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    Ref - Ozone - Wilchinsky1974

    Uploaded by

    Chanin Ngudsuntear

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    © All Rights Reserved
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    A QUANTITATIVE TEST FOR OZONE RESISTANCE OF RUBBER VULCANIZATES* Z. W. Wiucuinsky ann E, N. Kresan Exxon Cuemicat Company, Linpen, New Jersey 07036 INTRODUCTION In early investigations of ozone cracking of natural rubber vuleanizates, it was established that cracks would not be produced unless the rubber was stretched. Furthermore, it was found necessary to exceed a critical value of the stress or the strain in order to produce ozone cracking, these critical strain values being characteristic of the sample. As the critical strain for natural rubber vulcanizates is typically only about 3-5 per cent!#, this value could easily be exceeded in most applications. Consequently, there was considerable concern about the “degree of cracking,” which includes such factors as the density of cracks and the rate of crack growth. With the development of rubbers having high resistance to ozone attack, critical strains of significantly greater values are obtainable. For example, vulcanized blends of EPDM polymer with general purpose rubbers can be prepared that do not crack at strains of 20 per cent, implying values of critical strain ¢, greater than 20 per cent. Because of this improvement the field of application is greatly expanded in which the strain normally does not exceed ¢-; under this condition the rubber is not susceptible to ozone cracking. For such rubbers it would appear reasonable to characterize their ozone resistance in terms of ¢, or the critical stress o¢ rather than crack density or rate of crack growth. Although ¢. or a can be used, Braden and Gent? concluded that a more appropriate criterion for ozone cracking is the critical elastic stored energy density W., which is the area under the stress-strain curve up to the critical strain. Notwithstanding some of the attractive features of using the critical stress-strain parameters for evaluating ozone resistance, test procedures based on this principle have not been widely used, probably because of the difficulty of obtaining W. by conventional procedures. This drawback is practically eliminated by some procedural simplifications proposed here. Based on these simplifications, a test procedure was developed by which the critical stress strain parameters can be determined rapidly in a routine manner. Some inherent features of the proposed method are examined relevant to the precision of the measurements, and the quantitative feature is illustrated by comparisons with methods based on the time to first observed crack. EXPERIMENTAL DESCRIPTION OF THE TEST Our method is a modification of a scheme described by Andrews’. A tapered specimen is subjected to a tensile force such that the critical stress occurs some- * Presented at a joint meeting of the Rubber Division, American Chemical Society and the Macromolecular Science Division of the Chemical Institute of Canada, Toronto, Ontario, Canada, May 7-10, 1974. 895 896 RUBBER CHEMISTRY AND TECHNOLOGY A 8 c —+|20 b— Fia. 1—Specimen geometry. A: Starting specimen with fiducial marks at ends of tapered section. Nominal dimensions are Lo = 10 cm, a = 0.6 em. B: Specimen stressed on rack just prior to ozone exposure. C: Specimen after ozone exposure. Cracked zone at narrow end of taper is indicated. where within the tapered section, and, while thusly stressed, the sample is exposed to ozone. Cracks appear in the high-stress region toward the narrow end of the taper but are absent from the low-stress region toward the broad end. The position of the boundary (critical boundary) between the cracked and uneracked region is recorded. From this position, according to Andrews’ procedure, the critical strain ¢, was obtained from a previously determined strain distribution along the sample. The critical stress was then read from an independently determined stress-strain curve for this vuleanizate, and We was obtained from the area under this curve bounded by ¢;. However, in the proposed procedure, the critical stress is determined directly from the applied force and the cross sectional area at the critical boundary. The critical strain is calculated from the overall elongation and the position of the critical bound- ary. Finally, W. is calculated from