Search Results (19)

A series of linear isocyanate-free polyurethanes (NIPUs) were obtained via the aminolysis of erythritol dicarbonate (EDC) with polyethers (diamino-PEG, diamino-PPO, and diamino-PEG/PPO) and 1,12-diaminododecane (DADD), which acts as a chain extender to form hard segments. The obtained NIPUs contained different concentrations of DADD relative to the polyether (72.5–80 wt%). A detailed chemical structure analysis of the synthesized NIPU was performed using a combination of FTIR and ¹H NMR. FTIR spectra confirmed that the EDC/DADD segments formed a network of hydrogen bonds. This is reflected in WAXD diffractograms showing ordered crystalline domains originating in DADD. The reflections assigned to the EDC/DADD segments exhibited changes in their position and intensity with decreasing concentration, indicating an increase in interplanar spacing and a loss of higher-order order. WAXD also showed that the soft segments of PEG and PEG/PPO retain their ordered crystal structure regardless of the EDC/DADD content. At a larger length scale, SAXS revealed similar micromorphology for the different polyethers, with a broad peak indicating long-range order in the EDC/DADD-rich segments and a weak separation of the soft and hard phases. DSC analyses confirmed the complex phase behavior, where the PEG-based materials showed melting of crystalline fragments, and the amorphous PPO showed a glass transition. DMA indicated the stability of the glass transition temperature in the PPO samples and the presence of an unusual structural transition. The results emphasize the influence of the type of poly(ether) on the thermal and microphase properties of the studied non-isocyanate polyurethanes. Full article

The pre-oxidation process of Polyacrylonitrile (PAN) fibers is a complex procedure involving multiple stages of temperature increase and isothermal temperature retention. However, the impact of the temperature increase stage on PAN fiber has often been overlooked. To address this, samples were collected before and after the temperature increase and isothermal retention stages, treating them as separate influencing factors. Therefore, the pre-oxidation process can be divided into four distinct stages: (1) A temperature increase stage before the cyclization reactions: the PAN fiber’s small-size crystals melt, and the crystal orientation changes under fixed tension, leading to shrinkage and increased orientation of the micropore. (2) An isothermal retention stage before the cyclization reactions: The crystal structure maintains well, resulting in minimal micropore evolution. The PAN fiber’s crystal orientation and micropore orientation increased under fixed tension. (3) A temperature increase stage after the cyclization reactions: The PAN fiber’s crystal melts again, reducing the average chord length and relative volume of the micropore. However, the PAN fiber can recrystallize under fixed tension. (4) An isothermal retention stage after the cyclization reactions: Significant crystal melting of the PAN fiber occurs, but the highly oriented crystals are maintained well. The average chord length and relative volume of the micropore increase. Recommendations for improving the pre-oxidation process are made according to these stages. Full article

Coil–rod copolymers with a dendritic polyethylene (DPE) core and multiple helical poly(γ-benzyl-L-glutamate) (PBLG) arms (DPE-(PBLG)_n) were prepared by palladium-catalyzed copolymerization in tandem with ring-opening polymerization (ROP). Macroinitiator (DPE–(NH₂)₁₁) was firstly prepared by the group transformation of DPE–(OH)₁₁ generated from palladium-catalyzed copolymerization of ethylene and acrylate comonomer. Coil–helical DPE-(PBLG)₁₁ copolymers were prepared by ROP of γ-benzyl-L-glutamate-N-carboxyanhydride (BLG-NCA). These DPE-(PBLG)₁₁ copolymers could form thermoreversible gels in toluene solvent, and the dendritic topology of the DPE core increased the critical gelation concentrations. The self-assembled nanostructure of gels was fully characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and wide-angle X-ray diffraction (WAXD), and the morphology of the fibrous structure was a twisted flat ribbon through a self-assembled nanoribbon mechanism. The self-assembled fibers formed by DPE-(PBLG₄₅)₁₁ are more heterogeneous and ramified than previously observed fibers formed by PBLG homopolymer and block copolymers. Full article

