Rheological behavior and mechanical properties of PVC/MAP‐POSS nanocomposites

The polyhedral oligomeric silsesquioxanes which contains methylacryloylpropyl groups (MAP‐POSS) was synthesized. The MAP‐POSS/PVC nanocomposites were prepared. The influences of composition, shear rate' shear stress on melting rheological behavior of MAP‐POSS/PVC nanocomposites were discussed. The dynamic mechanical properties, mechanical properties, and morphology were determined by DMA, material tester and SEM, respectively. The result shows that the plastic times decreases and melt viscosity increases with increasing MAP‐POSS content. The n has a maximal value at 5 wt% MAP‐POSS content, but have best impact strength at 3%. MAP‐POSS can use as process aid and impact aid of PVC at appropriate contents. POLYM. COMPOS., 31:1822–1827, 2010. © 2010 Society of Plastics Engineers.     

Nanotailoring of polyurethane adhesive by polyhedral oligomeric silsesquioxane (POSS)

The development and commercialization of nanoparticles such as nanoclays (NCs), carbon nanotubes (CNTs) and polyhedral oligomeric silsesquioxanes (POSS) offers new possibilities to tailor adhesives at the nanoscale. Four types of POSS, with reactive mono-functional groups of isocyanatopropyl, glycidoxypropyl, aminoethyl and non-reactive octaphenyl, were incorporated in concentrations of 1, 3 and 5 wt% into a polyurethane (PU)-based adhesive. Thermo-mechanical bulk properties were studied using dynamic mechanical analysis (DMA). Adhesive properties were characterized in shear and peel modes. Atomic force microscopy (AFM) was used to study the nanoscale morphology. DMA measurements indicated that the neat PU possessed a glass transition temperature (T _g) of ≈ 30°C. The T _g of PU/POSS-glycidoxypropyl nanocomposite adhesive increased gradually with POSS concentration to 50°C for 5 wt%. PU/POSS-octaphenyl nanocomposite adhesive exhibited an increased T _g by 10°C for 5 wt%. The incorporation of POSS-isocyanatopropyl in the PU had no effect on the T _g. With respect to shear properties of POSS-octaphenyl-, POSS-isocyanatopropyl- and POSS-glycidoxypropyl-based PU nanocomposite adhesives, shear strength improved by 230, 178 and 137%, respectively, compared to neat PU. POSS-aminoethyl exhibited lower shear and peel strengths, while POSS-isocyanatopropyl provided the best balance of both higher shear and peel strengths compared to neat PU. It was concluded that the grafted functional group on the POSS and its reactivity with the PU network components were the decisive factors with respect to the thermo-mechanical, morphological and adhesive properties of the resulting nanocomposite adhesives. Consequently, the POSS/polyurethane based nanocomposite adhesives could be tailored for a large range of applications.     

Crystallization and morphology study of polyhedral oligomeric silsesquioxane (POSS)/polysiloxane elastomer composites prepared by melt blending

Composites of poly(methylvinylsiloxane) (“silicone”) elastomers with polyhedral oligomeric silsesquioxane (POSS) were prepared by melt blending. One goal was to establish conditions that would lead to morphologies different from that of a simple filler dispersed in a polymer matrix for the purposes of reinforcement. To this end, the study focused on the dispersion and state of POSS in silicone rubber blends as determined by X-ray diffraction (XRD), polarizing optical microscopy (POM), scanning electron microscopy (SEM), and analysis using a rubber processing analyzer (RPA). Of particular interest were the thermal stability of POSS macromers, and the effects of mixing temperature and subsequent vulcanization of the polysiloxane. The results showed that highly crystalline POSS macromers could undergo condensation reactions at 230 °C in air, leading to partially amorphous structures. Also, POSS crystals apparently dissolved in the polysiloxane at high temperatures and POSS crystals with hexahedral or flake-like structures recrystallized out upon cooling. Both crystallites and POSS molecules co-existed in these blends, with the amount of dispersed molecular POSS being increased at higher temperatures. The POSS molecules exhibited some physical interactions with the polysiloxane uncross-linked chains, but phase separation was induced by the process of cross-linking. In this curing process, POSS molecules could react with the polysiloxane, resulting in decreases in cross-link density. The original POSS crystals could also be dissolved in the polysiloxane during the initial curing stages, but recrystallization upon cooling gave regenerated crystals that were roughly spherical.     