the values of ¢, and ¢, by a relationship OZONE RESISTANCE 897 from the theory of rubber elasticity. Details of this simplified method are presently discussed. TEST SPECIMEN After brief experimentation with several versions of tapered samples, the gcometry shown in Figure 1A was adopted. The tapered section has a ratio of two for the widths at the ends of the taper, and a ratio of length to average width of approximately eleven, A die was fabricated to cut out test specimens from a molded pad of nominal 2 mm thickness. Fiducial marks were inscribed at the ends of the tapered section with the aid of a jig and templet, care being taken to use an inert marker. REQUIRED DATA It is necessary to know the sample width at each end of the taper and the length Lo of the tapered section. Once determined, these values are used for every specimen. Additional parameters needed in the test vary from sample to sample. The specimen thickness is measured at the ends and middle of the tapered section. Then the specimen is suspended by one end on a portable rack and a selected weight is hung at the lower end with the aid of a clamp, as shown in Figure 1B. ‘The applied force is reckoned on the total weight of sample and clamp; the small contribution due to a portion of specimen below a given point on the taper is neglected. After the specimen has been under stress for 16 h, the extended length L is measured with a cathetometer. The rack holding the™specimen is immediately placed in7an ozone chamber and left there for 24 h. Usually, the ozone concentration in the ozone-air mixture was 50 parts per 10* by volume and the oven temperature was 37.8° C (other conditions could, of course, be selected). After the exposure to ozone, the sample is removed from the rack and stretched vigorously to open up cracks whose walls might be stuck together. As indicated in Figure 1C, measurements are made of the length X. to the boundary of the cracked zone, and of the distance Ly between the fiducial marks, The latter might be slightly longer than Lo due to irreversible creep. From these data, calculations are carried out for oz, €2, We, and the clastic modulus Z, as indicated in the following sections. STRESS-STRAIN RELATIONSHIP At elongations below 75 per cent we found that the stress-strain relationship was rather well approximated by a Hookean equation in which a correction is made for the decreased cross sectional area. At a point X on the specimen the relationship can be written P/A,/)dy = Bex, q) where F is the applied force, 4x = (1 + €x) is the extension ratio at X, A, is cross sectional area at X of the undeformed specimen, and A,/Ay is the cross sectional area at X of the deformed specimen. Typical plots of the left side of Equation (1) as a function of ey, shown in Figure 2, are reasonably represented by straight lines, thus confirming the applicability of Equation (1) in the indicated extension range. For most cases which we have encountered, the 898 RUBBER CHEMISTRY AND TECHNOLOGY ao, MPa tc] 20 40 60 Ed 64% Fro. 2.—Typical plots for vulesnized EPDM /natural rubber blends indicating applicability of Equation (1). critical strain was below 50 per cent. Hence the simplified stress-strain relation- ship of Equation (1) is adequate for the intended applications, Critical stress.—In terms of the experimental data the critical stress can be determined by a = F/Cate(1 + Xe/L,)], (2) where a is the undeformed specimen width at the narrow end (x = 0) of the taper, and t, is the specimen thickness at X-, obtained by interpolation between two of the three thickness measurements. This is the so-called engineering stress, i.e., stress uncorrected for reduction in cross sectional area. Critical strain.—The overall or average elongation can be expressed Le Aw = zh xd. (3) OZONE RESISTANCE 899 The elastic modulus at a general point X is the same as that at X = 0. Hence by Equation (1) one obtains OAx/eq = 0e/e0- (4) Also, at X the stress is oy = F/[Ag(1 + X/Lo)]. (5) Combining this with Equation (4) and solving for Ay one obtains = (1+ X/Lo)/C(A/do) + (X/Lo)]. (6) Substituting this expression for \, into Equation (3) permits a simple quadra- ture leading to Equation (7). Hence, a solution to Equation (8) is av = 1+ Qo — 1)(1/%0) In Qo + 1), (7) where Ao is the elongation ratio at X = 0. From the experimental value of ay, one can evaluate do by Equation (7), and from this, one can calculate ¢, by the relationship = (1 