On thermal conductivity of micro‐ and nanocellular polymer foams

Many theoretical and empirical models exist to predict the effective thermal conductivity of polymer foams. However, most of the models only consider the effect of porosity, while the pore size effect is ignored. The objective of this study is to understand the effect of pore size on the thermal conductivity of polymer foams, especially when it reduces to the micro and nanometer scales. A wide range of pore sizes from 1 nm to 1 mm were studied in conjunction with the porosity effect using finite element analysis and molecular dynamics simulation methods. Experimental data was used to validate the modeling result. It is shown that the pore size has significant effect on thermal conductivity, even for microcellular and conventional foams. The contribution of heat conduction through air is negligible when pore size is reduced to the micrometer scale. The extremely low thermal conductivity of nanofoams is attributed to extensive diffusive scattering of heat carriers in the solid phase of polymer matrix, instead of air. This study provides quantitative understanding of the pore size effect on thermal conductivity of polymer foams. It is also shown that polyetherimide (PEI) nanofoams could have a thermal conductivity as low as 0.015 W/m‐K. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Matting films prepared from waterborne acrylic/micro‐SiO2 blends

Acrylic resin/micro‐SiO₂/polymethyl urea (AC/SiO₂/PMU) composites were prepared by physical blends of acrylic resin latex (AC), polymethyl urea resin (PMU), and modified SiO₂. The effects of SiO₂ and PMU content in the hybrid composites morphology and physical properties were investigated in detail using transmission electron microscopy (TEM), UV‐Vis spectrometry (UV‐Vis), scanning electron microscope (SEM), thermogravimetric analysis (TGA), and contact angle measurement. The results showed that introduction of SiO₂ into AC composites could increase the viscosity which caused by gelation and agglomeration of SiO₂. The TEM, SEM images, and TGA results indicated that hybrid membranes have phase separation. During the film formation process, a high number of PMU and SiO₂ particles of an appropriate size were stranded on the surface of the film to form matting surface. These results highlight the sensitivity of the gloss to the polymer morphology and surface. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41707.     

Hot‐fillable containers containing PET/PEN copolymers and blends

Bottles and containers made of PET are not suitable for hot filling since the limiting upper‐use temperature of this polymer is about 85°C. In the present study the properties and performance of bottles made from copolymers and blends of PET containing NDC groups and manufactured by the Injection Stretch Blow Molding (ISBM) process were investigated. These compositions possess advanced properties and can be used up to 95°C. The properties of these bottles were found to depend on their composition and microstructure. The glass transition temperature, the degree of crystallinity and the induced strains that were measured by differential scanning calorimetry and differential mechanical thermal analysis are reported. It was concluded that NDC‐containing PET based copolymers and blends could be processed by a one‐stage ISBM process into containers of improved properties and hot‐filling capabilities. Polym. Eng. Sci. 44:1670–1675, 2004. © 2004 Society of Plastics Engineers.     

Investigation of the nanocellular foaming of polystyrene in supercritical CO2 by adding a CO2‐philic perfluorinated block copolymer

Nanocellular foaming of polystyrene (PS) and a polystyrene copolymer (PS‐b‐PFDA) with fluorinated block (1,1,2,2‐tetrahydroperfluorodecyl acrylate block, PFDA) was studied in supercritical CO₂ (scCO₂) via a one‐step foaming batch process. Atom Transfer Radical Polymerization (ATRP) was used to synthesize all the polymers. Neat PS and PS‐b‐PFDA copolymer samples were produced by extrusion and solid thick plaques were shaped in a hot‐press, and then subsequently foamed in a single‐step foaming process using scCO₂ to analyze the effect of the addition of the fluorinated block copolymer in the foaming behaviour of neat PS. Samples were saturated under high pressures of CO₂ (30 MPa) at low temperatures (e.g., 0°C) followed by a depressurization at a rate of 5 MPa/min. Foamed materials of neat PS and PS‐b‐PFDA copolymer were produced in the same conditions showing that the presence of high CO₂‐philic perfluoro blocks, in the form of submicrometric separated domains in the PS matrix, acts as nucleating agents during the foaming process. The preponderance of the fluorinated blocks in the foaming behavior is evidenced, leading to PS‐b‐PFDA nanocellular foams with cell sizes in the order of 100 nm, and bulk densities about 0.7 g/cm³. The use of fluorinated blocks improve drastically the foam morphology, leading to ultramicro cellular and possibly nanocellular foams with a great homogeneity of the porous structure directly related to the dispersion of highly CO₂‐philic fluorinated blocks in the PS matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PEN/PTT共混聚酯的熔融行为

