Modeling particle inflation from poly(amic acid) powdered precursors. III. Experimental determination of kinetic parameters

Several concurrent phenomena occur during the thermal inflation of poly(amic acid) precursor particles leading to polyimide foams as part of the solid‐state powder foaming process. The precursor experiences bubble growth from within while volatiles desorb and the polymer itself increases its molecular weight and changes its backbone structure. These changes affect the transport properties of the material by modifying significantly the effective glass transition temperature, T_g. By studying the chemical transformations that take place during the inflation process (amidation and imidization reactions), a complete understanding of the material's molecular changes can be obtained and corresponding property changes can be followed. This article is the third of a series where the inflation of precursor materials for polyimide foams has been studied. The two previous articles in the series present numerical models that simulate the inflation process from first principles. In this article, the authors discuss the experimental and analytical methodologies employed to accurately characterize and incorporate the changes in material and transport properties as a function of the glass transition temperature. POLYM. ENG SCI., 2008. © 2008 Society of Plastics Engineers     

Modeling particle inflation from poly(amic acid) powdered precursors. I. Preliminary stages leading to bubble growth

Morphological characteristics of polyimide microstructures obtained by solid‐state powder foaming determine the geometric properties of the unit cell, in polyimide foams prepared by this process. Morphological analysis of precursor particles has shown that particle size and shape, as well as the presence of embedded microvoids, exert a strong influence on the final microstructure morphology. Of equal importance in the morphological development are processing conditions such as heating rate and primary blowing agent content in the particles, prior to thermal treatment. In the present paper, the first of two numerical schemes is presented. A numerical model has been developed to study the preliminary stages that lead to particle inflation. Based on this model, a parametric analysis is performed for pertinent governing parameters, with the purpose of determining their effect on the onset of particle inflation and the potential morphological characteristics of polyimide microstructures. It has been found that precursor particle morphology and nuclei density are the key parameters in determining the potential morphology of the microstructures, by limiting the number of bubbles that grow within each particle. POLYM. ENG. SCI., 47:560–571, 2007. © 2007 Society of Plastics Engineers.     

Preparation and characterization of high‐temperature resistance polyimide foams

A new high‐temperature resistance polyimide foam was synthesized from 2,3,3′,4′‐biphenyltetracarboxylic dianhydride (α‐BPDA) and p‐phenylenediamine (p‐PDA). The structures and foaming process of polyimide precursor powders were characterized by wide‐angle X‐ray diffractometer (WXRD) and the self‐made visualization device, respectively. The imidization degree, thermal mechanical properties and thermal stability of the polyimide foams with different post‐treatment temperatures were also measured by fourier transform infrared spectrometer spectrum (FTIR), dynamic thermal mechanical anaylsis (DMTA), and thermogravimetric analysis (TGA). Results showed that the inflation onset temperatures of polyimide precursor powders ranged from 122 to 135°C with varying the heating rate. And the increase in the imidization degree, glass transition temperatures (T_g) and temperatures for 5 wt% mass loss of high‐temperature resistance polyimide foams can be achieved with increasing post‐treatment temperature. It was quite surprising to find that T_g of high‐temperature resistance polyimide foam post‐treated at 420°C was up to above 450°C, and the char yield at 800°C was more than 60%. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Preparation and properties of polyimide/silica hybrid composites based on polymer‐modified colloidal silica

A new type of polyimide/silica (PI/SiO₂) hybrid composite films was prepared by blending polymer‐modified colloidal silica with the semiflexible polyimide. Polyimide was solution‐imidized at higher temperature than the glass transition temperature (T_g) using 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐diaminodiphenyl ether (ODA). The morphological observation on the prepared hybrid films by scanning electron microscopy (SEM) pointed to the existence of miscible organic–inorganic phase, which resulted in improved mechanical properties compared with pure PI. The incorporation of the silica structures in the PI matrix also increased both T_g and thermal stability of the resulting films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2053–2061, 2006     

Visualization study of foaming process for polyimide foams and its reinforced foams

