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.
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 ]
A major problem in studying the mechanical behaviour of semi-crystalline polymers is separating the effects of crystalline morphology. E. percentage crystallinity. The importance of considering the amorphous phase in understanding the deformation of semi-crystalline polymers has been emphasized by Heffelfinger & Schmidt (I965). simply by storing the material at different temperatures. Consequently it is difficult to separate the effects of these two parameters on the mechanical properties. Natural rubber may be rendered either amorphous or semi-crystalline.460
P. 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. Unfortunately changes in spherulite size are accompanied by variations in crystallinity. 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). and the change in mechanical properties with spherulite size has been investigated. 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. 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). This feature permits the properties of the amorphous phase to be studied separately from those of the semi-crystalline composite. Attempts have been made to investigate the effect of crystalline morphology on mechanical properties (Starkweather & Brooks I959.26 ?Cfor crystallization to take place. Hammer. Polymers in which the crystalline phase is always spherulitic initially have been used in these studies. the amount by which the films were extended prior to crystallization. Pritchard. Reed
of the amorphous phase in which it is embedded. the spherulites consisting of crystalline islands interspersed with radiating crystalline filaments and amorphous material. spherulite size and the contribution of the amorphous phase. Small pre-extensions up to 50 % caused the
. Thin films were stretched by varying amounts at room temperature prior to crystallization and then held at . Unstrained films crystallized in a spherulitic manner. 1964). without modifying the structure of the molecules.e. Koch & Witney 1959). THE
The crystalline morphology produced in thin cast films of uncrosslinked natural rubber has been previously studied (Andrews 1962. Dunn & Kelly I964. It offers certain advantages over other polymers for a study of the effect of crystalline texture on the mechanical properties of semi-crystalline polymers. The study of uncrosslinked natural rubber thin films showed that a wide range of crystalline morphologies were produced depending on the 'pre-extension'.
2. i. Natural rubber (cis-polyisoprene) is a polymer which may be obtained in a semi-crystalline form.
These five forms of crystalline morphology are sketched in figure 1. 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.-' 33--*e---------_ _
w -. _ . __----I
:`' `?? (. 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. In specimens subjected to very large pre-extensions.--
. 338. A..-.. These filaments were termed a-filaments by Andrews. I
C n? r
1'? . (c) 100%.
Vol.Tensile properties of natural rubber. the crystalline islands had entirely disappeared and only crystalline filaments running perpendicularly to the initial strain direction were observed.
spherulitic structure to become preferentially oriented with the filamentous component aligned perpendicularly to the direction of initial strain. The a-filaments were found to be arranged in ribbons or rows with their axes in the strain direction. little evidence of a-filaments was seen. (b) 50%..
rr I_T ---rr--
. When the preextension reached 100 %.
. The pre-extension direction is vertical..?
