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POLYETHYLENE GEL-

SPINNING

DINESH
AHEER
DESIGNING OF HIGH-
PERFORMANCE POLYMERS

n Small cross-sectional area per


chain
n

n Extended chain conformation


n

n Strong chemical bond in main


chain
BONDS
n Anisotrophy-diff. in binding energy
between atoms
n Covalent bond 500 times more
stronger than wanderwalls
n High mechanical properties- all the
molecules must be oriented in
direction of fibre axis
Strength-cross sectional
area
Polymer Cross sectional Theoretical Theoretical
area per single strength Modulus (gf/d)
chain(nm2) (gf/d)

PE 0.193 372 2775


PP 0.348 218 423
PA6 0.192 316 1406
PVA 0.228 236 2251
PET 0.217 232 1500
PAN 0.304 196 833
Modulus-contraction
Why Polyethylene first one
?
n Tenacity & modulus among flexible
polymers
n

n High crystallinity
n Lack of high intermolecular weight
polymerisation
D.P
n Defects
n Support drawing
n Crystallinity
MELT SPG OF UHMWPE
n High shear & elongational
viscosities
GEL SPINNING
n Dilution with solvent
n Morphological control through
crystallisation process
St rengt h –weakest
point ,m odulus-average
st ruct .
TYPES OF GEL
n Low stable-melt before clear
solution temp.-junctions are
micelles nature
n

n Most stable-melt above solution


clearing temp.-shish kebab-
<0.5%-stirring
n

n Melt at solution clearing temp-


GEL SPG METHOD
Factors affecting
properties
n Spinning temperature
n Polymer concentration
n Winding speed
n Additives
n Drawing conditions
TEMP-SHEAR VISCOSITY
F4

F7

F12

F18

F24

F60
continue
n Constant temp above 80oc
,increase in conc. viscosity
increase continuously
n <110oc-partial melting-low
interpenetrating-low viscosity
n >110oc-significant melting-high
interpenetrating-high viscosity
n >140oc-solvation-degradation-
disentanglement-low viscosity
F 12-150
BIREFRINGENC

F24-150

F54-150
E

DRAW RATIO
MAX D.R.-CONC.

130 o C
ACHIEVEABLE DRAW

150o C

170oC
RATIO

CONCENTRATION IN Kg/m3
TENSILE STRENGTH IN GPa

F 12-150

F24-150

F54-150

DRAW RATIO
WINDING SPEED-TENSILE
STRENGTH
Continue
n Spinning speed of 100 met/min

n Only stretching effect-enhanced


with D.R
n No adsorption-high SPG speed
ALUMINIUM STEARATE
continue
n Act as a lubricant
n Increase viscosity-reduce chain
slippage
n Metal ions more attraction towards
die wall
n High concentration reduce
interpenetrating power-low
strength
SPINNING TEMP
ORIENTATION-TEMP
continue

n For fibresstretched in the spin- line


the degree of c-axis
orientation decreases with
increasing spinning
temperature.
n Relaxation time
continue
n Increase in chain flexibility which
reduces the tendency of the
polymer molecules to being
adsorbed

n Allows a more rapid adjustment


to the elongationalflow field
MAX D.R-SPG
ORIENTATION
Continue
n Spinning speed 100 met/min,with
diff. winding speed & temp
n Shish kebab formation,restrict to
orient lamellar & low orientation
in shish kebab,stiff,plastically
deform on breaking of shish
kebab
n Higher no of defects
SHISH-KEBAB
TYPES OF SHISH KEBAB
SHISH KEBAB FORMATION
n HIGH MOLECULAR WEIGHT
n HIGH DEFORMATION RATES
n LOW TEMPERATURE
W.S- STRENGTH
W.S.-MODULUS
GRIFFITH EQUATION
σf=(2EGc/y2a)1/2 ………………..1 y=b(D/a)1/2

σf-1 =K(D-Do)1/2 +σo-1 ………….2 K=b/(2GcE)1/2

σf-1 =KD1/2 +σo-1 …………………3

σf-1 =[b/(2GcE)1/2 ]D1/2 +σo-1 ……………..4 T=nD2

σf-1 =b’(1/Gc)1/2 (T1/4 /E1/2 )+σo-1 ………………….5


CONTINUE
n Fracture through propagation of
cracks
n No. of cracks increases with
diameter
n Low cooling speed due to thicker
filament gives cracks on the
surface
n 120met/min –lower G –only reason
MORPHOLOGY