This study used scanning electron microscopy via 3D dissection coupled with synchrotron radiation with microfocal beams of both small-angle X-ray scattering and wide-angle X-ray diffraction to analyze the periodic crystal aggregates of unusual poly(p-dioxanone) (PPDO) dendritic cactus-arm-like ring bands upon crystallization with a diluent poly(vinyl alcohol) (PVA) that is capable of hydrogen bonding interactions with PPDO. Three-dimensional microscopy interior dissection clearly expounds that the banded periodic architectures are packed by alternately normal-oriented flat-on crystals underneath the valley, periodically interfaced/branched with horizontal-oriented edge-on fibrils underneath the ridge. The oblique angles between the valley’s flat-on crystals with the branches are ca. 25–45° (depending on gradient inclines and bending), which is also proved by the azimuthal angle in microbeam X-ray diffraction. The grating-like strut-rib assembly in the PPDO cactus-arm-like ring bands is further proved by novel iridescence tests. Full article

Polybutene-1 with form I crystals exhibits excellent creep resistance and environmental stress crack resistance. The filaments of polybutene-1 and its random copolymer with 4 mol% ethylene co-units were produced via extrusion melt spinning, which are expected to be in form I states and show outstanding mechanical properties. The variances in microstructure, crystallization–melting behavior, and mechanical properties between homopolymer and copolymer filaments were analyzed using SEM, SAXS/WAXD, DSC, and tensile tests. The crystallization of form II and subsequent phase transition into form I finished after the melt-spinning process in the copolymer sample while small amounts of form II crystals remained in homopolymer filaments. Surprisingly, copolymer filaments exhibited higher tensile strength and Young’s modulus than homopolymer filaments, while the homopolymer films showed better mechanical properties than copolymer films. The high degree of orientation and long fibrous crystals play a critical role in the superior properties of copolymer filaments. The results indicate that the existence of ethylene increases the chain flexibility and benefits the formation of intercrystalline links during spinning, which contributes to an enhancement of mechanical properties. The structure–property correlation of melt-spun PB-1 filaments provides a reference for the development of polymer fibers with excellent creep resistance. Full article

In this study, the structural and property changes induced in the highly ordered structure of preoriented poly(3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV films containing the β-form during annealing were investigated. The transformation of the β-form was investigated by means of in situ wide-angle X-ray diffraction (WAXD) using synchrotron X-rays. The comparison of PHBV films with the β-form before and after annealing was performed using small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The evolution mechanism of β-crystal transformation was elucidated. It was revealed that most of the highly oriented β-form directly transforms into the highly oriented α-form, and there might be two kinds of transformations: (1) The β-crystalline bundles may be transformed one by one rather than one part by one part during annealing before a certain annealing time. (2) The β-crystalline bundles crack or the molecular chains of the β-form are separated from the lateral side after annealing after a certain annealing time. A model to describe the microstructural evolution of the ordered structure during annealing was established based on the results obtained. Full article

The mechanical properties of two-component crystalline random copolymers are primarily based on their microstructure. At the same time, the influence of the composition on the crystallization behavior and crystal structure of these materials is also well known. Thus, in this study, a poly (butylene succinate-co-butylene terephthalate) random copolymer (PBST) with different molar ratios of butylene terephthalate (BT) was prepared. A systematic analysis of the crystallization behavior, crystal structure, and mechanical properties of PBST with different BT contents was carried out using WAXD, SAXS, and DSC analyses. The investigations showed that PBST-37.5 containing 37.5 mol% of BT content had the lowest strength and highest elasticity among the different compositions. This was because the two-component crystallization of poly (butylene terephthalate) (PBT) and poly (butylene succinate) (PBS) was greatly inhibited at the corresponding BT composition and the crystal growth was the least perfect, imparting poor strength to the PBT-37.5. Alternately, when the content of BT was 32.5 mol% in the PBST, the PBS segment could crystallize, and both PBT and PBS crystals were formed in the PBST-32.5. Thus, PBST-32.5 showed a higher material hardness than PBST-37.5. In contrast, when the BT content was greater than 37.5 mol% in the PBST, only PBT crystals existed in the PBST copolymer. Further, as the BT content increased, the crystal size of PBT gradually increased, which led to a closer packing of the crystal arrangement, increasing the crystallinity. This led to a gradual increase in the strength of the PBST material and a gradual decrease in its elasticity. Full article