. (d) 250%. (e) 500 % pre-extension. Crystalline morphologies in thin films of natural rubber with increasing degrees of pre-extension: (a) 0 %.1
showed identical orientation of the crystalline phase to that in thin films at equivalent pre-extensions. Further evidence of the similarity of the crystalline morphology in thin films and bulk material is given by studies on polychloroprene (Andrews & Reeve 197I). rows oriented in pre-extension direction as for 2 < As < 4 but with steadily increasing y-filament content
4 < As < 7
. stacks oriented in pre-extension direction as for 2 < A. have so far proved unsuccessful. except that crystallization rates. and reveals structures in outline which are similar in size and shape to those observed in the thin films (Reed I970). The changes in crystalline morphology with pre-extension in polychloroprene follow a similar pattern to those in natural rubber. A two-stage replica technique for electron microscope studies has been used to study fracture surfaces of crystallized bulk samples of natural rubber. Experimental studies to observe directly the crystalline morphology in bulk samples. a-filament lengths and y-filament lengths were all reduced by crosslinking. X-ray studies on bulk samples of polychloroprene. a-filament length decreasing and row length increasing with increasing A. lamellae width decreasing and stack length increasing with increasing A8. width and orientation to the rows of a-filaments observed in equivalently pre-extended thin films.. by taking thin sections from the crystallized samples for electron microscope investigation. < 4 but with steadily increasing y-filament content
2 < As < 4
row structure of a-filaments.462
P. 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. crystallized after varying degrees of pre-orientation. 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. Basically the same crystalline morphologies were found to exist as in the uncrosslinked films at corresponding pre-extensions. 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). E. 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. Hence crystalline lamellae in the bulk material correspond to the
The specimens were held at -26 ?C in their stretched condition. The time for maximum crystallinity to be achieved depends on the pre-extension. All specimens were held at . 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 . only 5 ?Cabove the crystallization temperature.I
a-filaments of the thin films at equivalent degrees of pre-extension. a special insulated specimen transfer device was used to transport the specimens from the refrigerator to the pre-cooled testing chamber (Reed 1966). Such data as have been obtained and discussed above support this assumption.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. This temperature has been shown to be the optimum crystallization temperature for natural rubber (Gent I954). while specimens pre-extended by 200 % achieved their maximum crystallinity of 30 % in 2 days. Larger pre-extensions resulted in more rapid crystallization. that samples of natural rubber stretched more than 300 % contain a light-scattering structure oriented in the direction of extension (Yau & Stein 1968). 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. This structure was identified with the y-filaments observed in equivalently oriented thin films.
3. The crystalline morphologies obtained with varying degrees of pre-extension (As) are summarized in the above table.Tensile properties of natural rubber.21 ?C. 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. using light scattering techniques. Unstretched specimens required 20 days at -26 ?C for a maximum crystallinity of 24 % to be obtained.190 to 20 ?C. It has also been demonstrated. Since the crystallized specimens begin to melt at .26 ?C for sufficient time to obtain maximum crystallinity.
120 to . 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.
. All the tensile tests were performed at an extension rate of 2 cm min--. it is possible that the amorphous regions remain oriented after crystallization. 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. The field of the present investigation may be divided into four regions. associated with type A curves. E. In all that follows the pre-extension ratio can thus be regarded as an index of the crystalline morphology present before testing commenced. Hence all tensile tests were repeated using orientated natural rubber samples instead of semi-crystalline samples.464
P. occurs for both types of material at intermediate pre-extensions below Tg. Mitchell & Meier I968). A brittle region. Tensile tests were performed over the temperature range . RESULTS
(a) Types of mechanical tensile behaviour Four different types of deformation were found within the experimental ranges of morphology and temperature studied. The sharp load drop at yield of the type B curve is replaced by a change in slope on the type C curve. 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. thus not allowing time for crystallization to occur.
4. With oriented amorphous samples the type B curve is associated with cold drawing. associated with type B curves. but with crystalline samples stress whitening without cold drawing is observed.26 ?C for each morphology. 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. It occurs at high pre-extension ratios in association with type C curves. For these tests the rubber samples were stretched to the required amount at room temperature and immediately quenched to the test temperature. and may not be distinctly different from the other ductile region below Tg. and may be typified by their respective load-extension curves shown in figure 2. The fourth region is also a ductile region. The three other regions exist below Tg. occurs below Tg for both types of material at small pre-extensions. Since the different crystalline morphologies were produced by varying the amount of orientation prior to 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. Ductile deformation. each region being associated with a particular type of deformation.
However. the fracture stress is not greatly affected by the crystalline morphology when the amorphous phase is rubbery. 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. Figure 4 shows the total extension to rupture (i.Tensile properties of natural rubber. Thus.e. I
strainFIGURE 2. unless the crystalline morphology is either spherulitic or has a high concentration of y-filaments. Deviations from the nearly constant fracture stress occur only when As = 1 or As > 6.