In this article, the foaming processes of polyimide foams and its reinforced foams were observed by a self‐made visualization device at different heating rates ranging from 10°C/min to 120°C/min. Contributing factors such as chemical structure of polyimide, fillers, and heating rate were investigated to determine the effects on the inflation onset temperature and morphological change of polyimide foam precursor powders. The results showed that the powder might grow into a single bubble mesostructure at a lower heating rate or a multibubble mesostructure at a higher heating rate. Because of the filling of reinforcing fillers, the inflation morphology of reinforced polyimide foam precursor powders show a different change trend with the increase of temperature compared to the pure polyimide foam precursor powders. For all kinds of polyimide foam precursor powders investigated in this article, the inflation morphologies showed a similar variation trend with different heating rates, and the final inflation degrees were slightly different. The inflation onset temperatures of all polyimide foam precursor powders studied decreased with increasing heating rate. POLYM. COMPOS., 2010. © 2008 Society of Plastics Engineers     

Microwave‐assisted synthesis and characterization of polyimide/functionalized MWCNT nanocomposites containing quinolyl moiety

Polyimide‐MWCNT nanocomposites were prepared by the reaction of a heterocyclic diamine monomer of bis(4‐amino‐3,5‐dimethylphenyl)‐2‐chloro‐3‐quinolylmethane (BACQM), pyromellitic dianhydride (PMDA) with unmodified MWCNT (MWCNT), acid‐functionalized MWCNT (acid‐MWCNT) or amine‐functionalized MWCNT (amine‐MWCNT) using microwave irradiation as well as by the conventional method. The structure of the monomer was confirmed by FTIR, ¹H‐NMR, and ¹³C‐NMR spectral techniques. The glass transition temperature (T_g) of the MWCNTs/polyimide nanocomposite was found to be higher than that of the unfilled polyimide system. The T_g's of both systems were higher when prepared with the microwave method than the conventional synthesis. The T_g's of the nanocomposites using acid and amine functionalized MWCNTs are greater than 300°C, in both methods. This is attributed to the presence of hydrogen bond and strong covalent bond in both the acid‐MWCNT/polyimide and amine‐MWCNT/polyimide systems. The morphological studies of the nanocomposites synthesized using microwave irradiation show that a distinct MWCNT nanofibrillar network is formed in the matrix when MWCNT or acid‐MWCNT is used. A homogeneous morphology, without distinct nanotube domains is seen when the amine‐MWCNT is covalently linked to the polymer. POLYM. COMPOS., 37:2417–2424, 2016. © 2015 Society of Plastics Engineers     

Effects of reactive end-capper on mechanical properties of chemical amplified photosensitive polyimide

Photosensitive polyimide (PSPI) was synthesized and characterized to replace the conventional polyimide buffer layer because direct patterning with PSPI could reduce the processing procedure to the half. Since PSPI should be dissolved in alkaline aqueous solution and have good mechanical properties after imidization, low molecular weight of PSPI was synthesized with reactive end-capper, which could extend the chain length of PSPI during imidization. Therefore norbornene end-capped PSPI precursor was synthesized with various 5-norbornene-2,3-dicarboxylic anhydride (NDA) content.Although molecular weight of PSPI decrease with increasing NDA content, the elongation at break and the glass transition temperature (T_g) of PSPI films imidized at 300 °C increased with increasing NDA content. On the other hand, elongation at break of PSPI films imidized at 350 °C decreased but T_g of those increased with increasing NDA content. Above T_g, thermal expansion coefficient decreased dramatically by introducing NDA end-capper. From mechanical and thermal properties of PSPI, it appears that low molecular weight of PSPI can be chain-extended and crosslinked during imidization.     

Time–temperature–transformation (TTT) cure diagrams: Relationship between Tg and the temperature and time of cure for a polyamic acid/polyimide system

Glass transition temperatures (T_g) were obtained vs. isothermal temperature (T_cure) and time of cure for a polyamic acid/polyimide system. A time–temperature–transformation (TTT) isothermal cure diagram was constructed to include the time to vitrification and iso-T_g curves. As for expoxies, the relationship between T_cure and the time to vitrification is S-shaped. Plots of T_g vs. T_cure show that solvent evaporation and chemical reaction are controlled by vitrification.     

