Fangfang Liu

Effect of Draw Ratio on the Morphologies and Properties of BPDA/PMDA/ODA Polyimide Fibers

Abstract3,3,4,4-Biphenyltetracarboxylic dianhydride/pyromellitic dianhydride/4,4-oxydianiline(BPDA/PMDA/ ODA) polyimide copolymer fibers with different draw ratios were prepared from the imidization of polyacrylic acid(PAA) fibers via a dry-jet wet-spinning process. Their morphologies, microcrystal orientations, thermal stabilities, and mechanical properties were investigated via scanning electron microscopy(SEM), wide angle X-ray diffraction( WAXD), thermogravimetric analysis(TGA), and tensile experiments. In order to acquire fibers with better mechanical performance, we aimed at obtaining the optimal draw ratio. Drawing during thermal imidization resulted in a decreased diameter of fiber from 25.8 μm to 16.9 μm corresponding to draw ratio from 1 to 3.5. WAXD results show that the degree of the orientation of the undrawn sample is 64.1%, whereas that of the drawn sample is up to 82%. The as-spun fiber and those with different draw ratios all exhibit high thermal stabilities, i.e., the temperature at a mass loss of 5% can reach as high as 570 °C. The tensile strengths and tensile modulus of the fibers increase with the draw ratios, and the maximum tensile strength and modulus are 0.90 and 12.61 GPa, respectively.

Synthesis and properties of novel polyimide fibers containing phosphorus groups in the main chain

A series of polyamic acid copolymers (co-PAAs) containing phosphorous groups in the main chain were synthesized using different ratios of two diamines, i.e., bis(3-aminophenyl)methyl phosphine oxide (DAMPO) and 4,4′-oxydianiline (ODA), with 3,3′,4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) by polycondensation in N,N′-dimethyacetamide (DMAc). The co-PAA solutions were spun into fibers by a dry-jet wet spinning process, and then polyimide copolymer (co-PI) fibers were obtained by thermal imidization. ATR-FTIR spectra and elemental analysis confirmed the chemical structure of PAA and PI fibers. The as-prepared PI fibers have smooth and dense surface as well as uniform diameter. Compared with the blank PI-0, the Tg values of co-PI fibers increased considerably with the increase in DAMPO content. TGA results indicated that the co-PI fibers possessed good thermal stability up to 510 °C and a residual char yield of up to 61% at 850 °C. All co-PI fibers exhibited excellent elongation, and their tensile strength and modulus can reach 0.9 GPa and 14.97 GPa when the molar ratio of DAMPO/ODA was 6/4 and the draw ratio was 3.0. The relationship between microstructure and mechanical property is also discussed.

Comparison of different methods for determining the imidization degree of polyimide fibers

In this study, polyimide fibers at different stages of imidization were characterized by TGA, DSC, and FTIR. The imidization degree (ID) calculated by TGA was based on the weight loss of each sample, which was caused by the imidization of residual amic acid groups. The results of TGA showed good regularity with the thermal treatment temperature of the PI fibers. For DSC, the ID was calculated based on the area of endothermal peak of each sample. Compared with TGA, DSC showed a relatively higher value because the endothermal peak was reduced by the exothermic re-formation of polyamic acid which may be partially degraded during thermal treatment. The IDs obtained by the FTIR spectra generally showed poorer regularities than those obtained by both TGA and DSC, especially for the results calculated using the 730 cm−1 band. Based on the 1350 cm−1 band, the obtained IDs showed better agreement with the TGA or DSC results. The results obtained by these three methods were compared and analyzed. The ID obtained by TGA showed much more reliability among these three methods.