The development of semi-aromatic polyamides with excellent mechanical properties has always been a popular research avenue. In this work, the semi-aromatic polyamide 12T (PA12T) with the maximum tensile strength of 465.5 MPa was prepared after stretching at 210 °C 4.6 times. Wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) were used to characterize the structural evolution of semi-aromatic polyamide 12T (PA12T) after stretching at different stretching temperatures and stretching ratios. The formation mechanism of this change in mechanical properties was investigated from different aspects of the aggregated structure such as crystal morphology, crystal orientation and crystallinity. The relevant characterization results show that the crystal structure, crystal orientation and crystallinity of PA12T were the highest when the sample was pre-stretched at 210 °C, which is crucial for improving the mechanical properties of PA12T. These findings will provide important guidance for the preparation of polymer materials with excellent mechanical properties. Full article

Composites suitable for rotational molding technology based on poly(ε-caprolactone) (PCL) and filled with hollow glass microspheres (HGM) or functionalized hollow glass microspheres (HGMf) were prepared via melt-compounding. The functionalization of glass microspheres was carried out by a silanization treatment in order to improve the compatibility between the inorganic particles and the polymer matrix and achieve a good dispersion of glass microspheres in the matrix and an enhanced filler–polymer adhesion. The crystallization behavior of materials was studied by DSC under isothermal and non-isothermal conditions and the nucleating effect of the glass microspheres was proven. In particular, the presence of silanized glass microspheres promoted faster crystallization rates and higher nucleation activity, which are enhanced by 75% and 50%, respectively, comparing neat PCL and the composite filled with 20 wt% HGMf. The crystalline and supermolecular structure of PCL and composites crystallized from the melt was evaluated by WAXD and SAXS, highlighting differences in terms of crystallinity index and structural parameters as a function of the adopted crystallization conditions. Full article

Conducting polymers, such as polyaniline (PANi) and polypyrrole (PPy), and their nanocomposites, are desired in a wide range of applications, including supercapacitors, lithium ion battery, chemical sensors, biosensors, barrier thin films, and coatings, because of their interesting electrical and electrochemical properties. It is well known that the properties of polymer nanocomposites depend on their chemical structure, as well as their microstructure, yet scientists and engineers have not fully understood how to properly control the structure of polymer nanocomposites. In this study, it is shown that the structure of polyaniline–montmorillonite clay nanocomposites (PACN) can be controlled by varying the ammonium persulfate (APS, oxidant) concentration. The structure of polyaniline and Cloisite 20A clay are, therefore, profoundly affected during the synthesis of PACN nanocomposites. The thickness of polyaniline crystal decreased with increasing oxidant concentration. Fourier transform infrared spectroscopy (FTIR) was used to determine the oxidation state of PANi. The structure of the nanocomposites was studied by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), wide-angle X-ray diffraction (WAXD), wide-angle X-ray scattering (WAXS), and small-angle X-ray scattering (SAXS). Electrochemical impedance spectroscopy (EIS) analysis of polyimide nanocomposite coatings containing PACN with varying levels of intercalation and exfoliation indicate that the coating impedance decreased with exposure time for some coating systems. It is shown that polyimide–PACN nanocomposite coating containing highly intercalated clay was more durable and maintained constant impedance after 20 weeks of exposure in a corrosive medium. Full article

A series of non-isocyanate poly(ether urethane) (PEU) were prepared by an environmentally friendly route based on dimethyl carbonate, diols and a polyether. The effect of the chemical structure of polyurethane hard segments on the properties of this kind of PEU was systematically investigated in this work. Polyurethane hard segments with different structures were first prepared from hexamethylene di-carbamate (BHC) and different diols (butanediol, hexanediol, octanediol and decanediol). Subsequently, a series of non-isocyanate PEU were obtained by polycondensation of the polyurethane hard segments with the polyether soft segments (PTMG2000). The PEU were characterized by GPC, FT-IR, ¹H NMR, DSC, WAXD, SAXS, AFM and tensile testing. The results show that the urea groups generated by the side reaction affect the degree of crystallization of hard segments by influencing the hydrogen bonding of the hard segments molecular chains. The degree of hard segment crystallization, in turn, affects the thermal and mechanical properties of the polymer. The urea group content is related to the carbon chain length of the diol used for the synthesis of hard segments. When butanediol is applied to synthesize hard segment, the hard segment of the resulting PEU is unable to crystallize. Therefore, the tensile strength and modulus of elasticity of butanediol-based PEU is lowest among three, though it possesses the highest urea group content. When longer octanediol or decanediol is applied to synthesize the hard segment, the hard segments in the resulting polyether-based polyurethane are crystallizable and the resulting PEU possesses higher tensile strength. Full article

