The Influence of Crystalline Texture on the Tensile Properties of Natural Rubber. I Author(s): P. E.

Reed Reviewed work(s): Source: Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences, Vol. 338, No. 1615 (Jul. 16, 1974), pp. 459-478 Published by: The Royal Society Stable URL: http://www.jstor.org/stable/78593 . Accessed: 17/02/2012 16:24
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Proc. R. Soc. Lond. A. 338, 459-478 (1974) Printed in Great Britain

The influence of crystalline texture on the tensile properties of natural rubber. I

BY P. E.REED Department of Materials, Queen Mary College, London E. 1 (Communicated by Sir Harry Melville, F.R.S. - Received 2 April 1973) The crystalline morphologies that are attainable in samples of natural rubber (n.r.), by extending the samples prior to crystallization, are reviewed. Specimens covering the full range of crystalline morphologies possible have been prepared and tensile tested between - 120 and - 26?C. The tensile behaviour of crystalline samples is compared and contrasted with that of oriented, but non-crystalline, identical natural rubber in the same temperature range. It is found that the tensile behaviour of semi-crystalline n.r. is dominated by the amorphous phase throughout the temperature range -120 to -26 OC.At temperatures above the glass transition temperature (Tg) of the amorphous phase, the crystalline phase acts mainly as a diluent of the amorphous phase. At temperatures below Tg, where the crystalline phase is set in a glassy matrix, it is found that the crystalline morphology does significantly affect the tensile behaviour. Attempts are made to differentiate the effects of crystallinity, crystalline morphology and orientation of the amorphous phase on the tensile properties of natural rubber.
1. INTRODUCTION

Many materials in common use are composite materials. In such composites as glass-reinforced plastics the constituents are deliberately selected and combined to produce a material with particular properties. Studies may be performed either separately on the individual constituents of these composites or on the composite itself to verify theoretical predictions of the mechanical behaviour (Kelly 1966). There exists a further type of composite material in which the constituents are chemically identical but exist in equilibrium with each other in different forms. Semi-crystalline polymers containing a low proportion of crystalline phase embedded in an amorphous matrix of the same polymer are such composites. No complete study of the variation in the mechanical properties of semicrystalline polymers with crystallinity and crystalline morphology appears to have been attempted. In the case of polyethylene terephthalate, Dixon & Jackson (1968) have shown that large changes in crystallinity produce only marginal variations in yield strength, modulus and fracture stress at temperatures below the glass transition temperature (Tg), while above Tg these properties are highly dependent on the crystallinity. Similar effects in raw rubber have been reported (Leitner I955). The effect of crystallinity on mechanical behaviour is thus dependent on the condition
[ 459 ]

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P. E. Reed

of the amorphous phase in which it is embedded. The importance of considering the amorphous phase in understanding the deformation of semi-crystalline polymers has been emphasized by Heffelfinger & Schmidt (I965). Attempts have been made to investigate the effect of crystalline morphology on mechanical properties (Starkweather & Brooks I959; Pritchard, Dunn & Kelly I964; Hammer, Koch & Witney 1959). Polymers in which the crystalline phase is always spherulitic initially have been used in these studies, and the change in mechanical properties with spherulite size has been investigated. Unfortunately changes in spherulite size are accompanied by variations in crystallinity. Consequently it is difficult to separate the effects of these two parameters on the mechanical properties. A major problem in studying the mechanical behaviour of semi-crystalline polymers is separating the effects of crystalline morphology, percentage crystallinity, spherulite size and the contribution of the amorphous phase. Natural rubber (cis-polyisoprene) is a polymer which may be obtained in a semi-crystalline form. It offers certain advantages over other polymers for a study of the effect of crystalline texture on the mechanical properties of semi-crystalline polymers. Natural rubber may be rendered either amorphous or semi-crystalline, without modifying the structure of the molecules, simply by storing the material at different temperatures. This feature permits the properties of the amorphous phase to be studied separately from those of the semi-crystalline composite. Natural rubber crystallizes relatively slowly and the amount of the crystalline phase is easily controlled up to a maximum of about 30 % (Goppel I948; Nyburg 1954). The greatest advantage of using natural rubber is the range of crystalline morphologies that may be generated by stretching the material to varying amounts before crystallization takes place (Andrews 1964). A further possibility is that the amorphous phase may be rendered either glassy or rubbery by testing the semi-crystalline material at temperatures either below or above the glass transition temperature of the amorphous phase. Studies may then be performed with the crystallites set either in a glassy or an elastomeric matrix and in each case the crystallites will be bonded to the amorphous phase by primary bonds.

