Free-radical evolution and decay in cross-linked polytetrafluoroethylene irradiated by gamma-rays

Electron spin resonance techniques were employed to investigate the effects of the absorbed dose and post-irradiation conditions on the evolution and decay of free-radicals in cross-linked polytetrafluoroethylene(XPTFE),induced byγ-ray radiation.Chain-end free-radicals,chain alkyl free-radicals,and tertiary alkyl free-radicals were detected when XPTFE was irradiated under Ar atmosphere.The corresponding peroxy free-radicals were formed upon exposure of irradiated XPTFE to air;the freeradicals concentration first increased linearly with increasing absorbed dose and then gradually saturated.The free-radicals yield under air atmosphere was greater than that under Ar,and the peroxy free-radicals were preserved for a relatively long time when irradiated XPTFE was stored under air atmosphere.The chain alkyl free-radicals may be converted to chain end free-radicals byβ-scission,while chain end free-radicals are more sensitive to oxygen than chain alkyl free-radicals.When the annealing temperature was raised above the a-transition temperature of XPTFE,the decay of the free-radicals was greatly affected and accelerated by the motion of the molecules over the long range.

Antimicrobial Expanded Polytetrafluoroethylene Film Prepared by 3-ray Radiation Induced Grafting of Poly（acrylic acid）

The simultaneous γ-ray-radiation-induced grafting polymerization of acrylic acid on ex- panded polytetrafluoroethylene （ePTFE） film was investigated. It was found that the degree of grafting （DG） of poly（acrylic acid） （PAA） can be controlled by the monomer concentration, absorbed dose, and dose rate under an optimal inhibitor concentration of [Fe2＋]=18 mmol/L. SEM observation showed that the macroporous structure in ePTFE films would be covered gradually with the increase of the DG of PAA. The prepared ePTFE-g-PAA film was im- mersed in a neutral silver nitrate solution to fabricate an ePTFE-g-PAA/Ag hybrid film after the addition of NaBH4 as a reduction agent of Ag＋ to Ag atom. SEM, XRD, and XPS results proved that Ag nanoparticles with a size of several tens of nanometers to 100 nanometers were in situ immobilized on ePTFE film. The loading capacity of Ag nanoparticles could be tuned by the DG of PAA, and determined by thermal gravimetric analysis. The quart- titative antibacterial activity of the obtained ePTFE-g-PAA/Ag hybrid films was measured using counting plate method. It can kill all the Escherichia coli in the suspension in 1 h. Moreover, this excellent antibacterial activity can last at least for 4 h. This work provides a facile and practical way to make ePTFE meet the demanding antimicrobial requirement in more and more practical application areas.

Experimental Study of Vacuum Ultraviolet Radiation Effects and Its Synergistic Effects with Atomic Oxygen on a Spacecraft Material-Polytetrafluoroethylene

Polytetrafluoroethylene (Teflon), a widely used spacecraft material, isstudied to investigate the vacuum ultraviolet (VUV) effects and its synergistic effects with atomicoxygen (AO) in a ground-based simulation facility. The samples before and after the experiments arecompared in appearance, mass, optical properties and surface composition. The reactioncharacteristics of Teflon are summarized and the reaction mechanisms are analyzed. The followingconclusion can be drawn: at the action of VUV the Teflon sample surface is darkened for theaccumulation of carbon; and when the sample is exposed to AO, the carbon is oxidized and thedarkening surface is bleached; the synergistic effects of VUV and AO may cause the erosion of Teflonmore severe.