AO-resistant properties of polyimide fibers containing phosphorous groups in main chains

A series of polyimide fibers containing phosphorus element derived from (3-aminophenyl) methyl phosphine oxide (DAMPO) diamine was exposed to an artificial atomic oxygen environment which simulated the space environment in low earth orbit (LEO). The mass loss, surface morphology, chemical composition, and mechanical properties of the fibers before and after atomic oxygen (AO) exposure were compared in detail with a blank sample. Results showed that the phosphor-containing fibers demonstrated lower mass change and less tensile strength reduction. SEM results showed that the fibers with phosphorous element had relatively dense surface after AO exposure. Meanwhile, XPS results indicated that a passivated phosphate layer, which could protect the following under-layer from attacking by AO, was formed on the surface of the fibers. These results indicated that the incorporation of diamine (DAMPO) into the main chains could protect the fibers for avoiding further erosion from AO exposure. Hence, the phosphor-containing PI fibers exhibits potential application in space fields.

Mechanical properties of polyimide/multi-walled carbon nanotube composite fibers

A series of polyimide (PI)/multi-walled carbon nanotube (MWCNT) composite fibers were prepared by copolymerizing a mixture of monomers and carboxylic-functionalized MWCNTs, followed by dry-jet wet spinning, thermal imidization, and hot-drawing process. The content of the carboxylic groups of MWCNTs significantly increased when treated with mixed acid, whereas their length decreased with treatment time. Both the carboxylic content and length of MWCNTs influenced the mechanical properties of the composite fibers. Fiber added with 0.1 wt% MWCNTs treated for 4 h exhibited the best mechanical properties, i.e., 1.4 GPa tensile strength and 14.30% elongation at break, which were 51% and 32% higher than those of pure PI fibers, respectively. These results indicated that a suitable MWCNT content strengthened and toughened the resultant PI composite fibers, simultaneously. Moreover, raising draw ratio resulted in the increase of tensile strength and tensile modulus of the composite fibers.

Synthesis and properties of novel polyimide fibers containing phosphorus groups in the side chain (DATPPO)

A series of polyamic acid copolymers (co-PAAs) containing phosphorous groups in the side chains were synthesized from [2,5-bis(4-aminophenoxy) phenyl] diphenylphosphine oxide (DATPPO) and 4,4′-oxydianiline (ODA) with 3,3′,4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) through the polycondensation in N,N′-dimethyacetamide (DMAc). The co-PAA solutions were spun into fibers by a dry-jet wet spinning process followed by thermal imidization to obtain co-polyimide (co-PI) fibers. FTIR spectra and elemental analysis confirmed the chemical structure of PI fibers. SEM results indicated that the resulting PI fibers had a smooth and dense surface, a uniform and circle-shape diameter. The thermogravimetric measurements showed that with the increase of DATPPO content, the resulting PI fibers possessed high decomposition temperature and residual char yield, indicating that the PI fibers had good thermal stability. The corresponding limiting oxygen index (LOI) values from the experiment results showed that the co-PI fibers possessed good flame-retardant property. Furthermore, the mechanical properties of the co-PI fibers were investigated systematically. When the DATPPO content increased, the tensile strength and initial modulus of the co-PI fibers decreased. However, the mechanical properties were improved by increasing the draw ratio of the fibers. When the draw ratio was up to 2.5, the tensile strength and initial modulus of the co-PI fibers reached up to 0.64 and 10.02 GPa, respectively. The WAXD results showed that the order degree of amorphous matter increased with increased stretching. In addition, the SAXS results displayed that valuably drawing the fibers could eliminate the voids inside and lead to better mechanical property. WAXD revealed that the orientation of the amorphous polymer influenced the mechanical properties of the fibers.