2. THE

CRYSTALLINE

MORPHOLOGY

OF NATURAL

RUBBER

The crystalline morphology produced in thin cast films of uncrosslinked natural rubber has been previously studied (Andrews 1962, 1964). Thin films were stretched by varying amounts at room temperature prior to crystallization and then held at - 26 ?Cfor crystallization to take place. The study of uncrosslinked natural rubber thin films showed that a wide range of crystalline morphologies were produced depending on the 'pre-extension', i.e. the amount by which the films were extended prior to crystallization. Unstrained films crystallized in a spherulitic manner, the spherulites consisting of crystalline islands interspersed with radiating crystalline filaments and amorphous material. Small pre-extensions up to 50 % caused the

Tensile properties of natural rubber. I

461

(a)

(b)

-?-??
C n? r

1'? . __----I

:`' `?? (;-' 33--*e---------_ _

w -.
. _ .

rr I_T ---rr--

,?
..--

_d
---

-_

--,.-...

(c)

(d)

,1
(e)

FIGURE1. Crystalline morphologies in thin films of natural rubber with increasing degrees of pre-extension: (a) 0 %, (b) 50%, (c) 100%, (d) 250%, (e) 500 % pre-extension. The pre-extension direction is vertical.

spherulitic structure to become preferentially oriented with the filamentous component aligned perpendicularly to the direction of initial strain. When the preextension reached 100 %, the crystalline islands had entirely disappeared and only crystalline filaments running perpendicularly to the initial strain direction were observed. These filaments were termed a-filaments by Andrews. The a-filaments were found to be arranged in ribbons or rows with their axes in the strain direction. Further increases in pre-extension beyond 100 % caused an increase in the number and length of the rows of a-filaments together with a decrease in the length of the a-filaments themselves. In specimens subjected to very large pre-extensions, little evidence of a-filaments was seen, but crystalline filaments running in the direction of strain were observed which were termed y-filaments. The density of the y-filaments in films pre-extended by 500 % was such that there was little room for a-filament growth. These five forms of crystalline morphology are sketched in figure 1.
29

Vol. 338. A.

462

P. E. Reed

More recently the work on the crystallization in thin films of natural rubber has been continued to study the effects of crosslinking on the process (Owen 1970). Basically the same crystalline morphologies were found to exist as in the uncrosslinked films at corresponding pre-extensions, except that crystallization rates, a-filament lengths and y-filament lengths were all reduced by crosslinking. The crystalline morphology in bulk samples of natural rubber is most likely a three-dimensional form of the morphologies observed in the thin films when crystallized in a similar manner. Experimental studies to observe directly the crystalline morphology in bulk samples, by taking thin sections from the crystallized samples for electron microscope investigation, have so far proved unsuccessful. A two-stage replica technique for electron microscope studies has been used to study fracture surfaces of crystallized bulk samples of natural rubber, and reveals structures in outline which are similar in size and shape to those observed in the thin films (Reed I970). The replicas show the outlines of spherulites in samples receiving no pre-extension prior to crystallization and the outline of ribbon shapes similar in length, width and orientation to the rows of a-filaments observed in equivalently pre-extended thin films. Further evidence of the similarity of the crystalline morphology in thin films and bulk material is given by studies on polychloroprene (Andrews & Reeve 197I). The changes in crystalline morphology with pre-extension in polychloroprene follow a similar pattern to those in natural rubber. X-ray studies on bulk samples of polychloroprene, crystallized after varying degrees of pre-orientation, showed identical orientation of the crystalline phase to that in thin films at equivalent pre-extensions. Hence crystalline lamellae in the bulk material correspond to the
TABLE 1
pre-extension ratio, AS 1 1 < As < 2 As
_

morphology in thin films spherulitic preferentially spherulitic oriented

expected morphology in bulk samples spherulitic preferentially spherulitic oriented

a-filaments perpendicular to initial pre-extension direction

sandwich of lamellae platelets and amorphous material with plane of platelets perpendicular to initial pre-extension direction lamellae platelet sandwich arranged in stacks; lamellae width decreasing and stack length increasing with increasing A8; stacks oriented in pre-extension direction as for 2 < A, < 4 but with steadily increasing y-filament content

2 < As < 4

row structure of a-filaments. a-filament length decreasing and row length increasing with increasing A,; rows oriented in pre-extension direction as for 2 < As < 4 but with steadily increasing y-filament content

4 < As < 7

Tensile properties of natural rubber.I

463

a-filaments of the thin films at equivalent degrees of pre-extension. It has also been demonstrated, using light scattering techniques, that samples of natural rubber stretched more than 300 % contain a light-scattering structure oriented in the direction of extension (Yau & Stein 1968). This structure was identified with the y-filaments observed in equivalently oriented thin films. The assumption that the crystalline morphology in the bulk samples is similar to that observed in thin films prepared under the same conditions of strain is made in the following interpretation of the mechanical test data. Such data as have been obtained and discussed above support this assumption. The crystalline morphologies obtained with varying degrees of pre-extension (As) are summarized in the above table.
3. EXPERIMENTAL