Proliferation of endothelial cell on polytetrafluoroethylene vascular graft materials carried VEGF gene plasmid

Objective： To investigate whether vascular endothelial growth factor （VEGF） gene plasmid carried by polytetrafluoroethylene （PTFE） vascular graft materials could transfect endothelial cells （ECs） and promote their growth. Methods： PTFE vascular graft materials carried with pCDI-hVEGF121, pCDI or pEGFP were incubated in Tris-buffer solution and the values of optical density of 260 nm at different time were plotted, then the DNA controlled release curve was made. ECs derived from human umbilical vein were seeded on the pCDI-hVEGF121/pCDI/pEGFP-PTFE materials or tissue culture plates, ECs numbers were counted and VEGF protein concentrations at different time were measured by enzyme-linked immunoadsorbent assay method. Green fluorescent protein （GFP） expression in ECs on pEGFP-PTFE materials was examined with fluorescence mi- croscopy. Results： The controlled release curve showed that the gene released from PTFE materials was rapid within 8 h, then slowed down and that the gene released continuously even after 72 h. At 24, 72 and 120 h, ECs number and proliferation rate of pCDI-hVEGFI21-PTFE materials were higher than those ofpCDI or pEGFP-PTFE materials （P〈0.05）. VEGF protein concentration of pCDI-hVEGF121-PTFE materials was higher than that of pC DI or pEGFP-PTFE materials at 6, 24, 72 and 120 h （P〈0.01）. GFP expression in ECs on the pEGFP-PTFE materials could be detected by fluorescence microscopy. Conclusion： PTFE graft can be used as a carrier of VEGF gene plasmid, VEGF gene carried by PTFE can transfect ECs and promote ECs growth.

Experimental study on mechanical properties of modified polytetrafluoroethylene

In order to study the mechanical properties of modified low-density polytetrafluoroethylene （PTFE）, universal testing machine is used for quasi-static tension and compression tests and Hopkinson bar test is for mechanical property under impact load. The mechanical properties of the samples with different length-diameter ratios under different impact loads are analyzed and dynamic response characteristics of the modified PTFE at different impact speeds are studied. The results show that, adding the copper powder in PTFE material can increase not only the tensile strength and elongation of the PTFE material sig- nificantly, but also the compressive strength; with the increase of strain rate, the yield strength of modified PTFE increases.

Affinity Adsorption of Bilirubin on Cibacron Blue F3GA-modified Microporous Polytetrafluoroethylene Capillary

Bilirubin removal from human plasma was obtained via an affinity microporous polytetrafluoroethylene（MPTFE） capillary. The new adsorbent comprised grafted glycidyl methacrylate（GMA） via radiation-induced polymerization as hydrophilic coating and reactive sites; ethylenediamine（EDA） as a spacer arm; Cibacron Blue F3GA（CB F3GA） as an affinity ligand; MPTFE capillary as the supporting matrix. The average density of CB F3GA attachment to MPTFE capillaries was found to be 136.5 μmol/g. The capacity of bilirubin adsorbed on affinity MPTFE capillaries is 76.1 mg bilirubin/g polymer（at 25℃）. This new adsorbent has advantages over both membrane and traditional micro-column, and this system is stable and easy to operate. The results of blood tests suggest the CB F3GA affinity capillary has good blood compatibility.

Composites on Base of the Ultradispersed Polytetrafluoroethylene and Graphite Oxide Intercalated Compounds

Composites based on ultradispersed polytetrafluoroethylene and intercalated graphite oxide compounds with dodecahydro-closo-dodecaborates and methods of their fabrication have been developed. The fabricated composites have been characterized using XRD analysis, and optical microscopy. These composites are distinguished with completeness of their combustion, since the combustion products comprise gaseous boron fluorine-containing compounds of boron, boron trifluoride (BF3), and boron oxyfluoride ((BOF)3). Besides, these composites are characterized with increased energy capacity as compared to purely oxygen-containing compounds, since the heat of formation of boron fluorine-containing compounds is higher than that of boron oxide. Introduction of ultradispersed polytetrafluoroethylene imparts composites with hydrophobicity, thus improving their functioning properties.

The Application of Polytetrafluoroethylene (PTFE) Fiber Grafted Acrylic Acid as a Cation Exchanger for Removing Cu^(12)

The polytetrafluoroethylene fiber grafted acrylic acid was used as a cation exchanger. The exchange capacity of the cation fiber is 3.06 mmol/g. The maximum Cu2+ adsorption capacity is 107.48 mg/g. It could be desorbed completely by 1mol/L HCl.