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. stress related to the actual cross-sectional area at rupture) with temperature and crystalline morphology. Typical stress-strain curves for the four different types of tensile behaviour of
natural rubber in the temperature range . pre-extension plus further extension during tensile testing) as a function of the same parameters. The load-extension curves in this region were always of the type D form. Above . except under test conditions close to transitions in deformation mode.70 ?Cthe fracture stress varies only slightly over the complete range of morphology. The inclusion of the crystalline phase in natural rubber apparently modifies. (b) Fracture stress and strain Figure 3 shows the variation of the true breaking stress (i. the mechanical behaviour of the amorphous material.
.120 to -26 ?C (arbitrary scales). This further endorses the conclusion that the crystalline morphology does not significantly affect the ultimate properties when the amorphous phase is rubbery. 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. but does not dramatically vary. 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.e.
for crystallized natural rubber.
FIGURE Variation of the exte 4.CD
3. indicated by the pre-extension ratio. pre-extension ratio. referred to the original u crystallized specimen length and crystalline morphology. Variation of fracture true-stress with temperature and crystalline morphology.
. for cry rubber.
5.5. since at this pre-extension strain crystallization occurs at room temperature. A transition to larger fracture stresses and elongation to rupture occurs at temperatures below .v / I
5.3.5 this transition takes the form of a rapid decrease corresponding to a change to brittle behaviour and type A load extension curves. FIGuURE Change in fracture stress with pre-extension ratio at .
10. However. The introduction of crystallinity in spherulitic form into a glassy amorphous matrix does not inhibit brittle failure in the case of natural rubber.2
. since a similar transition from brittle to ductile behaviour is observed with the oriented amorphous samples.Tensile properties of natural rubber.3
A transition in the fracture stress occurs at about .70 ?Cas the pre-extension ratio exceeds 2. and is associated with a change in the load-extension curve from type A to type B.120 ?Cfor (o) semi-crystalline natural rubber.70 ?.5
/o. When As < 2.
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 fracture stresses of semi-crystalline and oriented non-crystalline specimens for tensile tests performed at . which approximates to the glass transition temperature of the amorphous phase. This transition is 0. The transition may alternatively be related to the increasing orientation of the amorphous phase. ( x ) oriented natural rubber and (v) acrylonitrile-butadiene rubber. although in the latter case the transition occurs at lower pre-extension ratios. The data for noncrystalline natural rubber are not given beyond As = 3. data for acrylonitrile
.120 o0 are compared in figure 5.
When As > 2. is the same as that of the glassy amorphous material alone. (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 6.5 the fracture surface is a single plane transverse to the draw direction and typical of brittle fracture. Hence orientation of the amorphous phase. These latter curves are also reproduced dotted in figure 6 for ease of comparison. which is a non-crystallizing synthetic rubber.40 ?0 and then extended. 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. exhibit similar stresses at a given extension. The fivefold increase in fracture stress of the crystalline material is thus attributed mainly to changes in the crystalline morphology. Corresponding curves for the oriented non-crystalline specimens are shown in figure 7. or extended at room temperature and then cooled. and independent of the path taken to arrive at that state. The inset on figure 6 shows the initial form of the curves to a larger scale.468
P.5 in semicrystalline samples is associated with morphological changes is provided by the fracture surfaces of specimens tested below . No common curve is apparent for the semi-crystalline samples (figure 6). Figure 5 also shows that the fracture stress of the semi-crystalline spherulitic material (As = 1) at -120?C. are included in figure 5. which are in any case small over the range tested. When As < 2. Such behaviour is entirely consistent with rubber elasticity theory which states that the stress is a function of state. 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
. 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. E.5.70 ?C. At . but rather the curves are of similar form for all morphologies and displaced along the extension ratio axis. Reed
butadiene rubber (abr). Specimens cooled to . cannot alone account for the large rise in fracture stress of the semi-crystalline material. The starting extension ratio for each curve indicates the pre-extension ratio or initial morphology. 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 contains 24 % crystallinity. Figure 7 shows that the stress-strain curves of the oriented specimens fall on one single curve regardless of pre-extension ratio providing As < 5.5 a fibrous fracture surface is obtained and bunches of fibrous material are found in the vicinity of the fractured specimen. although it increases the fracture stress. Such fibrous material is consistent with the fracture path going round the stacks of lamellae or y-filaments. The fracture stress values when As > 6 appear to be an extrapolation of the brittle strength values when As < 2.120?C and at high pre-extensions (large y-filament content) the fracture stress decreases abruptly and brittle behaviour again obtains. Further evidence that the change in mechanical behaviour at As = 2.
