Carrier spinning method
Wet spinning
Wet spinning of PTFE usually in viscose or polyvinyl alcohol (PVA) as the
carrier, mix with PTFE powder or emulsion dispersion, and add a small amount of
boric acid, make spinning solution , perform wet spinning, spinning head placed
in sodium sulfate and ammonium sulfate coagulation bath, dope from the nozzle
in the coagulation bath solidified into fiber, fiber after leaching roller soft
water leaching, again after oil roller and drying roller respectively, in 380 ~
400 ℃ high temperature sintering,
remove PVA carrier carbide, stretch to make PTFE fiber under 350 ℃. This method of spinning spend process cumbersome, high
processing cost and energy consumption and time-consuming. Guo Yu-hai and
others invented a highly efficient rapid method of preparation of PTFE fiber.
This method will first evenly mix low relative molecular mass of volatile
organic solvent with water, in under the condition of stir with PVA, continue
to stir until completely dissolved, mixture of PVA water solution. Then the PVA
water solution and persulfate, PTFE dispersion mixing uniformity, dope. Then
borate or boric acid dissolved in water, with alkaline pH adjustment as
alkaline, mixture coagulation bath. Finally adopt the wet spinning equipment of
conventional , the spinning fluid conveying to the nozzle, through metering
pump metering, direct spinning in the coagulation bath, then drying, sintering
and stretch, the PTFE fiber is made.
Dry
spinning
This method is PTFE gel realized by dry
spinning. PTFE is first concentrated dispersion and PVA blended, add gel
regulator boric acid or Borate salts and alkalis adjust the pH to alkaline,
whisking to a sudden increase in the viscosity and gel formation, are spinning
solution. And then dry them using conventional spinning equipment, gas pressure
or screw spinning liquid to the spinning head, measured in metering pumps, dry
spinning, and then dried, prepared mixture of PTFE and PVA fiber. Finally using
conventional sintering and stretching equipment, will be mixed sintering to
remove PVA fiber, finally after stretching process stretching, PTFE fiber
preparation.
Carrier spinning method is the most mature
method of preparing PTFE fiber, and has been one of the few companies to
realize industrialization. Among them, Japan toray company USES mass fraction
60%, the average particle size was 0. 3 microns of PTFE, and the mass fraction
of 2% sodium alginic acid aqueous solution of the emulsoid mixed spinning, the
fiber by coagulation, bath again after washing, drying, and under 380 ℃ hot stretching, removal of alginic acid sodium, gain PTFE
fiber, its monofilament linear density of 0. 67 dtex and fracture strength of
l. 25 cN/dtex, elongation at break of up to 59%, the method of spinning dope
spinnability better than with viscose as carrier of PTFE dope spinnability.
Showa industries, the use of the 114 mass fraction of 60% PT – 100 FE dispersed
emulsion and cellulose of mass fraction of 8.9% viscose spinning solution
spinning, after solidification of the nascent fibers by water, squeeze liquid,
with 0. 05 mol/L Na0H processing, and the fiber heat treatment under 280 ℃ and hot stretching under 320 ℃, the final heat
treatment 72 h under 320 ℃, the fiber’s breaking
strength for 1. 16 cN/dtex elongation at break was 16.1%. In addition,
Beijing demonstration plant will be 60% mass fraction of PTFE emulsion and 10%
mass fraction of PVA solution in proportion of 1:1.5 the spinning solution
spinning, after solidification of the fiber by acetal, washing, drying,
sintering and stretch to PTFE fiber system.
Cutting film splitting method
Cutting film crack method in the early 1970 s by the Austrian Lenzing company
development and industrialization, in the preparation of PTFE fiber, need to
make PTFE powder sinter cylindrical PTFE parison, cutting it up with a certain
thickness of the film, and then by serrated tool divided into silk, above the
melting point (327 ℃) sintering, then through
stretching and end up with PTFE fiber heat treatment. This method can get the
fiber with microporous structure, and high strength. Multifilament can be used
as the sealing filler material, short fibers, can be used in the needle felt.