Influence of external load on friction coefficient of Fe-polytetrafluoroethylene

A coarse-grained molecular dynamics simulation model was developed in this study to investigate the friction process occurring between Fe and polytetrafluoroethylene(PTFE).We investigated the effect of an external load on the friction coefficient of Fe–PTFE using the molecular dynamics simulations and experimental methods.The simulation results show that the friction coefficient decreases with the external load increasing,which is in a good agreement with the experimental results.The high external load could result in a larger contact area between the Fe and PTFE layers,severer springback as a consequence of the deformed PTFE molecules,and faster motion of the PTFE molecules,thereby affecting the friction force and normal force during friction and consequently varying the friction coefficient.

Dependence of Mechanical Performance of Polytetrafluoroethylene Filament on Elongation of Dispersion Particles

The effect of elongation of particles in dispersion powders on mechanical performance of polytetrafluoroethylene(PTFE)flat filament is analyzed.Morphology and elongation of particles in four different PTFE dispersion powders are analyzed.Meanwhile,the correlation between elongation and diameter of dispersion particles is discussed.Strength-elongation curves of PTFE flat filaments made of four different dispersion powders are obtained from measurements of mechanical behaviors.Experimental results show that PTFE flat filament manufactured with dispersion particles having appropriate elongation(0.55-0.60)shows excellent mechanical performance.This work could be regarded as a reference for manufacturing high performance PTFE flat filaments.

Preparation and Selectivity of Molecularly Imprinted Polymer Coating on the Micro Pore Membrane of Polytetrafluoroethylene

In order to obtain mechanically stable membrane for practical application, the imprinted polymer was synthesized in the pores of polyfluoromembrane, the binding and transport ability of the membrane were studied.

Enhancing surface adhesion of polytetrafluoroethylene induced by two-step in-situ treatment with radiofrequency capacitively coupled Ar/Ar+CH_(4)+NH_(3) plasma

Although some progress in plasma modification of the polytetrafluoroethylene(PTFE) surface has been made recently,its adhesion strength still needs to be further improved.In this work,the surface of a PTFE sample was treated with a two-step in-situ method.Firstly,the PTFE surface was treated with capacitively coupled Ar plasma to improve its mechanical interlocking performance;then,Ar+NH_(3)+CH_(4) plasma was used to deposit an a-CNx:H cross-linking layer on the PTFE surface to improve the molecular bonding ability.After treatment,a high specific surface area of 2.20 and a low F/C ratio of 0.32 were achieved on the PTFE surface.Its surface free energy was increased significantly and its maximum adhesion strength reached77.1 N·10 mm^(-1),which is 56% higher than that of the single-step Ar plasma-treated sample and32% higher than that of the single-step Ar+CH_(4)+NH_(3) plasma-treated sample.

Effects of Stretching Parameters on Morphological and Mechanical Properties of Polytetrafluoroethylene Filaments

Comprehensive performances of polytetrafluoroethylene(PTFE) flat filaments used as suture materials in medical field can be affected significantly by morphological and mechanical characteristics.Due to low tensile strength and non-uniform morphology,PTFE flat filaments cannot be applied widely as medical sutures.In order to solve flaws above,PTFE flat filaments with constant linear density,550 dtex,are manufactured and dependences of morphology,frictional features and mechanical behaviors on stretching ratio and temperature are also analyzed.The results indicate that PTFE flat filaments with high tensile strength(1 922.0 cN) and excellent apparent performance can be manufactured at optimal stretching ratio and temperature,18.0 and350 ℃,respectively.

Composites on Base of the Ultradispersed Polytetrafluoroethylene and Chitosan Salts

Composites based on ultradispersed polytetrafluoroethylene and chitosan salts (nitrate, perchlorate and dodecahydro-closo-dodecaborate) and methods of their fabrication have been developed. For this purpose, the ultrasonic effect on the mixture of the aqueous gels of chitosan salts with dry UPTHE or UPTFE ethanol dispersion with propeller agitators. Introduction of ultradispersed polytetrafluoroethylene improving their functioning properties, namely high combustion efficiency and resistance to air moisture.