In situ iodoalkane-reduction of graphene oxide in a polymer matrix: an easy and effective approach for the fabrication of conductive composites

In situ chemical reduction (ISCR) of graphene oxide (GO) dispersed in a polymer matrix has been regarded as an effective path to fabricate electrically conductive graphene/polymer composites due to the combination of perfect dispersion of GO in a polymer matrix and high electrical conductivity of graphene. However, there are only very limited number of reducing agents that can be applied to the ISCR process for the fabrication of graphene/polymer composites. Herein, we report a highly efficient reducing agent, 1,2-diiodoethane, which can be used in the preparation of graphene (IGO)/polyimide (PI) composites via the ISCR process. The results showed that the electrical conductivity of IGO/PI composites with 2.5 wt% of IGO was 2.22 S m−1, nearly seven orders of magnitudes higher than that of GO/PI without the addition of 1,2-diiodoethane. Moreover, the tensile strength and modulus of IGO/PI composites were increased by about 43% and 52% as compared with that of the pure PI, respectively. Furthermore, 1,2-diiodoethane and its decomposition products would not remain in the composites. The ISCR-based methodology can be extended to many other polymer composites and thus paves the way for easy and effective fabrication of conductive polymer composites.

Atomic oxygen resistance of polyimide fibers with phosphorus-containing side chains

A series of polyimide (PI) fibers were spun and exposed to atomic oxygen (AO). The PI fibers contained phosphorus in the macromolecular side chain, which was derived from DATPPO diamine. An AO exposure experiment was conducted in a ground-based AO-effect simulation facility. The changes in the surface morphologies and compositions of PI fibers before and after AO erosion were investigated by field emission scanning electron microscopy and X-ray photoelectron spectrometry (XPS). After AO exposure, the phosphorus-containing PI fibers exhibited a denser surface morphology compared with that of the pure PI fibers. XPS results indicated that phosphate species formed on the surfaces of phosphorus-containing PI fibers after AO exposure protected against further erosion. After AO erosion, the mass loss of phosphorus-containing PI fibers was lower than that of pure PI fibers. Moreover, at an AO fluence of 5.0 × 1020 atoms per cm2, the retention of tensile strength and Youngs modulus of phosphorus-containing PI fibers were 64.87% and 66.04%, respectively, which were higher than those of pure PI fibers. The results of the current study are crucial for understanding the relationship between polymer structure and AO-resistant properties of PI fibers to develop new materials with low-earth orbit applications.

Preparation and Properties of Imidazole-containing Polyimide/Silica Hybrid Films

Imidazole-containing polyimide/silica(PI/SiO2) hybrid films were prepared from 3,3′,4,4′-biphenyltetra-carboxylic dianhydride(BPDA) and 2,2′-di(p-aminophenyl)-5,5′-bibenzimidazole in N,N-dimethylacetamide(DMAc) by sol-gel method and thermal imidization. The hybrid film with high silica mass fraction up to 40% was transparent. Scanning electron microscope(SEM) and transmission electron microscope(TEM) results of the film indicate a homogeneous dispersion of silica nanoparticles in the polyimide matrix. One hybrid film PI/SiO2 with 15% SiO2 exhibits better mechanical properties with a tensile strength of 222 MPa, an elongation at break of 12%, and a tensile modulus of 5.66 GPa. The reinforced mechanism on mechanical properties was also studied.

Surface modification of high-performance polyimide fibres by using a silane coupling agent

ABSTRACT The silane coupling agent 3-aminopropyltriethoxysilane (KH-550) was used to modify the surface of two kinds of high-performance polyimide (PI) fibres (i.e., PI-1 and PI-2). The surface chemical composition, morphologies and roughness of modified PI fibres were characterised by XPS, SEM and AFM. Results showed that the elemental ratio between O and C, the surface oxygen concentration and the surface roughness increased with KH-550 concentration. However, the interfacial shear strength (IFSS) and interlaminar shear strength (ILSS) values of PI fibre/epoxy resin composites increased and then decreased with KH-550 concentration. When KH-550 concentration was increased to 4 wt%, the IFSS and ILSS values reached their maximum point. At this point, the IFSS values were found increase by 17.3% and 8.3% for PI-1 and PI-2, respectively, compared with their pristine state. Meanwhile, the ILSS values of PI-1- and PI-2-reinforced composites were found increase by 22.4% and 24.1%, respectively. Graphical Abstract GRAPHICAL ABSTRACT