(a) Specimen preparation Dumb-bell shaped specimens were stamped from sheets of natural rubber 2 mm thick having the following composition and which had been cured at 130 ? for 30min: parts by mass smoked sheet stearic acid zinc oxide phenyl fl-naphthylamine 2-mercaptobenzthiazole sulphur 100 1 5 1 0.5 3

The specimens were mounted in suitable clamps for tensile testing and then stretched at room temperature by the required amount to produce the desired crystalline morphology. The specimens were held at -26 ?C in their stretched condition. This temperature has been shown to be the optimum crystallization temperature for natural rubber (Gent I954). The time for maximum crystallinity to be achieved depends on the pre-extension. Unstretched specimens required 20 days at -26 ?C for a maximum crystallinity of 24 % to be obtained, while specimens pre-extended by 200 % achieved their maximum crystallinity of 30 % in 2 days. Larger pre-extensions resulted in more rapid crystallization. All specimens were held at - 26 ?C for sufficient time to obtain maximum crystallinity. The tensile tests were performed in a special environmental chamber attached to an Instron Universal testing machine (Reed 1966). The chamber could be maintained at any desired temperature in the range - 190 to 20 ?C. Since the crystallized specimens begin to melt at - 21 ?C, only 5 ?Cabove the crystallization temperature, a special insulated specimen transfer device was used to transport the specimens from the refrigerator to the pre-cooled testing chamber (Reed 1966).
29-2

464

P. E. Reed

(b) Tensile testing A study was made of the effects of crystalline morphology and temperature of testing on the tensile behaviour of semi-crystalline natural rubber. Specimens were pre-extended by amounts varying between 0(As = 1) and 600 % (As = 7) and crystallized to give the complete range of morphologies shown in table 1. In all that follows the pre-extension ratio can thus be regarded as an index of the crystalline morphology present before testing commenced. Tensile tests were performed over the temperature range - 120 to - 26 ?C for each morphology. Since the different crystalline morphologies were produced by varying the amount of orientation prior to crystallization, it is possible that the amorphous regions remain oriented after crystallization. It is important to check whether observed mechanical behaviour is attributable to the presence of a particular crystalline morphology or to the orientation of the amorphous regions. Hence all tensile tests were repeated using orientated natural rubber samples instead of semi-crystalline samples. For these tests the rubber samples were stretched to the required amount at room temperature and immediately quenched to the test temperature, thus not allowing time for crystallization to occur. No data for amorphous oriented specimens are available for comparison with the semi-crystalline data when the pre-extension ratio exceeds 4 because natural rubber strain crystallizes rapidly at room temperature when extended by more than 300 % (Nyburg I954; Mitchell & Meier I968). All the tensile tests were performed at an extension rate of 2 cm min--.

4. RESULTS

AND

DISCUSSION

(a) Types of mechanical tensile behaviour Four different types of deformation were found within the experimental ranges of morphology and temperature studied, and may be typified by their respective load-extension curves shown in figure 2. The field of the present investigation may be divided into four regions, each region being associated with a particular type of deformation. The first region is associated with type D curves and occurs with both oriented amorphous and crystalline materials at temperatures above Tg when the amorphous phase is rubbery. The three other regions exist below Tg. A brittle region, associated with type A curves, occurs below Tg for both types of material at small pre-extensions. Ductile deformation, associated with type B curves, occurs for both types of material at intermediate pre-extensions below Tg. With oriented amorphous samples the type B curve is associated with cold drawing, but with crystalline samples stress whitening without cold drawing is observed. The fourth region is also a ductile region, and may not be distinctly different from the other ductile region below Tg. It occurs at high pre-extension ratios in association with type C curves. The sharp load drop at yield of the type B curve is replaced by a change in slope on the type C curve.

Tensile properties of natural rubber. I

465

strainFIGURE 2. Typical stress-strain curves for the four different types of tensile behaviour of

natural rubber in the temperature range - 120 to -26 ?C (arbitrary scales).

The iour types of behaviour are common to both oriented amorphous and semicrystalline materials. This suggests that the basic deformation mode of the semicrystalline material is that associated with the amorphous phase at all temperatures. However, comparison of the limits of temperature and pre-extension under which the four types of behaviour are obtained for the crystalline and oriented amorphous materials reveals significant differences. The inclusion of the crystalline phase in natural rubber apparently modifies, but does not dramatically vary, the mechanical behaviour of the amorphous material, except under test conditions close to transitions in deformation mode. (b) Fracture stress and strain Figure 3 shows the variation of the true breaking stress (i.e. stress related to the actual cross-sectional area at rupture) with temperature and crystalline morphology. Reference to table 1 enables the pre-extension ratio (As)to be related to the crystalline morphology present at the start of the tensile test. Figure 4 shows the total extension to rupture (i.e. pre-extension plus further extension during tensile testing) as a function of the same parameters. Above - 70 ?Cthe fracture stress varies only slightly over the complete range of morphology. The load-extension curves in this region were always of the type D form. Deviations from the nearly constant fracture stress occur only when As = 1 or As > 6. Thus, unless the crystalline morphology is either spherulitic or has a high concentration of y-filaments, the fracture stress is not greatly affected by the crystalline morphology when the amorphous phase is rubbery. The extension to rupture (figure 4) follows the same pattern as the fracture stress above -70 ?C and exhibits a constant value for much of this range. This further endorses the conclusion that the crystalline morphology does not significantly affect the ultimate properties when the amorphous phase is rubbery.

