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You are on page 1of 4

**Pressure dependence of the shear
**

modulus of various polymers

E. J O N E S P A R R Y , D. T A B O R

Physics & Chemistry of Solids, Cavendish Laboratory, University of Cambridge

**A torsion pendulum has been used to measure the shear modulus of a range of
**

polymers as a function of applied hydrostatic pressure at 20~ The pressure medium was

usually nitrogen gas and the maximum pressure 20000 psi. The results show that the

shear modulus of each polymer is increased by the application of pressure, and the

magnitude of the increase is greatest for experiments carried out at temperatures just

above an atmospheric relaxation temperature. The increase in shear modulus takes a

finite time, of the order of minutes, to be achieved, the equilibrium value being reached in a

shorter time at higher temperature.

**I. Introduction increased with pressure. More recently Pugh et
**

The elastic properties of polymers are very dif- al [4] measured the pressure dependence of the

ferent from those of most other solids - their Young's modulus of polystyrene, polymethyl-

tensile and shear moduli are significantly lower methacrylate, high density polyethylene and

than, for example, metals or inorganic solids. nylon 66 up to an applied pressure of 7 kbar. The

Polymers consist of long chain molecules which modulus of polystyrene and polymethylmetha-

in amorphous polymers are randomly arranged. crylate increased slightly with pressure but the

Semi-crystalline polymers are made up partly of increase was far greater for the polyethylene

ordered regions and partly of amorphous and nylon samples.

regions. The elastic moduli of polymers cannot Most investigators have observed the pressure

arise primarily from the bending or stretching of dependence of modulus by measuring the

the main chain or indeed of crystallites; if it gradients of stress/strain curves obtained at

were, the modulus would be far larger than that different pressures, a different sample being used

observed. The elastic properties are mainly due to at each pressure. The results described in this

the uncoiling or sliding of chains over one paper, by contrast, were obtained by using one

another in response to an applied stress. The polymer sample at various applied pressures.

molecular mobility of the chains is strongly The shear modulus was determined by means

influenced by the available free volume. If the of a torsion pendulum which was constructed

polymer is compressed, the free volume will be within a high pressure chamber as previously

reduced; the intermolecular forces between described [5]. Specimens were subjected to

segments will increase and the elastic modulus strains of less than 1 ~ at 1 Hz and the pressure

would be expected to increase. was varied from atmospheric to 20 000 psi (1.4

Hydrostatic pressure has been shown to have a kbar). In general the pressure medium employed

significant effect on the mechanical properties was nitrogen gas. However, because nitrogen

of polymers. Ainbinder et al [1] showed that the plasticizes PTFE, the experiments on this poly-

Young's modulus of a number of polymers mer were carried out Jn helium gas. In the

increased when pressure was applied. Mears et experiments where the shear modulus was

al [2] found similar behaviour in polyethylene measured as a function of pressure the polymer

and polypropylene. Measurements of shear was left for at least an hour at any one particular

modulus as a function of pressure were carried pressure before any measurements were made.

out by Rabinowitz et al [3] on polymethyl- The low density polyethylene was WNC 71

methacrylate, polyethylene terephthalate and (ICI) of density 0.9028 while the high density

polyethylene.The shear moduli of these polymers polyethylene was Marlex 6001 of density 0.9600.

9 1974 Chapman and Hall Ltd. 289

E. J O N E S PARRY, D. TABOR

**The polypropylene was extrusion moulded, of
**

medium crystallinity and density 0.8738. The

natural rubber sample was cured for 20 min at

142~ and was formed from 100 parts by weight 2.sx 6~ -

of smoked sheet, 4 parts by weight of zinc oxide, 1o ',

4 parts by weight of tetramethyliuram disulphide, 1.8x10 7

and 1 part by weight of phenyl beta naphthyl-

amine. The rigid polyvinyl chloride consists of

150 parts by weight of Breon PVC, 0.75 parts by . UNPLASTICIZEDPVC

weight of calcium stearate and 1.5 parts by weight

NYLON6

of an organo tin stabilizer. The plasticized PVC , x,6~

is similar but 50 parts by weight of Breon is

replaced by the same weight of dialkyl phthalate. PRESSURE(psi xlO -3)

The polyvinyl fluoride was a sample prepared by

Figure 2 Pressure dependence of the shear moduli of

Du Pont while the PVDF was Kynar 200

various polymers at 20~C.

(Pennsalt). The P C T F E was quenched from the

melt and had a density of 2.082, while the

P T F E was a commercial medium crystallinity

sheet. The nylon 6 was injection moulded and of

density 1.112 at 20~ while the P M M A was ICI i x . i 0 1 ~ PET

"Perspex" and the Bakelite type E10P. The PET %

was amorphous ICI "Melinex" of density 1.337 PVF

g cm -3 at 23~ .while the PC was amorphous 5xi0 9

Makrolon.