Rheology of unsaturated polyester resins. I. Effects of filler and low-profile additive on the rheological behavior of unsaturated polyester resin

Measurements were taken of the bulk rheological properties of concentrated suspensions of particulates in unsaturated polyester resins, using a cone-and-plate rheometer. The particulates used were clay, calcium carbonate, and milled glass fiber. With clay and milled glass fibers, shear-thinning behavior of suspensions was observed at low shear rates or low shear stresses as the concentration of particulates was increased, whereas concentrated suspensions of calcium carbonate exhibited Newtonian behavior over the range of shear stresses or shear rates investigated. The cone-and-plate rheometer was also used for measurements of the bulk rheological properties of various mixtures of polyester resin and low-profile additives. For low-profile additives, solutions, in styrene, of poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) were used. It was found that the bulk viscosities of all mixtures of polyester resin and PVAc solution lie between those of the individual components, whereas the bulk viscosities of some mixtures of polyester resin and PMMA solution go through a minimum and a maximum, depending on the composition of the mixture. While all mixtures of polyester resin and PVAc solution exhibited negligible normal stress, some mixtures of polyester resin and PMMA solution exhibited noticeable normal stresses. It should be mentioned that polyester resin follows Newtonian behavior. It turned out that all mixtures of polyester resin and PVAc solution exhibited clear, homogeneous solutions, whereas mixtures of polyester resin and PMMA solution exhibited optical heterogeneity, i.e., turbidity. When polyethylene powders were used as low-profile additives, suspensions of polyester resin and polyethylene powders exhibited negative values of normal stress as the concentrations of suspension reached a critical value. When both filler and low-profile additive were put together in polyester resin, the rheological behavior became quite complex, indicating that some interactions exist between the filler and the low-profile additive.     

Flame retardant effect of polyhedral oligomeric silsesquioxane and triglycidyl isocyanurate on glass fibre‐reinforced epoxy composites

Polyhedral oligomeric silsesquioxane (POSS) and triglycidyl isocyanurate (TGIC) were added to an aerospace grade epoxy resin (EP) individually or in combinations at low concentrations. The EP samples containing additives were cast into resin laminates and also used to produce glass fibre‐reinforced composite laminates. The flammability of the two types of laminates was studied by limiting oxygen index, UL‐94 and cone calorimetry. The cone results indicated that the use of POSS (10 wt%) in EP can significantly decrease resin/composite's peak heat release rate, total heat release, and CO production. The mechanical performance in flexural modes of the fibre‐reinforced composite laminates was not adversely affected by the addition of POSS and TGIC in the resin. POSS containing samples had better retention of mechanical properties after exposure to radiant heat in a cone calorimeter compared with other samples. The results of thermogravimetry (TG), TG‐FTIR, and dynamic FTIR indicated that the thermal degradation behavior of the EP is significantly changed by the addition of POSS. POSS can get grafted on the EP's main chain during earlier stages of decomposition and form a stable char layer to protect the underlying material from further decomposition. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Investigation of Crystal Morphology and Shock Sensitivity of Cyclotrimethylenetrinitramine Suspension by Rheology

Crystal morphology and shock sensitivity of a series of cyclotrimethylenetrinitramine (RDX) particles suspended from ethylene glycol were investigated. Flow rheology was employed to measure the rheological properties of the suspensions at constant temperature; it was observed that the stress‐shear rate and viscosity behavior of the suspensions were controlled by the particle morphology. The viscosity of the RDX suspensions changed with the roundness/smoothness of RDX crystals at all applied shear rates. The suspensions containing crystals with smoother morphology showed reduced viscosity. When the viscosity data was compared to the shock sensitivity results from the RS‐RDX Round Robin study, a good correlation was obtained. This study has validated the use of flow rheology to indicate the morphology and shock sensitivity of crystalline particles.     