CD

cD I1

pre-extension ratio
FIGURE

3. Variation of fracture true-stress with temperature and crystalline morphology, indicated by the pre-extension ratio, for crystallized natural rubber.

FIGURE Variation of the exte 4. referred to the original u crystallized specimen length and crystalline morphology, pre-extension ratio, for cry rubber.

Tensile properties of natural rubber. I

467

A transition in the fracture stress occurs at about - 70 ?, which approximates to the glass transition temperature of the amorphous phase. When As < 2.5 this transition takes the form of a rapid decrease corresponding to a change to brittle behaviour and type A load extension curves. The introduction of crystallinity in spherulitic form into a glassy amorphous matrix does not inhibit brittle failure in the case of natural rubber. A transition to larger fracture stresses and elongation to rupture occurs at temperatures below - 70 ?Cas the pre-extension ratio exceeds 2.5, and is associated with a change in the load-extension curve from type A to type B. This transition is 0.5
/o,
0

00

10.3.2

.v / I

^o

o0.3

5
pre-extension ratio

.9

5. FIGuURE Change in fracture stress with pre-extension ratio at - 120 ?Cfor (o) semi-crystalline natural rubber, ( x ) oriented natural rubber and (v) acrylonitrile-butadiene rubber.

coincident with the change from an aligned spherulitic morphology to the fully developed lamellar sandwich structure with the lamellae set normal to the strain axis initially. The transition may alternatively be related to the increasing orientation of the amorphous phase, since a similar transition from brittle to ductile behaviour is observed with the oriented amorphous samples, although in the latter case the transition occurs at lower pre-extension ratios. The fracture stresses of semi-crystalline and oriented non-crystalline specimens for tensile tests performed at - 120 o0 are compared in figure 5. The data for noncrystalline natural rubber are not given beyond As = 3.5, since at this pre-extension strain crystallization occurs at room temperature. However, data for acrylonitrile

468

P. E. Reed

butadiene rubber (abr), which is a non-crystallizing synthetic rubber, are included in figure 5. The graph shows that the fracture stress of crystalline material increases fivefold in the range 1 < As < 5 while the fracture stresses of the oriented materials exhibit only a two fold increase. Hence orientation of the amorphous phase, although it increases the fracture stress, cannot alone account for the large rise in fracture stress of the semi-crystalline material. Figure 5 also shows that the fracture stress of the semi-crystalline spherulitic material (As = 1) at -120?C, which contains 24 % crystallinity, is the same as that of the glassy amorphous material alone. Hence the dramatic rise in fracture stress of the semi-crystalline material with changing morphology cannot be explained in terms of changes in the crystalline content, which are in any case small over the range tested. The fivefold increase in fracture stress of the crystalline material is thus attributed mainly to changes in the crystalline morphology. At - 120?C and at high pre-extensions (large y-filament content) the fracture stress decreases abruptly and brittle behaviour again obtains. The fracture stress values when As > 6 appear to be an extrapolation of the brittle strength values when As < 2.5. Further evidence that the change in mechanical behaviour at As = 2.5 in semicrystalline samples is associated with morphological changes is provided by the fracture surfaces of specimens tested below - 70 ?C. When As < 2.5 the fracture surface is a single plane transverse to the draw direction and typical of brittle fracture. When As > 2.5 a fibrous fracture surface is obtained and bunches of fibrous material are found in the vicinity of the fractured specimen. Such fibrous material is consistent with the fracture path going round the stacks of lamellae or y-filaments. (c) The region of rubber-like behaviour Stress-strain curves for the complete range of crystalline morphologies studied from tensile tests performed at -40 ?C are shown in figure 6. The inset on figure 6 shows the initial form of the curves to a larger scale. Corresponding curves for the oriented non-crystalline specimens are shown in figure 7. These latter curves are also reproduced dotted in figure 6 for ease of comparison. The starting extension ratio for each curve indicates the pre-extension ratio or initial morphology. Figure 7 shows that the stress-strain curves of the oriented specimens fall on one single curve regardless of pre-extension ratio providing As < 5. Such behaviour is entirely consistent with rubber elasticity theory which states that the stress is a function of state, and independent of the path taken to arrive at that state. Specimens cooled to - 40 ?0 and then extended, or extended at room temperature and then cooled, exhibit similar stresses at a given extension. The deviation from the common curve in figure 7 when As > 5 can be attributed to stress relaxation associated with crystallization (Gent 1954) during preparation for testing. No common curve is apparent for the semi-crystalline samples (figure 6), but rather the curves are of similar form for all morphologies and displaced along the extension ratio axis. Comparison of the curves for the crystalline and oriented samples shows that the major effects of introducing the crystalline phase are to increase the rate of