1/do)/[%e/Le) + 1/20], (8) where ¢. is expressed as a fraction. Equation (8) is obtainable from Equation (6) by setting \y = 1+ € and X = Considering Equation (6), one may ask what value of X/Lo will give x = dev. The answer is easily obtained for a selected value of do. From Equa- tion (7), the corresponding value of Nay can be calculated, and setting this value equal to A, in Equation (6), one can then solve for X/Lo. When this is done, it is found that X/Lo varies only slightly for relatively wide ranges of do and Mey. For example, for values of Ao between 1.16 and 2.00, the values of Aay range from 1.103 to 1.589 while the corresponding values of X/Lo are in the narrow range 0.436 to 0.410, Using a rough average of 0.42 for X/Lo, one can write the following approximation in accordance with Equation (6): Nav = (1 + 0.42)/[(1/do) + 0.42]. (9) If calculations of X by Equations (9) and (7) are compared for values of ho up to 18, one finds that the error made by using Equation (9) is within the limits £0.002. By substituting the value of Ao from Equation (9) into Equation (8) one obtains Equation (10). For fractional extensions up to about 0.45, a convenient procedure is to use the approximation = (142 — 1.42/hav)/L(Xe/Lo) — 0.42 + 1.42/rav Je (10) For the intended elongation range the calculation error in e, is within +0.002 as shown above. Critical elastic stored energy density——This quantity is calculated from o. and e- by the following relationship from classical theory of rubber elasticity : We = dacte(h? + 2)/(2 + de + 1). qn) Elastic modulus—Finally, the elastic modulus can be obtained from oe 900 RUBBER CHEMISTRY AND TECHNOLOGY ‘Taste I Erect or Operatine Conprtions on Cririca STRESS Ozone concen- Condi- tration, Chamber tioning parts per temp., Exposure oe, Sample time, h 10° by vol. °C time, h MPa 1A 4 50 38 24 0.46 20 50 38 24 0.46 1B 4 100 38 24 0.40 20 100 38 24 0.40 1c 1 200,000 2% 0.25 0.43 4 200,000 25 0.25 0.51 1D 7 50 38 3 0.46 6 0.42 10 0.42 4 0.40 22 037 30 0.36 # All samples have same composition: 20 EPDM, 80 natural rubber, 40 HAF black, 10 oil, 5 ZnO, 1 stearic acid, 1.2 sulfur, 0.2 TMTDS, and 1.5 MBTS. Cure: 30 min at 153° C. and ¢, through the application of Equation (1). One can thus write E = deoe/te (12) Alternatively, this quantity can be obtained from the average extension ratio and oc. the stress at X = 0.42Lo, by the following relationship: E = day (00.42)/ (dav — 1). (13) This relationship is justified if Equation (10) is used. The use of Equation (10) implies that Aay = Ao.a2. One can then evaluate E by substituting the experimental value Agy for Ao.«2 in the relationship E = o.4290.42/ Qo. — 1). (14) The result is Equation (13). PRECISION CONSIDERATIONS Estimates of precision for the critical parameters and E were made from eight replicate determinations for samples from five replicate mixes of an EPDM/natural rubber formulation. The average values and the standard deviations (in parentheses) are: ¢, = 0.437 (0.025) MPa, e, = 0.181 (0.016), W. = 42.0 (3.0) kJ/m*, and E = 2.90 (0.12) MPa. Expressed as a percentage of its respective parameter, the standard deviations are 5.5 per cent for ., 8.9 per cent for ec, 7.2 per cent for Wz, and 4.0 per cent for E. In the latter form, the precision limits were found to be in reasonable agreement with estimates made at other levels of the parameters for a variety of vulcanized blends of EPDM polymers with general purpose rubbers. Studies were also carried out to determine how sensitive the critical param- eters are to ozone concentration, exposure time, and conditioning time under stress. As these bear upon the precision of the desired measurement, the findings will be briefly discussed. OZONE RESISTANCE 901 The data in Table I list results obtained under a variety of test conditions. Results for samples 1A and 1B indicate that the conditioning time under stress, up to 20 h, does not have a significant effect on the critical stress. In practice, the longer conditioning time is preferable as the creep rate is smaller, hence errors in determining Nay due to variations in conditioning time are smaller. For example, a typical value of crecp rate at time ¢ = 4h is 0.2 per cent ho, whereas at 16 h it is 0.05 per cent h-, Thus at the conditioning time of 16 h used in the routine test, an error of say 12 min in conditioning time will lead to an error in Agy of only 0.01 per cent. Increasing the ozone concentration increased the