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Summary
Chapter Rubber Raw Material Testing
describes chemical analyses of raw materials used in the rubber and tyre-making
industry. This part is dedicated to a principal explanation of basic determinants in
raw material analysis. Such analyses are used primarily to determine basic chemical
and physical-chemical constants that are directly related to purity of the used raw
materials. The second part describes chemical analyses of vulcanizates. More
complex procedures are used and instrumental analytical methods are applied in
chemical analyses of vulcanizates. This part explains principles of instrumental
analyses used in rubber-making practice.
Chapter Rubber Compound and Vulcanizate Testing
is related to the chapter on Rubber Raw Material Testing and provides a
comprehensive description of the system of testing rubber compounds, materials
and vulcanizates, starting from sampling and testing vessels up to evaluation of test
results according to specific standards.
The chapter is divided into four parts as follows:
Vulcanizate Testing
(determining stress-strain properties, hardness, rebound resilience, tear
strength, resistance to abrasion, aging test, dynamic tests, adhesion tests)
Table of contents
Summary ................................................................................................................... 2
Table of contents ....................................................................................................... 3
TESTING OF RUBBER RAW MATERIALS, MIXTURES AND
VULCANIZATES ..................................................................................................... 5
1. Testing of rubber raw materials ........................................................................... 5
2. Chemical analysis of vulcanizates........................................................................ 8
2.1 Determination of extractive parts ............................................................................ 9
2.2 Determination of sulphur........................................................................................ 10
2.3 Determination of polymers ..................................................................................... 11
2.3.1 Instrumental methods of determination............................................................................12
Introduction..................................................................................................... 22
1.1 Preparation of tyres for laboratory tests ............................................................... 22
Static measurements......................................................................................... 23
2.3
2.4
Static measurements......................................................................................... 50
3.2
3.3
Fatigue tests....................................................................................................... 54
3.4
3.
4.
2.2
3.2
3.3
3.4
Testing of vulcanizates.................................................................................... 87
4.1
4.1.1
Assessment of tensile properties (ISO 37, ASTM D 412) ..........................................87
4.1.2 Hardness assessment (ISO 7619, DIN 53 505, ASTM D 2240) ......................................93
4.1.3
Assessment of reflection elasticity (ISO 4662, DIN 53 512)......................................95
4.1.4
Assessment of structural strength (ISO 34-1, ASTM D 624) .....................................96
4.1.5
Abrasive resistance assessment (ISO 4649, DIN 53 516)...........................................97
4.2
4.2.1
508)
4.2.2
4.2.3
4.2.4
4.2.5
4.2.6
4.2.7
Ageing tests........................................................................................................ 98
Assessment of accelerated thermal ageing in air (ISO 188, ASTM D 865, DIN 53
99
Assessment of accelerated thermal ageing in oxygen (ASTM D 572) .....................100
Assessment of resistance against ozone influence (ISO 1431-1)..............................100
Assessment of liquids influence (ISO 1817, DIN 53 521, ASTM D 471)................102
Assessment of permanent tensile deformation (DIN 53 518) ...................................104
Assessment of permanent compressive deformation (ISO 815) ...............................105
Assessment of the brittle temperature limit (ISO 812, ASTM D 746)......................106
4.4
4.4.1
4.4.2
4.4.3
4.4.4
Where:
n2 1
2
n +2
Ratio between compound refraction index at defined temperature and constant wave
length and its density:
Mol refraction Rm is composition of specific refraction and compound M mol
weight:
Rm = r M =
n 2 1 M
n2 + 2
Mol refraction of a certain substance does not depend on temperature and pressure,
at the same time it is only slightly influenced by a change of consistency. Mol
refraction of organic compounds can be figured out as a sum of atom and bonding
refractions that are tabulated. Comparison of experimental and calculated refraction
values is used for confirmation of compound structure.
Refractive index is characteristic magnitude that defines purity of rubber raw
materials and solvents.
Viscosity it is a measure of inner liquid friction. Newtons equation determines
viscosity as a constant of proportionality between tangential stress and speed
gradient (d/dy).
=
d
dy
With oils a viscosity density constant is used. Higher value of viscosity density
constant shows higher portion of aromates in oil. It can be figured out in according
to the relation:
VHK =
PRI (Plasticity Retention Index) this mechanical testing substitutes more time
demanding and more expensive analysing determination of heavy metals in rubbers.
It is based on the matter of fact that some heavy metals present in the rubber sample
at increased temperatures cause destruction of rubber polymer string (polymer
molecular weight is dropping down as well as its physical-mechanical properties
viscosity, plasticity). Raw rubber sample is recalendered and divided into two parts.
One of them is thermally loaded with 140C for 30minutes. Plasticity value
(plasticity deformation measure) will be determined for both samples.
PRI is figured out as follows:
P
PRI = 30 100 %
P0
The most used acetone extract. Out of the sample acetone extracts resins, free
sulphur, in acetone soluble softeners and antioxidants, procesing rubber aditives,
mineral oils, waxes, organic accelerators and their reactive products and fat acids. It
partially extracts bituminous substances, highly molecular hydrocarbons and soaps.
Content of free sulphur, wax and mineral oils may be determined of acetone extract.
Chloroform extracts bituminous substances and we can consider it as indicator of
mixture components presence. Chloroform extract involves also other components
including small rubber amounts. It is applied on the sample that was extracted by
acetone in advance (after determination of acetone extract). In according to analysis
it is also possible to extract by other softeners, e.g. ethanol dilution of potassium
hydroxide (KOH), total extract (extraction ETA) and others.
Extraction takes place in extraction equipments (e.g. extraction device according to
Soxhlet or Twisselman). Exact sample backfill is being extracted for a rated period
by appropriate solvent. Evaluation may be executed in two ways. The first one
reclines upon weighing of extracted sample after perfect removal of solvent rest
from the sample (vulcanizates have the property to swell up in organic solvents) it
can be done by drying, the best way to do that is in vacuum dryer (differential
weighing). The second way is based on weighing of the distillation bulb with the
extract after evaporation of extracting agent (direct extract weighing).
T
he first method, providing that solvent quantity will be removed out of the sample,
provides more correct results. In the second case there might be some losses due to
volatility of some components (e.g. amines formed by decomposition of some
accelerators).
Obtained extract is used for further determinations (content of non-saponifiable
share in acetone extract, content of paraffinic hydrocarbons or content of mineral
oil).
Content of non-saponifiable share is determined in the rest from acetone extract. 1
M dilution of KOH is added to the rest from acetone extract and it is being heated
under reverse cooler. Hydrolysable components are submitted to hydrolysis and
then they are extracted by diethyl ether. The share of acetone extract that has not
been hydrolyzed will be evaluated. The content of paraffinic hydrocarbons is
determined after previous testing. Absolute ethanol is added to the sample, it is
cooled down to -5C and precipitated paraffin is filtered and weighed.
10
amount of sulphur in rubber (added sulphur, sulphur issued from raw materials).
Determination of sulphur is carried out by several methods. The principle for all of
them is oxidation of sulphur atoms onto sulphur dioxide or sulphates.
Nowadays determination of sulphur is executed by the means of elementary
analyzer. Elementary analyzers allow determination of not only sulphur but also
content of nitrogen, carbon, hydrogen and oxygen. The sample is being burnt in the
oxygen atmosphere at the temperature higher than 1200C; burnt gases are cleared
and lead into detector. The most used detectors are either thermal conductivity
detector or infra-red detector. Sample weigh between hundredths of milligrams up
to approximately 1g, detection limits are in dependence on sample type and detector
type from 0.005mg. The whole analysis is lasting for 15minutes.
It is usual to use methods of volumetric or gravimetric analyses in operational
laboratories. The most often used is the method of sample burning, which contains
sulphur in according to Schniger. The sample is packed into ash less paper that
does not contain sulphur compounds and it is burnt in oxygen atmosphere in
Erlenmeyers flask. Burnt products are absorbed in dilution of hydrogen peroxide.
Generated sulphur dioxide is absorbed in dilution and at the same time it is oxidized
while sulphates are being formed. Sulphates may be assessed by gravimetric
analysis, by precipitation with soluble barium salt or by volumetric methods. Final
determination of sulphates is possible to carry out also by the use of automatic
titrator.
Determination of free sulphur is executed in the sample of butanone extract or in the
sample of vulcanizate by boiling with sodium sulphite. In the first case free sulphur
is extracted into butanone. After adding of bromine it is oxidized while sulphates
are being formed and they are determinated by volumetric method and by
precipitation with BaCl2.
With the second method sulphite reacts while boiling with elementary sulphur when
tiosulphate is being formed and it is assessed by titration.
2.3 Determination of polymers
Determination of polymer type and amount belongs to essential determinations.
There are various methods; the most used are, however, instrumental methods of
chemical analysis. At the same time determination of polymers ranks among the
most complex analyses.
Procedures based on volumetric methods:
Determination of polyisoprene rubber amount (NR) is based on sample oxidation by
chrome-sulphuric mixture. Polyisoprene is oxidized while acetic acid is being
formed. Formed acetic acid is determined after distillation alkali metrically by
dilution of NaOH. Other present polymers influence the determination.
11
12
DTG /(%/min)
Flow /(ml/min)
TG /%
TG
100.00
1.00
-11.27 %
-19.76 %
80.00
DTG
200.0
0.00
679 .5 C
-1.00
150.0
60.00
-2.00
-37.85 %
-3.00
40.00
100.0
-1.64 %
-4.00
382 .8 C
887 .5 C
20.00
-18.60 %
50.0
0.00
455 .7 C
nitrogen
air
100.0
-5.00
-6.00
0.0
200.0
300.0
400.0
800.0
900.0
Temperature [C]
Figure No. 2: Comparison between TG record of the same sample in vacuum and
the record in nitrogen atmosphere. The blue curved line means measuring executed
in vacuum and the red curved line means measuring executed in N2 (significantly
better separation of volatile softeners from the beginning of sample polymer matrix
decomposition).
Many decomposition actions run at approximately same temperatures. Due to that
fact the beginning and the end of these actions are difficult to be noticeable;
therefore the first derivation of TG curve is used. We get so called DTG curve and
its minimum (if appropriate maximum) presents the greatest rate of weight change
and this temperature is usually evaluated as characteristic temperature. This
temperature is, however, influenced by geometric sample configuration and location
13
mg
10
TG record
Conversion curves
kJmol^-1
Activation energy
300
8
50
200
6
100
4
0
200
alpha(1%)
h
400
200
400
50
alpha(3%)
alpha(5%)
alpha(2%)
1.5e+006
1.0e+006
5.0e+005
0.0e+000
-20
20
40
60 C
Figure No. 3: Kinetic measuring by the means of TG, executed at different heating
rates.
There is a possibility of thermo-gravimetric analyzer connection the most often with
infra-red or mass spectrometer that allows to identify pyrolyze gases and on their
basis to identify components in the sample. Sometimes there is thermogravimeter
used to be connected with gas chromatograph. This technique is indicated as EGA
Evolved Gas Analysis. TG measuring and spectra monitoring are executed at the
same time and the software permits its simple and fast processing. So called GramSchmidt diagram is evaluated, it shows dependence between overall absorption
(concentration) of forming pyrolyze gases and the time or temperature.
14
15
891.93
Absorbance Units
0.025
0.020
0.015
0.010
0.005
0.000
1800
1600
1400
1200
1000
800
Wavenumber cm-1
16
17
18
S
N
S N
H
SH
H2N
19
20
21
Introduction
Laboratory tyre tests are carried out in laboratories under exactly defined and
regulated conditions. The advantage of laboratory tests lies in their high degree of
repeatability and reproducibility, which is given with the ability of exact regulation
of testing conditions and parameters. Depending on the character of the Testing we
include under these parameters velocity, radial load, inflating pressure, camber
angle, angle of directional deviation, temperature of the environment, relative
humidity of the environment, as well as the duration period of individual test steps.
Laboratory tyre tests can be classified according to several viewpoints. One method
of classification is the division according to the use into individual vehicle
categories:
tyre tests for passenger cars,
tyre tests for utility vehicles,
tyre tests for agricultural vehicles and forest tractors, multi-puropse vehicles,
earthmoving machines and special vehicles ,
tyre tests of solid tyres and solid wheels for industrial carts, manipulators,
barrows, etc.