F *+* PtCD

2 m

ca

Q
tl

h3

extension ratio
FIGURE 6. Simple elongation stress-strain curves

extens

FIGURE 7. Simple elonga

for semi-crystallized natural rubber at -40 ?C. Extension ratio values plotted include both extension during tensile testing and pre-extension prior to crystallization. Dotted curves indicate equivalent data for oriented amorphous specimens. Insert shows start of some curves to a larger scale.

for oriented amorph - 40 ?C.Extension rat both test extension an temperature. Pre-exten *, A = 1.8; A, A = 8 = 5.5; o, A8= 7.

470

P. E. Reed

strain hardening and reduce the overall extension to fracture. Curves shown in figure 6 are for the maximum crystalline content of approximately 30 %. Less crystallinity results in curves intermediate between the solid curves in figure 6 for crystalline and the dashed curves for oriented amorphous samples. On initial examination of the results it appears that the crystalline phase may merely serve as a filler in the amorphous matrix. The modulus of the crystalline phase must exceed that of the amorphous phase when the latter is rubber-like, and, from considerations of simple composite theory (Holliday I966), the modulus of the composite will increase with crystalline content. The enhancement of the modulus should depend only on the volume fraction of crystalline phase present according to simple composite theory. Since the crystalline content is approximately constant for all samples tested, the stress-strain curves for all semi-crystalline samples may be expected to fall on a common curve. Clearly no such common curve exists for the crystalline samples in figure 6, even after allowance is made for the pre-extension. It is thus considered that both the crystalline content and to a lesser extent the crystalline morphology affect the form of the stress-strain curve at temperatures above the Tg of the amorphous phase, although the ultimate strength does not apparently vary with the morphology. Variations in the modulus in small strain tensile tests have been attributed to changes in the aspect ratio (i.e. ratio of length to width) of the crystalline phase (Halpin & Kardos I972), the modulus increasing with aspect ratio. When 2 < As < 5 the aspect ratio of an individual lamella within a stack of lamellae is considered to decrease with increasing pre-extension as outlined in table 1. Such a reduction in aspect ratio should result in a decrease in modulus according to Halpin & Kardos rather than the increase observed. The stiffening effect may result from the stacks of lamellae acting in concert to serve as fibrillar reinforcement, since the aspect ratio of a stack of lamellae increases with pre-orientation in contrast to that for an individual lamella. Alternatively the increasing modulus, or strain hardening rate, with pre-orientation may result from orientation of the amorphous phase. Evidence of residual orientation is shown by the stress required to maintain the specimens at the pre-orientation extension after crystallization. Stress-strain curves in figure 6 do not commence at zero stress when As > 2.5. The initial stress on each curve indicates the stress required to maintain the pre-extension after crystallization, and increases with pre-extension. Although these stresses are small, they correspond to significant extension in the amorphous phase if the same residual stresses are applied to the amorphous phase alone. The increase in residual stress with orientation suggests increasing residual orientation in the amorphous phase after crystallization. Such orientation can contribute to the increasing strain hardening rate with preextension as will be discussed in a subsequent paper. (d) Behaviour below Tg Three regions of distinctly different behaviour are observed below Tg for both oriented amorphous and semi-crystalline materials. Figures 8 and 9 show, for the

Tensile properties

of natural rubber. I

471

-0.2
4Qe

exte.nA4^y^si*L^'
2tio

^*:8

^ temperature
w1ot20 0 -100

^"120

FIGURE8. Variation of brittle fracture stress and yield stress with temperatureand initial

orientation for oriented amorphous natural rubber. Brittle fracture and yield are indicated by shaded and plain surfacesrespectively. _0.4

-0.3

-02

.0.1

temperaturel

9. FIGURE Variationof brittle fracturestress and yield stresswith temperatureand crystalline

morphology, indicated by pre-extension ratio, for semi-crystalline natural rubber. Brittle fracture and yield are indicated by shaded and plain surfaces respectively.

amorphous and semi-crystalline materials respectively, the variation in brittle fracture stress or yield stress with temperature and degree of pre-extension. The region of brittle fracture is shown by the shaded region and the fracture stress is plotted. The plain surface indicates the variation of the yield stress where ductile behaviour obtains. A trough appears in each of the yield surfaces in figures 8 and 9, with the lowest point at approximately As = 3 in figure 8 and As = 4 in figure 9. At pre-extensions below these values ductile deformation is associated with type B