rate of attack on the rubber. Sample 10 in Table I, which was exposed to very high ozone concen- tration, broke within about 15 min; whereas samples 1A and 1B, at low levels of ozone concentration usually used showed only surface cracks after 24 h. However, note that the variations in the critical stress are statistically within the precision of the test whereas the ozone concentration varied by a factor of 4000. One can conclude that variations in ozone concentration normally encountered in the chamber during the test should not significantly affect the precision of the test. Sample 1D in Table I was removed from the ozone chamber several times for inspection to determine the effect of exposure time on the measured value of ¢:. A clearly defined cracked zone was developed within the first three hours, On successive inspections the cracked zone was observed to have advanced slightly toward the low-stress end of the sample. It has not been ascertained whether the vigorous stretching of the sample during the inspections for terminal cracks contributed to the steady decline in ., or whether the new cracks (at greater X) were formed as a consequence of growth of the erstwhile terminal cracks. Stress inhomogeneities would be produced in adjacent un- cracked regions, and might result in a local stress exceeding a. even though the average stress over the cross section is smaller than ¢.. However, considering the observed trend at face value, it is evident that the rate of change occuring at an exposure time of 24 h is rather slow so that errors due to exposure time could be easily held to a negligible level. For example, an error as large as +10 min would lead to an estimated error of only about + 10 per cent in the measured value of o. RESULTS: Although the primary reason for developing the present test method was for evaluating products of commercial interest, details of such application will not be discussed here. Instead, experimental results to be presented are intended to illustrate some features of the method that have been alluded to earlier. Specifically, these concern the use of I. as a single parameter for rating ozone resistance and the relationship between results obtained with the proposed test and tests based on the time to first observed crack. USE OF W, AS A CRITERION FOR OZONE RESISTANCE If samples of the same elastic modulus are compared, then either the critical stress or the critical strain can be used for rating ozone resistance, for both parameters will increase or decrease simultancously. However, for samples of different moduli, comparisons based on only ¢. or only ¢ might not always rate the samples in the same order. For example, one of two samples may have 902 RUBBER CHEMISTRY AND TECHNOLOGY Tape IL Crrricat Srress-Srrain Paramerers as Function oF Evastic Mopuius ‘A, 20 EPDM/80 poly (isoprene) vulcanizates* Relative cone, of cure E, Fey fer We Sample package MPa MPa % AJ /m? 28 0.75 175 041 30.9 61 2B 1.00 2122 0.46 26.1 64 20 1.25 3.07 0.87 2,22 66 2D 1.50 3.18 0.54 20.7 59 B. 25 EPDM/75 poly (isoprene) vulcanizates* 2B 0.75 174 0.35 26.0 50 oF 1.00 2/38 0.43 223 51 2G 1:25 278 0.48 203 50 2H 1.50 342 0.54 187 53 C. Std. dev., as % of parameter A 15 18 56 B 7 4 29 * Formulation: 100 rubber, 40 HAF black, 10 oil, 5 ZnO, 2 stet ® Cure package of relative concentration 1.0 in phr: 1.2 sulfur, Cured 30 min at 153°C. © Formulation : Similar to “a” except carbon black was mixture of 20 HAF and 60 MT. ie acid. .2 TMTDS, 1.5 MBTS. a larger ¢. but a smaller ¢,. To cope with this situation and arrive at a meaningful rating the possibility of using W, asa criterion was explored. Portions of a compound stock were vulcanized to different elastic moduli by varying the concentration of the curatives. The vulcanizates were then evaluated for ozone resistance. From the results for two master batches summar- ized in Table II it can be noted that with increasing modulus E the critical stress increases and the critical strain decreases, whereas, W. remains fairly constant. Thus by using W. as a criterion, the elastic modulus of the vulcanizate is essentially eliminated as a variable in ozone resistance. These results for compounded rubber blends are in agreement with those obtained by Braden and Gent for natural rubber gum vuleanizates. COMPARISON WITH TIME-TO-CRACKING METHODS A widely used test for rating the ozone resistance of rubber vulcanizates is the ASTM? test D-1149, in which