Dotted curves indicate equivalent data for oriented amorphous specimens. A. Extension ratio values plotted include both extension during tensile testing and pre-extension prior to crystallization.40 ?C.
for oriented amorph .Extension rat both test extension an temperature. A = 1.F *+* PtCD
FIGURE 6. o. A8= 7. Simple elonga
for semi-crystallized natural rubber at -40 ?C. Pre-exten *.
.5. Simple elongation stress-strain curves
FIGURE 7. A = 8 = 5. Insert shows start of some curves to a larger scale.8.
Although these stresses are small. with pre-orientation may result from orientation of the amorphous phase. from considerations of simple composite theory (Holliday I966). The modulus of the crystalline phase must exceed that of the amorphous phase when the latter is rubber-like. the modulus increasing with aspect ratio. ratio of length to width) of the crystalline phase (Halpin & Kardos I972). (d) Behaviour below Tg Three regions of distinctly different behaviour are observed below Tg for both oriented amorphous and semi-crystalline materials. The increase in residual stress with orientation suggests increasing residual orientation in the amorphous phase after crystallization. Less crystallinity results in curves intermediate between the solid curves in figure 6 for crystalline and the dashed curves for oriented amorphous samples. or strain hardening rate. the modulus of the composite will increase with crystalline content. and increases with pre-extension. Alternatively the increasing modulus. Reed
strain hardening and reduce the overall extension to fracture. E. and. Variations in the modulus in small strain tensile tests have been attributed to changes in the aspect ratio (i. 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. The enhancement of the modulus should depend only on the volume fraction of crystalline phase present according to simple composite theory. the stress-strain curves for all semi-crystalline samples may be expected to fall on a common curve. Curves shown in figure 6 are for the maximum crystalline content of approximately 30 %. Figures 8 and 9 show. Stress-strain curves in figure 6 do not commence at zero stress when As > 2. they correspond to significant extension in the amorphous phase if the same residual stresses are applied to the amorphous phase alone.e.470
P. for the
. Evidence of residual orientation is shown by the stress required to maintain the specimens at the pre-orientation extension after crystallization. even after allowance is made for the pre-extension. Since the crystalline content is approximately constant for all samples tested.5. The stiffening effect may result from the stacks of lamellae acting in concert to serve as fibrillar reinforcement. 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. Clearly no such common curve exists for the crystalline samples in figure 6. Such orientation can contribute to the increasing strain hardening rate with preextension as will be discussed in a subsequent paper. The initial stress on each curve indicates the stress required to maintain the pre-extension after crystallization. since the aspect ratio of a stack of lamellae increases with pre-orientation in contrast to that for an individual lamella. Such a reduction in aspect ratio should result in a decrease in modulus according to Halpin & Kardos rather than the increase observed. On initial examination of the results it appears that the crystalline phase may merely serve as a filler in the amorphous matrix.
At pre-extensions below these values ductile deformation is associated with type B
. The plain surface indicates the variation of the yield stress where ductile behaviour obtains. _0. for semi-crystalline natural rubber. indicated by pre-extension ratio.1
9. Variation of brittle fracture stress and yield stress with temperatureand initial
orientation for oriented amorphous natural rubber. the variation in brittle fracture stress or yield stress with temperature and degree of pre-extension. I
of natural rubber.
amorphous and semi-crystalline materials respectively. Brittle fracture and yield are indicated by shaded and plain surfacesrespectively.4
-0.0. 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 9.2
exte. The region of brittle fracture is shown by the shaded region and the fracture stress is plotted.3
. FIGURE Variationof brittle fracturestress and yield stresswith temperatureand crystalline
w1ot20 0 -100
FIGURE8. Brittle fracture and yield are indicated by shaded and plain surfaces respectively.