472

P. E. Reed

curve (figure 2), and a load drop at yield is observed. At greater pre-extension values than the low point of the trough, ductile deformation is associated with type C curves. In the latter case the yield stress is taken as the stress at the abrupt change in slope of the stress-strain curve. Each type of behaviour occurs with both oriented amorphous and semi-crystalline materials, but under slightly different conditions of temperature and pre-orientation. Hence the fundamental behaviour must again be attributed to the deformation of the amorphous phase. (i) Region of brittle behaviour The shaded areas in figures 8 and 9 show the regions where brittle fracture obtains for oriented amorphous and semi-crystalline materials respectively. Comparison of the two shaded areas shows that (a) the fracture stresses of the semi-crystalline samples exceed those of the oriented amorphous samples at all values except at As = 1, (b) the region of brittle behaviour extends to higher As values in the case of the semi-crystalline samples at temperatures below - 90 ?C, (c) brittle behaviour occurs immediately below Tgwhen As = 1 (unoriented) in the case of the amorphous material, but does not occur until about 20 ?C below Tg in the case of the semicrystalline material containing spherulites. The identical fracture stresses of the amorphous and semi-crystalline materials when As = 1 show that the inclusion of a crystalline phase does not automatically increase the brittle fracture strength. The enhanced brittle fracture stress in the semi-crystalline samples when As > 1 must be attributable to the arrangement of the crystalline phase (i.e. crystalline morphology), rather than the mere presence of crystallinity. This view is supported by further tests using a series of specimens which contained mainly parallel lamellae (figure 1 c), alined at various angles to the tensile test strain axis initially. The greatest enhancement of the brittle fracture stress occurred when the lamellae were normal to the test direction. Samples in which the lamellae were alined in the direction of tensile testing showed no enhancement of the brittle fracture stress over that of the unoriented amorphous material. It is not clear to what extent the lamellae width affects the strengthening mechanism in the brittle behaviour region, since a transition to ductile deformation occurs with increased pre-orientation before any significant change in the lamellae width is attained. (ii) Brittle-ductile transition Both oriented amorphous and semi-crystalline materials yield and undergo subsequent plastic deformation at temperatures below Tg, provided the preextension is sufficiently large. The minimum pre-extension required to cause ductile behaviour increases with decrease in temperature as shown in figures 8 and 9. The similarity in behaviour of the oriented amorphous and semi-crystalline samples suggests that yield is associated with the amorphous phase, since this is common to both cases. Since the brittle-ductile transition occurs over a narrow

Tensile properties of natural rubber.I

473

range of pre-orientation, any effect of crystalline morphology on the transition is not apparent. The presence of the crystalline phase inhibits yielding, increasing the pre-extension required to change the behaviour from brittle to ductile by approximately 100 % at each test temperature below - 90 ?C. Results from the oriented amorphous material alone show that, at any particular temperature, yield occurs when the orientation of the amorphous phase achieves a critical value. If yield initiates in the amorphous phase at a critical value, the shift of the brittle-ductile transition to higher pre-extension in the case of the semi-crystalline samples suggests that the orientation in the amorphous phase of the semi-crystalline material is less than in the oriented amorphous counterpart at any given pre-extension. At temperatures between - 90 and - 70?0 the semi-crystalline material is ductile over the whole range of pre-orientation, although the oriented amorphous material is brittle for small degrees of pre-orientation. Non-homogeneous deformation occurs when a spherulitic structure is present. Instead of one load decrease at yield on the load-extension curve prior to the propagation of a single yield band, several load decreases are observed as extension proceeds, producing a saw-tooth form of loadextension curve. Each load decrease is associated with the formation of a new yield band in the specimen. Any attempt at interpretation of the yield mechanism occurring in the semi-crystalline samples containing a spherulitic structure is made more difficult by the non-homogeneous deformation.
0.05

- 0.03-

0.03

I.crystalline oriented

'

0.01-

I,

extension ratio
FIGURE

10. Stress-strain for semi-crystalline and oriented amorphous natural rubber at - 80 ?C,for specimens pre-extended by 80 % at room temperature prior to crystallization and/or tensile testing. Extensions plotted include the pre-extension.