Fibers of poly(4-hydroxybutyrate) (P4HB) have been submitted to both hydrolytic and enzymatic degradation media in order to generate samples with different types and degrees of chain breakage. Random chain hydrolysis is clearly enhanced by varying temperatures from 37 to 55 °C and is slightly dependent on the pH of the medium. Enzymatic attack is a surface erosion process with significant solubilization as a consequence of a preferent stepwise degradation. Small angle X-ray diffraction studies revealed a peculiar supramolecular structure with two different types of lamellar stacks. These were caused by the distinct shear stresses that the core and the shell of the fiber suffered during the severe annealing process. External lamellae were characterized by surfaces tilted 45° with respect to the stretching direction and a higher thickness, while the inner lamellae were more imperfect and had their surfaces perpendicularly oriented to the fiber axis. In all cases, WAXD data indicated that the chain molecular axis was aligned with the fiber axis and molecules were arranged according to a single orthorhombic structure. A gradual change of the microstructure was observed as a function of the progress of hydrolysis while changes were not evident under an enzymatic attack. Hydrolysis mainly affected the inner lamellar stacks as revealed by the direct SAXS patterns and the analysis of correlation functions. Both lamellar crystalline and amorphous thicknesses slightly increased as well as the electronic contrast between amorphous and crystalline regions. Thermal treatments of samples exposed to the hydrolytic media revealed microstructural changes caused by degradation, with the inner lamellae being those that melted faster. Full article

To characterize the interfacial microstructure and interaction at a nanoscale has a significant meaning for the interface improvement of the nanocomposites. In this study, the interfacial microstructure and features of aligned multiwalled carbon nanotube (MWNT) and conjugated polymer polyimide (PI) with three molecular structures were investigated using small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and fluorescence emission spectroscopy. It was found that aligned MWNT/PI nanocomposites had a nonideal two-phase system with the interfaces belonging to long period stacking ordered structure. Attributed to the π–π stacking effect, MWNT/BTDA-MPD presented the most regular arrangement verified by fractal dimension. By adopting a one-dimension correlation function, each phase dimension in aligned MWNT/PI nanocomposites was calculated and verified by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The π–π stacking was demonstrated to be an important interaction between MWNT and PI via WAXD and fluorescence emission spectroscopy, and it was influenced by the linkage bond between benzene rings in PIs. This work is of significance to reveal the interfacial features between conjugated polymer and carbon nanotubes (CNTs), which is favorable for the interface design of CNT-based high performance nanocomposites. Full article

Time-resolved simultaneous measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) (and FTIR spectra) were performed for various kinds of crystalline polymers in isothermal melt-crystallization processes, from which the common features of the structural evolution process as well as the different behaviors intrinsic to the individual polymer species were extracted. The polymers targeted here were polyethylene, isotactic polypropylene, polyoxymethylene, aliphatic nylon, vinylidene fluoride copolymer, trans-polyisoprene, and poly(alkylene terephthalate). A universal concept of the microscopically viewed structural evolution process in isothermal crystallization may be described as follows: (i) the small domains composed of locally regular but more or less disordered helical chain segments are created in the melt (this important information was obtained by the IR spectral data analysis); (ii) these domains grow larger as the length and number of more regular helical segments increase with time; (iii) the correlation among the domains becomes stronger and they approach each other; and (iv) they merge into the stacked lamellar structure consisting of the regularly arranged crystalline lattices. The inner structure of the domains is different depending on the polymer species, as known from the IR spectral data. Full article

To provide knowledge to improve the mechanical performance of Polyamide 12 (PA12) sintered products, we have studied experimentally the mechanical response and structure development under constant strain rate of compression moulded and laser sintered PA12 by means of in situ small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) experiments. It is found that at low temperatures, i.e., below the glass transition temperature, the brittle failure of laser sintered samples is determined by the fast formation of voids that originate at the beginning of the macroscopic plastic deformation. This effect appears to be faster at temperatures below room temperature and it is less effective at higher temperatures. When tested at 120 ${}^{\circ }$ C, sintered PA12 shows a better mechanical response in terms of yield stress and a comparable strain at break with respect to moulded PA12. This can be explained by considering that sintered samples have slightly thicker crystals that can sustain higher stress at high temperature. However, this also leads to the formation of a larger number of voids at low testing temperatures. This work does not attempt to quantify the micromechanics behind crystals deformation and disruption, but it provides a deeper insight in the difference between the mechanical response of moulded and sintered PA12. Full article