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.

Comparison of the Structural Evolution ofβPolypropylene during the Sequential and Simultaneous Biaxial Stretching Process

In this work,the lamellar structural evolution and microvoids variations of βpolypropylene(β-PP)during the processing of two different stretching methods,sequential biaxial stretching and simultaneous biaxial stretching,were investigated in detail.It was found that different stretching methods led to significantly different lamellae deformation modes,and the microporous membranes obtained from the simultaneous biaxial stretching exhibited better mechanical properties.For the sequential biaxial stretching,abundant coarse fibers originated from the tight accumulation of the lamellae parallel to the longitudinal stretching direction,whereas the lamellae perpendicular to the stretching direction were easily deformed and separated.Those coarse fibers were difficult to be separated to form micropores during the subsequent transverse stretching process,resulting in a poor micropores distribution.However,for the simultaneous biaxial stretching,theβcrystal had the same deformation mode,that is,the lamellae distributed in different directions were all destroyed,forming abundant microvoids and little coarse fibers.

A Universal Equipment for Biaxial Stretching of Polymer Films

A biaxial stretching equipment was designed and constructed to enable fundamental studies of the relationship between film processing conditions and structures of oriented film products. With programmable drive motors and scissorlike mechanism, all stretching modes, including uniaxial stretching with constant and free width, simultaneous and sequential biaxial stretching, can be applied to a square-shaped sheet. Parameters related to film stretching manufacturing, such as temperature, draw ratio and stretching speed can be set independently to meet the requirement of different polymers. The force information during stretching is recorded by two miniature tension sensors in two directions independently, which can monitor the mechanical stimulus and stress response. Using this equipment, experiments are conducted to investigate the influence of stretching parameters on the structure of polypropylene films, which provides an effective method to tailor the processing conditions to obtain the films with desired properties.

Further study of rubber-like elasticity: elastic potentials matching biaxial data

By virtue of the rational interpolation procedure and logarithmic strain, a direct approach is proposed to obtain elastic potentials that exactly match uniaxial data and shear data for elastomers. This approach reduces the determination of multi axial elastic potentials to that of two one-dimensional potentials, thus bypassing usual cumbersome procedures of identifying a number of unknown parameters. Predictions of the suggested potential are derived for a general biaxial stretch test and compared with the classical data given by Rivlin and Saunders （Rivlin, R. S. and Saunders, D. W. Large elastic deformation of isotropic materials. VII： experiments on the deformation of rubber. Phill. Trans. Royal Soc. London A, 243, 251-288 （1951））. Good agreement is achieved with these extensive data.

Superior Ductile and High-barrier Poly(lactic acid)Films by Constructing Oriented Nanocrystals as Efficient Reinforcement of Chain Entanglement Network and Promising Barrier Wall

It is a daunting task to develop a promising strategy at an industrial scale for simultaneously ameliorating ductility and gas barrier performance of poly(lactic acid)(PLA)films in the application of green packaging.In this work,biaxial stretching and constrained annealing were employed to prepare transparent PLA films with superior ductility and barrier properties.The oriented nano-sized crystals induced by biaxial stretching were developed into regularαform during constrained annealing,which could not only serve as“nano-barrier wall”to impede the diffusion and dissolution of gas molecules,but also strengthen amorphous chain entanglement network as physical crosslink to enhance ductility.As a result,the as-prepared PLA films exhibited an outstanding comprehensive performance with a low oxygen and water vapor permeability coefficient of 0.733×10^(-14) cm^(3)·cm·cm^(-2)·s^(-1)·Pa^(-1) and 3.82×10^(-14) g·cm·cm^(-2)·s^(-1)·Pa^(-1),respectively,outstanding ductility with elongation at break of 66.0%,high yield strength of 84.2 MPa,and good transparency of more than 80%at 550 nm.The new insight in the relationship between microscopic amorphous and crystalline structure and macroscopic performance is conducive to alleviating the intrinsic defects of brittle and insufficient barrier PLA films without the aid of any heterogenous modifiers,facilitating their widespread commercialization in the booming sustainable packaging market.