Effect of composition on the properties of PEM based on polybenzimidazole and poly(vinylidene fluoride) blends

Inadequate performance, short term durability and high cost of polymer electrolyte membrane (PEM) are the major roadblocks that need to be resolved for successful commercialization of high temperature PEM fuel cell. In this report, we investigated the viability of previously developed miscible blend membranes of polybenzimidazole and poly (vinylidene fluoride) (PBI/PVDF), as potential PEMs. In addition, we have carried out several advanced analytical techniques such as dynamic mechanical analysis (DMA), ¹³C CP-MAS solid state NMR (SS-NMR) and wide-angle X-Ray diffraction (WAXD) to prove the miscible behavior of the polymer pair. Sub-ambient temperature DMA studies confirmed the miscible behavior of PBI/PVDF blends at different compositions based on single T_g criterion. SS-NMR and WAXD showed the presence of interactions between the functional groups of the polymers and their dependence on blend composition. Thermogravimetric analysis of phosphoric acid (PA) doped and undoped blend membranes confirmed the improved thermal stability of the membranes compared to neat PBI. The membranes exhibited excellent oxidative stability than pristine PBI membrane. The swelling ratio and volume after dipping in PA was found to be significantly low in the blend membranes owing to the hydrophobic nature of PVDF. Among the blends prepared, 90/10 and 75/25 membranes showed higher proton conductivity than PBI, attributed in part, to electronegativity of fluorine and crystallinity of PBI in PA that activate proton transport. The results demonstrated the potential usefulness of the blend membranes as PEM in fuel cell.     

Rheological study of the gelation of cross-linking polyhedral oligomeric silsesquioxanes (POSS)/PU composites

The gelation process of N-Phenylaminomethyl-POSS/PU (polyurethane) nanocomposites during curing and at the stable state after curing was investigated by rheology. An increase in dynamic shear moduli, G′ and G″, was observed during the dynamic temperature ramps of the sample. In time-resolved mechanical spectroscopy (TRMS), G′ and G″ increased with curing time at constant curing temperatures over a wide of frequencies. The gelation time of the composites decreased with the rise of curing temperature or with the increase of POSS concentration. The relaxation exponent n at the critical gel was around 0.73. The gel stiffness S decreased as curing temperature increased or as POSS concentration increased. After the completion of the curing reaction, the critical concentration of POSS beyond which the gelation of POSS/PU composites would happen was found around 2.5 wt%. The viscoelastic properties of crosslinking POSS/PU fitted time–temperature-superposition well which implied the incorporation of multifunctional POSS into PU increased the homogeneity of crosslinking POSS/PU composites. Surprisingly, the modulus of the fully cured materials between 2.7 wt% and 6 wt% could also be supposed onto a master curve at high temperature, which implied self-similarity of network near the critical gel. The similar microstructure of POSS/PU at stable state was also confirmed by TEM. The network formation mechanism and the fine structure of the crosslinking POSS/PU were firstly investigated which would provide technical and theoretical basis for other hybrid crosslinking systems.     

环氧树脂对PA6/EPDM-g-MAH共混体系性能的影响

将两种不同型号的环氧树脂（EP(903)、EP(619D)）分别与PA6/EPDM-MA体系进行共混,制备了PA6/EPDM-MA/EP三元共混物。通过力学测试、动态流变(DMA)、差示扫描量热法（DSC）研究了不同EP添加量和环氧当量对PA6/EPDM-MA/EP共混体系性能的影响。实验结果表明：添加EP可以提高PA6/EPDM-MA共混物的拉伸强度,缺口冲击强度,并随着EP含量的增加而增加;而PA6/EPDM-MA/EP三元共混体系的动态储能模量（G′）,复合黏度（η*）随着EP含量的增加而增大,损耗因子（tanδ）减小;结晶度比未加环氧的共混物的结晶度稍高,并且随着环氧含量增加先增加后降低。此外,添加EP(903)的共混物各种性能变化比EP(619D)快。     

Phenolic resin-trisilanolphenyl polyhedral oligomeric silsesquioxane (POSS) hybrid nanocomposites: Structure and properties