From the viewpoint of the character we divide tyre tests dependent on the condition
of the tested tyre in following manner:
static tests and measurements during these tests no rolling and rotation of
the tyre occurs and the properties are being measured in static condition
dynamic tests the principle of these tests is the simulation of tyre rolling on
a testing device equipped with a drum, usually in a shape of a cylinder with
a defined surface, for the purpose of tyre life determination,
special dynamic measurements their aim is the determination of various
properties of a rotating tyre, which influence the behaviour of the vehicle
during operation.
1.1 Preparation of tyres for laboratory tests
The procedure of tyre preparation for laboratory tests is usually described in
national standards and regulations. Prior to the fitting, tyres, tubes and flaps
undergo a visual inspection for the purpose of the visible defects detection. Prior to
the tests the tyres can be exposed to non-destruction analyses and tests (rntgen,
ultrasound, holography, interferometry, uniformity test). Tested are tyres, which
have been produced at least 120 hours prior to the test start. For the purpose of
operativeness, this time can be reduced for production quality control up to 24
hours. During this period tyres are being conditioned in a room at a temperature
from 5 to 30C, during last 12 hours at the temperature of the test room. Only after
that it is allowed to mount the tyre on a rim (respectively together with the tube and
flap) and to proceed according to the relevant methodology of the test. The tyre is
Matador Rubber s.r.o 2007
22
being mounted ot the test rim in such a way, that no damage can occur to the tyre,
tube or flap. In order that the bead fits well on rim shoulder, the inflation pressure
can be doubled, but maximally up to 1 200 kPa (for passenger car tyres maximally
up to 600 kPa). Thenafter the inflation pressure shall be adapted to a value required
by the methodology and checked for any pressure drop. With a pressure drop
exceeding 20 kPa, the airtightness must be checked by means of immersing into
water, with the use of a water-detergent mixture or by means of a special agent for
leakage detection.
In case of need, the tyre can be additionally stabilized with a running-in at a drum
test device. This run in is usually carried out at a speed of 60 to 120 km/h, at a load
corresponding from 0,8 up to 1-multiple load of the maximum permitted tyre load
and at an inflation pressure corresponding to this load. The stabilization by means
of a run in , which can last for 1 to 6 hours, serves for the securing the stability of
specific properties and to eliminate mechanical stresses, which act in the tyre after
its cure.
Passenger car tyres include a group of tyres, which is destined predominantly for
car categories M1, N1, O1 and O2, i.e. cars for passenger transport up to a weight
of 3,5 t ( up to 9 seats including the driver, respectively), vehicles up to a load of
3,5 t designated for load transport (mainly pick-up-type vehicles and light trucks)
and their braked or unbraked trailer vehicles with a total weight up to 3,5 t. This
group can include also a part of tyres designed for vehicles of the M1G category,
i.e. free time vehicles (SAV Sport Activity Vehicles, SUV Sport Utility
Vehicles) [1]. Laboratory tyre tests of this kind consist of static measurements,
dynamic tests and special dynamic measurements. Laboratory tyre tests, in contrary
to the testing under exploatation, are carried out with the use of reinforced disc
wheels, consisting of a reinforced disc and reinforced rim. These disc wheels are
manufactured from steels according to STN EN 10020 [2] by turning, in contrary to
pressed or cast disc wheels used on cars. These reinforced disc wheels have very
tight production dimensional tolerances and are designed for loads exceeding
several times the permissible loads of tyres formed together by casing, valve (or
tube and flap in case of tube type tyres) and inflating medium.
2.1
Static measurements
As has been already mentioned before, during static measurements, the properties
and chracteristics of casings and tyres are determined in a non-rotating state.
Following measurements predominantly belong to the static measurements:
measurement of tyre weight,
measurement of tyre crown thickness,
measurement of tread hardness,
measurement of basic tyre outer dimensions,
measurement of static radial strength,
measurement and analysis of tyre footprint,
Matador Rubber s.r.o 2007
23
24
6
210 kPa
240 kPa
260 kPa
8
250 kPa
280 kPa
300 kPa
Bias-belted tyres
Standard tyres: 170 kPa
Radial tyres
Standard
Reinforced
180 kPa
230 kPa
Total tyre width is evaluated depending on tyre design and profile ratio. Tyres with
so-called normal profile (profile number 82, which is not mentioned on the sidewall
in the tyre size designation) have their profile width values listed together with the
measuring rim width in a chart. For tyres of metric series with designated profile
ratio, the profile width is calculated according to following relation:
S = S 1 + K ( A A1 ) ,
(1)
25
26
magnitude [7]. The test is carried out on a test device consisting of a supproting
part with a a shaft, bearing the tested inflated tyre. Another substantial part is the
measuring table with a supporting flat plate, parallel with the tyre rotation axis.
During the test, radial load and radial deformation are recorded. The inflating
pressure usually corresponds to the maximum tyre load, but can be selected due to
the purpose of measurement. Prior to the tyre load itself, the slack circumference of
the tyre is measured with a steel strip. This serves for the calculation of static
radius. Afterwards the tyre is pressed onto the measuring table with a velocity of
0,8 to 2,5 mm.s-1. The tyre deformation is recorded beginning from the moment of
the tyre contact with the measuring table up to the radial load corresponding 150%
of the maximum tyre load. It is measured at least on four different locations of the
tyre, evenly distributed on the tyre circumference. The inflation pressure is not
adjusted during the test. Arithmetical mean value is calculated from the measured
dependencies of radial deformation at load corresponding to 75, 100 a 125 % of
maximum permissible tyre load. Static radial strength of the tyre Cr in kN.mm-1 is
calculated according to the equation:
Cr =
Fr125 Fr 75
S r125 S r 75
(3)
where: Fr125 radial load corresponding to 125 % of maximum tyre load in kN,
Fr75 radial load corresponding to 75 % of maximum tyre load in kN,
Sr125 arithmetical mean of radial tyre deformation values at radial load
corresponding to 125 % of the maximum tyre load in mm,
Sr75 arithmetical mean of radial tyre deformation values at radial load
corresponding to 75 % of the maximum tyre load in mm.
Statictyre diameter rs is calculated as follows:
rs =
where:
l0
Sr
2
(4)
Static radial strength of the tyre is a very important property, because it deals with
deformation properties of the tyre , which happen under real exploatation conditions
of the tyre as a part of vehicle chassis assembly. Apart from static radial strength,
static lateral, circumferential and torsional strength can be measured, by which
detailed information about the tyre strength in all directions can be obtained.
Static tyre footprint is evaluated from the footprint, prepared on the same load
equipment, where the static radial strength is being measured. The tyre, consisting
27
28
29
Table 3 Tyre inflating pressure for tyre strength test and bead resistance to rim
skid according to the Regulation FMVSS Nr.109 in dependence from the maximum
permissible tyre inflation pressure
Maximum
permissible tyre
inflating pressure
in PSI
32
36
40
60
Maximum
permissible
tyre
inflating pressure in
kPa
24 28 30 34 35
0 0 0 0 0
Maximum
permissible tyre
inflating pressure
in kPa (1)
290 330 350 390
Inflatin
18 22 18 22 18
g
165 193 221 359
230 270 230 270
0 0 0 0 0
pressur
e in kPa
(1) Only for CT casings (tyres with reversed bead)
Test is being carried out at a surrounding temperature of (255) C. The tyre is
being fastened on the measuring device shaft and measuring locations on the
sidewall are being numbered. The mandrel must be located closest possible to the
tyre alignment plane so that the test location is in the middle of the tread pattern
(Picture 2). The measurement is carried out at least in five locations roughly evenly
distributed on the tyre circumference. The criterion for the test end is either the tyre
puncture, the reaching of required value of deformation work (puncture energy), or
contact of inner tyre rubber with the rim. The result of the test is puncture energy,
calculated as mean value of individual measurements. For individual measurements
it is calculated as follows:
W=
F .P
2.103
(5)
30
Table 5 Minimum puncture energies for passenger car tyres with cross-ply and 6
inch profile width, J
Maximum permissible inflating pressure
Cord material
280
kPa
300
kPa
340
kPa
291
373
186
373
186
373
Polyamide
(nylon)
polyester
441
588
294
588
294
588
or 294
Table 6 Minimum puncture energies of passenger car tyres with cross-ply design
and with a profile width less than 6 inches, J
Maximum permissible inflating pressure
Cord material
280
kPa
300
kPa
340
kPa
212
283
113
283
113
283
Polyamide
(nylon)
polyester
331
441
220
441
220
441
or 220
31
32
leading to bead skid from rim of the test disc wheel is being measured. The dvice
for bead rim skid must fulfill these conditions:
it must be capable of exerting a force , which stresses the tyre at least to 300 %
of the load corresponding to maximum tyre load,
it must fasten the tyre in such a manner , that its rotational axis and segment
travel direction are paralel,
it must allow the repetition of the test at least on four different locations on the
tyre circumference.
The principle of the device is given in the Picture 3. The shaped segment serving for
pressing of the sidewall is manufactured from aluminium, with a determined surface
roughness. The tyres are being tested under inflation according to table 3.
33
Table 7 Distance A of the pressing segment from the vertical tyre axis
Code
of
nominal
diameter
19
18
17
16
15
14
13
12
11
10
320
340
345
365
370
390
415
Picture 4 Detail of a shaped segment acting on the tyre sidewall during test of
a tubeless tyre bead resistance against rim skid
For the tread evaluation of new and retreaded tyres, as well as tyre wear resistance
and for the evaluation of the tyre wear, serves the measurement of read groove
depth and of the tread wear indicators height. For the measurement of read
Matador Rubber s.r.o 2007
34
groove depth and of the tread wear indicators height depth gauges are used, with the
support base surface of at least 450 mm2 and scale increments 0,1 mm, eventually
even more precise. Prior to the measurement all impurities, which could influence
the measurement, are removed from the tyre tread. Some regulations and standards
require measurement of read groove depth, resp. of the tread wear indicators on
a tyre inflated at least to 50 % of the maximum permissible inflating value, others
do not require any specific conditions during measurement (EEC Regulations Nr.
30, Directive 92/23/EEC and FMVSS Nr. 109) [4, 5, 8]. The tip of the depth gauge
must be perpendicular to the tread surface during measurement. The depth of tread
grooves is determined at least on six locations uniformly distributed round the tyre
circumference. It is measured in the proximity of tread wear indicators in the main
tread grooves. Main tread grooves are in the sense of the definition of EEC
Regulation Nr.30 the wide grooves located in the central part of tyre tread, which
comprise inside tread wear indicators. In case of tyre measurement under irregular
wear of the tread surface, the measurement is carried out in the location with
smallest tread groove depth. The height of wear indicators is determined in such
a manner, that the tread groove depth in immediate proximity of wear indicators at
its toe is measured first and afterwards the tread groove depth direct on the indicator
is being measured. The difference of these values provides the wear indicator
height. The wear indicator height in some regulations is given in a following way:
( 1,60 +00,,60
00 )mm for passenger car tyres according to EEC Regulation Nr. 30 and
Directive 92/23/EHS,
1,60 mm for passenger car tyres according to regulation FMVSS Nr. 109.
The result of the measurement is the arithmetical mean of individual tread groove
depth and tread indicators height measurements on new and retreaded tyres. At
tread groove depth of tyres in operation, the result is the smallest value of tread
groove depth. This divverence in evaluation is caused by the fact, that the
legislation in individual countries prescribes the minimum residual tyre tread
groove depth of vehicles in the public traffic and this is connected with minimum
safety requirements on vehicle handling, especially on wet surface.
With the measurement of seating forces in the tyre bead the radial stiffness of the
tyre bead is determined. Radial stiffness of the bead is a parameter, which is
in significant relation with the safety and fitting capabilities of tubeless tyres on the
rim of a disc wheel. Low radial stiffness can bear as a consequence bead skid from
the rim at application of lateral forces on the tyre during various driving
manoeuvres in transversal inclination. High radial stiffness has in contrary as
a consequence a difficult tyre fit on rims equipped with safety humps , where
a damaging of the bead wires and consequent tyre burst can occur during the
overrun of the safety hump. Therefore an optimum radial bead stiffness of the tyre
must be secured, which lies between so-called safety limit and limit of fitting
capability.
