Properties,Morphology and Structure of BPDA/PPD/TFMB Polyimide Fibers

The mechanical properties of fibers were notably improved by incorporating 2,2＇-bis（trifluoromethyl）benzidine（TFMB） into 3,3＇,4,4＇-biphenyltetracarboxylic dianhydride（s-BPDA） and p-phenylenediamine（PPD） backbone.The best strength and modulus of BPDA/PPD/TFMB polyimide（PI） fiber（diamine molar ratio of PPD/TFMB= 90/10） were 1.60 and 90 GPa,respectively,which was over two times that of BPDA/PPD PI fiber.SEM image showed that the cross-section of fibers at each stage was round and voids free.Besides,the ＂skin-core＂ and microfibrillar structure were not observed.The thermal properties of PI fibers were also investigated.The results showed that the fibers owned excellent thermal stability,moreover,the structural homogeneity of fibers were significantly improved by heat-drawn stage.The T g values were found to be around 300 °C by dynamic mechanical analysis（DMA）.Wide angle X-ray diffraction（WAXD） and small angle X-ray scattering（SAXS） experiments indicated that the order degree of longitudinal and lateral stacks,the molecular orientation and the structural homogeneity of fibers were improved in the preparation process of fibers.

Characterization of Oxygen Plasma Modified Polyimide Fibers Interfacial Adhesion Performance by Single Fiber Fragmentation Test

The application of polyimide( PI) fibers in the field of composite materials has been limited because of their smooth surface and chemical inertness. In order to overcome these problems,oxygen plasma was used to modify the surface of fibers. The single fiber fragmentation test( SFFT) was used to characterize the interfacial adhesion performance of PI fiber as a simple and accurate analysis method. It was found that the interfacial shear strength between the fiber and resin after oxygen plasma modification was increased by 54% compared to the untreated fiber. Meanwhile, the surface micromorphology,chemical composition, wettability of fibers and the interface morphology at the fiber fracture were analyzed by field emission scanning electron microscope( FESEM), X-ray photoelectron spectroscopy( XPS),contact angle measurement and polarizing microscope,respectively. All of these results demonstrated that the single fiber fragmentation test for analyzing the interfacial adhesion of PI fibers was effective.

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.

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.

Preparation of High-performance Polyimide Fibers with Wholly Rigid Structures Containing Benzobisoxazole Moieties

In this work, a fully rigid coplanar symmetric heterocyclic unit was introduced into the rigid polyimide macromolecular backbone structure to prepare high-performance polyimide fibers. The novel co-polyimide(co-PI) fibers based on 3,3',4,4'-biphenyltetracarboxylic anhydride(BPDA), p-phenylenediamine(PDA) and 2,6-(4,4'-diaminodiphenyl) benzo[1,2-d:5,4-d'] bisoxazole(PBOA) were fabricated via a twostep wet-spinning method. The effects of benzobisoxazole moiety on spinnability, aggregation structure, and mechanical properties of fibers were systematically discussed. The detailed structural analysis revealed that the well-defined aggregation structures of co-PI fibers were obtained from initial amorphous structure when post hot-drawing temperature was higher than 460 ℃ under proper drawing ratio, and the incorporation PBOA into BPDA-PDA structures produced more compact structural co-PI fiber than homo BPDA-PDA fiber. The BPDA-PDA/PBOA co-PI fibers exhibited optimum tensile strength and modulus of 2.65 and 103 GPa, which increased by 182% and 84% compared to the homo BPDA-PDA fiber, respectively.

Structural Performance and Characterization of Polyimide Doped Activated Carbon Fibers for Mercury Adsorption

Structure characteristics about activated carbon fibers (ACF) and polyimide (P84) doped ACF modified by HNO3 solution were studied to apply in mercury removal in coal-fired flue gases. The P84, which was always used in the non-woven fabric for bag filter, was intermingled with polyacrylonitrile-based ACF (PAN-ACF) in the weight ratio of 1∶1 in order to make the doped ACF with P84 (doped-ACF-P84). Then the doped-ACF-P84 fibers were modified by HNO3 solution. The structure and morphology of doped-ACF-P84 were characterized and compared with those of ACF and doped-ACF-P84 modified by HNO3solution. The results show that the modified doped-ACF-P84 fibers have almost the same pore structure and specific surface area comparing with the original one. However, contrasted with the original PAN-ACF, the doped-ACF-P84 fibers modified by HNO3 solution have more oxygen-containing groups used for mercury removal. In particular, they have more lactone and carboxyl groups.