The structure and properties of organic-inorganic hybrid nanocomposites prepared from a resole phenolic resin and a POSS mixture containing >95 wt% trisilanolphenyl POSS was investigated by POM (polarized optical microscopy), SEM, TEM, WAXD, FT-IR, DSC, and TGA techniques. Composites with 1.0-10.4 wt% of POSS were prepared by dissolving the POSS and the phenolic resin into THF, followed by solvent removal and curing. Both nano- and micro-sized POSS filler aggregates and particles were shown to be heterogeneously dispersed in the cured matrix by POM, TEM, SEM, and X-EDS. POSS was found everywhere, including in both dispersed phase domains and in the matrix. The nanocomposite morphology appears to form by a multi-step POSS aggregation during the process of phase separation. Both the matrix and dispersed ‘particulate’ phase domains are mixtures of phenolic resin and POSS. POSS micro-crystals act as the core of the dispersed phase. The bigger dispersed domains consist of smaller particles or aggregates of POSS molecules that exhibit some order but regions of matrix resin are interspersed. A WAXD peak at 2θ∼7.3° indicates crystalline order in the POSS aggregates. This characteristic peak's intensity increases with an increase in POSS loading, suggesting that more POSS molecules have aggregated or crystallized. FT-IR spectra confirm that hydrogen bonding exists between the phenolic resin and POSS Si-OH groups. This increases their mutual compatibility, but H-bonding does not prevent POSS aggregation and phase separation during curing. TGA measurements in air confirmed the temperature for 5% mass loss in increases with increase of POSS loading and at T>550° the thermal stability increases more sharply with POSS loading. The nanocomposite glass transition temperatures (T_g) are only slightly be affected by the POSS filler.     

Structure and dynamics of polyethylene/clay films

The relationships between structure and rheology of polyethylene/clay hybrid composite blown films were investigated through rheological tests both in shear and elongational flow. Two polymer matrices (low density polyethylene, LDPE and linear low density polyethylene, LLDPE) with different relaxation kinetics were used. Independently from the matrix, morphological analyses (TEM, XRD, and SEM) indicate that the hybrid structures are similarly constituted of delaminated platelets or tactoids having a relevant degree of orientation along the draw direction. This strongly affects the rheological behavior of materials. However, despite the similarities emerged from morphological analyses, both shear (steady shear and oscillatory) and elongation measurements show a negligible effect upon the rheology of LDPE‐based nanohybrids. Conversely, relevant increases of shear viscosity, dynamic moduli and melt strength of LLDPE‐based nanohybrids have been detected. The effects of homopolymer relaxation kinetics have been investigated by means of stress relaxation tests. The results obtained seem to be consistent with the existence of a roughly bimodal population of dynamical species: a matrix component behaving like the homopolymer, and a fraction interacting with the filler, whose rheological behavior is controlled by the particles and their interactions with the polymer. Mechanical properties of hybrid films were also investigated. Differently from what happens in the melt state, the solid‐state properties mainly depend on the filler amount. The relative increases of tensile modulus and melt strength are of the same order of magnitude for both the matrices used, indirectly confirming the similarities in hybrids structures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4749–4758, 2006     

Catalytic and reinforcing effects of polyhedral oligomeric silsesquioxane (POSS)-imidazolium modified clay in an anhydride-cured epoxy

In this article, we report novel epoxy-based hybrids prepared via incorporating 1,2-dimethyl-3-(benzyl-heptaisobutyl-POSS) imidazolium chloride (POSS-IMC) and POSS-IMC-modified clay (POSS-MMT) into the resin based on 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (ECHM) and hexahydrophthalic anhydride (HHPA). We demonstrate that both POSS-IMC and POSS-MMT can reduce the cure temperature of the epoxy/anhydride system, and the catalyzing effect involves chemical reactions between POSS-IMC and ECHM/HHPA, which may lead to the attachment of POSS cages at chain ends. The incorporation of the POSS-IMC, free and ionically bonded in clay, gives rise to dissimilar morphologies that affect the thermo-mechanical properties of the hybrids. The ECHM/HHPA/POSS-IMC resin exhibits a slight improvement in glassy modulus as compared with the neat ECHM/HHPA resin, which is attributed to the formation of sub-micron and nano-sized POSS domains that act as physical cross-link points hindering polymer chain motions. The much enhanced reinforcing effect of POSS-MMT is ascribed to the effective stress transfer between the matrix and clay layers that may originate from the strong interactions between the pendent POSS in the network and POSS attached to the clay surfaces. Reduction in coefficient of thermal expansion (CTE) was also found for the hybrids.     

