10 Strength and fracture of polymers
10.1 Theoretic strength
The dependence of quasi elastic force F
between particles on distance (Orowan)
Orowan's model – energy for particle move is in equilibrium with energy for new surface creation (2γ0)
2a0
m = 20
+ Hook's law → ideal strength σi σ0 – maximal stress
E – modulus of elasticity
E 0
i = m = γ0 – surface energy
x0 x0 – balanced particle distance
typically max. force when distance increases by 10 – 20 % → σi ≈ 0.1 E
i – metals 101 GPa, ceramic up to 102 GPa
real strength metals and ceramic: 102 – 103 MPa
highly oriented polymers
orientation direction (covalent bonds) → E = 101 to 102 GPa
orientation cross-direction (van der Vaals forces) → E = 3 to 8 GPa
real moduli E close to theoretic ones, real strength much lower (1 to 2decadic orders)
isotropic polymer glass (random orientation) → E depends on intermolecular attraction forces
(CED)
10.2 Technical strength
the effect of loading rate, temperature, humidity, corrosion environment ..
usually short term test with deformation (tensile, bending) increasing slowly (mm/min) at room temp.
stress – force related to original cross-section area
Tensile curves
1 – high modulus filament (oriented)
2 – brittle plastics (cured reactive resins,
amorphous polymers)
3 – semi crystalline plastics (high crystallinity)
4 – semi crystalline plastics (medium or low
crystallinity)
5 – amorphous plastics at temp. close to Tg
6 – blends of amorphous plastics with elastomers
7 – non-crystallizing cured rubbers
8 – crystallizing cured rubbers
Fracture classification
brittle f. – no marks of plastic deformation
– fracture surface perpendicular to stress
ductile f. – large plastic deformation before fracture (cold drawing) necking
– complex mechanism (viscoelastic characteristics) – temperature, deformation rate
- decrease in cross-sectional area
- strain hardening (stiffening)
Ductile-brittle transition temperature Tb
linear plastics with flexible chain (PE, PTFE, ...) – usually much lower Tg
symmetrical structure, large substituents (PMMA, PS, ..) – close to Tg
highly crosslinked reactive resins – high Tb
Tb – increased with deformation rate, the presence of notch
– decreased at compression load
1 – slow deformation
2 – fast deformation
brittle fracture at tensile ductile fracture at tensile ductile fracture at compression
10.3 Plastic deformation during fracture
brittle fracture × ductile fracture
analogous deformation processes in the process of crack initiation and propagation
plastic deformation at wide temperature range from temperature below Tb
(ductile-brittle transition temperature) up to Tg or Tm
strong weak
a – crazing, crazes ([Link] – microscopic cracks
- perpendicular to tensile stress
- iniciation in highly stressed regions (scratches, flaws, molecular non-homogeneities), suppressed by
compression and hydrostatic stress
- total volume increases
b – shear band – narrow zone of intense shearing strain, usually of plastic nature, developing during severe
deformation of ductile materials
- under angle of 50-60°(X-shaped) to tensile or compression stress
- formed under all types of loading
- no change in volume
Conditions for craze and shear band formation
shear band critical stress
c = 0 – m 0 material parameter (depending on T and deformation rate)
Poisson ratio
m mean normal stress [(x + y + z)/3]
crazes │x – y│ ≥ A + B/I1 I1 first stress invariant (x + y + z)
A, B material parameters (dep. on T and environment)
Polymer structure effect:
- higher free volume – chain segment rearranging is more easy
- linear amorphous plastics with brittle fracture at room temp. (PS, PMMA) better conditions for crazing
- plastics with less flexible chains (PC, PPO, cellulose deriv., …) with secondary transitions - conditions for
shear bands or blocking of craze growth conditions for ductile fracture during long term loading and
macroscopic deformation with strengthening during short term loading
The role of crazes for polymer toughening
Crazes can make crack formation more easy by their sequential opening and connecting;
can slow down crack formation (new crazes absorb elastic energy) – toughening
- elastomer particles (size, volume fraction)
Shear bands – preferably at temp. below Tg,
when two (almost perpendicular) lines cross cavity,
can initiate quasi brittle cracks in semi crystalline plastics
(PP, HDPE)
10.4 Fracture mechanics
([Link]
polymers /E = 1/30 to 1/60 (theory around 1/10)
reasons: defects stress concentrators
deformation in local defect vicinity can be 102 to 103 times higher than average
FM studies the effect of extrinsic stress on process
defects, weak points, stress concentration crack formation crack propagation fracture
Energetic criterion (Griffith)
(a body with the crack of length l = 2c)
potential energy wp = w0 – we + 20, w0 elastic energy of the body
(without crack)
we lost part of elastic energy
0 surface energy
elastic material (Hook) we = 0,52 l2 /E, parameter close to 1;
energy balance
critical length lc (for dwp/dl = 0)
2 E 0
lc =
2
2 E 0
Griffith criterion usually written as c =
l
where c is critical stress for propagation of crack with the length of l
the energy we is used for the new surface creation (20) and also for another processes
2 E ef
0 ef c =
l
ef = 0 + wk + wve + wd + wdis wk – energy for craze formation (plastic deformation)
wve – energy for visco elastic deformation
wd – energy for cavities formation (in crazes)
wdis – dissipated energy (heat)
Linear (elastic) fracture mechanics (= elasticity + isotropic)
(there is also elastic-plastic fracture mechanics)
Stress in the front of crack tip is considerably non-homogenous and high stress intensity factor K
polar coordinates (r, ) if c r :
K 3
x cos 1 sin sin
(2r )1/ 2 2 2 2
K 3
y cos 1 sin sin
(2r )1/ 2
2 2 2
K 3
xy sin cos cos
(2r )1/ 2 2 2 2
fracture when K Kc (critical value); ( no fracture if K Kc )
Fracture modes
Tensile loading Kc KIc – (for plastic) more accurate than nominal stress
The assessment of crack propagation rate
time dependence
dc
= A KIb KI – the extent of stress intensity factor
dt A, b, n – material parameters
cyclic loading
dc
= A KIn N – number of cycles
dN
10.5 Molecular theory
Simultaneous action of heat fluctuations and extrinsic stress → destruction processes on molecular level
(free radicals, sub microscopic defects)
The dependence of filament strength on time at different
temperatures
u = 0 exp [(U0 – ) / k T] u – time to break
0 – atomic (temperature) oscillation time (10–12 to 10–12 s)
U0 – activation energy of bond breaking (without stress)
– polymer structure related parameter (sensitivity to stress)
k – Boltzmann constant
Empiric relations for lifetime u forecast
u = B -b B, b – material parameter
for stress p (critical stress), unlimited lifetime at p
temperature dependence of b :
b = log (d / ) where = /RT
d material parameter
time–temperature superposition in coordinates u – log T0/T