(ii) Brittle-ductile transition Both oriented amorphous and semi-crystalline materials yield and undergo subsequent plastic deformation at temperatures below Tg. (c) brittle behaviour occurs immediately below Tgwhen As = 1 (unoriented) in the case of the amorphous material. (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. The minimum pre-extension required to cause ductile behaviour increases with decrease in temperature as shown in figures 8 and 9.472
P. It is not clear to what extent the lamellae width affects the strengthening mechanism in the brittle behaviour region. The similarity in behaviour of the oriented amorphous and semi-crystalline samples suggests that yield is associated with the amorphous phase. 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. 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. alined at various angles to the tensile test strain axis initially. At greater pre-extension values than the low point of the trough. Each type of behaviour occurs with both oriented amorphous and semi-crystalline materials. The enhanced brittle fracture stress in the semi-crystalline samples when As > 1 must be attributable to the arrangement of the crystalline phase (i. Since the brittle-ductile transition occurs over a narrow
. since this is common to both cases. 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. Hence the fundamental behaviour must again be attributed to the deformation of the amorphous phase. since a transition to ductile deformation occurs with increased pre-orientation before any significant change in the lamellae width is attained. Reed
curve (figure 2). provided the preextension is sufficiently large. but does not occur until about 20 ?C below Tg in the case of the semicrystalline material containing spherulites. (b) the region of brittle behaviour extends to higher As values in the case of the semi-crystalline samples at temperatures below .e. ductile deformation is associated with type C curves.90 ?C. rather than the mere presence of crystallinity. E. In the latter case the yield stress is taken as the stress at the abrupt change in slope of the stress-strain curve. and a load drop at yield is observed. This view is supported by further tests using a series of specimens which contained mainly parallel lamellae (figure 1 c). but under slightly different conditions of temperature and pre-orientation. The greatest enhancement of the brittle fracture stress occurred when the lamellae were normal to the test direction. crystalline morphology).
90 ?C.0.8. having pre-extension ratios of 1. producing a saw-tooth form of loadextension curve.crystalline oriented
0. 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. Extension at constant load after initial yield is associated with cold drawing in the case of oriented amorphous samples. any effect of crystalline morphology on the transition is not apparent. The stress-strain curves for oriented amorphous and semi-crystalline samples. The semi-crystalline samples exhibit strain hardening immediately after
. Instead of one load decrease at yield on the load-extension curve prior to the propagation of a single yield band. yield occurs when the orientation of the amorphous phase achieves a critical value. at any particular temperature. suggests that the amorphous phase seeks to achieve a natural draw ratio of 4 on yielding. Termination of the deformation at constant load at an extension ratio of 4. Stress-strain for semi-crystalline and oriented amorphous natural rubber at .80 ?C. Results from the oriented amorphous material alone show that.
If yield initiates in the amorphous phase.for specimens pre-extended by 80 % at room temperature prior to crystallization and/or tensile testing.
I. If yield initiates in the amorphous phase at a critical value.90 and . regardless of pre-orientation.
0. subsequent deformation is certainly modified by the presence of a crystalline phase. Non-homogeneous deformation occurs when a spherulitic structure is present. 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.01-
.70?0 the semi-crystalline material is ductile over the whole range of pre-orientation.Tensile properties of natural rubber.I
range of pre-orientation. several load decreases are observed as extension proceeds. Each load decrease is associated with the formation of a new yield band in the specimen. are compared in figure 10. Extensions plotted include the pre-extension. increasing the pre-extension required to change the behaviour from brittle to ductile by approximately 100 % at each test temperature below .03-
0. At temperatures between . although the oriented amorphous material is brittle for small degrees of pre-orientation. The presence of the crystalline phase inhibits yielding.