35
The test is carried out on a device equipped with jaws, consisting of individual
segments, which are expanded by means of hydraulic cylinders. Each segment pair,
located opposite to each other has a dynamometer, which is measuring the segment
force acting on thetyre bead and vice-versa (figure 5). Apart of that, the device must
be equipped with a segment position sensor compared to zero position,
corresponding to nominal rim diameter. The test is normalized in the methodology
of German Rubber Industry association WdK 116 [9]. The tyre can be tested at least
after 72 hours after its production. Prior to the measurement the tyre must be stored
and conditioned at least fo 24 hours under room temperature (235) C in vertical
position. Jaws, dependent on tyre bead parameter, are mounted on the testing
machine. Nominal jaws diameter Dnom, corresponding to the so-called zero position
is listed in the Table 8. This position is checked with the help of so-called
calibrating rings, having precise shape and inner diameter and are laid on jaws in
the same manner like the tyre bead. The streading velocity of the jaws is set to
6 mm.min-1. Talc is applied on both tyre beads. Tyre is laid with its serial side (side
comprising DOT, or serial number) on jaws, which are in their initial position
completely drawn back to the minimum diameter, allowing tyre bead fitting. After
resetting of dynamometers, the jaws are spread to a diameter Dnom+0,8 mm,
securing tyre bead prestressing before measurement, after which the jaws travel
back into their initial position. The value of radial bead stiffness is determined by
repeated spreading of the jaws at tyre bead deformation values of Dnom-0,29 mm for
the safety limit and Dnom+0,38 mm for the fitting limit. Afterwards the bead on the
opposite tyre side is measured in the same manner. So far a repeated measurement
must be carried out on the same tyre, this can be done after 48 or 72 hours
respectively, due to the tyre relaxation.
Table 8 Nominal jaw diameter serving as zero position for the measuring of
seating forces in the tyre bead, according to the Standard WdK 116
Nominal jaws diameter
Nominal rim diameter code Dnom
[mm]
10
251,87
12
302,67
13
328,07
14
353,47
15
378,87
16
404,27
17
435,22
18
460,62
19
486,02
20
511,42
21
536,82
22
562,22
36
Picture 5 Testing machine for measuring of seating forces in the tyre bead. View of
the jaws, consisting of individual segments.
Prior to the test the tyre and rim undergo a visual check. Tyre beads must not be
damaged. Testing rim must be clean, not injured and must have a relevant surface
ptotection treatment. Tyre beads and rim shoulders are painted with fitting grease
and the tyre is fitted in way, that no tyre bead as well as no tubeless valve damage
can occur.
Under method A the tyre is inflated to a value corrsponding to maximum
permissible load. Afterwards i tis immersed into water. After immersion no bubbles
can escape into water through the tyre walls , bead area or the valve. So far as air is
leaking through the valve, spring insert, or the entire valve are exchanged for new
and test is repeated.
During test under method B the temperature in the test room is kept during the
conditioning as well as during the measuring itself in a span of (255) C. Prior to
the measuring the tyre id conditioned for 24 hours under above mentioned inflating
pressure. Afterwards the inflating pressure is adjusted again to this value and tyre is
stored for a period of 28 days. After this period the tyre air pressure loss is
measured by a manometer of precision class 0,6 maximum. The value of pressure
drop shall not be smaller than 5kPa. In case, that the initial and final temperature in
the test room differ from each other, a calculation of pressure loss p in kPa to
a reference temperature 25 C is to be carried out according to following equation:
37
p + 100 p2 + 100
p = (t ref + 273). 1
t1 + 273 t 2 + 273
(6)
2.2
By means of dynamic tests the durability characteristics of tyres are checked by the
rolling on outer or inner surface of steel testing drum under fulfilment of prescribed
conditions of speed, radial load, inflating, temperature of the environment, camber,
directional deviation, acceleration, braking and duration period of individual steps.
Duration of dynamic tests is set either by prescribed time limit, or the discontinuity
of tyre structure and integrity. Speed tests of passenger car tyres are focused on
checking of tyre durability under high speeds, close to, or exceeding the speed
rating of the tyre. Their duration is short in comparison with fatigue tests. Typical
duration of high speed tests is cca 60 to 150 minutes, dependent on test type speed
rating, and tyre design. Typical tyre damage at speed tests is the tearing of rubber
from the tread, tearing of tread blocks and separation of reinforcing strips
(breakers). At high speed tests, a radial tyre load of cca from 68 % to 85 % of
maximum permissible tyre load is used. This level of load allows the use of steel
disc wheels, or eventually disc wheels manufactured from light alloys, instead of
special reinforced ones.
Single-position or double-position testing machines are used for high speed tests.
The main part of this machine is a steel drum with a smooth surface. Drums with
a diameter of 2 000 mm 1 % or 1 707 mm 1 % are used for passenger car tyres
testing. These are prescribed in individual international and national standards and
regulations. In the past, drums with diameters of 1 592 mm, or 1 512 mm
respectively, have been used. The drum is fitted in a supporting frame, which must
secure the needed stiffness of the whole machine. The drum is driven by an electric
motor with the help of driving belts. Further, the machine is equipped with one or
two test positions, consisting of a rotary head, on which the tested tyre is fitted.
Rotary head is seated on bearings with low friction. Usually it has a disc brake for
simplifying of disc wheel fit and for its braking after finishing of the test. Testing
position is also equipped with a system of end position sensors, securing the
withdrawing of the tyre at separation in the tyre casing, or at decreasing of the
dynamic radius of spinning tyre due to inflating pressure drop (Picture 6). Testing
position can be equipped with a mechanical device for camber adjustment, or
directional deviation adjustment. The tyre is pressed preumatically or hydraulically
on the test machine drum. At present, the use of mechanical loading with the help of
38
weights or endless screw is abandoned. The testing machine can be also equipped
with a system of regulation, measuring, or eventually monitoring of test parameters
like drum speed, radial load, temperature of the environment, dynamic tyre radius,
camber angle, directional deviation angle, inflating pressure or tyre temperature.
For high speed tests, higher requirements are put on regulation precision and test
parameter measuring, than for fatigue tests.
Basic and most widely used high speed test for passenger car tyres is test in
accordance with EEC Regulation Nr. 30 [4]. By this test the basic safety
characteristics of tyres are verified. The principle of this speed test, as well as of all
speed tests is gradual drum speed increase aunder a constant radial load in
prescribed time steps until the prescribed time duration is reached, or a tyre
destruction takes place.
New or retreaded tyre is fit on a prescribed testing rim. The tyre is inflated to
relevant pressure listed in Table 9:
Table 9 Tyre inflating pressure in kPa for tests according to methodology EEC Nr.
30
Tyres with cross-ply Tyres with radial
Bias belted
Speed design (bias ply)
design
tyres
categor
Conventional
ply
Reinfor
y rating
Normal
ced
4
6
8
Normal
L, M, N 230
270
300
240
280
P, Q, R, 280
300
330
260
300
260
T, U, H 280
320
350
280
320
280
V
300
340
370
300
340
W
320
360
Y
320
360
39
Table 10 Multipliers for the maximum tyre load for the determination of radial
load according to EEC Regulation Nr.30
Multiplier of the maximum tyre
Speed category symbol
load for determination of radial
load
0,8
H
V
0,728
W, Y
0,68
The pressure in the tyre is not adjusted during the test and a constant radial load is
maintained. The temperature in the test room during the test is kept in a span of
(255) C or at a higher temperature, if the manufacturer agrees. During the test,
following conditions are continuously fulfilled:
1. Tyres of speed category 120 km/h (Symbol L) up to 270 km/h (Symbol W):
Time duration of a continuous transition from zero speed to the initial speed is
10 minutes. The tyre is then spinning at this speed for another 10 minutes.
Afterwards, the speed is increased by 10 km/h in steps after every 10 minutes,
until the maximum test speed is not reached. This speed step lasts for 20
minutes and then the tyre is stopped.
2. Tyres of speed category 300 km/h (Symbol Y):
Time duration of a continuous transition from zero speed to the initial speed is
10 minutes. The tyre is then spinning at this speed for another 20 minutes.
Afterwards, the speed is increased by 10 km/h in steps after every 10 minutes,
until the maximum test speed is not reached. This speed step lasts for 10
minutes and then the tyre is stopped.
Initial test speed is a speed corresponding to the speed category of the tyre,
reduced by 40 km/h in case of a test drum with a diameter of 1 707 mm 1 % or
by 30 km/h in case of a test drum with a diameter of 2 000 mm 1 %.
Maximum test speed is a speed corresponding to the speed category of the tyre,
reduced by 10 km/h in case of a test drum with a diameter of 1 707 mm 1 % or
corresponding to the tyre speed category in case of a test drum diameter of
2 000 m 1 %.
With tests of tyres suitable for speed above 300 km/h, one additional test is carried
out according to EEC Regulation Nr. 30. A radial load, corresponding to 80 % of
maximum load assigned to maximum speed set by the tyre manufacturer is used.
The starting time from zero to maximum speed as set by the manufacturer is 10
minutes. Then the tyre is being tested at this testing speed for 5 minutes. The test is
carried out continuously.
Tyre submitted to these tests shall not show any tread, ply or cord separations, as
well as rubber tearings or cord breakage.
40
41
42
Table 12 Inflating pressure for high speed test according to Regulation FMVSS Nr.
139
Tyre type
Inflating
[ kPa ]
P-metric:
Standard
Reinforced
220
260
LT:
Load Range C
Load Range D
Load Range E
320
410
500
CT:
Standard
Reinforced
270
310
pressure
Run-in and subsequent cooling of the tyre is carried out in the same way as in
previous case, under a radial load corresponding to 85 % of the maximum tyre load
designated on the sidewall. Test is run continuously and without any interruption
for 90 minutes and consists of three subsequent steps with a duration of 30 minutes
at speeds of 140, 150 and 160 km/h. Radial load during test is 85 % of the
maximum tyre load, the inflation is left freely increasing. Immediately after the tyre
test, its inflating pressure is measured. The tyre is left to cool down for 1 hour.
Then the air is deflated out of the tyre, the tyre is dismantled from the test rim and
checked whether it corresponds to the set requirements.
2.3
Tyre fatigue tests are dynamic tests serving to establish the tyre durability. The
duration of these tests is much longer than with speed tests. Typical time span of
fatigue tests for passenger car tyres is 80 to 250 hours. Fatigue tests are usually
carried out at a constant speed. Other test parameters, like radial load and inflation
can be constant during the tests, but can also be modified.
Test conditions are chosen according to the fact, on which tyre part the test is
focused. No universal fatigue test exists. Fatigue tests are usually focused on tyre
beads and carcass area, mainly reinforcing strips. At bead fatigue tests a lower
speed and higher load is used. These test conditions provide lower tehermal and
mechanical stress of the tyre in the crown area and a higher load in tyre bead area.
During bead fatigue tests a speed of 60 km/h is normally used, radial load is chosen
dependent on test methodology and tyre aspect ratio from 1,5 to double maximum
permitted tyre load. Inflating pressure depends on tyre methodology, but usually it
is 250 kPa. Fatigue tests are generally executed at temperatures (255)C, but
temperatures of test rooms (383)C are used more and more often.
Matador Rubber s.r.o 2007
43
At carcass fatigue tests a speed of 80 to 120 km/h i sused and a radial load
representing 1,2 to 1,6-times of the maximum premissible tyre load. Tyre is usually
over-inflated in this test. These test conditions secure tyre injuries typical for this
kind of test: tread separations, separations of reinforcing strips (breakers), tearing of
tread blocks, cracks between tread blocks in tread grooves, or broken cords,
respectively.
After the execution of speed, as well as fatigue tests, the tyres are analyzed and
reasons of tyre injury are searched for. For the reason of analysis the tyre is usually
cut in radial direction in two locations in such a manner, that the damage of the tyre
can be evaluated from the collected section. Optical microscopy can be also used in
this operation.
2.4
44
During force method, the reaction force at the tyre shaft is measured, from which
passive losses caused by shaft friction and aerodynamic tyre resistanse are
subtracted. These passive losses are measured as the force on tyre shaft during tyre
rolling, at a load close to 50 N, i.e. practically withour rolling resistance. The rolling
resistance is then calculated as:
(7)
45
During the torque method, the driving torque M of the test drum with tyre at
prescribed radial load is measured, as well as passive torque Mp under tyre radial
load cca 50 N. The tyre rolling resistance is then calculated from the following
equation:
Fr =
M Mp
R
(8)
Fr
F
(9)
(10)
(R1 / R2 )(R2 + rT )
R1 + rT
(11)
46
During the measurement of dynamic directional chracteristics, the lateral force and
reversing torque of a tyre rolling at constant speed on the surface of test drum are
established. From dependence of lateral force, or reversing force on the angle of
directional deviation , the directional stiffness, or reversing torque stiffness, is
established. Dynamic directional characteristics have big expressive value in
relation to tyre behaviour on vehicle steering axles, where they determine the tyre
behaviour in relation to transfer of lateral forces under given steering wheel wind
and relating angle of directional deviation of the wheels. The lateral force and
reversing torque are measured on so-called multiple-component heads ( twocomponent, five-component, six-component). These are special hubs, on which disc
wheels are mounted comprising inside a set of tensometers or piezoelectric sensors,
after an amplification on measuring amplifier, capable of measurement of
individual force and torque components acting on tyre:
Radial force,
Lateral force,
Circumferential force,
Reversing torque,
Pitch torque
Braking or eventually deriving torque.
