CHAPTER 6 PROPERTIES OF VULCANIZATES

RUBBER SCIENCE AND ENGINEERING

20-MTSC-642-001 Spring 2002 MW 2:00-3:15 422D RIEVESCHL W.J. van Ooij 501E ERC Phone 556-3194 Fax 556-3773 Email: vanooiwj@email.uc.edu , wim.vanooij@uc.edu URL: http://www.eng.uc.edu/~wvanooij Prerequisites : Basic knowledge of organic chemistry Knowledge of mechanical properties of materials (e.g., NAPOM)

PROPIEDADES DE LOS VULCANIZADOS [1]

INTRODUCTION [1]

So far we have discussed:

Elastomers Compounding Fillers Processing Vulcanization Vulcanizate Properties Applications of the Vulcanizates

Which ones exist and what are their basic properties? What do we mix into the elastomers and why? The most important additive to the elastomer and the least understood How do we mix these ingredients into the elastomers? How do we form and cure the mixtures into strong elastic materials? What are the properties of the vulcanizates and how are they tested? The major application is automobile tires; each application has its own set of additional, specific test methods

PROPIEDADES DE LOS VULCANIZADOS [2]

TEST METHODS

Some important tests for rubber properties done in industry:

1. Tests of Raw Materials: the material is mixed with other compounding ingredients using a standard formulation and standard mixing procedures; standard sheets are then vulcanized from the standard compound; its properties are then tested; specs are given in various ASTM methods (see Long, page 174); we will not discuss them here (note: before a supplier is approved, the rubber company has to do all this work) 2. Tests for Processibility: ASTM D1646 and D2084 are used; see VULCANIZATION [5] and [6] for the latter (rheometer); D1646 is shown on the next page 3. Tests of Rubber Vulcanizates: comprise >70% of all ASTM rubber test methods; the methods are summarized in ASTM D297; there are more than 200 test methods
Tensile tests stress-strain curves Stiffness including hardness, indentation Elastic recovery compression set, tension set Durability aging, liquid, ozone, light Fatigue test dynamic flexing (cracking) Abrasion tests tread wear Temperature effects high and low T, with and without oxygen Tear resistance with or without nick or cut Electrical tests electrical conductivity, static charging

PROPIEDADES DE LOS VULCANIZADOS [3]

TEST FOR PROCESSIBILITY [1]

Mooney viscosimeter; ASTM D1646

The Mooney viscosity scale is arbitrary and based on one rate of shear Processing is more difficult and requires more energy if the Mooney viscosity increases Sensitive to the condition of the apparatus, temperature of the rubber, and slippage This test does not provide the modulus or the time required for vulcanization (t 90 ); it only measures the first part of the rheometer curve

Processibility equipment can also measure die swell = % increase in diameter or area after extrusion Is caused by relaxation after elongation

PROPIEDADES DE LOS VULCANIZADOS [4]

TEST FOR PROCESSIBILITY [2]

Mooney scorch curve

Notice the meaning of T5 and T 35

PROPIEDADES DE LOS VULCANIZADOS [5]

TEST OF VULCANIZATES [1]

Tensile tests
Using the sample geometry shown left, the following properties are determined from a stress-strain curve obtained on a tensile test machine (e.g., Instron)

Test sample geometry

Stress- strain curve for rubber test piece

Tensile strength = stress at failure (MPa) Ultimate elongation = strain at failure (% of original length, e.g., 450%) 100, 200, 300% modulus = stress at 100, 200, 300% elongation Stiffness = modulus (stress/strain), see secant modulus above right; elongation at specified stress (ASTM D1456); more common is stiffness from hardness or ball indentation tests

PROPIEDADES DE LOS VULCANIZADOS [6]

TEST OF VULCANIZATES [2]

Hardness

Resistance to indentation Important property Expressed as number depending on instrument used Shore durometers are most widely used Their scale is from 0 to 100 Shore A is for soft rubber Shore D for harder products

Hardness testers 7

PROPERTIES OF VULCANIZATES [7]

Die C tear sample

TEST OF VULCANIZATES [3]

Other tear samples

Tear Resistance

cut

Ease of tearing of rubber when nicked or cut varies considerably Depends on: rate of tearing, crystallization of rubber (NR), amount and type of filler, shape of sample and others Results between tests do not agree No tests correlates well with field service Resistance is expressed as N/m (lbs/in) Sensitive to state of cure and often shows a sharp maximum Undercure give smooth curves, tighter cure 8 gives knotty tear especially with black/NR