Thermomechanical and thermogravimetric analyses of systematic series of polyimides

Twelve polyimides which differ systematically in chemical structure were investigated in nitrogen through the temperature range ?190° rlhar2; 500°C by torsional braid analysis. The degradative regions were also examined in nitrogen by thermogravimetric analysis. Relationships between chemical structure/thermal history, processibility, thermomechanical behavior, and weight loss are discussed. A logical thermal program for converting the precursor polyamic acid solutions to solid polyimides was developed. High-temperature, thermally induced chemical reactions could be regulated so as to preferentially freeze out longer-range relaxations and extend the glass state behavior to well above its original load-limiting T_g. Materials made from more flexible molecules had lower glass transitions, softened more through the T_g, and had simpler damping spectra and lower thermal stability than materials made from more rigid molecules. A commercially available polyimide film and polyimide-forming varnish of undisclosed structures were examined by torsional pendulum and torsional braid analyses, respectively. The thermomechanical spectra of the film and cured varnish were similar to the spectra of one structural type of polyimide.     

Synthesis and characterization of side‐chain polyimides for second‐order nonlinear optics via a post‐azo‐coupling reaction

A two‐step, generally applicable synthetic approach for nonlinear optical (NLO) side‐chain polyimides was developed. This included the preparation of a preimidized, organosoluble polyimide with benzene moiety pendant from main chains, followed by the covalent bonding of the NLO chromophores onto the polyimide backbone via a post‐azo‐coupling reaction. The degree of functionalization of polyimides was estimated by UV‐VIS spectroscopy. The glass transition temperature (T_g) of a polyimide decreased by only 10–20°C after the functionalization, which was much smaller than the decrease in T_g when the chromophores were chemically bonded to the polyimide main chains through an ether linkage using a post‐Mitsunobu condensation. The solubility and thermal stability of polyimides were also studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 290–295, 2000     

Relaxation behavior and activation energy of relaxation for polyimide and polyimide–graphene nanocomposite

The relaxation behavior of polyimide and its nanocomposite containing 10 wt % of graphene was studied by using the dynamic mechanical spectrometer. Dynamic mechanical analysis of polyimide and its composite was performed as a function of temperature and frequency in the temperature range of 25–480 °C and frequency range between 0.05 and 100 Hz. The effect of increasing frequency of testing from 0.05 to 100 Hz is a significant shift from the glass transition temperature, T_g, to higher temperature from 360 °C at 0.05 Hz to 420 °C at 100 Hz. The tan δ peak height for both α and β transitions decreased with increasing test frequency from 0.24 at 0.05 Hz to 0.08 at 100 Hz, due to increasing restriction to chain motion. At any given testing frequency, the T_g for the composite was shown to be higher than that for the matrix by about 5–10 °C. The Arrhenius equation was used to calculate the activation energy for both α and β transitions. The activation for α and β transitions for the composite and polyimide matrix were determined to be 688 and 537 kJ/mol and 313 and 309 kJ/mol, respectively, indicating that a significant increase in the energy barrier to chain relaxation occurred as a result of reinforcement of polyimide with low weight fraction of graphene. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43684.     

Glass transition temperature (Tg) versus fractional conversion for a linear thermosetting polyamic acid ester–polyimide system

The relationship of the glass transition temperature, T_g, to fractional conversion, x, for the conversion of the cyclohexylmethyl ester of the benzophenone tetracarboxylic dianhydride–oxydianiline polyamic acid to polyimide has been investigated using dynamic mechanical analysis (torsion pendulum, TBA). The glass transition temperature and conversion measurements were obtained on a single solvent-free polyamic acid ester specimen during cooling after heating to successively higher cure temperatures. Conversion was determined from the intensity of a sub-T_g mechanical relaxation peak that has been assigned to a relaxation of the cyclohexyl group. The resulting T_g versus x relationship is nonlinear. The T_g versus x relationship is adequately modeled using an expression derived by Couchman. © 1994 John Wiley & Sons, Inc.     