4X107 : . naturalrubber

2. R e s u l t s

Figs. 1 to 3 show the room temperature pressure 2 X107-~ ,- . . . . . , , ,

dependence of the polymers which have been 2 4 6 8 10 12 14 10' t8

studied in this investigation. The shear moduli PRESSURE(psixlO-3}

are increased by the application of hydrostatic Figure 3 Pressure dependence of the shear moduli of

pressure, but by differing amounts. The largest various polymers at 20~C.

increase over the total pressure range of c.

20 000 psi is a fourfold increase for the plasticized

PVC while the shear modulus of polypropylene is also increased by a large amount. These two

polymers have glass transition temperatures of

18 and 2~ at 1Hz and the effect of pressure is

to shift the temperature of the transition upwards

PTFE~ towards that of the test (21~ the effective

~,l x t d ~ p onset of the glassy state causes the large increase

in the shear modulus. For all the other polymers

the modulus varies almost linearly with pressure.

Fig. 4 shows the time-dependence of the shear

modulus at 10 000 psi for plasticized PVC, low

~ pp

LDPE density PE, and P C T F E at 20~ and P C T F E at

45 ~C. The modulus reaches its maximum value

1xt, after a finite time which is of the order of 5 min.

6xlO8 P L A S ~ This time-dependence is presumably due to shear

stresses which are produced when a hydrostatic

pressure is applied to a non-homogeneous

1x l O " ~ ~ ~ - - - ~ medium. Thus the applied pressure does not

1 3 s 7 ~ fi 11 1~ 17 simply press the molecules closer together - it

PRESSURE{psixtO-3} slides them into new positions against a "vis-

Figure 1 Pressure dependence of the shear moduli of cous" resistance. When the temperature of the

various polymers at 20~C. test is increased as for P C T F E the equilibrium

290

PRESSURE DEPENDENCE OF THE SHEAR MODULUS OF VARIOUS POLYMERS

6'5xt~ l

s.8• 9 L~ PCTFE at 2 0 ~

magnitude with the applied hydrostatic pressure.

By using finite strain elasticity theory they

derive the linear relationship

G'=Go'+

(5-4v)(1-

(1 + v)

v)

P

3.,x,o' i ~ o

PCTFE at 45~

where G' is the shear modulus at pressure p,

Go' the atmospheric pressure value of the shear

modulus, and v is Poisson's ratio which is

assumed constant. The gradients of the curves

l.Txldi o 0 0

of G' against p (Figs. 1 to 3) can be used to

LDPE a t 20~ compute values of v if this equation is assumed

1.4x109 correct. For the non-linear curves the gradient

has been approximated to that of a straight line

4.5x108- joining the G' values at atmospheric and peak

PVC at 20 ~C o pressure. The results are shown in Table I.

In our experiments the maximum applied

2.s• ~ pressure is about 1.24x 10' dyn cm -2 so that

; lb 1; Meals' theory should be particularly applicable

TIME (mini

to LDPE, rubber, plasticized PVC and PP. None

Figure 4 Time dependence of the shear modulus G' at of these polymers give reasonable theoretical

10 000 psi. values of v, nor indeed do many of the polymers

in Table I. Our results do not therefore support

maximum value of G' is reached in a shorter this theory.

time. Associated with this polymer at 20~ Fig. 3 includes a plot of G' against p for the

is a relaxation time of the order of 1.5 min while natural rubber sample. The theory of rubber

at 45~ the relaxation time falls to 0.5 min. This elasticity gives the following result for the shear

time-dependent process has an "activation modulus of an elastic network

energy" of about 5 kcals. _ ri 2

G'= Nk'l'~2

3. Discussion

Mears et al [2] have studied the theoretical where N is the number of network chains per

increases in modulus with pressure for cases cubic centimetre, k is Boltzman's constant, T

where the tensile modulus is comparable in is the temperature, r,:2 is the square of the vector