利用差示扫描量热仪对不同配比的聚萘二甲酸乙二醇酯/聚对苯二甲酸丙二醇酯(PEN/PTT)共混体系的熔融行为进行了分析,发现在共混体系中两组分形成各自的晶体,PEN和PTT的熔点均随另一组分含量的增加而下降。根据Nishi-Wang方程,按300℃计算,由PEN/PTT共混体系中PEN熔点下降计算所得到的相互作用能密度为-0．214 2 J/cm~3,相互作用参数为-0．006 8,表明PEN/PTY共混体系在熔融态是热力学性质稳定的相容体系。     

PET/PEN共混体系的研究进展

主要综述了PET/PEN共混体系的研究进展,重点讨论了PET/PEN共混体系的相容性、酯交换反应、热性能以及结晶性能,并对其在国内外应用前景做了展望。     

The changes of transesterification level in PET/PEN blends with the addition of PET–PEN copolymer

The extent of transesterification in poly(ethylene terephthalate) (PET)/poly(ethylene‐2,6‐naphthalate) (PEN) blends with the addition of PET–PEN copolymers was examined by DSC and ¹H‐NMR measurements to evaluate the factor affecting the reaction level at a given temperature and time. Both block (P(ET‐block‐EN)) and random (P(ET‐ran‐EN)) copolymers were used as the copolymers. At a given treatment temperature and time, the level was increased by the addition of P(ET‐block‐EN) into PET/PEN blends. On the other hand, a reverse change was observed when P(ET‐ran‐EN) was mixed with PET/PEN blends. During the treatment, an inhomogeneous phase of the blends changed into the homogeneous one; however, the change showed little effect on the reaction level. The effects of molecular weight on the reaction level were also examined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Supercritical CO2 assisted processing of polystyrene/nylon 1212 blends and CO2‐induced epitaxy on nylon 1212

Polystyrene/nylon 1212 blends were prepared with supercritical CO₂ as the substrate swelling agent and monomer/initiator carrier. Original nylon 1212 and blends were characterized with differential scanning calorimetry (DSC), polarizing microscopy, wide‐angle X‐ray diffraction, and scanning electron microscopy (SEM). A novel phenomenon, CO₂‐induced epitaxy, was discovered, and its mechanism was deduced. Thermal analysis performed with DSC indicated that the polystyrene/nylon 1212 blends had thermal stability superior to that of virgin nylon 1212. The DSC and SEM measurements indicated that incorporated polystyrene could notably improve the mechanical performance of nylon 1212. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2023–2029, 2004     

PET/PEN blends of industrial interest as barrier materials. Part I. Many-scale molecular modeling of PET/PEN blends

Mesoscale molecular simulations, based on parameters obtained through atomistic molecular dynamics and Monte Carlo calculations, have been used for modeling and predicting the behavior of PET/PEN blends. Different simulations have been performed in order to study and compare pure homopolymer blends with blends characterized by the presence of PET/PEN block copolymers acting as compatibilizer. A many-scale molecular modeling strategy was devised to evaluate PET/PEN blend characteristics, simulate phase segregation in pure PET/PEN blends, and demonstrate the improvement of miscibility due to the presence of the transesterification reaction products. The behavior of distribution densities and order parameters of the compatibilized blends demonstrates that mixing properties improve significantly, in agreement with experimental evidences. Barrier properties such as oxygen diffusivity and permeability have also been evaluated by finite element simulations. Accordingly, many-scale modeling seems to be a successful way to estimate PET/PEN blend properties and behavior upon different concentrations and processing conditions.     

Relationship between cell morphology and impact strength of microcellular foamed high‐density polyethylene/polypropylene blends

Polymer blends, such as those resulting from recycling postconsumer plastics, often have poor mechanical properties. Microcellular foams have been shown to have the potential to improve properties, and permit higher‐value uses of mixed polymer streams. In this study, the effects of microcellular batch processing conditions (foaming time and temperature) and HDPE/PP blend compositions on the cell morphology (the average cell size and cell‐population density) and impact strength were studied. Optical microscopy was used to investigate the miscibility and crystalline morphology of the HDPE/PP blends. Pure HDPE and PP did not foam well at any processing conditions. Blending facilitated the formation of microcellular structures in polyolefins because of the poorly bonded interfaces of immiscible HDPE/PP blends, which favored cell nucleation. The experimental results indicated that well‐developed microcellular structures are produced in HDPE/PP blends at ratios of 50:50 and 30:70. The cell morphology had a strong relationship with the impact strength of foamed samples. Improvement in impact strength was associated with well‐developed microcellular morphology. Polym. Eng. Sci. 44:1551–1560, 2004. © 2004 Society of Plastics Engineers.     