During the assesment, regulated inflation is used, i.e. the inflating pressure is during
the measurement maintained at a constant, preset value. The tyre is pressed on test
drum and is kept rolling for a certain period of time at preset speed and radial load,
zero camber angle and zero directional deviation, which is needed for its thermal
stabilization. This time is at least 30 minutes. Directional deviation angle is then
changed to preset value and a preset rate of directional deviation angle change the
transition from given value into opposite side takes place, under simultaneous
registering the dependence of lateral force size and reversing torque on the
directional deviation angle. At a certain value of directional deviation angle, the tyre
is not capable of bearing the lateral forces any more and tyre slipping on drum
surface takes place, which is demonstrated by the decrease of absolute value of
lateral force, as well as reversing torque together with increase of absolute value of
directional deviation.
Forces and torques which originate during tyre rolling are influenced by many
factors: surface type and roughness, speed, temperature, water on the surface,
dynamic properties of condition changes in tyre operation, driving and braking tyre
torques, etc. The properties of forces and torques are in their substance independent
on speed, as long the tyre is rolling without extensive slipping in the contact area
with the surface. Dry surface test have shown, that speed influence is low in a wide
extent of directional deviation angle. More methods can be used for the test. One of
47
four variable inputs (radial load, inflating pressure, directional deviation angle,
camber) changes usually gradually or in a jump, with others remaining constant.
2.4.5 Measurements on high speed uniformity test
High speed uniformity test is carried out additionally to common tyre uniformity
test on testing machines, which are in their design similar to testing machines for
high speed tests. The essential part of the machine is a drum, fitted and driven in
a base frame, having a diameter of 1 500 to 3 000 mm, smooth surface and a tyre
loading system. The frame has the property that it is sufficiently rigid and has own
high frequences, causing that a resonance of the system is eliminated during high
speed measurement of a rotating tyre. During high speed uniformity test similar
properties are being measured, than on a common uniformity test. But as
a consequence of high rolling speeds, centrifugal forces are acting on the tyre and
the tyre behaviour is similar to behaviour under real conditions on the vehicle.
2.4.6 Measurement of temperature distribution
Rotation of a loaded tyre and its continual deformation cause as their consequence
heat generation, manifested by temperature increase of the tyre closed in the tyre
and by tyre temperature increase. This tempereture rises continuously, until it
reaches a balanced level under stabilized test conditions, where the heat formation
rate is equal to heat passage from the tyre into environment. Temperature
distribution in the tyre, like temperature values themselves depend on radial load,
camber, speed of rotation and temperature of the environment. In the location where
a separation or tyre integrity breach takes place, a local temperature increase occurs.
The measurement of tyre temperature can therefore be during destruction tests
utilized as an effective instrument for the disclosure of beginning tyre injuries.
Continuous temperature measurement inside the tyre is very complicated, as
resistance or voltage temperature sensors have to be built into the tyre body and
such sensors act as foreign element in the casing and influence its behaviour.
Contact-free optical measurement of surface temperature of the tyre is therefore
utilized in the practice. Cameras, sensitive to infrared area of radiation are used
here, capable of temperature measurement of rotating bodies. Afterwards there is no
difficulty to process a signal of such camera in a computer, display the tyre surface
and to assign a specific display colouring to each temperature interval (figure 7).
The measurement of rotating tyre temperature has its significance apart from
product quality control also in the verification of dynamic mathematical tyre model.
48
49
Tyres for utility vehicles comprise a group of tyres, designed mainly for vehicles of
categories M2 and M3 (buses), vehicles of category N2 and N3 ( vehicles designed
for load transportation) and vehicles of category O3 and O4 (braked trailers with
a total weight more than 3,5 t) [1].
The character of the tests and measurements is the same as with tests of tyres
designed for passenger cars. There is a certain difference with dynamic tests, where
a bigger emphasis is laid on fatigue tests of the carcass and tyre bead, and a smaller
emphasis on speed tests. This is corresponding with the philosophy, that the
maximum designed speed of this vehicle category, given also by the obligatory use
of speed restrictors, set from 80 do 100 km/h, dependent on vehicle category.
Because the principle of tyre tests for truck tyres is similar to the test principle of
passenger car tyres, only the differences to these methodologies will be mentined in
the following.
3.1
Static measurements
Tyres for utility vehicles and their trailers are submitted to following tests:
Tyre weight measurement,
Measurement of tyre crown thickness,
Measurement of tread hardness,
measurement of basic tyre outer dimensions,
measurement of static radial strength,
measurement and analysis of tyre footprint,
measurement of specific pressure distribution in the tyre footprint,
measurement of mandrel puncture strength in the tyre crown,
determination of tyre resistance to water pressure destruction,
measurement of bead resistance to rim skid of a tubeless tyre,
Matador Rubber s.r.o 2007
50
measurement of the tread groove depth and the height of tread wear indicators,
measurements of tyre surface electric resistance .
Weight, crown thickness and tyre trad hardness are measured in the same way
as with passenger car tyres. The measurement of outside tyre dimensions
is equivalent, with the difference, that as inflating presssure value for measurement,
the inflating pressure corresponding to maximum tyre load is used, which is set by
the tyre manufacturer, eventually by charts in poblications of tyre producers,
associations. During assesment of tyre dimensions according to EEC Regulation
Nr.54 [12] the same procceding i sused, as with evaluation of passenger car tyres in
accordance with EEC Regulation Nr.30. The difference is in the coefficients
(factors) a and b, listed in the Table 13:
Table 13 Coefficient values a and b, needed for the calculation of outer tyre
diameter limiting values
Design
a
b
Radial
nominal profile width less or equal to
1,04
305 mm
Radial
1,02
nominal profile width bigger than 305
mm
0,97
Cross-ply
(diagonal)
1,08
nominal profile width less or equal to
305 mm
Cross-ply
(diagonal)
1,04
nominal profile width bigger than 305
mm
For M+S tyres , the limiting value Dmax is increased by further 1 %.
Tests of static radial, tyre footprint and contact pressure distribution in the
tyre footprint are equivalent to tests for passenger car tyres.
The test of tyre carcass strength and resistance strength to mandrel puncture in
the tyre crown in accordance with the Regulation FMVSS Nr. 119 has a big
importance for utility vehicle tyres [13]. By this test, the compliance with
conditions for tyre strength marking Load Range is verified, which is important
mainly for non-european countries, where the load index is not used as a part of the
tyre description. The tyre is inflated to a pressure corresponding to tyre load in a
twin-assembly, prior to the test. If the tyre description on the sidewall contains only
the maximum load for a single assembly, the inflating pressure corresponding to
maximum load in a single assembly is used. Mandrel with the same geometry, as
described in the chapter 2.1 is used for the test, with a diameter depending on tested
tyre. The mandrel diameter dependent on tyre size is listed in the Table 14:
51
Table 14 Mandrel diameters for utility car tyres and their trailers
Mandrel
Tyre type for
diameter
[mm]
Light utility vehicles
19,05
Tyres for rims with a nominal tyre rim diameter 12 and
19,05
less
Tyres different from those listed above:
Tubeless:
With nominal rim diameter 17,5 and less
19,05
With nominal rim diamater bigger than 17,5:
31,75
Load Range F or less
38,10
Load Range higher than F
Tube type:
31,75
Load Range F or less
38,10
Load Range higher than F
Minimum puncture energies corresponding to Load Range designation according to
Regulation FMVSS Nr. 119 are listed in Table 15.
Table 15 Minimum puncture energies in J for utility car tyres in accordance with
Load Range designation according to Regulation FMVSS Nr. 119
Load Tyre characteristics, due to nominal rim diameter code
Rang 12
and 17,5
viac ako 17,5
e
all
tubeless
T.type tubeless T.type
tubeless
A
68
226
B
136
294
C
203
362
769
576
D
271
514
893
735
E
339
576
1 413
972
F
407
644
1 786
1 413
712
2 283
1 695
H
769
2 600
2 091
J
2 826
2 204
L
3 052
3 221
3 391
Note:
For the assesment of tyres with viscose cord, puncture energies with
a size 60 % from listed values are used.
Test proceeding and its evaluation are identical with the proceeding in case of
passenger car tyres.
Measurement of tyre surface electric resistance has big importance for vehicles
designed for transportation of flammable and explosive substances. It is very
52
important, that rubber, which has properties of insulators under normal conditions,
is capable of transferring the accumulating electric charge from the motor vehicle or
the trailer, preventing an electric discharge accompanied by a spark. Such a spark
could cause a fire or explosion of the transported material. Surface electric
resistance is measured on a clean and dry tyre. An ohmmeter for assesment of
insulating resistances equipped with special electrodes and a range of 1010
minimum i sused for the measurement. During measurement the compliance with
the measuring conditions is important, especially relative humidity of surrounding
air, which can influence to a big degree the electric resistance measurement, and
which can not exceed the value 55 %. Electric surface resistance is assessed on five
locations by means of special ring electrodes between the tread centre and
a locationon the sidewall, where tyre contacts the rim. Other method is the surface
electric resistance measurement directly on the vehicle. For this method,
a conductive plate, insulated from the earth, is positioned under the wheel, and
electric resistance between this plate end the wheel rim is measured. . None of the
measured values of surface electric resistance can exceed the value of 1.106 .
3.2
Speed tests
Speed tests for utility vehicle tyres have an importance mainly for tyres for light
utility vehicles, as for example pickups, van type vehicles, lorries, pick-up, SUV
Sport Utility Vehicles, SAV Sport Activity Vehicles. They have smaller
importance for tyres designed for trucks, buses and their trailers, where high speed
tests are usually not executed. Nevertheless, test methodologies are provided, used
by some tyre manufacturers and test laboratories.
Stress-mechanical deformation and thermal stress occur during high speed tests,
mainly in the tyre crown. Typical reasons for test termination of such test are the
reinforcing strip and tread separation, or tearing of tread blocks of rubber from
thetyre tread.
A high speed example for light utility vehicle tyres is test methodology according to
EEC Regulation Nr. 54, valid for tyres with load index 121 and less with speed
category 160 km/h and higher [12]. New tyre is fitted on a test rim. For a tyre
designed for a tube use, a new tube is utilized, or a combination of tube, valve and
flap. The tyre is inflated to a pressure corresponding to the maximum tyre load, or
to the inflating pressure corresponding to the maximum tyre load in a single
assembly. The inflated tyre is conditioned at the temperature of test room (255) C
for at least 3 hours, then the tyre inflation is adjusted to the above-mentioned
pressure. Afterwards, the tyre is fitted on a test shaft and is pressed on the smooth
outside surface of the driven test drum, whereby its width is at least so big as the
tread width of the tested tyre. Radial load is chosen according to drum diameter in
following way:
53
3.3
Fatigue tests
The goal of fatigue tests is the same as with passenger car tyres, i.e. the
establishment of tyre durability in its various parts. Usual duration time of fatigue
tests for utility vehicle tyres is from 50 to 250 hours. Fatigue tests are usually
executed at a constant speed. Basic fatigue test is a test, accepting the requirements
of EEC Regulation Nr. 54 [12]. The tyres are tested at a inflating pressure
corresponding to PSI symbol, or at an inflating pressure marked on the tyre for
maximum tyre load in a single-assembly. Prior to the test, tyres are conditioned at
the room temperature (255) C, at which they are also tested. The inflating
pressure is not adjusted during the test and is left to increase gradually. This test is
the fundamental safety test in european territory and serves as the base for the tyre
homologization. Test conditions for the test are listed in the Table 16. Tyres for
special use are tested at a speed corresponding to 85 % of the prescribed speed for
equivalent normal tyres. Tyres with load index 122 or higher and with a speed
category symbol higher than M are not produced for the use in road traffic so far.
For this reason they can not be awarded with a homologation and such test is not
carried out.