Effect of Expanded Polytetrafluoroethylene Combined with Autologous Ear Cartilage in Nasal Plastic Surgery

Objective:To explore the effect of combined application of expanded polytetrafluoroethylene and autologous ear cartilage in nasal plastic surgery.Methods:76 cases of nasal plastic surgery patients in our hospital from September 2019 to September 2020 were selected as the research objects and divided into experimental group(38 cases,treated with expanded polytetrafluoroethylene+autologous ear cartilage surgery)and control group(38 cases,treated with autologous ear cartilage surgery).The treatment effect,appearance score and complications were compared.Results:The total effective rate of the experimental group(97.37%,37/38)was higher than that of the control group(78.95%,30/38),P<0.05;After treatment,the appearance score of the experimental group was(8.97±0.37),which was significantly higher than that of the control group(P<0.05);The total incidence of complications in the experimental group(5.26%,2/38)was significantly lower than that in the control group(21.05%,8/38),P<0.05.Conclusion:In the process of nasal plastic surgery,the combined application of autologous ear cartilage surgery and expanded polytetrafluoroethylene has obvious effect,improves the appearance of patients,and has less postoperative complications,which is worthy of promotion.

Robust, breathable, and chemical-resistant polytetrafluoroethylene (PTFE) films achieved by novel in-situ fibrillation strategy for highperformance triboelectric nanogenerators

In the era of advanced wearable electronic devices,the triboelectric nanogenerators(TENGs)as energy harvesting and self-powered sensing units hold great promise.Selecting appropriate triboelectric material is the crucial factor to optimize the performance of TENG,while polytetrafluoroethylene(PTFE)stands out as a highly versatile option among the various materials.In this study,we present an ultrafine nanofibrous PTFE(NF-PTFE)films prepared by novel in-situ fibrillation strategy as the triboelectric material in TENG devices.The innovative processing methodology facilely addresses the dilemma between high porosity and fine pore size of traditional porous PTFE films,meanwhile achieves exceptional mechanical strength,hydrophobicity,air permeability,and chemical resistance of the films.With the integration of nanofibrous PTFE films into contact-separation mode TENG and droplet-based TENG,these devices realize the peak electrical output of 131 V/10.8μA and 54 V/14μA with great durability,which surpass the performance of TENGs using traditional expanded PTFE films.Furthermore,a smart glove capable of recognizing hand gestures is proposed,which demonstrates the versatility,flexibility,and practicality of this material for potential use in smart devices.This reported NF-PTFE film provides insights for the design of high-performance TENG device for advanced wearable electrical applications.

IMPROVEMENT OF CREEP RESISTANCE OF POLYTETRAFLUOROETHYLENE FILMS BY NANO-INCLUSIONS

To improve creep resistance of directional polytetrafluoroethylene （PTFE） films, epoxy grafted nano-SiO2 is mixed with PTFE powder before sintering and calender rolling. The aligned macromolecular chains （especially those in amorphous region） of the composite films can be bundled up by the nanoparticles to share the applied stress together. In addition, incorporation of silica nanoparticles increases crystallinity of PTFE and favors microfibrillation of PTFE in the course of large deformation. As result, PTFE films exhibit lower creep strain and creep rate, and higher tensile strength and hardness. The work is believed to open an avenue for manufacturing high performance fluoropolymers by nano-inclusions.

