBN) or hydroxyl‐terminated polybutadiene/styrene (HTBS), was synthesized by solution polymerization. Differential scanning calorimetry (DSC), Fourier‐transform infrared (FT‐IR) spectroscopy, and positron annihilation lifetime (PAL) spectroscopy were used to investigate the morphologies and free volumes of these polyolefin‐based polyurethanes. The free volumes were closely related to the morphologies of such PUs. HTBN‐based PUs showed the lowest degree of phase separation, the smallest fraction of free volume and smallest hole radius among the three types of polyolefin‐based PUs, while the HTPB‐based PUs displaying the largest values. The diffusion and permeation coefficients decreased with decreasing degree of phase separation and increasing content of hard segments. The transport data were in relation to the free volume and fitted the Fujita free‐volume model. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of organically modified attapulgite/polyurethane nanocomposites

Polyurethane (PU) nanocomposites filled with attapulgite (ATT) nanorods were synthesized and characterized with thermal analysis, dynamic mechanical analysis (DMA), and mechanical testing. The formulations were based on 4,4′‐methylene bis(phenyl isocyanate) (MDI), polytetrahydrofuran, 1,4‐butanediol, and inorganic ATT premodified with MDI. The original and premodified ATT (ATT–OH and ATT–MDI) nanorods were characterized with thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. The analysis revealed that 17 wt % MDI was grafted/adsorbed onto the surface of ATT as a result of the modification. Pristine PU and ATT–MDI/PU nanocomposites were characterized with scanning electron microscopy, differential scanning calorimetry, and TGA. The mechanical tests and DMA showed an increase in the storage modulus and Young's modulus with increasing ATT–MDI content. The crystallinity of the hard and soft segments and thermal stability showed enhancements over those of the neat resin. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of UV-cured epoxy acrylate/POSS nanocomposites

In this study, epoxy acrylate (EA)/vinyl-polyhedral oligomeric silsesquioxane (POSS) nanocomposites were prepared through in situ polymerization and by UV-curing technique. The vinyl-POSS monomers were added to EA matrix by physically blending at loadings between 0 wt.% and 15 wt.%. The microstructure of the EA/vinyl-POSS composites was studied by X-ray diffraction (XRD) measurements, and the result indicated that the separate POSS domains were present in EA/POSS composites. Aggregates were observed in the nanocomposites by SEM and the EDS results indicated that there were vinyl-POSS molecules existing in the EA matrix. TEM images further proved there were both POSS aggregates and monomers dispersed in the EA matrix. The kinetics of the photopolymerization was investigated by real time FTIR spectroscopy. The DSC analysis showed that the increasing POSS content caused a decrease on the composite's glass transition temperature. TGA measures confirmed that the degradation mechanism of EA was not affected by POSS and the nanocomposites thermal stability was slightly improved with the increasing of POSS loadings. It can be seen that the degradation rate slowed down with the increasing of POSS content and the 50% mass loss temperature of EA/POSS hybrids all increased conspicuously relative to plain EA.