54
66 %
84 %
101 %
M
72
F
32
32
G
40
40
J
48
48
K
56
56
121
L
64
56
70 %
88 %
106 %
or less
4h
6h
M
80
64
75 %
97 %
114 %
N
88
75 %
97 %
114 %
P
96
75 %
97 %
114 %
A detailed test, but for non-european territories, originates from the Iegulation
FMVSS Nr. 119 [13]. The method of the test is here similar, but due to the fact, that
in these territories the tyres are designated neither with speed category, nor the load
index, the method of the test depends on the Load Range Index. Test conditions are
listed in the Table 17. Prescribed test temperature is 35 C.
Table 17 Test method according to Regulation FMVSS Nr. 119
Load as percentage of load corresponding
Load
Drum speed
to maximum tyre load in a single-assembly
Range
[km/h]
7h
16 h
24 h
(1)
(2)
A, B, C, D 80
75
97
114
E
64
70
88
106
F
64
66
84
101
G
56
66
84
101
H, J, L, N
48
66
84
101
(1) 4 hours for tyres submitted to high speed requirements
(2) 6 hours for tyres submitted to high speed requirements
Both tests serve mainly for certification purposes, or, partly, for quality control. Due
to tyre type the test lasts only 34, or 47 hours. Bead fatigue tests and carcass fatigue
tests serve for real assesment of tyre durability.
55
Bead fatigue tests are executed at lower speeds and a higher load. This
combination of testing conditions provides the stress of the tyre in the bead area.
The inflation in these tests is regulated and maintained at a value of 75 % to 100 %
of the inflating pressure corresponding to maximum permissible load in a singleassembly. The speed in bead fatigue tests varies in dependence on the methodology
between 20 and 60 km/h. To prevent any injury in the tread crown area, having the
biggest thickness of rubber in the shoulder, tyres must be adjusted prior to the bead
fatigue tests. Rubber behaves as a thermal insulator and transfers very poorly the
heat originated by repeated tyre deformation. During bead test of an unadjusted
tyre, heat accumulation would take place in tyre shoulder due to the unstable
process, leading to thermal degradation of the material in the shoulder and to
separations in the tyre crown area, which is not the goal of bead fatigue tests.
Cutting-off the tread and subsequent roughening of this surface reduces the thermal
resistance of the tyre, which is proportional to the material thickness. In this way,
the dissipation of produced heat is better and no injury takes place in the tyre
shoulder. The radial load in this type of tests usually varies between 1,3- and do 2,4times of the maximum tyre load in a single-assembly. Radial load during test is
either constant, or is gradually increased in individual load steps. Prior to the test
the tyre is conditioned at least for 3 hours at the test room temperature, which is
(255) C, or (383) C.
Carcass fatigue test are focused on tyre durability in the area of tread and tyre
reinforcing strips. Tyre does not require any special preparation before the test. The
tyre conditioning prior to the test takes at least 3 hours at the temperature of the test
room. Inflating pressure is regulated during the test, its value usually corresponds to
the value for maximum tyre load in a single-assembly, or is given in a table from
tyre manufacturers, associations (e.g. European Tyre and Rim Technical
Organisation). Speed during tests usually varies between 40 and 80 km/h, load from
100 % of maximum permissible load and higher. Load is constant during the test, or
is eventually increased in steps. Some tyre manufacturers carry out carcass fatigue
tests also with a non-zero directional deviation angle at a constant lateral force.
Tyre fatigue tests for light utility vehicles are similar as tyre tests for passenger cars.
Test speeds usually vary from 30 km/h for bead tests, and from 40 km/h for carcass
fatigue tests.
3.4
Special dynamic tyre measurements for utlility vehicles are similar to tyre
measurements for passenger cars. These measurements consist of assesment of
rolling resistance, dynamic directional characteristics, tyre noise development and
temperature distribution on tyre surface. Each laboratory carries out these tests
according to own methodologies
The only normalized methodology in this area is the measurement of rolling
resistance, which is normalized in the form of International Standard ISO 9948
Matador Rubber s.r.o 2007
56
[15]. But this standard is used in different variations, because not all parameters of
the test are described precisely. The assesment is realized on drum test machines
with a drum parameter of 1 700 to 3 000 mm at a test room temperature of 20 to 30
C under stabilized regulated conditions, at zero camber angle and zero directional
deviation. A very precise test device must be used for the measurement, because
small forces and torques are measured in the presence of bigger forces ( of a higher
order). Physical measurement principle is the same, as with the assesment of tyre
rolling resistance for passenger cars (see Chapter 2.4). Following methods are used
for the establishment of rolling resistance:
force,
torque,
performance,
decceleration method.
Tyre is rolling on a smooth steel drum during the measurement. The use of a drum
with a rough surface is also allowed, with a roughness of 180 m. The surface
temperature of the test drum at the start of the test must be roughly the same as
surrounding temperature. During the establishment of rolling resistance, the
pressure is left to increase freely, i.e. the tyre valve is closed during the
measurement. The inflating pressure at the beginning of the test corresponds to the
inflating pressure corresponding to maximum permissible tyre load in a singleassembly. Priorr to the measurement, the tyre must be run in on the test machine
with a drum diameter of at least 1 700 mm, a run in on the vehicle is eventually also
permitted. The conditions for tyre run in the Standard ISO 9948 are not precisely
described. The tyre run in normally lasts 6 hours at a speed of 60 km/h, a radial load
corresponding to 80 % of maximum permitted tyre load in a single-assembly and an
inflating pressure coreresponding to maximum permitted tyre load in a singleassembly. The speed and duration of individual steps in the Standard ISO 9948 is
not clearly prescribed. One of possible examples for rolling resistance measuring
method is given in the Table 18:
Table 18 Example of tyre rolling resistance measuring method for utility vehicles
Duration
Drum
speed
Step
[min]
[km/h]
1
150
50
2
45
60
3
45
80
4
45
90
The recording of individual measured variables and their processing is the same as
with measurement of tyre rolling resistance for passenger cars. The difference lies
in the application of rolling resistance temperature correction to 25 C, which is
calculated due to following equation:
57
Fr 25 = Fr [1 + K (t 25)]
(12)
This group comprises tyres used on tractors, suspended machines and trailer
vehicles in agriculture, forestry, mining works in quarries, mines, on earthmovinch
machines, military vehicles, etc. Tests of such tyres are executed with the help of
similar test methodologies, like for utility vehicle tyres. The test choice depends on
the planned use of respective tyres, with an emphasis on critical areas. These are
e.g. the requirement for low contact pressure in the tyre footprint in agriculture,
resistance to punctures during the use in mining industry, etc.
The only internationally recognized regulation, but also valid only for tyres used in
the area of agriculture and forestry, is the EEC Regulation Nr. 106 [16]. From the
point of view of fundamental safety, two tests are important according to this
regulation, the establishment of tyre resistance against destruction from water
pressure and dynamic test by load and speed.
During the test by ware pressure, the tyre strength and its resistance to increased
inflating pressure is verified. New tyre is mounted on a special reinforced rim or on
a test device equipped with solid circular discs with a seating surface for the tested
tyres, allowing the adjustment of their distance corresponding to rim width. Rims,
or these special discs used for the test, must withstand without any deformation the
highest possible value of pressure attainable during this test. In case of disc use, tyre
beads are thoroughly centered and the outside distance between the beads is
adjusted to the value corresponding with rim width in dependence from the tested
tyre dimension. The tyre is gradually filled with water in such a way, that the air is
pressed out. Then the device is started and the water pressure inside the tyre is
increased to rech gradually a pressure value, which is 2.5-times higher than the
maximum inflating pressure, as set by the tyre manufacturer. Under any
58
circumstances, the pressure can not be, according to EEC Regulation Nr. 106, lower
than 600 kPa, or higher than 1 000 kPa. Afterwards, the constant value of this
pressure is maintained for at least 10 minutes. After expiration, the pressure is
gradually reduced to zero value, the tyre is dried and inspected. As long as the
pressure inside the tyre exceeds the pressure of the environment, nobody is
permitted to stay in the test room, which must be securely closed. During the test,
the tyre must withstand the test pressure and no damage of beads, used reinforcing
materials and separastions of individual tyre parts can take place.
Dynamic test under load and speed is carried out on a test device with a drum
diameter of 1 707 mm and its width corresponding at least the tread of the tested
tyre. The test according to this method is realized only in case of tyres with speed
category 65 km/h (Symbol D). Tyre preparation and test method is the same as for
tyre tests for utility vehicles according to EEC Regulation Nr. 54 (see Chapter 3.3).
Test conditions are given in the Table 19. The test room temperature is maintained
in a span of 20 to 30 C.
Table 19 Program of test under load and speed according to EEC Regulation Nr.
106
Load as load percentage
Drum speed
Step duration
corresponding
Step
to
[km/h]
[h]
maximum tyre load
1
7
66 %
20
2
16
84 %
3
24
101 %
59
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
60
Tyres dedicated for the tests are fit on assembly machine to the wheel rims
prescribed by testing vehicle producer for given vehicle type and tyre dimension,
afterwards these are pumped up to pressure prescribed by vehicle producer and
balanced on the wheel balancing machine. The tyres prepared in this way are
mounted onto the testing vehicle.
61
2. Special tests
2.1 Subjective tests
For this reason we appointed drivers who are able to manoeuvre with vehicle under
extreme situations on the limit of the tyres possibilities and at the same time they
are able to review very sensitively behaviour of the tyres from subjective point of
view. The tyres are evaluated from view of driving properties, noise emitted by
rolling of tyres on the road and driving comfort, i.e. extent of pleasantness during
vehicle handling with given tyres.
Driving properties:
zero position - during straight drive on flat track covered with asphalt or concrete
surface by steady balance speed in two scopes: 40 - 60 km/h and 110 - 130 km/h.
Driver performs during drive an oscillating motion of the steering wheel from
small deviation up to the moment when the vehicle recognizable reacts to the
driving direction change. Afterwards the driver makes the steering wheel
deviation (approx. 20) under constant speed and leaves the steering wheel
released. We evaluate how big the tyre effort to return steering back into direct
position is. During manoeuvring we evaluate sensitiveness of the steering around
62
the basic position of the steering wheel and tire self-aligning torque of the
steering.
reaction respond during this test the driver evaluates by ca 90 turning of the
steering wheel how big delay of the tyres on the front and rear axle is. The test is
performed under different speed according to attainable technical conditions
given by maximum vehicle speed and the tyres speed rating (60, 100, 140 km/h).
sensitiveness to a rut this test is performed during normal road traffic. Stretch
of a road with a ruts without big uphill gradient and in straight direction must be
selected for this test. Passing through the road ruts is in longitudinal
and crossway (crosswise) direction in the closed angle. Acceleration and
deceleration is done during drive in tracks or crossover. During this test we
evaluate the vehicle behaviour, its tendency to copy the tracks and intensity of
necessary steering corrections.
changed load it is tested under constant speed on the circular track with big
side acceleration of ca 0,7g at the lowest possible gear driving position engaged.
Steady-state circular-course driving is followed by sudden deceleration without
changed steer angle. We monitor the change of the path curvature radius caused
by changed speed, steering mechanism system flexibility rate and consequential
change of the wheels loading. During this test the tyres should not cause
oversized path curvature.
transient characteristic it is based on straight vehicle movement and monitoring
is oriented to ability of the vehicle to change direction and side force increase
after very fast steering angle and steering wheel holding.
marginal range - it is tested under fast steering direction changes, most
commonly in slalom road, eventually during obstacle avoidance manoeuvre. We
evaluate the scope of such steering wheel deviations still allowing vehicle
control and tyres cannot increase anymore the side force under additional
steering wheel deviation. We evaluate also way of the tyres transmission from
status that still allows reacting on the direction change to the sideslip status
(sudden or gradual transition into skidding).
Noise
63
Driving is done under low speed in scope from 30 km/h to 50 km/h and also under
higher speeds:
- smooth asphalt surface,
- smooth asphalt surface with repairs on the road,
- concrete surface with joints and sporadic unevenness (road surface bumps),
- undulated road - reversed reaction to over-springing (absorption) of the
tyres.
Vehicle passes also through single obstacles, e.g. repairs on the road, channel
covers, plates placed on the tract in cross or sidelong direction. We evaluate passage
hardness trough the obstacle and absorption, speed and size of vibrations transferred
by tyres into the vehicle structure, seats and steering wheel. Under low speed we
evaluate vulnerability of tyres to create vibrations.
We evaluate each of the tests set according to 10-point scale (Table 1). Verbal
evaluation of the driver containing observation of tested tyres is also important.
64
65
continual frozen ice area. Also during this test it is important to have chassis of
the vehicle in good technical conditions and settled climatic conditions.