New segment in new theory of polymer

Melting temperature (T_m) can be divided in two steps of (T_m–T_g) and T_g in the glass transition temperature. There are respective segments in both steps. The difference of elongation, which causes a separation between two arrays in segment, is of two kinds: mechanical and thermal. T_g is given as disappearance of the segment, which would not be so if the kind of elongation were the same. A prefix of micro at Brown on T_g is meaningless, because the segment can be explained from a different point view the phenomena shown as a sign of melting at T_g. T_g between polymer and components of C? C bond in repeat unit is given as T_g = Σ[1/n(1%)/a_i] = Σ[(1/n)T_gi], where α is the linear coefficient of thermal expansion, n is the total number of components, T_gi, α_i is the value of component i. A magnitude of elongation of component C_i is given as α_i with the result, which the side chains have functioned like a weighting function. Strength of linear polymer is connected with the total number of segments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Novel polypropylene microporous membranes via spherulitic deformation – Processing perspectives

The processing boundaries for initiating intra-/inter-spherulitic deformation to create microporous polypropylene membranes by lamellar separation are delineated. The processing parameters are: annealing temperature, extension ratio, stretching rate, and stretching temperature. A fixed set of extrusion conditions was chosen for producing precursor films having similar spherulitic morphologies. The morphological changes indicating the occurrence of intra-/inter-spherulitic transition on a spherulitic scale can also be detected on a lamellar scale by WAXS examination via analysis of the α-form orientation index. Membrane porosity measurements showed a consistent correlation with the observed values of the α-form orientation index. Increasing the extension ratio did not change the microstructure in the non-annealed sample; however, the lamellae can be further oriented in the annealed samples. Inter-spherulitic deformation became obvious at slow stretching rates; intra-spherulitic deformation was favored at fast stretching rates. The DSC thermal analysis of the precursor films showed two significant endothermic discontinuities (T₁ at 0 °C and T₂ at 40 °C) in both non-annealed and annealed precursor films; T₁ is believed to be the conventional T_g of polypropylene whereas T₂ appears to originate from the rigid-amorphous fraction trapped within the lamellar “wells” where the amorphous phase is surrounded by the R-lamellae and the T-lamellae. The lamellae could break down or slip from the lamellar knots as stretching temperatures are high enough to minimize the influence of the rigid-amorphous fraction, and the annealed lamellae can still be oriented without a catastrophic cold-drawn deformation.     

High molecular weight polypropylene nanospheres: Synthesis and characterization

The high molecular weight (MW) polypropylene with average particle size of 60 nm was synthesized by controlled growth mechanism using Ziegler–Natta catalyst. The atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) studies showed that PP nanoparticles were spherical in shape. Structure and crystallinity were concomitantly studied through Fourier transform infrared spectroscopy and X‐ray diffraction, respectively. It shows nanospherical PP particles with more crystallinity (～ 75%) compared with macrosized PP (～ 59%). In addition, differential scanning calorimetry studies revealed the finite particle size effect on T_g and the scale dependence T_g followed a first order exponential trend. As particle size goes down to nano‐ scale from macrosize, continuous elevation of T_g's were observed from ?25 to ?11°C. This phenomenon was directed to configuration entropy of single spherical nanoparticles of PP. The mechanical properties and surface roughness were also evaluated through AFM. At last, the properties of nanosized PP were compared with micron and macrosized particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanical,thermal, and electric properties of polyurethaneimide elastomers

Linear polyurethaneimide elastomers (PUI) were obtained from polyether- or polyester-diols, diphenylmethane diisocyanate or bitolylene diisocyanate and pyromellitic acid dianhydride. It was found that these polymers have considerably better mechanical properties than typical linear polyurethanes (PU). The elastic modulus and stress at break increase with contents of the hard polyimide segments. The softening temperatures and thermal stability of the PUI at 500°C were higher than the ones of PU with similar hard segment contents. Electric properties of PUI were close to the ones of conventional PU. It was shown that cellular PUI had considerably lower dielectric constant. T_g's of the soft segments PUI were less than T_g's corresponding to PU. It is connected with greater phase separation of the hard imide segments from the soft polyether– or polyester–urethane matrix.     