氨基POSS/环氧树脂有机无机杂化材料的动态力学性能

为了提高环氧树脂(EP)的综合性能,以含氨基官能团的笼型倍半硅氧烷(POSS)作为EP的改性剂,得到有机-无机POSS改性EP杂化树脂;然后以4,4′-二氨基二苯基砜(DDS)为固化剂对杂化树脂进行固化,得到有机-无机杂化材料。重点考察了POSS含量对杂化材料动态力学性能的影响。结果表明:不同杂化材料体系均呈单相结构,POSS在EP基体中分散较均匀,说明两者间相容性良好;随着POSS含量的不断增加,杂化材料体系的玻璃化转变温度(Tg)增大,与传统杂化材料不同的是损耗峰强度随POSS含量增加而降低,但损耗峰宽度几乎不变。     

Self-assembled structure formation from interactions between polyhedral oligomeric silsesquioxane and sorbitol in preparation of polymer compounds

This study investigated the factors responsible for molecular interactions leading to self-assembly between the molecules of sorbitol and polyhedral oligomeric silsesquioxane (POSS) carrying organic and inorganic side groups. The study also assessed the utility of such molecular adducts as processing aids which will aid preparation of polymer compounds, films, and spun fibers. Several POSS molecules containing silanol functionalities and alkyl and phenyl substituents were used to separately evaluate the effects of hydrogen bonding and π?π interactions on formation of molecular adducts. The molecular adducts were studied using differential scanning calorimetry, wide angle X-ray diffraction, scanning electron microscopy, mass spectrometry, oscillatory shear rheology, and molecular dynamics simulation. The study revealed that POSS-sorbitol self-assembled structures were formed only when hydrogen bonding and π?π interactions worked cooperatively. In addition, self-assembled molecules were of amorphous nature although POSS and sorbitol were crystalline.     

Rheological and crystallization enhancement in polyphenylenesulfide and polyetheretherketone POSS nanocomposites

Polyhedral oligomeric silsesquioxane (POSS) additives have been shown to increase melt‐flow and crystallization in thermoplastics. In this study, the effect of incorporation of trisilanolphenyl‐POSS molecules in polyphenylenesulfide (PPS) and polyetheretherketone (PEEK) on rheology, crystallization kinetics, and thermal and mechanical properties was evaluated. Parallel plate rheometry revealed a reduction in the viscosity of PPS and PEEK with the addition of POSS. The magnitude and concentration dependence of rheological modification were shown to depend on the polymer structure and POSS solubility. Isothermal crystallization kinetics were analyzed using the Avrami model and it was found that the addition of POSS accelerated the crystallization rate of PPS blends with no significant effect on PEEK blends. Interestingly, no statistical difference in degradation temperature, tensile modulus, or tensile strength of PPS or PEEK blends was observed. The findings indicate the potential for improvements in melt viscosity and crystallization of high temperature thermoplastics with tailored POSS/polymer interactions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44462.     

四氨酯化合物的合成及其对液体双酚A环氧树脂的流变控制及固化性能的影响

利用羟基(-OH)和异氰酸酯基(-NCO)的简易反应合成了含4个氨酯键(-NHCOO-),两端基为十六碳烷链(-C16H33)的四氨酯化合物,并用作液体双酚A环氧的流变改性剂。利用傅里叶红外(FTIR)、差示量热扫描仪(DSC)、偏光显微镜和扫描电镜(SEM)对四氨酯化合物及其环氧复配物进行了表征分析。通过流变仪、动态力学分析仪(DMA)及万能试验机等对环氧复配物的流变性及其固化物性能进行了研究。结果表明,四氨酯化合物借助氢键作用和范德华力可在液体环氧基体中自组装形成合适及可控的分子聚集体形态,从而实现对液体环氧复配物流变性的有效控制。5%的四氨酯化合物可使环氧复配物拥有与含10%工业用气相二氧化硅(RY200)的环氧复配物一样的触变性。同时,四氨酯化合物的相变特性使其环氧复配物的流变性具有热可逆性。另外,环氧固化性能受四氨酯化合物影响较小。     