Slalom test it is manoeuvre consisting of the road part in determined length
with marked obstacles by means of plastic road cones that must be by-passed in
slalom way. Goal of this test is monitoring of the tyres under extreme side
loading, discovering of the side toughness influence and adhesion to manoeuvre
passing speed. Measured item is the passing time and vehicle cross acceleration.
During this test it is necessary to pass the manoeuvre in shortest possible time
and that put high demands on drivers technique and routine practices. Measured
values are statistically processed.
Passing manoeuvre the test represents by-passing of suddenly created
obstacle by lateral breakaway from normal traffic lane into contra-flow-lane and
repeated return into normal lane. By its character it reminds bypassing living
animal suddenly running onto the road thus it is sometimes called "reindeer test".
Goal of this test is determining the vehicle steering control during usage of
individual types of tyres under limiting situations and high speeds. Demands on
maintaining the vehicle stability are high. The tests are performed on track with
shape determined by ISO 3888 suggestion. The test requires high manoeuvring
abilities of the driver and separate regulation for order and number of tested tyres
that are mutually compared. It is time demanding test and lasts many days
depending on amount of the tyres alternatives. During test it is also necessary to
pass the manoeuvre in shortest possible time.
Trailing throttle / free coasting by means of this test we compare size of the
tire rolling resistance share to total vehicle passive resistance. Principle of this
test consists in moving of the vehicle by speed of 45 km/h and afterwards the
gearing mechanism is put into neutral position. We measure a distance passed by
vehicle before total stoppage. It is important to perform the test under lowest
possible wind speed and changes.
Noise measurement on vehicle is the test result of which provides very
important information about tested tyres noise level created by tyres during
rolling on the road in interaction with the whole vehicle they are installed on.
The noise is measured during passing of the vehicle in specified distance from
microphone of the measurement sound-level-meter. This is an important value
because lower noise of the vehicle tyres is an important factor for protection of
favourable living environment.
Effective rolled perimeter this is the only test when it is not necessary to
compare results with reference tyres. The test is performed under constant speed
of 60 km/h on approximate distance 100 meters. Except passed distance we
record also amount of the tyre rotations. Distance representing one rotation is
searched value. This value provides information about suitability of the tested
66
tyres usage on vehicle normally using different tyres (e.g. other - similar
dimension) from view of correctness of speedometer data. Effective rolled
perimeter for one measurement is:
s
o=
[m;m,-]
n
where o effective rolled perimeter of the wheel,
s actual passed distance on measured track,
n number of the wheel rotations on measured track.
67
2.
2.1
Determination of Viscosity and Scorch (DIN 53 523, ASTM D
1646, ISO 289)
68
to 2.00 rpm (revolutions per minute). Large rotor diameter is 38.10 mm, while the
small one is 30.48 mm; both discs are 5.54 mm wide. Mooney viscosity is normally
measured at temperature 100 C using large rotor. Small rotor is used only for
rubbers or compounds having their viscosity above the instrument upper limit
(usually 200 ML).
Test is carried out as follows [1]: specimen is put in the instrument heated chamber,
which is then closed. Due to high dependency of viscosity on temperature,
specimen is given approximately one minute to preheat to required temperature
(measurement at isothermal conditions). After the first minute is elapsed, rotor
starts torque measurement is initiated. Rotor torque is usually read in the fourth
minute and subsequently calculated to viscosity. When the measurement is
completed, rotor stops. Mooney viscosity curve is shown on Figure 1.
69
measured on switched-off rotor in second 30 and 60. Mooney stress relaxation (in
%) is calculated according to formula:
MR 30 =
M 30
.100
ML(1 + 4)
[%]
(1)
MR 60 =
M 60
.100
ML(1 + 4)
[%] ,
(2)
where: M30 value of viscosity in Mooney units 30 seconds from rotor switch-off,
M60 value of viscosity in Mooney units 60 seconds after rotor is started.
One of useful tests is a scorch time and scorch speed determination (t5, t35). Scorch
time is the time elapsed to the point, when scorching starts at determined
temperature (as a criteria we use increase of ML or MS viscosity by 5 units from the
minimum value; this value is very important for determination of time during which
the product safely withstands process temperature without scorching, before it is to
be vulcanized in press). Scorch time curve is shown on Figure 2.
[min]
(3)
Scorch time is determined at 120C or 140C (any other used temperature must be
recorded in test protocol).
Among commonly used testing instruments we may include viscometer MV 2000E
made by Alpha Technologies:
70
2.2
Determination of vulcanization properties (DIN 53 529, ASTM D
2084)
71
72
t10 is the time required for torque increase by 10 % of difference between the
minimum and the maximum vulcanization curve torque.
t90 is the time representing 90 % of the difference. t90 is the basis for
assessment of so-called vulcanization optimum.
Mmax and Mmin are maximum and minimum torque values characterizing the
compound stiffness.
The vulcanization velocity constant can be
calculated from the vulcanization curve; vulcanization curves measured at
different temperatures serve for calculation of the vulcanization activating
energy.
Torque
M max (60)
M max
M 98
M 90
]N.m
[
M 50
Mo
M min
t 50
t 90
tr (98)
time
[min. ]
02
73
(4)
[ Nm]
Compound scorch time t02 is the time, when the torque exceeds the value Mmin
by 0,1 N.m at the rotor oscillation amplitude 1, and by 0,2 N.m at the rotor
oscillation amplitude 3 or 5. In other words, it is the time, when the torque
exceeds the Mmin value (at the given temperature) by 1 or 2 units (of the range 100).
Optimum time of vulcanization t90 this may be considered the time required for
reaching 90 % of the maximum achievable torque or network density, at the given
temperature [8.5].
M 90 = M min + 0,9.(M max M min ) = M min + 0,9.M
[min]
(5)
Time in minutes equal to the value M90 is called the optimum time of vulcanization
t90. The above described method may be used for determination of vulcanizing time,
equal to any torque change (e.g. by 50%). The time representing M50 is called the
half-time of the vulcanization t50.
Approximate time of vulcanization t90 it is being determined for compounds
[min]
(6)
Time equal to the M90 value will be an approximate vulcanization time (t90). This
time may, however, significantly vary from the actual vulcanization time, required
for reaching of the complex optimum properties of the given compound.
Reversal period tr (98) is the time in minutes, in which the maximum torque
drops by 2 %; this time is equal to the value M98 in the sloped-down section of the
curve.
M 98 = M min + 0,98.(M max M min )
[min]
(7)
Time equal to the value M98 on the vulcanization curve is called the reversal period
- indicated as tr (98).
74
Rr =
100
(t r (98) t max )
[min 1 ] ,
(8)
100
( t 90 t 02 )
[min 1 ] ,
(9)
2,3
( t 90 t 02 )
[min 1 ]
(10)
This is an auxiliary value that serves for estimate of non-isothermal behavior of the
vulcanization, if the measurement is done at several temperatures.
Vulcanization
characteristics
are
measured
on
instruments
called
vulcameters(older instruments, offering graphical record as the only output,
should be called vulcanographs) or rheometers. Older instruments have
a biconical rotor installed in the heated chamber (Fig. 12.4); newer ones are
rotorless. The rotorless instruments use smaller specimens, thus partly eliminating
result errors caused by the specimen heat transfer kinetics (the most commonly
known instrument is MDR 2000 (Moving Die Rheometer) made by Alpha
Technologies, former Monsanto).
75
The rotor-free instrument functions as following: the specimen is placed into the
heated chamber, which has the bottom part oscillating at the given frequency and
amplitude. The oscillations are transferred through the specimen to the mould upper
part, where is the torque sensor. The torque that increases as the vulcanization
proceeds, is recorded.
3.
76
= .
(11)
= G.
(12)
3.2
Classification of liquids
Liquids may be in general divided into the following groups [22] (Fig. 5):
viscous fluids Newtonian and non-Newtonian (pseudoplastic and dilatant)
fluids with time-dependant deformation speed factor (thixotropic and
rheopectic)
fluids with plastic speed factor (Bingham)
fluids with elastic speed factor (elastoviscous and viscoelastic)
77
Viscosity curves
1
Viscosity
Shear stress
Flow curves
4
2
1
4
2
&
Shear rate
&
Shear rate
1
Newton fluid
Pseudoplastic fluid
Dilatant fluid
Bingham fluid
Fig. 5 Flow curves of individual types of fluids (gives the relationship between the
tension and the shear rate) Newtonian behavior is characterized by linear flow
curve, other kinds of liquids (pseudoplastic, dilatant, bingham) are non-Newtonian
Newtonian liquids are purely viscous liquids, and their rheological behavior is
described by the formula:
= Z .
(13)
Decrease of viscosity of polymeric melts is monitored over the wide range of shear
deformation rates; at high shear rate values, the viscosity may be several orders
lower than at low shear rates. This Newtonian behavior of polymeric liquids is very
important for practical processing of elastomers; viscosity decrease makes
78
= K .
(14)
This model contains two parameters, where K is the coexistence coefficient, and n
is an index, characterizing rate of variation from the Newtonian behavior.
For Newtonian liquids, n = 1, for pseudoplastic liquids n < 1 (in contrast to dilatant
liquids, where n > 1). If we modified the formula (14) as following,
= K . n1 . = Z .
(15)
Z = K .
(16)
The advantage of the exponential model is its simplicity it contains only two
parameters, which can be easily experimentally determined. However, a certain
disadvantage of this model is that for constant values of the parameters K and n, it
approximates experimentally obtained values and only in relatively narrow
range of the shear rate values (interval of one, to two orders) [22].
3.3
Several factors have influence on the polymeric melts viscosity. The most
significant factors influencing the melt viscosity are temperature,
pressure/tension, molecular characteristics, volume of added filler, and
structure of the polymeric string and addition of auxiliary processing
additives. In general, the influence of these factors may be characterized by
increase, resp. decrease of the viscosity curve, where
temperature, fluxes and processing additives are acting towards decreasing of
viscosity, and
pressure, molecular weight, structural branching, and adding of filler are
viscosity increasing factors [22].
79
(17)
where constant B, characterizes polymer and its molecular weight, and Ea is the
activation energy of the polymeric melt flow.
For amorphous polymers, with the temperature exceeding the glass transition
temperature (Tg) by less than 100C, the Arrhenius relation can not describe the
viscosity temperature dependency correctly. In such temperature interval, the
Williams Landel Ferry formula (18) is used for description of thermal
dependency:
log
c1g (T Tg )
=
g c2 g + (T Tg )
(18)
(19)
(20)
where m is the defined ratio of actual, and apparent volume of the filler in
dispersion.
80
Critical molecular weight of polymer Me is the weight exceeding the value, above
which the melt viscosity is influenced by angulations of macromolecular string
segments. The melt viscosity below the critical molecular weight Me is an nonlinear function of the molecular weight Mw, however, if molecular weight exceeds
the critical molecular weight Me, the viscosity in the area of low shear rate values is
an exponential function of the molecular weight, and described by the formula:
= K. Mw
(21)
3.4
Measurement of rheometric properties of substances
rheometry
Rheometry is an extensive branch of science, studying rheological properties of
substances. In general, it includes rheometric methods, methodology and
instruments on which the measurements are performed rheometers. Rheometric
methods may be divided into two basic groups, depending on obtained state values,
which may be either absolute, or just informative:
81
Plate-plate type rheometers are suitable for the Mooney viscosity measurements; the
shear rate changes along the plate diameter. The flow curve can be plotted from the
shear stress (formula 22) and the shear rate (formula 23), both - based on directly
measured values and exact geometry of rheometer function elements - equaling:
= 2Mt / R3 ; = (.R ) / h
(22), (23)
= 3Mt / 2 R3 ; = /
(24), (25)
where is the conical angle between the plate and the cone [22].
Oscillating (rotorless) rheometers are working on the principle described in the
Chapter 2.2. Among these instruments, commonly used for the flow properties
measurement, we may include rheometers MDR 2000 (mentioned above) and RPA
2000).
82
The difference between the two instruments is, that while neither frequency, nor
amplitude oscillation can be changed during measurement on the instrument MDR
(and the new processing technologies require better knowledge of compounds
rheological properties), this is possible on the instrument RPA 2000 (Rubber
Process Analyzer). In addition to changing of amplitude (from 0,02 to 90), and
frequency (from 0,033 Hz to 33 Hz), there is also the possibility to change
temperature (from 40C to 200C). RPA 2000 allows measuring of viscoelastic
properties of raw, vulcanized, and overvulcanized compounds. Figure 7 shows the
instrument testing chamber.