Such differences in moduli of the amorphous phases could be due to variations in extension. If composite theory is invoked in the present case. since non-Hookean behaviour occurs at temperatures above Tg. If the properties of the amorphous phase are different in the two samples. In all these previous cases. The similarity of figures 11 and 12 shows that the amorphous phase dominates the small strain elastic behaviour of the semi-crystalline material. at the test strain rates adopted. The specimens deform uniformly throughout their length. contrasting with the oriented amorphous behaviour. Starkweather & Brooks I959. The modulus of the oriented amorphous material is always slightly greater than that of the semi-crystalline material when As > 2. 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. crystallinity was introduced without initially orienting the amorphous phase. the moduli of the respective amorphous phases will differ. Stress whitening occurs as deformation proceeds. the modulus of the composite exceeds that of the matrix. however. The usual large increase in the modulus occurs with both types of material at the glass transition of the amorphous phase.474
P. at least macroscopically. Comparison of these figures shows that the changes in moduli with temperature and pre-orientation are similar for both types of material. on the effect of increasing crystallinity on the modulus. In the present case the modulus of the semi-crystalline sample is compared with that of the oriented amorphous material at equivalent pre-extensions. There are. and the inclusion of the crystalline phase does not compensate for this difference. 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. Keller & Pope I97 ). provided the modulus of the matrix is not changed by the addition of the new phase. is thus attributed to
.4. At temperatures above Tg the modulus of both types of material increases with pre-extension. E. Halpin & Kardos have used composite theory to explain the effect of increasing crystallinity on the modulus. possibly due to the formation of voids as a result of incompatibility of the amorphous and crystalline phases during straining. (e) Elastic modulus The initial tangent modulus is used to define the elastic modulus at very small strains. Reed
yield. Halpin & Kardos I972) showing that the introduction of a crystalline phase increases the modulus. When the modulus of the introduced phase exceeds that of the matrix in which it is set. since the modulus of the amorphous material increases with strain. however. small variations between the two figures which are significant.4. The discrepancy between the present work and that reported by other researchers. 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. This contradicts previously reported data (Leitner 1955. Mechanisms of yielding in semi-crystalline polymers have been discussed by other researchers (Peterlin 197I. in contrast to the presently reported work.
This again emphasizes the dominating role of the amorphous phase.Tensile properties of natural rubber. for semi-crystalline natural rubber. Initial tangent modulus plotted against temperature and
pre-extension for oriented amorphous natural rubber. Initial tangent modulus plotted against temperature and crystalline morphology.
variations in orientation of the amorphous phase resulting from the method of introducing the crystallinity. indicated by pre-extension ratio. a small increase in orientation from the non-oriented state results in a twofold increase in modulus for both types of material.
E. 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
FIGURE11. At temperatures below Tg.e
The crystalline morphology thus appears to affect the elastic modulus at A. CONCLUSION
The mechanical behaviour of a semi-crystalline polymer is determined by the behaviour of the crystalline and amorphous phases acting in concert. is not modified by the inclusion of the crystalline phase. 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. 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
. which are common to both semi-crystalline and oriented amorphous materials. 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 %. The same property expressed as engineering stress shows an apparent increase in strength with crystallinity. calculated as true stress. Reed
was observed in this region due to the experimental method used. The tensile strength above Tg. 2 and As > 6 at below Tg. It is apparent. This behaviour has been compared with that of oriented amorphous natural rubber throughout the same range.476
P.s 2 and A. 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. 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. Generally it is difficult to separate the contribution of each phase to the observed behaviour of the polymer. 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. however. > 6. At values intermediate between these values the modulus of both types of material is similar.
5. Fracture surfaces from such specimens are highly fibrous. and higher elastic moduli result. This similarity in behaviour shows that. Four regions of distinctly different tensile behaviour have been identified within the range of the investigation. It appears that these effects are related mainly to the crystallinity present and are not greatly affected by the form of crystalline morphology. Hence the y-filaments serve as fibre reinforcing for the glassy amorphous phase. E. since variations in strain at rupture are not then taken into consideration. Although the stress-strain curves for the oriented amorphous and semi-crystalline materials are similar within any one particular region of tensile behaviour. The crystalline phase thus appears to act mainly as a diluent of the amorphous phase when the latter is an elastomer. that the modulus of the semi-crystalline material exceeds that of the oriented amorphous equivalent at A.