10 MET/MIN 60MET/MIN
MORPHOLOGY

10 MET/MIN 60MET/MI
N
CONTINUE
n Low speed –thicker skin-defect-
poor drawability due to stress
concentration in skin region
n Solvent rich region in centre is also
a defect
n Inhomogeneous shish kebab
struct. –poor draw ability
SHISH-KEBAB-FIBRILLAR
Stress-strain
Fb = n fb ………………..1

σb=Fb/[Π(D/2)2 ] …………..2

D ∞ 1/ϵ½ ………………….3

σb∞ Fb ϵ…………………..4
D.R-1.4 D.R-3.0
D.R-4.0 D.R-6.0
D.R-9.0
DRAWING TEMP-MODULUS
WET FIBRE-TEMP- DRY
70TO130 oc FIBRESECOND
ONE FOE TEMP
AT143oc
continue
n In both cases no effect of temp
below 130oc For D.R <30
n Linear one
n D.R>30-voids-depart from linearity
n Dry fibre 143oc –relaxation of
macro molecules
n Wet fibres –impossible-complete
dissolution
TENSILE STRENGTH-
TEMP
continue
n No effect of temp & solvent
n Depends upon molecular weight-
increase max D.R
DRAWING TEMP-MAX DRAW
RATIO
A-DRY B-WET
Continue
n Higher draw ratio at 120oc in wet-
plasticizing effect of solvent
n >120oc –lack of strength –
dissolution
n Strain rate –very slow-wet fibres
dry –does not follow this curve
Two stage drawing
n Temp-120oc-first stage drawing
n Temp-145oc-second stage drawing
n Low no of defects
n Better drawability
n High draw ratio
PRODUCERS
n DSM(Dutch State Mines)-dyneema
n AlliedSignal-U.S company-spectra
n Mitsui-Japanese company-Tekmilon
REFERENCES
 1.High-strength polyethylene fibres from solution and gel
spinning
 p.j. barham, a. kellerh. i-i. wills physics laboratory,
university of bristol, tyndall a venue, bristol, uk
 Journal of materials science 20 (1985) 2281-2302

2.Spinning and drawing properties of ultrahigh-molecular-weight


polyethylene fibers prepared at varying concentrations and
temperatures
 tao jian', wei-de shyu, we-tang lin,
 kan-nan chen, and jen-tautyeh'
 Polymer engineering and science, november2003, voi. 43, no.
77
3.Effects of spinning conditions on the mechanical properties of

ultrahigh- molecular-weight polyethylene fibers


 yasuo ohta,hiroki murase,takeji hashimoto
 Journal of polymer science: part b: polymer physics, vol. 43,
 4.Structral development of ultra high molecular weight
polyethylene fibres:transformation from kebab to shish
through hot drawing process of gel spun fibres
 yasuo ohta,hiroki murase,takeji hashimoto
 Journal of polymer science: part b: polymer physics, vol. 48,
1861–1872 (2010)
5.Formation and structure of high mechanical performance

 fibers. ii. flexible polymers


 takeshi kikutani
 Journal of applied polymer science, vol. 83, 559–571 (2002)
6.High-speed gel-spinning of ultra-high molecular weight

polyethylene
 a.j. pennings*, r.j. van der hooft, a.r. postema, w.
hoogsteen, and g. ten brinke
 Polymer bulletin 16, 167-174 (1986)
 7.Elastic flow instabilities and shish-kebab formation
during gel-spinning of ultra-high molecular weight
polyethylene
 jan smook, albertj. pennings
 Journal of materials science 19 (1984) 31-43
8.Jel-spun polyethylene fibrespart 1 influence of spinning

temperature and spinlinestretching on morphology


and properties
 w. hoogsteen, r. j. van der hooft, a. r. postema, g.
ten a. j. pennings brinke,
 Journal of materials science 23 (1988) 3459-3466
9.Ultra-high strength polyethylene filaments by solution

spinning/drawing. 3. influence of drawing temperature


 paul smith and piet j. kemstra
10.Composite materials : science & engineering by
Krishan kumar chawla
11.Textile spinning and weaving technology by
P.V.Vidyasagar
12.Fibrous materials by Krishan kumar chawla