Research and clinical translation of trilayer stent-graft of expanded polytetrafluoroethylene for interventional treatment of aortic dissection

The aortic dissection(AD)is a life-threatening disease.The transcatheter endovascular aortic repair(EVAR)affords a minimally invasive technique to save the lives of these critical patients,and an appropriate stent-graft gets to be the key medical device during an EVAR procedure.Herein,we report a trilayer stent-graft and corresponding delivery system used for the treatment of the AD disease.The stent-graft is made of nitinol stents with an asymmetric Z-wave design and two expanded polytetrafluoroethylene(ePTFE)membranes.Each of the inner and outer surfaces of the stent-graft was covered by an ePTFE membrane,and the two membranes were then sintered together.The biological studies of the sintered ePTFE membranes indicated that the stent-graft had excellent cytocompatibility and hemocompatibility in vitro.Both the stent-graft and the delivery system exhibited satisfactory mechanical properties and operability.The safety and efficacy of this stent-graft and the corresponding delivery system were demonstrated in vivo.In nine canine experiments,the blood vessels of the animals implanted with the stent-grafts were of good patency,and there were no thrombus and obvious stenosis by angiography after implantation for 6months.Furthermore,all of the nine clinical cases experienced successful implantation using the stent-graft and its postrelease delivery system,and the 1-year follow-ups indicated the preliminary safety and efficacy of the trilayer stent-graft with an asymmetric Z-wave design for interventional treatment.

Biaxial stretching of polytetrafluoroethylene in industrial scale to fabricate medical ePTFE membrane with node-fibril microstructure

Expanded polytetrafluoroethylene(ePTFE)is promising in biomedical fields such as covered stents and plastic surgery owing to its excellent biocompatibility and mechanical properties.However,ePTFE material prepared by the traditional biaxial stretching process is with thicker middle and thinner sides due to the bowing effect,which poses a major problem in industrial-scale fabrication.To solve this problem,we design an olive-shaped winding roller to provide the middle part of the ePTFE tape with a greater longitudinal stretching amplitude than the two sides,so as to make up for the excessive longitudinal retraction tendency of the middle part when it is transversely stretched.The as-fabricated ePTFE membrane has,as designed,uniform thickness and node-fibril microstructure.In addition,we examine the effects of mass ratio of lubricant to PTFE powder,biaxial stretching ratio and sintering temperature on the performance of the resultant ePTFE membranes.Particularly,the relation between the internal microstructure of the ePTFE membrane and its mechanical properties is revealed.Besides stable mechanical properties,the sintered ePTFE membrane exhibits satisfactory biological properties.We make a series of biological assessments including in vitro hemolysis,coagulation,bacterial reverse mutation and in vivo thrombosis,intracutaneous reactivity test,pyrogen test and subchronic systemic toxicity test;all of the results meet the relevant international standards.The muscle implantation of the sintered ePTFE membrane into rabbits indicates acceptable inflammatory reactions of our sintered ePTFE membrane fabricated on industrial scale.Such a medical-grade raw material with the unique physical form and condensed-state microstructure is expected to afford an inert biomaterial potentially for stent-graft membrane.

Synergistic modification of the tribological properties of polytetrafluoroethylene with polyimide and boron nitride

Polytetrafluoroethylene(PTFE)blended with polyimide(PI)and filled with boron nitride(BN)is prepared through cold pressing and sintering for composites with remarkable wear resistance and reduced coefficient of friction(COF).The characterizations show that BN and PI at different levels,improve the hardness,dynamic thermo-mechanical modulus,thermal conductivity,and tribological properties of PTFE.PI boosts the dispersion and bonding of BN in PTFE.In dry sliding friction of a block-on-ring tribometer,the wear rate and COF of 10:10:80 BN/PI/PTFE reduce to almost 1/300 and 80%of those of pure PTFE,respectively,as the wear mechanism transition from being adhesive to partially abrasive.This occurs only when the additives BN and PI induce a synergistic effect,that is,at concentrations that are not higher than ca.10 wt%and 15 wt%,respectively.The obvious agglomeration at high percentages of added PI and severe conditions(400 N and 400 rpm)induce strong adhesive failure.The variations in the tensile properties,hardness,crystallization,and microstructure of the composites correspond to different effects.The multiple parameters of the plots of wear and friction are transformed into their contour curves.The mechanism transition maps aid in understanding the influence of various test conditions and composite compositions on the contact surfaces in the space-time framework of wear.