Computational rheology of carbonaceous mesophases

Mesophase pitches are multicomponent discotic nematic liquid crystals (DNLCs), whose characteristic molecular weight is intermediate between low molar mass and polymeric nematic liquid crystals. Flow modelling of these fluids is performed using a previously formulated mesoscopic viscoelastic rheological theory [J. Non-Newtonian Fluid Mech. 94 (2000) 87] that takes into account flow-induced texture transformations. A complete extra stress tensor equation is developed from first principles for liquid crystal materials under non-homogeneous arbitrary flow. This mesoscopic viscoelastic model has been adapted to describe the rheology of flow-aligning thermotropic DNLCs as models of mesophase pitches. We develop a fundamental understanding of the relations between rheology and flow of carbonaceous mesophases using theory and simulation by characterizing the steady and transient shear rheological material functions of flow-aligning DNLCs. Predictions for simple shear flow (under non-homogeneous conditions) for the apparent shear viscosity and first normal stress differences are presented. The predicted relations among rheological properties, shear-induced microstructure, processing conditions and material parameters of discotic mesophases are characterized and discussed.     

双酚A型苯并二噁嗪树脂粘接性能研究

以环氧树脂(EP)、双马来酰亚胺(BDM)作为纯双酚A型苯并二噁嗪(BA-a)树脂的改性共聚单体,研究了不同改性BA-a体系的粘接性能和热稳定性能。结果表明:纯BA-a树脂与钢材之间的拉伸剪切强度为15.34 MPa,说明纯BA-a树脂具有作为胶粘剂的潜力;当m(BA-a)∶m(EP)∶m(BDM)=100∶60∶0或100∶27∶27时,改性BA-a体系的拉伸剪切强度为24.81 MPa或21.36 MPa,160℃时凝胶时间为150 min或20 min;改性BA-a体系的热稳定性能依次为BA-a/甲基四氢苯酐体系>BA-a/EP体系>BA-a/BDM体系>纯BA-a体系。     

Cure behavior of epoxy/MWCNT nanocomposites: The effect of nanotube surface modification

The effect of carboxyl and fluorine modified multi-wall carbon nanotubes (MWCNTs) on the curing behavior of diglycidyl ether of bisphenol A (DGEBA) epoxy resin was studied using differential scanning calorimetry (DSC), rheology and infrared spectroscopy (IR). Activation energy (E_a) and rate constants (k) obtained from isothermal DSC were the same for the neat resin and fluorinated MWCNT system (47.7 and 47.5 kJ/mol, respectively) whereas samples containing carboxylated MWCNTs exhibited a higher activation energy (61.7 kJ/mol) and lower rate constant. Comparison of the activation energies, rate constants, gelation behavior and vitrification times for all of the samples suggests that the cure mechanisms of the neat resin and fluorinated sample are similar but different from the carboxylated sample. This can be explained by the difference in how the fluorinated nanotubes react with the epoxy resin compared to the carboxylated nanotubes. Although the two systems have different reaction mechanisms, both systems have similar degrees of conversion as calculated from the infrared spectroscopic data, glass transition temperature (T_g), and predictions based on DSC data. This difference in reaction mechanism may be attributed to differences in nanotube dispersion; the fluorinated MWCNT system is more uniformly dispersed in the matrix whereas the more heterogeneously dispersed carboxylated MWCNTs can hinder mobility of the reactive species and disrupt the reaction stoichiometry on the local scale.     

The effect of POSS on the thermal properties of epoxy

Summary The thermal properties of a series of inorganic-organic diglycidyl ether of bisphenol A/octa(aminpropyl)silsesquioxane (EP/POSS-NH₂) composites of were systematically investigated. These thermal properties included dynamic mechanical properties, glass transition temperature and thermal degradation temperature. Dynamic mechanical analysis (DMA) and Thermogravimetric analysis (TGA) were adopted. Results showed that the incorporation of POSS into epoxy resin could improve the thermal stabilities of epoxy significantly.