Dixon. R. J. Goppel. & Schmidt. Phys. Leitner. the inclusion of the crystalline phase causes a shift in the ductile-brittle transition to higher temperatures at any given value of preextension. 43. Andrews. Gent. & Pope. which increases with decreasing temperature. & Reeve. P. Sci. H. T. D. 3. A 270. H. Lond. E. 169. 464. appl. Mat. 30 Vol. 9. 1972 J. Hammer. At temperatures below Tg. A. N. Andrews. L. Sci. C. variations in crystalline morphology having little effect on the tensile behaviour. G. It is considered that the formation of a crystalline phase in the equivalently oriented sample causes a relaxation in the amorphous phase. Heffelfinger. J. 1966 Composite materials. C. Amsterdam: Elsevier. F.
. Keller. Oxford University Press. & Jackson. I962 Proc. the stacks being alined in the test direction.. I968 J. J. Sci. I97I J.I
in the amorphous phase resulting from the method of forming the different crystalline morphologies. 1. Soc. The author is indebted to Professor E. 1955 Trans. Mat. Sci. Sci. Poly. Soc. L. it appears that both crystalline morphology and crystallinity affect the tensile strength. 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 . 1959 J. Kelly. Farad Soc. 338. 453. 51. Soc. London. A 277. 562. Halpin. E. 232. H. M. Mat. 2235. Farad. F. appl. R. R. 197I J. A. When the amorphous matrix is glassy. E. Consideration of the data for the oriented amorphous material alone shows that the transition is related to a minimum critical orientation. however. The crystalline phase appears to act mainly as a diluent of the amorphous phase when the latter is an elastomer. E. Lond. J. appl. The lamellae stacks appear to act as fibre reinforcement since the fracture surfaces of these stronger samples is fibrillar. I954 Trans. B. J. B. H. 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. 521.26 ?C. Andrews for suggesting the topic of investigation and many useful discussions. C. A. & Whitney. 50. 6. I965 J. 1015. Koch. elastic modulus and the form of the stress-strain curve. A. & Kardos. I948 Rubber Technology Conference. A. 2661. 547. 6.
REFERENCES Andrews. Poly. I966 Strong solids. J.. Such an increase cannot be explained on the basis of variations in crystalline content or in terms of changes in amorphous phase orientation. Holliday. The author also thanks the Natural Rubber Producers Research Association for providing the samples for the investigation. 1964 Proc.Tensile properties of natural rubber. This dramatic increase in tensile strength is thus attributed to changes in the crystalline morphology. M. Below Tgit is found that a fivefold increase in fracture stress occurs within the range of crystalline morphologies studied.120 to . and results in the shift in brittle-ductile transition to higher temperatures for the crystalline samples.
P. I968 J.. W. P. 1. Reed
Mitchell. I970 Crystallization in thin films of natural rubber. 8. H. Poly. S. I959 J. Sci. P. P. & Stein. Nyburg. Poly. Starkweather. Sci. appl. 1. appl. J. 6. & Brooks. Peterlin. Pritchard. S. Thesis. 236. C. 197I J. D. C. Ph. I970 The influence of crystalline texture on the tensile properties of natural rubber. R. Phys. 1964 J. E. Sci. J. Thesis. Sci. A. & Meier. 1751. A-2. E. Owen. 1954 Br. T. appl.
. Yau. Sci. & Kelly. 321. E. Mat. J. Reed. Sci. 1. Poly. 91.D. Poly.D. University of London. R. A-2. W. P. R. 6. 5. Mat. Dunn. Reed. 6. E. I966 J. Ph. 1689. University of London. 490. I968 J.