83
volume flow rate Q - is determined from the volume of melt, which flows
through the capillary over the defined time; this value may be considered
equal to the shear rate
pressure drop in capillary ( p/L) defines the difference between the
capillary input and output pressures, and is relative to the unit length; the
pressure drop in capillary may be considered a value equal to the shear
stress.
The measured values Q and ( p/L) may be used for determination of shear rate and
stress values, based on the melt flow curve may be plotted; its rheological properties
can be characterized by the exponential rheological model [22].
For analysis of capillary ratios, we assume that the melt flow in the capillary is:
Based on the capillary shape, the capillary rheometers are divided as following:
Based on the melt flow analysis performed in the circle cross-section capillary, the
flow curve may be plotted from the following relations between the shear rate and
the shear stress:
= (m + 3)
Q
P.R
; =
3
2L
.R
(26, 27)
where R is the capillary diameter, L is its length, m is the index of deviation from
the Newtonian flow (here m= 1/n), Q is the melt volume.
The displacement (volume of extruded melt) is determined as follows (28):
m +1
Q = .R 3 .v0
m +3
(28)
= (4m + 2 )
Q
;
T .H 2
w =
H .P
2L
(29, 30)
where H is the rectangular die opening/hole height, T is the rectangular die opening
width, and L is the capillary length.
84
end effects at the capillary input (unsteady flow), and output (shrinkage, or
growing after the nozzle)
outgoing flow kinetic energy
slip at the capillary walls
capillary elastic deformation
heat losses (i.e. transformation of pressure energy into thermal energy) etc.
Among the most commonly used correction methods, we may include Bagley
correction and Rabinowitsch correction.
Bagley correction corrects the flow unsteadiness at the capillary input (i.e. it is the
capillary length-related correction); this method must be used with relatively short
capillaries, shorted than L/R <50, where the pressure drop at the capillary input
doesnt reach constant values. The capillary shall be extended by so-called fictious
length, so as to keep the pressure drop constant over the whole capillary length.
In capillary rheometry, the indirectly determined values of shear stress and shear
rate have their apparent meaning, i.e. they are equal to the melt with the Newtonian
behavior. Since polymeric melts show considerable deviation from the Newtonian
behavior, a correction must be applied on calculated apparent shear values, in order
to achieve better characteristics of the polymeric melt pseudoplasticity. For this
purpose, the Rabinowitsch correction is used, which based on the exponential
model corrects apparent values of the shear stress and rate [22].
Capillary rheometers are among the most commonly instruments used in the
capillary rheometry. For characterization of rubber compounds, the suitable
capillary rheometers are laboratory spiral devices (offered on market by several
companies, e.g. Thermo Haake, or Brabender).
85
86
4.
Testing of vulcanizates
4.1
Tensile tests give an orientation view about rubber material properties. Besides this
they are used also for inspection of the technological processes smoothness, e.g.
mixing quality of rubber mixture. They were used also for optimum curing
assessment before implementation of rheometers into rubber practice etc.
Dependency of loading on prolongation is characteristic for each rubber mixture.
Graphic expression of this dependency is so called tensile curve. It is possible to
discover maximum loading and prolongation from this curve but also the loading
necessary for some prolongation modulus, serving very often as evaluation
measure of rubber elastic properties. This modulus is not identical with Youngs
elastic modulus that indicates the stress needed for doubling of original length.
Modulus stated in rubber practice for specified prolongation expresses internal
stiffness (STN ISO 37) presents following definitions [3]:
tensile stress S the stress causing elongation of the original testing piece,
elongation E elongation incurred by tensile stress acting on the testing
piece,
tensile strength TS maximum tensile stress recorded during elongation of
the testing piece till breaking moment,
87
breaking tensile strength TSb the tensile stress recorded in the moment of
the testing piece breaking,
breaking elongation Eb tensile deformation of the testing piece operation
length in breaking moment,
elongation at specified stress Es tensile deformation of the testing piece
operation length during achievement of tensile stress specified value,
stress at specified elongation Se the tensile stress causing specified
prolongation of the testing piece operation length,
strength at yield limit Sy the tensile stress in the first point on stressdeformation curve where additional deformation increase runs without any
stress increase. This point is defined by the curve inflexion point or it is the
curve maximum point,
elongation at yield limit Ey the tensile deformation in the first point on
stress-deformation curve; next deformation increase is not followed with the
stress increase,
length of the testing piece operation part in the shape of double-sided blades
beginning distance between marked points determining operating part in
narrowed part of testing piece in shape of double-sided blade, used for
measurement of elongation.
88
(x > 2)
89
90
Tensile tests are done on shredders by suitable loading scope. Different types of
testing pieces are used for test (see: obrzky\IMG_6998.jpg). The most frequently
used testing pieces have shape of double-sided blade, but sometimes also testing
pieces in shape of rings are used. The main criterion for selection of testing pieces
in shape of rings or blades is:
tensile strength: testing pieces in shape of double-sided blades are more suitable
for statement of tensile strength. Rings afford lower (sometimes much lower)
values of tensile strength than double-sided blades
elongation at brake: rings offers approximately same values as double-sided
blades under provision that:
elongation of rings is calculated in percentages from their initial internal
perimeter
double-sided blades are cut-off in upright orientation direction, if marked.
Double-sided blades are used always when monitoring of orientation influence is
required. The rings are not suitable as testing pieces for this test.
The testing pieces are prepared by cutting with suitable cutting knife (see: nect
figure) from cured plate or ring.
91
sided blades in accordance with STN ISO 37 are stated in tab. 1 according to [3]
and their shape is shown on Fig. 9:
75
50
35
6,00,5
4,00,1
4,00,1
2,00,1
7,50,5
3,00,1
92
Fig. 10: Detail of the testing piece in shape of double-sided blade fixed in jaws of
shredder. There is shown also fixing of extensometer jaws for assessment of
elongation.
In some cases, tensile test can discover value of equilibrium modulus, tensile
elasticity and relative static hysteresis, eventually relative static relaxation. Tensile
equilibrium modulus is stated on testing piece in shape of double-sided blade or
ring in such way that testing piece is stretched with speed 500 mm.min-1 up to
achieved required prolongation of the testing piece operating part. In this moment
the stretching is stopped and falling stress is recorded; it will stabilize on value
characterizing specified material. Tensile elasticity is ratio of returned work to work
delivered during fluent stretching and releasing of testing piece, relative static
hysteresis is defined as ratio of difference between delivered work and returned
work to delivered work during its fluent stretching and releasing. Tensile elasticity
and relative static hysteresis is calculated from areas rate under tensile curve.
4.1.2 Hardness assessment (ISO 7619, DIN 53 505, ASTM D 2240)
93
where:
K.P
,
d
(32)
Different structures of hardness testers are used for rubber hardness testing (e.g.
electronic hardness tester ZWICK Shore A: next figure).
where:
(33)
Hardness tester Shore D is used for measurement of small testing pieces; it differs
from Shore A hardness tester by different compressive force and spike geometry.
Matador Rubber s.r.o 2007
94
(34)
Depth of tested piece must be at least 6 mm. To achieve this thickness, the testing
piece can be produced from thinner layers, but because of possible imperfect
contact between layers the results on such connected pieces may not correlate with
results achieved on pieces produced from one piece. The testing piece must be
sufficiently big to allow measurement in distance bigger than 12 mm from its
border. Because of strong visco-elastic (during hardness measurement viscous)
rubber properties, the hardness measurement must be performed in strictly specified
time after applied hardness tester to testing piece. The standard STN 62 1431
specifies this time onto 15 s 1 s [12.5].
Rubber hardness is increased with addition of any fillers and it is linear up to high
concentrations. Influence of fillers is characterized by filler constant depending on
filler type and it is related to the value of oil adsorption.
4.1.3 Assessment of reflection elasticity (ISO 4662, DIN 53 512)
95
Testing piece should have diameter 29 mm 0,5 mm and thickness 12,5 mm 0,5
mm. If testing pieces are prepared from products having lower thickness, it is
possible to place them at each other. If testing pieces are prepared by means of
pressing or cutting with rotation knife, thus they should not contain bracing
material.
Procedure for measurement of reflection elasticity is this: the first testing piece will
be fixed to apparatus and pendulum will fall six times on sample surface but the
first three strokes are not taken into account. Next three strokes are taken into
median calculation. The same process is done with the second testing piece. Result
of this test is stated as arithmetic average value from medians of two testing pieces
[5].
4.1.4 Assessment of structural strength (ISO 34-1, ASTM D 624)
This test belongs to structural tests together with assessment of abrasion resistance.
Assessment principle consists on tensile loading of suitable testing piece. Selection
of suitable testing piece is very important because mostly under influence of big
rubber deformation ability and high value of structural strength of wrongly selected
shape and size of testing piece the value of breaking force expresses tensile strength
instead of structural strength (force needed for breaking the vulcanizate structure).
Following types of testing pieces are used (Fig. 11):
crescent (without notch),
graves (with notch or without notch),
trousers.
The tests are performed on shredders similarly as in case of tensile properties
assessment; deformation speed is 500 mm.min-1. Result is expressed as force
needed for breaking of the sample with specified thickness in kN.m-1 [6].
96
a.
b.
c.
Fig. 11: Shapes of testing pieces for structural strength assessment (a- crescent,
b- graves, c- trousers)
4.1.5 Abrasive resistance assessment (ISO 4649, DIN 53 516)
The abrasive resistance assessment is important mostly for products that are
frictionally loaded during their exploitation (e.g. tire treads/protectors, covering
layers of conveyor belts). Product life can be expected in accordance with the
abrasive resistance stage. Until now approximately 30 different laboratory
apparatuses types were developed for the abrasive resistance assessment. But there
is no criterion existing for examination of the specific apparatus applicability.
Absolute conformity between laboratory results of abrasiveness and vehicle tests
practically does not exist.
The method procedure (Bussen-Schlobach method) is based on fact, that testing
piece in shape of roller with diameter 16 mm and minimum height of 6 mm is
rubbed on roller having its surface covered with abrasive agent. Standard abrasivecoated papers with alumina (Al2O3) grains of specified size are used as abrasive
agent. Standard mixture on such surface should have the weight loss of 180 220
mg after completed path of 40 m and pressure of 10 N. Testing piece is reground
before testing, then its weight is measured and it is rubbed on rotating roller covered
with the abrasive agent. The weight loss is discovered after completed path of 40 m
and relative volume loss V is calculated (for non-rotating testing piece):
V =
where:
Vt .200
mg
[mm 3 ] ,
(35)
97
Abrasive resistance index ARI for identical testing piece (rotating or non-rotating)
is calculated on the basis of this formula [7]:
ARI =
where:
Vs
.100
Vt
[%] ,
(36)
4.2
Ageing tests
98
The most ageing resistant rubbers are those not containing double linkages in chain
(saturated rubbers). Majority of products are produced from non-saturated rubber
types. The most significant influence on rubber has ozone present in the air in
concentrations from 0,01 ppm up to 0,06 ppm, that is created on the Earths surface
under ultraviolet radiation effect eventually the electric discharges in atmosphere.
Ozone received its name under characteristic odor (from Greek word ozein,
which means bad smelling, and it is toxic). Ozone reacts with non-saturated
carbons of rubber hydrocarbon in exposed and deformed rubber, molozonit is
created and this is changed into isoozonit in next stage. Consequently cracks are
created across the stress direction. Accrued crack exposes un-attacked rubber and
originally small cracks are rapidly increasing.
Aerial oxygen causes so called oxidation ageing of the rubber. Under normal
temperature this ageing will occur only after very long period, but increased
temperature greatly accelerates oxidation ageing. The less resistant rubbers are
those with great concentration of double linkages (oxygen attacks the most reactive
area in the rubber chain) and that is in case of non-saturated rubbers in alphaposition to double linkage (on carbon atom adjacent to non-saturated carbon).
Hydro-peroxides are created, and those are dissolved under increased temperature
or catalytic effect (light, rubber toxicants) onto free radicals (mainly type RO2).
Radicals afterwards react with rubber hydrocarbon and thus splitting or screening of
the rubber chains occurs. In polyisoprenes predominates splitting of chains,
reversely oxidation screening in homo-polymers and butadiene co-polymers.
Sulfur vulcanizates lacking ozone are subject to changes that are directly
proportional to increasing concentration of polysulphidic cross-links (anaerobic
ageing). Disulphidic and monosulphidic cross-links are created from polysulphidic
cross-links and additional new cross-links are created from released sulphur.