If yield initiates in the amorphous phase, subsequent deformation is certainly modified by the presence of a crystalline phase. The stress-strain curves for oriented amorphous and semi-crystalline samples, having pre-extension ratios of 1.8, are compared in figure 10. Extension at constant load after initial yield is associated with cold drawing in the case of oriented amorphous samples. Termination of the deformation at constant load at an extension ratio of 4, regardless of pre-orientation, suggests that the amorphous phase seeks to achieve a natural draw ratio of 4 on yielding. The semi-crystalline samples exhibit strain hardening immediately after

474

P. E. Reed

yield, contrasting with the oriented amorphous behaviour. The specimens deform uniformly throughout their length, at least macroscopically, at the test strain rates adopted. Stress whitening occurs as deformation proceeds, possibly due to the formation of voids as a result of incompatibility of the amorphous and crystalline phases during straining. Mechanisms of yielding in semi-crystalline polymers have been discussed by other researchers (Peterlin 197I; Keller & Pope I97 ). (e) Elastic modulus The initial tangent modulus is used to define the elastic modulus at very small strains, since non-Hookean behaviour occurs at temperatures above Tg. The variation of the moduli of the semi-crystalline and oriented amorphous materials with temperature and pre-orientation are shown in figures 11 and 12 respectively. Comparison of these figures shows that the changes in moduli with temperature and pre-orientation are similar for both types of material. The usual large increase in the modulus occurs with both types of material at the glass transition of the amorphous phase. The similarity of figures 11 and 12 shows that the amorphous phase dominates the small strain elastic behaviour of the semi-crystalline material. There are, however, small variations between the two figures which are significant. At temperatures above Tg the modulus of both types of material increases with pre-extension. The modulus of the oriented amorphous material is always slightly greater than that of the semi-crystalline material when As > 2.4. This contradicts previously reported data (Leitner 1955; Starkweather & Brooks I959; Halpin & Kardos I972) showing that the introduction of a crystalline phase increases the modulus. In all these previous cases, however, crystallinity was introduced without initially orienting the amorphous phase, in contrast to the presently reported work. Halpin & Kardos have used composite theory to explain the effect of increasing crystallinity on the modulus. When the modulus of the introduced phase exceeds that of the matrix in which it is set, the modulus of the composite exceeds that of the matrix, provided the modulus of the matrix is not changed by the addition of the new phase. In the present case the modulus of the semi-crystalline sample is compared with that of the oriented amorphous material at equivalent pre-extensions. If the properties of the amorphous phase are different in the two samples, the moduli of the respective amorphous phases will differ. If composite theory is invoked in the present case, the results may be explained by suggesting that the modulus of the amorphous phase in the semi-crystalline sample is less than that of the oriented amorphous sample alone when As > 2.4, and the inclusion of the crystalline phase does not compensate for this difference. Such differences in moduli of the amorphous phases could be due to variations in extension, since the modulus of the amorphous material increases with strain. This interpretation is consistent with the earlier suggestion that the orientation of the amorphous phase of the semi-crystalline material is less than in the oriented amorphous counterpart at equal pre-extensions. The discrepancy between the present work and that reported by other researchers, on the effect of increasing crystallinity on the modulus, is thus attributed to

Tensile properties of natural rubber.I

475

?r

E.
OS0

Pre-extensOn rato

240

eloC

FIGURE11. Initial tangent modulus plotted against temperature and crystalline morphology, indicated by pre-extension ratio, for semi-crystalline natural rubber.

pre-extension ratio

t,e

FIGURE 12. Initial tangent modulus plotted against temperature and

pre-extension for oriented amorphous natural rubber.

variations in orientation of the amorphous phase resulting from the method of introducing the crystallinity. At temperatures below Tg, a small increase in orientation from the non-oriented state results in a twofold increase in modulus for both types of material. This again emphasizes the dominating role of the amorphous phase. At pre-extension ratios greater than 2 the modulus of the oriented amorphous material was found to be essentially constant for all pre-extensions, although considerable scatter of the data

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was observed in this region due to the experimental method used. It is apparent, however, that the modulus of the semi-crystalline material exceeds that of the oriented amorphous equivalent at A,s 2 and A, > 6. At values intermediate between these values the modulus of both types of material is similar. The crystalline morphology thus appears to affect the elastic modulus at A, 2 and As > 6 at below Tg. temperatures At large values of pre-extension the modulus of the semi-crystalline material again rises rapidly. The crystalline morphology at these values of pre-extension is predominantly that of y-filaments alined in the direction of testing. Fracture surfaces from such specimens are highly fibrous. Hence the y-filaments serve as fibre reinforcing for the glassy amorphous phase, and higher elastic moduli result.