In addition, the PTFE film or sheet can also be
cut into tiny width, and then direct tensile narrow fabric made of high
strength PTFE fibers. But it is difficult to maintain uniform obtained by
cutting along the longitudinal direction through the narrow width of the
fabric, and narrow fabric tends to end part of fibril, so much stretch in
narrow fabric PTFE fibers easily broken or through partial cutting in the
longitudinal direction of the film are filament PTFE membrane orientation.
Along the membranes of the longitudinal direction and in the transverse
direction of the film with a z shape or linear-convex shape embossed and cut,
the resulting filament including individual fibrils partially broken rule the
network structure. PTFE fibers produced this way the individual fibrils with
small average size and uniform size.
Japan Asahi of into Corporation through cutting
film crack legal into has high stretch strength, and resistance chemical
performance excellent of PTFE yarn. will containing hole rate 48% of PTFE film
tear into 222 dtex of fiber, again on its added twist to 750 twist/m, in 440 ℃ and 1 000 m/min Xia stretch, get of fiber line density for 55
dtex, and containing hole rate 1%, modulus up to 294 cN/dtex.
Paste extrusion spinning method
Paste extrusion spinning usually PTFE powder 16% ~ 25% with mass fraction of
volatile lubricants mixes, tune into a paste, made of shaped prefabricated
embryos, and under certain pressure through a spinneret with a strip of die
extrusion spinning, and then by drying, sintering, high stretch under high
temperature, non-uniform white yarn. In addition, can also squeeze film
extrusion equipment or thin strips, then by a rolling process to remove
additives, and longitudinal cutting, drawing and fluffy after processing, are
PTFE fibers were made by paste extrusion of thin wall, small diameter and
permeability of PTFE hollow fiber. PTFE powder in conditions below its melting
point made of PTFE hollow fiber, and then fired 10 min at 350 ℃, 250 ℃ under 400%, was
0.76 mm inner diameter and wall thickness of 0.10 mm, diameter of less than
0.15 mm hollow fibers.
In 1997, M. Shimizu proposes a method for
preparing high strength and PTFE fibers by paste extrusion. Added to the PTFE
powder mass fraction 20% of lubricants, embryo, extrusion, gained single wire,
heated treatment and then 350 ℃ 1.5h, and 387 ℃ to 50 mm/min of speed stretching 10 times, received strength as
much as 1.56 ~ 2.82 GPa PTFE fibers.
The PTFE powder was mixed with a lubricant
(isoparaffin oil Isopar-E) to form a paste, standing at 0 ℃ 180 h at 40 ℃ cure 30 h, make
the mix full wetting and swelling, then press embryo and extrusion , handle 2 h
under 340 ℃, and then to 0. 5 c/min
speed down to room temperature, finally stretching to get in a 370 c PTFE
fiber, 3.5 ~ 4.0 cN/dtex the fracture strength, elongation at break is 22%.
Melt spinning method
Melt spinning is PTFE content to 4% ~5% of
perfluorinated ethylene copolymer of perfluoro-n-propyl ether mixed spinning
melt, after spinning by screw extrusion machines pump quantitative pressure
injection hole, making it into a fine stream into the air, and cooling in the
spinning channel into the wire. PTFE fibers high strength of this method, but
PTFE supermolecular structure changes after melting, leading to its ductility
disappeared and molecular chain orientation stretch is blocked, together with
PTFE high viscosity and apparent flexibility, PTFE melt fiber prepared by screw
extruder for direct comparison difficult, difficult to achieve
industrialization. Plunger extrusion method can overcome this difficulty. The
plunger in the extrusion process, due to extremely low surface energy of PTFE
and wall-slip phenomenon, reduce unnecessary shear in the flow process, so they
can be on PTFE melt spinning. Li Min and other person in Donghua university,
are prepared by the PTFE fibre with high molecular weight. Tervoort by high
relative molecular mass such as PTFE and PTFE mixed with low relative molecular
mass, melt processing, preparing PTFE filament. Properties of PTFE fibers
produced this way worse than that of pure PTFE fiber with high molecular
weight.