a specimen is held at a fixed extension during exposure to ozone and the time to first detected crack is taken as a criterion of ozone resistance. From our extensive record of ozone tests, typical examples are presented in Table III comparing the critical stress-strain parameters with the static ASTM test in which the sample elongation was 20 per cent. The samples were grouped into three categories according to their critical strain. In the first category are samples for which e- is significantly greater than 20 per cent. No cracking was observed for these up to the duration of the ASTM test (1000 h). Thus all the samples in this category would get the same “good” rating on the basis of the time to first detected crack; however, it can be noted that there is a wide range of ozone resistance among these samples if W’, is used as a criterion. At the other extreme, category III, are samples for which éz is significantly less than 20 per cent. All these samples were observed to OZONE RESISTANCE 903 Tasue IIL Comparison or Crirican Srrpss-Srrain Paramerers with Time To Crackina Is Static Test Time to fe oe We first visible Category Sample? -% MPa kJ/m?* rack, bh I. «significantly 3A 39.0 0.65 138 >1000 greater than 20% 3B 30.6 0.50 83 31000 3C 26.7 0.58 83, >1000 3D 430.50 65 >1000 IL. «¢ close to 20% 3h 23.20.46 56 8 to >1000 3F 204 O41 44 8B to >1000 3G 19.0 0.45 45 8 to >1000 TIL. ¢ significantly 3H 182.4. 38 8 to 60 smaller than 20% 31 144 0.33 25 6to8 ay 5 (041 244 6 3K 83 0.39 16.4 30 * Vulcanizates of various EPDM/natural rubber blends compounded with black and cil. develop cracks within only 6 to 8 h, hence all would be given a “poor” rating, although the ozone resistance as measured by W. again show that the samples do differ significantly among themselves. In the second category, for which ¢. is close to 20 per cent, the time to cracking is erratic, so precise ratings cannot be made on this basis, At best, the time to first observed crack is only a quali- tative rating, and in many cases merely classifies the sample into category Tor II. In another ozone test using the time to first crack as a criterion of ozone resistance, the specimen is extended cyclically between selected limits. Results in this test can be related more conveniently to the critical stress than to the other critical parameters. However, one should recognize that in the cyclic extension of a specimen, the stress at maximum extension is greater than that obtained for a static strain of the same magnitude. This can be inferred from Figure 3, in which it can be noted that the stress under static conditions rapidly relaxes to values below the peak cyclic stress. It was, therefore, more appropriate to make comparisons with this dynamic test in terms of peak STRESS ° 2 4 6 e 10 12 4 6 TIME, MINUTES Fic. 3.—Stress decay in cyclic and static extension. Up to time ¢ specimen was stretched cyclically; at ¢ and thereafter, specimen was held at the maximum extension of the cyclic motion, 904 RUBBER CHEMISTRY AND TECHNOLOGY ----¢, Lae ae A 4 lab 4 E10 4 g fo 1 1 1 = 6 3! T T T a 8 oe 4 ©. L ‘O01 0 100 HOURS Fig. 4—Peak stress during dynamic ozone test of EPDM/natural rubber vulcanizates. Conditions were: Ozone concentration, 100 parts per 10°; temperature, 37.8° C; frequency, 2 cycles per min. A: Peak applied stress was smaller than ¢, of sample. B: Peak stress was greater than o, of sample. stress, which was measured with a load cell attached to the stationary end of the sample. When the critical stress of a sample was significantly greater than the applied oyelic peak stress, as is the case in Figure 4A, no ozone cracking was observed, However, if c. was significantly smaller than the applied peak stress, cracks were observed in a rather short time. For the sample of Figure 4B, cracking occurred within about an hour. These limited results indicate that the general behavior of the samples in the dynamic time-to-cracking test can be predicted from their critical stress-strain parameters and stress-relaxation behavior. DISCUSSION AND CONCLUSIONS Several comments based on experience with the test, as well as some overall conclusions are offered. In stressing the specimens an effort was made to select loads that would produce representative zones of cracking and no cracking. Usually the boundary between these zones was located in the central half of the tapered section (0.25

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