5. CONCLUSION

The mechanical behaviour of a semi-crystalline polymer is determined by the behaviour of the crystalline and amorphous phases acting in concert. Generally it is difficult to separate the contribution of each phase to the observed behaviour of the polymer. Interpretation of the tensile behaviour of natural rubber has been helped in the present investigation by the ability to study the behaviour of the oriented amorphous material separately from that of the semi-crystalline composite. A systematic experimental study has been made of the effect of crystalline morphology on the tensile behaviour of natural rubber over a wide temperature range. This behaviour has been compared with that of oriented amorphous natural rubber throughout the same range. Four regions of distinctly different tensile behaviour have been identified within the range of the investigation, which are common to both semi-crystalline and oriented amorphous materials. This similarity in behaviour shows that, for the material tested, the amorphous phase dominates the tensile behaviour at temperatures both above and below the Tgof the amorphous phase: the maximum crystallinity possible in natural rubber is approximately 30 %. Although the stress-strain curves for the oriented amorphous and semi-crystalline materials are similar within any one particular region of tensile behaviour, small differences are significant in understanding the role of the crystalline morphology. At temperatures above Tgthe inclusion of the crystalline phase increases the rate of strain hardening and decreases the extension to rupture. It appears that these effects are related mainly to the crystallinity present and are not greatly affected by the form of crystalline morphology. The tensile strength above Tg, calculated as true stress, is not modified by the inclusion of the crystalline phase. The same property expressed as engineering stress shows an apparent increase in strength with crystallinity, since variations in strain at rupture are not then taken into consideration. The crystalline phase thus appears to act mainly as a diluent of the amorphous phase when the latter is an elastomer. Small variations in the form of the stress-strain curves for the semi-crystalline samples may be attributable to differences in crystalline morphology or may be due to variations in the orientation

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in the amorphous phase resulting from the method of forming the different crystalline morphologies. At temperatures below Tg, the inclusion of the crystalline phase causes a shift in the ductile-brittle transition to higher temperatures at any given value of preextension. Consideration of the data for the oriented amorphous material alone shows that the transition is related to a minimum critical orientation, which increases with decreasing temperature. It is considered that the formation of a crystalline phase in the equivalently oriented sample causes a relaxation in the amorphous phase, and results in the shift in brittle-ductile transition to higher temperatures for the crystalline samples. Below Tgit is found that a fivefold increase in fracture stress occurs within the range of crystalline morphologies studied. Such an increase cannot be explained on the basis of variations in crystalline content or in terms of changes in amorphous phase orientation. This dramatic increase in tensile strength is thus attributed to changes in the crystalline morphology. The maximum strength is attained with a morphology which is thought to be stacks of lamellae arranged in a crystalline-amorphous sandwich and set in an amorphous matrix, the stacks being alined in the test direction. The lamellae stacks appear to act as fibre reinforcement since the fracture surfaces of these stronger samples is fibrillar. Comparison of the tensile behaviour of oriented amorphous and semi-crystalline natural rubber has shown that the amorphous phase dominates the behaviour in the temperature range - 120 to - 26 ?C. The crystalline phase appears to act mainly as a diluent of the amorphous phase when the latter is an elastomer; variations in crystalline morphology having little effect on the tensile behaviour. When the amorphous matrix is glassy, however, it appears that both crystalline morphology and crystallinity affect the tensile strength, elastic modulus and the form of the stress-strain curve. The author is indebted to Professor E. H. Andrews for suggesting the topic of investigation and many useful discussions. The author also thanks the Natural Rubber Producers Research Association for providing the samples for the investigation.
REFERENCES Andrews, E. H. I962 Proc. R. Soc. Lond. A 270, 232. Andrews, E. H. 1964 Proc. R. Soc. Lond. A 277, 562. Andrews, E. H. & Reeve, B. I97I J. Mat. Sci. 6, 547. Dixon, E. R. & Jackson, J. B. I968 J. Mat. Sci. 3, 464. Gent, A. N. I954 Trans. Farad Soc. 50, 521. Goppel, J. M. I948 Rubber Technology Conference, London. Hammer, C. F., Koch, T. A. & Whitney, J. F. 1959 J. appl. Poly. Sci. 1, 169. Halpin, J. C. & Kardos, J. L. 1972 J. appl. Phys. 43, 2235. Heffelfinger, C. J.. & Schmidt, P. G. I965 J. appl. Poly. Sci. 9, 2661. Holliday, L. 1966 Composite materials. Amsterdam: Elsevier. Keller, A. & Pope, D. 197I J. Mat. Sci. 6, 453. Kelly, A. I966 Strong solids. Oxford University Press. Leitner, M. 1955 Trans. Farad. Soc. 51, 1015. 30 Vol. 338. A.

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Mitchell, J. C. & Meier, D. J. I968 J. Poly. Sci. A-2, 6, 1689. Nyburg, S. C. 1954 Br. J. appl. Phys. 5, 321. Owen, P. I970 Crystallization in thin films of natural rubber. Ph.D. Thesis, University of London. Peterlin, A. 197I J. Mat. Sci. 6, 490. Pritchard, R., Dunn, T. & Kelly, P. 1964 J. appl. Poly. Sci. 8, 1751. Reed, P. E. I966 J. Mat. Sci. 1, 91. Reed, P. E. I970 The influence of crystalline texture on the tensile properties of natural rubber. Ph.D. Thesis, University of London. Starkweather, H. W. & Brooks, R. E. I959 J. appl. Poly. Sci. 1, 236. Yau, W. & Stein, R. S. I968 J. Poly. Sci. A-2, 6, 1.