Fast pH‐thermo‐responsive copolymer hydrogels with micro‐porous structures

Micro‐porous copolymer hydrogels were prepared by γ‐ray irradiation of mixed solutions of N‐isopropylacrylamide (NIPAAm) and acrylic acid (AAc) above the lower critical solution temperature (LCST). From Cryo‐SEM observations, the gels were found to consist of three‐dimensional fibrous micro‐gels and micro‐pores. The copolymer gels swelled at temperatures below the LCST and shrunk at temperatures above it, and they showed rapid volume transitions on a time scale on the order of a minute when experiencing temperature changes between 10 and 40°C. The transition times for thermal shrinking were almost the same regardless of AAc composition, but the transition times for thermal swelling were increased with increasing AAc contents. The copolymer gels also showed rapid volume transitions with time constants on the order of an hour on experiencing pH changes between 2 and 12. The transition times for pH volume change at 10°C were within one hour, except for the gels containing only small amounts of AAc. On the other hand, the transition times for pH‐dependent volume change at 40°C were increased with increasing AAc content. The lower responsiveness of the transition results from an increase in hydrophobicity arising from the formation of inter‐ and intra‐molecular hydrogen bonds between the non‐ionized carboxylic acid groups and the amide groups. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 75–84, 2003     

Study on the nonisothermal crystallization process of mLLDPE/EVA blends using FTIR micro‐spectroscopy

The nonisothermal crystallization process has been investigated by Fourier transform infrared (FTIR) micro‐spectroscopy for the 40/60 wt % blends of metallocene linear low density polyethylene (m‐LLDPE) and ethylene/vinyl acetate copolymer (EVA) at the molecular level. In the cooling process, thermal spectra of mLLDPE/EVA blends were collected between 150°C and 67°C at 1°C interval. According to the van't Hoff equation at constant pressure, the changes of absorbance ratio corresponding to high and low vibrational states were calculated; hereby, apparent enthalpy differences of vibration energy states transformation (?H_v) of characteristic groups could be obtained. Combining with DSC analysis, two exothermal peaks were examined in the crystallization process, corresponding to mLLDPE‐rich and EVA‐rich domains, respectively; while in comparison of the ?H_v values of various characteristic groups corresponding to the two exothermal peaks, the bending vibrational mode of methylene groups has been found to make a prominent contribution to the movement and regular arrangement of mLLDPE and EVA chain segments towards each rich domain in the crystallizing process. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 261–267, 2005     

Formation of poly‐vinyl‐alcohol structures by supercritical CO2

Poly‐vinyl‐alcohol (PVA) porous structures have been prepared using a supercritical phase inversion process in which supercritical carbon dioxide (SC‐CO₂) acts as the nonsolvent. First, we tested the versatility of the SC‐CO₂ phase inversion process, forming PVA/dimethylsulfoxide (DMSO) solutions with polymer concentrations ranging from 1 to 35% (w/w) and changing the process parameters. We worked at temperatures from 35 to 55°C and pressures from 100 to 200 bar obtaining different membranes morphologies: dense films, membranes with coexisting morphologies, and microparticles. However, we did not produce symmetric or asymmetric porous membranes. To obtain this result, we used casting solutions formed by adding acetone to DMSO with the aim of modifying the affinity between SC‐CO₂ and the liquid solvent. In this series of experiments, we obtained asymmetric membranes with skin layer thicknesses lower than 10 μm. The results obtained in this work have been explained considering that the membranes formation mechanism is related to the kinetics of the process; i.e. the affinity between the solvent (mixture of solvents) and SC‐CO₂. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of blending sequence on micro‐ and macrostructure of PA6/mEPDM/EPDMgMA blends reinforced with organoclay

The structure of the PA6/mEPDM/EPDMgMA/organoclay ternary hybrids was characterized and related to its properties. The nanoblends were prepared through four different blending sequences based on one‐ or two‐step processes: (1) The PA6/organoclay nanocomposite was prepared and then mixed with the mEPDM+ EPDMgMA compound; (2) the mEPDM+EPDMgMA+ organoclay compound was first prepared and then mixed with PA6; (3) the PA6, mEPDM, EPDMgMA, and organoclays were blended in one step; and (4) the PA6/mEPDM/EPDMgMA blend was prepared and then mixed with the organoclay. The microscopic study of the nanoblends showed a relationship between the blending sequence and the dispersion of the organoclay and the rubber. Nevertheless, the mechanical characterization showed slight differences bet ween the blending sequence because of the presence of the organoclay in the matrix, rubber, or interface. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,characterization, and performance evaluation of PES/EDA‐functionalized TiO2 mixed matrix membranes for CO2/CH4 separation