Dry-spun Polyimide Fibers with Excellent Thermal Stability,Intrinsic Flame Retardancy and Ultralow Smoke Release

Polymer fiber with an ultrahigh thermal stability,superior flame retardancy and low smoke release during combustion is urgently needed and a crucial challenge for developing advanced fireproof textiles.In this study,a series of high-performance polyimide fibers are synthesized by copolymerizing 4,4'-diaminodiphenylmethane(MDA)into the pyromellitic dianhydride-p-phenylenediamine(PMDA-PDA)backbone for synergistically solving the technical challenge of poor fiber processing ability of these polyimides with a high inherent molecular rigidity.The glass transition temperature(Tg)of resultant fibers with the PDA molar ratio over 50 mol%reaches above 420℃ and their 10 wt%weight loss temperature(T10%)is within 543-633℃.For the typical fiber containing 80 mol%of PDA,the limiting oxygen index(LOI)reaches 39%and exhibits a rapid self-extinguishing performance after deviating from the flame.Meanwhile,this fiber exhibits the minimum heat release rate of 14.1 kW/m^(2) in a long ignition time of 813 s during combustion,revealing its better flame retardancy than the well-known Nomex fiber with a heat release rate of 140.6 kW/m^(2) during the 120 s ignition.Meanwhile,the total smoke production of this polyimide fiber is only 1/9 of the Nomex fiber.Accordingly,the excellent flame retardancy of polyimide fibers indicating them more attractive as the fireproof materials in the field of emergency protection.

A 3D graphene/polyimide fiber framework with improved thermal conductivity and mechanical performance

The integration of electronic components and the popularity of flexible devices have come up with higher expectations for the heat dissipation capability and comprehensive mechanical performance of thermal management materials.In this work,after the modification of polyimide(PI)fibers through oxidation and amination,the obtained PDA@OPI fibers(polydopamine(PDA)-modified pre-oxidized PI fibers)with abundant amino groups were mixed into graphene oxide(GO)to form uniform GO-PDA@OPI composites.Followed by evaporation,carbonization,graphitization and mechanical compaction,the G-gPDA@OPI films with a stable three-dimensional(3D)long-range interconnected covalent structure were built.In particular,due to the rich covalent bonds between GO layers and PDI@OPI fibers,the enhanced synergistic graphitization promotes an ordered graphitized structure with less interlayer distance between adjacent graphene sheets in composite film.As a result,the optimized G-gPDA@OPI film displays an improved tensile strength of 78.5 MPa,tensile strain of 19.4%and thermal conductivity of 1028 W/(m·K).Simultaneously,it also shows superior flexibility and high resilience.This work provides an easily-controlled and relatively low-cost route for fabricating multifunctional graphene heat dissipation films.

Scalable Reaction-spinning of Rigid-rod Upilex-S^(■) Type Polyimide Fiber with an Ultrahigh T_(g)

In the family of polyimide(PI)materials,Upilex-S^(■) film has been a shining star through the research PI materials due to its appealing merits.Unfortunately,the wholly rigid-rod backbone and easily formed skin-core micromorphology and microvoids of Upilex-S~type PI lead to the high difficulty in melt-and wet-spinning fabrication.Herein,we propose a facile and scalable method,reaction-spinning,to fabricate the Upilex-S^(■) type PI fiber,in which the rapid solidification of spinning dope and partial imidization take place simultaneously.Thus,the stability and mechanical strength of as-spun fibers can be improved,and the microvoids in fibers can be greatly reduced in relative to the wet-spun fibers.The resultant Upilex-S^(■) type PI fiber shows higher tensile strength and modulus than most commercial thermal-oxidative polymeric fibers with an ultrahigh glass transition temperature T_(g) of 478℃.Moreover,the WAXS and SAXS results indicate that orthorhombic crystals are formed for Upilex-S^(■) type PI fiber in the post hot-drawing process.Increasing the hot-drawing temperature results in a continuous crystallization and high orientation of PI chains in amorphous phase and perfects the existing lamellar structure,which make a great contribution to the improved mechanical property.