PROPERTIES OF VULCANIZATES [8] Abrasion Resistance

TEST OF VULCANIZATES [4]

NBS Abrader

Gives relative abrasion resistance compared with a standard compound Widely use for shoe soles Drum rotates at 45 rpm No. of revs to wear compound 2.5 mm is measured (ASTM D1630) The pico abrader is used for tread wear of tires (ASTM D2228) Two tungsten carbide knives are rubbed over the surface and the weight loss is measured
weights

sample abrasive paper on rubber-covered drum

In the tire industry actual road tests need to be performed on a test track

PROPERTIES OF VULCANIZATES [9] Elastic Recovery

TEST OF VULCANIZATES [5]

Compression set is the amount (in %) by which a standard test piece fails to return to its original thickness after having been subjected to a standard compressive load or deflection for a fixed period of time ASTM D395 method A = constant load ASTM D395 method B = constant deflection Aging is included in the test, typically 22 hrs at 70C or 70 hrs at 100C, depending on the type of rubber Equipment for compression set measurement using method B There are many other tests for creep, tension set and stress relaxation

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PROPERTIES OF VULCANIZATES [10] Heat aging [1] Durability [1]

TEST OF VULCANIZATES [6]

Dumbbell samples are heated in air in test tubes At 70C or higher (up to 120C for unsaturated rubbers) The difference in ultimate elongation before and after heating is the criterion for durability All rubbers deteriorate but rate depends on time, temperature and composition There are many other accelerated heat aging tests One variation is ASTM D454, aging at 127C at 550 kPa pressure (air bomb); very drastic; rubber deteriorates in hours

Equipment for heat aging ASTM D865 11

PROPERTIES OF VULCANIZATES [11] Heat aging [2] Durability [2]

TEST OF VULCANIZATES [7]

Rubber samples are heated at 70C in 2 MPa oxygen (some rubbers at 80C) Samples are heated in individual vessels to avoid cross contamination Heating time is 1-5 days

Several ASTM tests exist for testing resistance to ozone; ASTM D149 is widely used Severe surface cracking can occur at 0.00001% O3 in the air; antiozonants can prevent it Ozone attack depends on rubber strain, so tapered or bent loop samples are used

Equipment for oxygen bomb aging ASTM D572

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PROPERTIES OF VULCANIZATES [12] Durability [3]

TEST OF VULCANIZATES [8]

Comparison between natural aging and accelerated aging for an NR tread compound is shown here Note the accelerating factor on the horizontal axis Conclusion: the ASTM D865 test (page 10) gives the best correlation and can be used to predict service life

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PROPERTIES OF VULCANIZATES [13]

TEST OF VULCANIZATES [9]

Resilience, Heat Buildup and Temperature Effects

Resilience is ratio of returned to impressed energy Heat buildup is the amount of impressed energy that is absorbed A pendulum is released from a catch at a point marked 100 and hits a rubber specimen held on an anvil The pendulum has a standard weight and dimensions The scale at the point of rebound is less than 100; this is the energy recovered; the difference is the percent of energy loss

Tg

Goodyear and Lpke resiliometers

Rebound vs. T

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PROPERTIES OF VULCANIZATES [14]

TEST OF VULCANIZATES [10]

The Goodrich flexometer for heat buildup is ASTM D623 The sample is positioned between heated anvils The top one is connected to an adjustable eccentric driven at 1800 rpm Samples are loaded between 0.7 and 2.1 MPa The stroke is between 4.4 and 9.4 mm Under the lower load, high quality elastomers will reach an equilibrium T after 25 min Under the higher load and stroke, all but the highest quality rubber will blow out The blow-out time is a measure of the resistance to failure The brittle point (ASTM D746) is that temperature at which a specimen becomes brittle and will shatter upon bending or impact Elastomers are far superior to plastics in lowtemperature performance They can be compounded for low-T performance

Equipment for heat buildup and low T

The brittle point can be as low as 100C 15 (silicones)

PROPERTIES OF VULCANIZATES [15] Temperature Effects

TEST OF VULCANIZATES [11]