N.m.r. studies on the effect of water on the glass transition of polystyrene

These investigations are concerned with water-polymer interactions in polymer latices. It is known that water can act as a plasticizer for many solid polymers and cause a reduction in the glass transition temperature, T_g, of the amorphous regions. Experiments were carried out to determine whether pulsed n.m.r. techniques could be used to study the T_g of a polymer suspension and hence the influence of water and electrolyte on it. From T₁ and T₂ proton relaxation measurements as a function of temperature on polystyrene latex systems it was shown that the presence of water lowers the T_g of the polymer particles (by about 10°C), the effect being slightly greater in the presence of concentrated electrolyte. The extent of electrolyte penetration into the particles was deduced by studying relaxation as a function of particle diameter in latices containing paramagnetic Mn²⁺ ions. Using simple theories of relaxation and spin diffusion it was concluded that for all but the smallest particles electrolyte penetration is restricted to a very thin shell of the order of 1 nm. These conclusions were supported by the results of similar measurements on PTFE particles.     

How the infrared radiation affects the film formation process from latexes?

In this study, the effect of the infrared radiative heating (IRH) was investigated on the film formation from composites of polystyrene (PS) latex particles and poly vinyl alcohol (PVA). The films were prepared as a pure PS and a mixture of PS and PVA particles at equal compositions at room temperature and they were annealed at elevated temperatures above the glass transition temperature (T_g) of PS for 10 min by using IRH technique. Identical experiments were performed by using standard convectional heating technique in oven as comparison. It was shown that the activation energy for the film formation from PS latex particles decreased considerably in IRH annealing technique. Photon transmission (PT) and steady state fluorescence (SSF) techniques were used to monitor the film formation process at each sintering step. Minimum film formation temperature, T_o, and healing temperature, T_h, were determined by the data obtained from the SSF and the PT measurements for each heating processes. The film formation was modeled as a void closure and as an interdiffusion stage below and above T_h, respectively. Scanning electron microscopy (SEM) was used to examine the variation in morphological structure of annealed composite films. It was observed that IRH heating causes more homogenous and more flat film surface than films annealed in the oven. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43289.     

Dye leveling in PET fibers. II. Mathematical model

A mathematical model is developed for the dye leveling process. Good agreement between experimental and theoretical data supports the validity of the proposed model. Also, the applicability of the proposed model is shown through its effectiveness in predicting leveling times, when the working temperature is above the T_g of the fibers. The results demonstrate that chain mobility is a prerequisite for rapid leveling, and that morphological changes in the fiber during the migration process are important and must be considered.     

Molecular simulation of the glass transition and proton conductivity of 2,2′‐benzidinedisulfonic acid and 4,4′‐diaminodiphenylether‐2,2′‐disulfonic acid‐based copolyimides as polyelectrolytes for fuel cell applications

The glass transition temperatures (T_gs) and proton conductivities of polyimides synthesized from naphthalene‐1,4,5,8‐tetracarboxylic dianhydride (NTDA), 2,2′‐benzidinedisulfonic acid (BDSA), 4,4′‐diaminodiphenylether‐2,2′‐disulfonic acid (ODADS), and non‐sulfonated diamine monomers have been predicted using molecular dynamics simulations. The specific volumes for two dry and four hydrated NTDA‐based polyimides were plotted versus temperatures above and below T_gs to obtain the glass transition temperatures. The simulation results suggest that the ODADS‐based polyimide membranes exhibit lower T_gs and thus better mechanical properties than the BDSA‐based polyimides, which may be attributed to the high mobility of backbones of ODADS as supported by the vectorial autocorrelation function (VACF) results of this study. In addition, comparison of the simulated T_gs for the dry and hydrated ODADS‐based polyimides has shown that water content in polyimides can affect their T_gs. The proton conductivities of a representative polyimide in both dry and hydrated conditions have been obtained from molecular dynamics simulations of the proton and hydronium ion diffusion. The simulated conductivity for the hydrated NTDA‐ODADS/BAPB cell is in reasonable agreement with the experimental value obtained from the AC impedance method. The relationship between the chemical composition, chain flexibility, and the glass transition and proton conduction of these NTDA‐based polyimides was explored on the basis of VACF and pair correlation function analysis. Copyright © 2006 Society of Chemical Industry