TABLE I

**Polymer Go' dyn cm-2 I/Go' dG" dyn_1 cm -2 Calculated v
**

ap

PET 9.11 X 109 6.06 • 10 -11 0.63

PC 9.29 x 10' 5.10 x 10 -11 0.69

P V C rigid 1.18 x 10 l~ 7.05 x 10 -11 0.55

LDPE 1.10 x 109 6.59 • 10 - l ~ 0.58

PVDF 7.00 x 109 4.49 x 10 - l ~ 0.16

PTFE 8.50 x 109 3.07 x 10 - l ~ 0.22

PCTFE 5.33 x 109 3.59 x 10 - l ~ 0.32

HDPE 8.30 x 109 2.82 x 10 -1~ 0.26

Rubber 2.47 x 10 r 3.83 x 10 -1~ 0.98

PVF 6.21 • 109 1.52 x 10 -1~ 0.52

Nylon 6 1.08 • 101~ 1.34 • 10 -1~ 0.40

Bakelite 2.54 • 101~ 1.05 • 10 -1~ 0.22

Plasticized P V C 1.24 • l0 s 2.35 • 10 -9 0.75

PP 3.79 • 109 1.09 • 10 -~ 0.07

PMMA 1.57 • 10 l~ 1.00 • 10 -1~ 0.38

291

E. J O N E S P A R R Y , D. T A B O R

r~ associated with the ith network chain and has a far smaller effect on the modulus than it

rf e is the mean square end to end length that the would if the test temperature had been above the

chain would assume in free space if the network atmospheric relaxation temperature. The

junctions were severed. Tobolsky and Shen [6] presence of secondary relaxations complicates

maintain that re~ is a function of volume and the pressure dependence of shear modulus and

therefore of pressure and modify the equation of can only be completely removed by carrying out

state for the force F in a rubber network to experiments at temperatures below that at which

relaxations occur at atmospheric pressure.

The pressure dependence of the shear modulus

F = A L2

has been observed to be time-dependent and for

three polymers studied the modulus reaches

where Lo is the length and Vo the volume of a

equilibrium within 15 rain. This arises partly

rectangular strip of rubber at zero force and

because the application of pressure to a non-

zero pressure, L is the length and V the volume

homogeneous medium produces a shear stress.

at temperature T and pressure p, ~ = dln r~2/d In

This causes chains to slide over each other against

V, and A is a constant.

a "viscous-like" resistance: the effect is time

-dlnG' -dlnG' dp d l n G ' dependent and at higher temperatures the time to

Y- dlnV= dp dlnV dp

9 X -1

reach equilibrium is shorter. The time-depen-

dence also arises because of the finite time

where x is the compressibility. Using our data required for molecules in the amorphous regions

and a value for x given by Weir [7] ~, = 0.003. to reach equilibrium after the application of

Therefore while Tobolsky and Shen may be pressure9 This suggests that thermodynamic

correct in their assumption that r~2 is a function treatments are unjustified in considering hydro-

o f volume, this particular value of ~, shows that static pressure as a simple variable.

the effect must be very small indeed.

Acknowledgements

4. Conclusion We wish to express our thanks to the Thomas

The shear moduli of all the polymers studied and Elizabeth Williams Scholarship Fund for an

have been found to increase by the application of award to one of us (E.J.P.) and to Dr P. B.

hydrostatic pressure. In most cases the modulus Bowden for helpful discussions.

varies almost linearly with pressure9 Plasticized

PVC and PP are exceptions because of the References

presence of the atmospheric glass transition just 1. S. B9 A I N B I N D E R , M9 G. L A K A and YU I 9 MAIORS~

**below the temperature of the test. The applica- Mekkanika Polimerov 1 (1965) 65.
**

tion of pressure shifts these polymers into the 2. D. R. MEARS, K. D. PAE and J. A. SAUER, J. AppL

Phys. 40 (1969) 4229.

glassy state and hence increases the modulus by a 3. S. R A B I N O W I T Z ~ I. M. W A R D and s. s. c. PARRY~

greater amount 9 Secondary relaxations in P T F E J. Mater. Sci. 5 (1970) 29.

and P M M A are known to be shifted upwards in 4. H. P U G H ~ E. F. C H A N D L E R ~ L. H O L L I D A Y and J.

temperature by the application of pressure and to MANN, J9 Polymer Eng. and Sei 11 (1971) 463.

occur at temperatures close to that of the test 5. E. JONES PARRY and D. TABOR, J. Phys. D. (to be

(at 1 Hz) [8]. However, in our experiments, the published 1973).

moduli of these polymers does not increase 69 A. TOBOLSKYand M. o, SHEN, J. Appl. Phys. 37

markedly with pressure. For P M M A this is (1966) 1952.

presumably because the /3 relaxation is accom- 7. G. E. WEIR, J. Nat. Bur. Stand. 50 (1953) 321.

panied by only a small fall in modulus. In the 8. E9 JONES PARRY and D. TABOR, J. Mater. ScL 8

(1973) 1510.

case of P T F E the test temperature is just below the

atmospheric/3 relaxation temperature, so that the Received 21 May and accepted 6 July 1973.

upward shift of this relaxation with pressure

292

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