Temperature affects the properties of rubber more than any other factor! At high temperatures, further vulcanization occurs At even higher T, the rubber molecules are depolymerized (remember the Banbury mixer in which depolymerization is done in a controlled way, with or without a peptizer) At higher T the rate of oxidation or rubber is accelerated (and AO is consumed faster) Even in non-oxidizing atmosphere, tensile strength, ultimate elongation and stiffness are affected At low temperatures some rubber will crystallize and become hard (first order transition; second order transition is general stiffening due to cooling) Whether crystalline or not, all rubbers have a Tg, which is well below RT (plastic above RT!) The exact T g of a rubber depends on whether the rubber is deformed: the lower the rate of deformation, the lower the T g There are many ASTM tests procedures for determining the effect of temperature on properties or to determine the lowest temperature of serviceability of a rubber vulcanizate ASTM D1349 gives 18 test temperatures between 75C and 250C DTA is a useful technique to determine the behavior of rubber over a wide range of temperatures It detects crystallization effects and Tg At elevated T, the DTA curve can indicate volatilization, oxidation, pyrolysis or vulcanization 16

PROPERTIES OF VULCANIZATES [16]

TEST OF VULCANIZATES [12]

Flex Resistance or Fatigue Testing [1]

Dynamic flexing deteriorates rubber properties or of the structure of which the rubber is a part The existing test methods do not correlate well with service, yet they are useful in development work Popular test are DeMattia, Goodrich flexometer, Firestone flexometer, Ross flexing apparatus and the Scott flexing machine The tire industry uses the DeMattia (with very high strain) for soft compounds, such as sidewall, innerliner and off-the-rod treads; it is too severe for belt compounds The Monsanto Fatigue-to-Failure (ASTM D4482) is used for many compounds as the strain can be varied and the sample undergoes a pulse/relaxation type of deformation similar to a compound going into and coming out of the footprint The various specialized tests have different applications: Scott for tests that are used to produce separation in rubber-fabric combinations; DuPont for ply separation tests; DeMattia for producing surface cracks by repeated bending (crack initiation); Monsanto for crack initiation + crack growth; Ross is for soling; TEXUS is for cut growth resistance Fatigue of rubber in service arises from the development of small cracks; these cracks grow under repeated deformation eventually leading to catastrophic failure Fatigue originates at minute flaws where the stress is the highest in tires this is the belt edge The cracks form in rubber by one of two causes: a) ozone scission (sidewalls); b) mechanooxidative rupture 17

PROPERTIES OF VULCANIZATES [17]

TEST OF VULCANIZATES [13]

Flex Resistance or Fatigue Testing [2]

Samples are 25 x 6.5 x 150 mm with a transverse groove The grips approach each other from 19 to 76 mm; cracking occurs in the groove which simulates a groove in a tire tread Flexing speed is 300 cycles per min. After a number of cycles, the specimens are rated by comparison with a set of standards (see insert) grade 0 to 10 Test can be continued until all samples become cracked; number of flexures is then recorded Test can be done at non-ambient temperature and in gases other than air

DeMattia flex machine

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PROPERTIES OF VULCANIZATES [18]

TEST OF VULCANIZATES [14]

Flex Resistance or Fatigue Testing [3]

Used mainly for soling materials Test pieces are 25 x 150 mm They are flexed to an angle of 90 at 100 flexings/min. One end is clamped, the other can slide between rollers during flexing Before the test a 2.5 mm cut is made with an awl at the point of maximum flex In the tests the cut growth is measured in 2.5 mm increments

Ross flex machine

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PROPERTIES OF VULCANIZATES [19]

TEST OF VULCANIZATES [15]

Flex Resistance or Fatigue Testing [4]

Dumbbell samples are subjected to a repeated strain cycle and the number of cycles to failure is recorded for each sample The test is a combined measure of crack initiation and crack growth Notice that tests should include a zero strain condition (e.g., by a slight bend) Tests which do not include a zero strain condition can give significantly different results The maximum strain imposed on the sample can be varied over a wide range by changing the cams Fatigue properties can be compared for equal conditions of strain or equal strain energy conditions, see next page

Monsanto Fatigue-to-Failure tester 20

PROPERTIES OF VULCANIZATES [20]

TEST OF VULCANIZATES [16]

Flex Resistance or Fatigue Testing [5]

Compared here are black-filled rubbers vs. extension ratio or strain energy The latter is calculated from the stress-strain curve for a prefatigued sample and integrating the area under the curve up to the extension used in the test Comparison at equal strain energy eliminates differences due to differences in modulus The degree of mixing has a strong influence on the fatigue properties

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PROPERTIES OF VULCANIZATES [21] Weather Resistance [1]

stressed by bending around a mandril

TEST OF VULCANIZATES [17]

sponge

Effect of weathering on inadequately protected rubbers Outdoor exposure of stressed rubber strips on the roof of a plant or test farms is widely done There are several ASTM tests, e.g., D518 and D1171 Rubber inherently has a very poor weathering resistance, but is protected by additives The factors that contribute to the degradation are: heat, oxygen, moisture, light (200-250 nm) and O 3 at 1 ppm or higher levels Similar to paint and other polymers, there are accelerated tests for rubber compounds 22