Poor adhesion between hydrophobic polymers and hydrophilic inorganic fillers is a challenge that encumbers a high separation performance of mixed matrix membrane (MMM). In this study, Titanium(IV) oxide (TiO₂) nanoparticles were functionalized using ethylenediamine (EDA) before embedment in poly(ether sulfone) (PES) polymer matrix. MMMs were synthesized through dry phase inversion technique. Membranes morphology and nanoparticles dispersion was drastically enhanced posterior amine modification indicating an improved adhesion between the polymer and filler particles. Membranes thermal stability was likewise improved as higher degradation temperatures were perceived for PES/EDA–TiO₂ MMMs. Gas separation evaluation for pure carbon dioxide (CO₂) and methane (CH₄) gases revealed a remarkably enhanced separation performance upon amine‐grafting of TiO₂ as EDA‐TiO₂ MMMs exhibited a higher separation performance as compared to MMMs with pristine TiO₂. The highest ideal separation factor achieved was 41.52 with CO₂ permeability of 10.11 Barrer at an optimum loading of 5% wt of EDA‐TiO₂ which is threefold higher as compared to neat PES membrane and approximately twofold higher than MMMs with pristine TiO₂, respectively, at the same filler loading. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45346.     

Diffusion and desorption of CO2 in foamed polystyrene film

Based on the existence of the pores in foamed polystyrene (PS), foamed‐non‐Fickian diffusion (FNFD) model was proposed, for the first time, to regress the desorption data obtained by gravimetric method. Results showed that FNFD model could accurately describe the diffusion behavior of CO₂ out of foamed PS, and well predict the solubility of CO₂ in foamed PS. The characterization of scanning electron microscopy indicated that there were abundant pores in the foamed PS, and the pores store most of CO₂, which would diffuse in the pores, adsorb to the wall of the pores, penetrate across walls of the pores, diffuse in the matrix of PS, and desorb out of PS. The mass of CO₂ in the pores of foamed PS was expressed as a function of foaming pressure and temperature according to foaming kinetics. Results showed that the values calculated by this function agreed well with the values obtained from the FNFD model. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45645.     

Effect of different organic amino cations on SAPO‐34 for PES/SAPO‐34 mixed matrix membranes toward CO2/CH4 separation

Mixed matrix membranes (MMMs) embedded with functionalized SAPO‐34 were successfully synthesized and characterized. Two different types of organic amino cation, namely ethylenediamine (EDA) and hexylamine (HA), were used to functionalize SAPO‐34 particles prior to MMM synthesis. In this work, the effects of different functionalizing agents on the membrane morphology, pore size, and CO₂/CH₄ gas separation properties were investigated. Surface modification of SAPO‐34 was confirmed via X‐ray photoemission spectroscopy (XPS) where the presence of nitrogen atom was observed for the samples functionalized with amino cations. The dispersion of EDA‐functionalized SAPO‐34 particles was found to have better polymer/filler interface morphology as shown by field emission scanning electron microscopy (FESEM) analysis. The gas separation performance revealed that PES containing EDA‐functionalized SAPO‐34 exhibited better CO₂/CH₄ separation performance as compared to the MMMs containing HA‐functionalized SAPO‐34. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43387.     

Controlling micro‐ and nanofibrillar morphology of polymer blends in low‐speed melt spinning process. Part III: Fibrillation mechanism of PLA/PVA blends along the spinline

The effects of spinning conditions on the fibrillation process of poly(lactic acid) (PLA) and poly(vinyl alcohol) (PVA) polymer blends in an elongational flow within the fiber formation zone are systematically and thoroughly investigated. By considering the relationship between the changes in filament parameters with the focus on the maximum axial strain rate (ASR) and tensile stress at maximum ASR and the morphological evolution of the dispersed PLA phase along the spinline, the fibrillation process from rod‐like to nanofibrillar structures of the dispersed PLA phase in a binary blend with PVA matrix is elucidated. The final morphology of the dispersed PLA phase in PLA/PVA blends is controlled by the changes in the spinning conditions. The lengths and diameters of the PLA fibrils are caused not only by the deformation of their initial sizes but also by the combination of the deformation, coalescence, and break‐up process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44259.