PROPERTIES OF VULCANIZATES [22] Weather Resistance [2]

TEST OF VULCANIZATES [18]

In this chamber rubber samples are tested for discoloration by exposing them to a standard source of UV light under controlled conditions ASTM D1148, 925, 750 describe the conditions This test is performed with white or light colored products

Weather-o-meter for rubber

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PROPERTIES OF VULCANIZATES [23] Weather Resistance [3]

TEST OF VULCANIZATES [19]

The component of the weathering conditions responsible for the cracking under stressed or strained conditions is ozone, O 3 The severity of the attack is modulus dependent and a direct function of the ozone concentration The strain at which maximum ozone damage occurs is lower for rubbers that crystallize upon stretching, such as polyisoprene Ozone cracking does not occur in saturated polymers, it is an attack of the double bond The extent of damage increases with degree of main chain unsaturation This sensitivity is one of the reasons why NR is not used in treads or sidewalls There are several ASTM tests, e.g., D1149 The ozone concentration in such tests is typically 50-100 ppm Outdoor dynamic testing using the Goodrich flex machine

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PROPERTIES OF VULCANIZATES [24] Dynamic Properties [1]

TEST OF VULCANIZATES [20]

Rapid cycles of loading/unloading occurs in tires, belts, shocks mounts, diaphragms, tank track pads, and many others The question of how elastomers respond has been extensively studied in the last decade Cyclic stresses are modeled as a sine curve, i.e., stress builds up smoothly and declines smoothly in both direction s The two extremes in dynamic responses are elastic vs. viscous materials A viscous damper is a cylinder filled with a fluid of high viscosity; a piston can move in the cylinder but the liquid can flow through the clearance between the cylinder and the wall When a force is applied to the piston it will move, causing the fluid to flow through the clearance The flow lags behind the force and the viscous flow of the liquid translates all the energy of the pistons motion to heat due to internal friction: 0% energy is stored A steel spring is completely elastic: the spring deforms in complete synchronization with a force so that the deflection is maximum when the force is at its maximum As it is forced to deflect, the spring stores 100% of the energy expended through the application of the force to compress it The ratio of the deformation to the force is a constant (the spring constant) 25

PROPERTIES OF VULCANIZATES [25] Dynamic Properties [2]

phase or loss angle, delta elastic force

TEST OF VULCANIZATES [21]

deflection

damping force (viscous) complex force (rubber)

Force diagram for rubber specimen Rubber is neither purely elastic nor purely viscous in its dynamic behavior: some energy is stored and some is dissipated It has a complex dynamic spring rate K* and a complex modulus E* 26

PROPERTIES OF VULCANIZATES [26] Dynamic Properties [3]

TEST OF VULCANIZATES [22]

loss; heat

Mechanical model of dynamic response of rubber

Relationship between complex, storage and loss moduli

The complex modulus E* is the vector sum of the two: E is the storage modulus (100% is stored); the E is the loss modulus (100% is lost, 0% is stored); the angle between the two is d For rubber in shear, G and G are used Both E* and d depend on the compound formulation The degree of storage can be measured in the resilience test (see properties [14]) The loss factor or tan d = E/E is measured more accurately in a Dynamic Mechanical Analyzer as a function of T: it measures the tiny time delay between the force applied and the strain being reached; that plus the complex spring rate gives E, E and tan d NR has a loss factor of 0.08-0.14; very damped polymers can get to 0.3 or higher; a higher factor means: more energy is converted to heat when the rubber is repeatedly strained

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PROPERTIES OF VULCANIZATES [27] Dynamic Properties [4]

TEST OF VULCANIZATES [23]

Thus, higher levels of strain and faster cycling of the stress on the rubber will increase the heat that is liberated We arrive at the important conclusion that for ANY rubber compound, past some point, the amount of strain and the frequency of the dynamic input will combine to produce heat faster than can be conducted away, and heat buildup in the rubber (which is a poor thermal conductor!) can go out of control, possibly resulting in catastrophic failure Since the belt region of a steel-belted tire undergoes the highest shear, such a tire will blow out by complete belt separation (BLB mode) The chances of experiencing such an event increase with the speed (higher frequency of dynamic input), and with the degree of underinflation (higher strain) Two other factors are the outside temperature (conduction!) and vehicle load (higher strain) Important advice: keep the tires inflated, obey the speed limits and do not overload the vehicle!

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