Rubber module is growing and also other physical-mechanical properties of rubber
are changed (ductility and dynamic loading resistance are decreased) [2].
4.2.1 Assessment of accelerated thermal ageing in air (ISO 188, ASTM D 865,
DIN 53 508)
99
operating area at least 3 and maximum 10 times per hour. Method B utilizes testtubes inserted in heated metal block, eventually liquid baths with the same air
exchange as used in method A. Testing pieces must not fill the thermostat chamber
volume for more than 10 % from its volume. Distance in between testing pieces in
thermostat must not be smaller than 10 mm and distance of the testing piece from
the chamber wall less than 50 mm for method A and for method B these values are
minimum 5 mm and 10 mm. Temperature selection and time of increased
temperature influence is chosen in accordance with the test goal and rubber
character (increased temperature effect should not cause visible damage on testing
pieces. One from following temperatures is used for testing: 70C, 100C, 125C,
150C, 175C, 200C, 225C, 250C, 300C and 350C. The test duration is 24, 72,
168, 240 hours or multiples of 168 hours. It is not recommended to perform
common tests of different rubber types because of sulphur migration,
antidegradants, peroxide eventually softeners. In marginal conditions it is allowed
to place into thermostat chamber at the same time testing pieces composed of the
same type rubbers with approximately same sulphur content and one accelerant
type, with content of one antidegradant type, with content of approximately same
softeners amount of equal type. Changed values of the physical-mechanical
properties (symbol S) (except hardness) is calculated on the basis of formula (37)
(symbols A1, A0 express specific physical-mechanical property (e.g. strength,
ductility etc.):
S=
A1 A 0
.100
A0
[%]
(37)
where:
(38)
Principle and also procedure of the method is equal with the previous method,
difference is only in usage of different testing equipment that consists of the oxygen
chamber and thermostat. After removal of the air from chamber the pressure of
oxygen inside of the chamber will be adjusted to 2,1 MPa and temperature to 70C
[9].
4.2.3 Assessment of resistance against ozone influence (ISO 1431-1)
The testing pieces are exposed to static tension stress in closed chamber at constant
temperature in atmosphere containing specified ozone concentration. The testing
pieces are periodically inspected if there are no cracks on their surface. Three
alternatives of evaluating procedures are described as to select the ozone
concentrations and exposition time:
100
The test is performed under one of these ozone concentrations: 25 pphm, 50 pphm,
100 pphm, 200 pphm. Preferably the tests run at 40C, but also other temperatures
can be used, e.g. 23C. Normally the tests are performed at one value or more
prolongation values (tensile deformation): 5%, 10%, 15%, 20%, 25%, 30%, 40%,
50%, 60%, 80%.
The testing pieces are deformed during method A by tension to 20 % ductility and
then inspected after 72 hours of exposition in testing chamber, if there are no ozone
cracks shown on their surface. Also other values of deformation and exposition
times can be used. Result of the test is statement on attendance or absence of cracks,
eventually degree of cracking is stated (description of cracks). Under method B the
testing pieces are deformed onto one or more prolongation values (ozone spectrum)
Matador Rubber s.r.o 2007
101
and occurrence of ozone cracks is inspected after 2, 4, 8, 16, 24, 48, 72 and 96
hours, eventually also in other suitable intervals after the lapse of this time. The
time when crack occurs during each deformation is recorded. Under method C the
testing pieces are deformed onto four deformation values and surface of testing
pieces is inspected in intervals used under method B to enable to determine
threshold deformation. The result of this test is stated in range with threshold
deformation specifying the highest prolongation value without observed cracks
creation and the lowest prolongation value with cracks creation discovered [10].
Next evaluation method for resistance against ozone is test assessment of rubber
resistance against ozone by threshold deformation method on testing pieces in
trapezium shape (STN 62 1529). The testing piece of trapezium shape (see figure
above) is fasten into fixture in such way that bottom part of the piece in contrary to
the top one is not deformed. The range of deformation values is chosen from six
possible ranges. The piece fastened in this manner is continuously deformed along
its height from zero deformation up to maximum. The test duration (24, 8 and 4
hours) is selected in accordance with used ozone concentration (50, 100 and 200
pphm of ozone). The threshold deformation is calculated as ratio of distance of the
first created crack from non-deformed edge and maximum deformation value to the
height of the whole testing piece. It is indicated in %. The testing piece from
vulcanized rubber is shown on Fig. 13:
Fig. 13: Testing piece for assessment of resistance against ozone by threshold
deformation method
4.2.4 Assessment of liquids influence (ISO 1817, DIN 53 521, ASTM D 471)
102
degree (except rubber cross-linking degree also active fillers influence the swelling,
as they reduce constitutional degree of swelling). Besides these two above stated
forms of liquids influence (extraction of ingredients from rubber and liquid
absorption), the solvent may chemically react with the rubber. Absorption effect is
usually bigger than extraction effect, which normally leads to increased volume of
testing piece. Curve course dependency of volume change on time results in the fact
that volume of testing piece grows quickly at the beginning, than the volume change
grows slower and in linear way. Liquid absorption as well as extraction of soluble
rubber components (e.g. softeners) has influence on physical-mechanical properties
of vulcanizate (change of volume, dimensions, weight, tensile properties, hardness
etc.).
During assessment of resistance against liquids it is very important to select correct
testing temperature and air access amount, as increased temperatures speed up
rubber oxidation, evaporation or destruction of testing liquid. As the speed of liquid
penetration into rubber depends on several factors, it is not possible to select only
one time interval for test (it is recommended to evaluate the liquid influence after
some intervals to achieve time change curve of physical-mechanical properties,
preferably chosen testing time leads to steady state).
Assessment of the volume and weight change is done on three testing pieces with
volumes from 1 cm3 up to 3 cm3 and thickness of 2 mm. Testing pieces are fully
immersed into tank with testing liquid and they must neither touch each other
nor the tank walls. Liquid volume must be 15 times bigger than volume of testing
pieces. Percentage change of volume or weight is calculated according to these
formulas:
V100 =
(m 3 m 4 + m 5 ) (m 1 m 2 + m 5 )
.100
(m1 m 2 + m 5 )
m 100 =
m 3 m1
.100
m1
[%]
[%] ,
(39)
(40)
103
l .l
A 100 = A B 1.100
l a .l b
where
[%] ,
(41)
Physical properties changes can be stated immediately after testing liquid influence
or after it removal or drying. Evaluated is change in tensile properties and hardness,
but in specific cases also other physical-mechanical properties. Testing piece for
assessment of tensile properties should have shape of ring or double-sided blade
according to standard ISO 37, testing piece for assessment of hardness should have
thickness of 2 mm and other dimensions at least 8 mm (ISO 48). Test procedure,
selection of solvent, liquid effective time and testing temperature is identical with
the procedure used for assessment of changed dimensions. Tests without liquid
drying must be done within 3 minutes after taking test piece out of testing liquid.
Assessment of physical properties change after drying should be done on testing
pieces dried at temperature 40C and pressure of 20 kPa, dried onto constant weight
(weight change after 30 minutes should not overrun 1 mg). Results expression is the
same as during assessment of accelerated thermal ageing.
The test of liquid influence is done only on one surface in case of relatively thin flat
materials that are exhibited to liquid influence on one side. A special fitting is used
for this test and that allows contact of testing piece with liquid only from one side.
Changed weight per unit area is evaluated (g.m-2) [11].
4.2.5 Assessment of permanent tensile deformation (DIN 53 518)
Goal of this test is to assess the permanent tensile deformation value of the
vulcanizate that characterizes viscous share of rubber viscous-elastic behavior. It
serves for evaluation of appropriate usage of rubber products as tire-tubes,
membranes, gloves. Value of permanent tensile deformation as well as compressive
deformation depends on vulcanizate structure. The higher ratio of polysulphidic
cross-links contained in vulcanizate, the higher values of permanent deformations
are achieved. This phenomenon is related to the strength of cross-links, the less firm
is cross-link the easier cracking occurs and during this also mass flow happens.
After some time new cross-links are created and those provide fixation of the piece
deformed shape.
Basis of the test are in assessment of remaining length on operating part of testing
piece loaded under constant deformation conditions, testing temperature during
testing period. The testing pieces are used according to standard STN ISO 37 type
1, shape of double-sided blade. After fixing the testing piece into fixture it is
deformed to one from prescribed deformation values (25 %, 50 %, 100 %, 200 %,
300 %). Selected value should not be higher than 1/3 of the tested rubber ductility.
For normal assessment it is suggested to use value of the constant deformation
Matador Rubber s.r.o 2007
104
100%. After that the sample is inserted together with fixture (see next figure) into
hot-air oven preheated onto specified temperature (23C, 70C, 85C, 100C,
125C, 150C) and is left there during specified period (24 hours, 72 hours, 168
hours). After testing piece removal the distance between marks is measured
and permanent deformation value is calculated on the basis of this formula (42):
TD =
l1 l 0
.100
ls l0
[%] ,
(42)
where: l0 distance between reference marks on testing piece before test in mm,
ls distance between reference marks of stretched testing piece in mm,
l1 distance between reference marks on testing piece after recovery in mm.
105
4.2.7 Assessment of the brittle temperature limit (ISO 812, ASTM D 746)
Basis of this method are in assessment of temperature, when the testing piece
remains intact. On the basis of this value an approximate temperature limit for
usability of this product under low temperatures is discovered.
Testing pieces with width of 6mm, length of 25mm and thickness of 2mm are used
for this test (operating part of double-sided blade for tensile test). Testing piece is
fixed into testing equipment that creates fixing unit with movable hammer having
moving speed (2,0 0,2) m.s-1 and cooling chamber with mixer and temperature
sensor. The hammer falls down onto the sample after its fixing and cooling (by
mixture of denatured alcohol with solid carbon oxide). Damage of the sample after
this impact is detected. The temperature regarded as brittle limit is that one, when
the sample still remains without cracking [14].
4.3 Dynamical tests
All the above mentioned tests are static tests, it means that sample is relatively
standstill during the test. But many rubber products are dynamically loaded during
exploitation (e.g. automotive tire during movement, material destruction occurs
very often under dynamic loading and that is in spite of the fact that deformations
are not higher than critical the reason is in fatigue of material). From this reason
appropriate usage of rubber mixture in automotive tire is determined by knowledge
106
of its dynamical properties. The tests are suitable in particular for dynamically
loaded mixtures e.g. sidewalls of the automotive tire.
4.3.1 Assessment of resistance against cracks creation and growth by
crimping (ISO 132, ISO 133)
This test is based on repeated bending of the testing piece by constant frequency
when the surface change is monitored (crack created in narrowed sample part) or
crack dimensions artificially created before test (width of initial crack is 2 mm) in
dependence on number of bends. In the first case a graph is designed where damage
degree is stated on y axis and corresponding number of bends is put on x axis. The
points will show a curve and amount of bends needed for each damage degree can
be deducted. The test set-up is shown on Fig. 15. Growth of cracks is evaluated in
similar way as creation of cracks, only axis y is used for plotting the crack size.
Amount of bends needed for following growth of cracks is deducted from achieved
dependency [15]:
from l0 to l0 + 2 mm,
l0 + 2 mm to l0 + 6 mm.
l0 + 6 mm to l0 + 10mm.
107
Testing piece in shape of roller with diameter 20 mm and length of 100 mm is fixed
into rotation jaws of the DPGi apparatus and required bending angle is adjusted by
movement of the fixing unit. Bending magnitude is controlled by means of a radius
gauge. The testing piece rotates with frequency 15 Hz. During assessment of fatigue
resistance, the testing piece is kept in rotation up to its destruction and consecutive
reading of performed revolutions. Material warming is determined by measurement
of sample internal temperature after completion of some amount of revolutions
(most often after 10 000, 20 000 and 30 000 revolutions) by means of appropriate
sensor [16]. The test principle is clear from Fig. 16.
Adhesion tests
108
This method is based on assessment of adhesion between rubber and fabric cord on
the basis of measured force needed for tearing out the cord from molded rubber
block. The testing piece has shape of H letter, where the name H-test comes
from. The test principle is clear from Fig. 18:
109
A cord sample is cured into rubber roller (see next figure), that is loaded with
pressure in the middle part (Fig. 19). Deformation is adjustable in extent from 35 %
to 55 %, deformation frequency is 7,5 Hz. The testing piece is dynamically stressed
under increased temperature (80 C).
After finished deformation the roller is cut into three parts taking care to leave the
cord intact. The cord is cut near that dynamically stressed part. In this way three
testing pieces are achieved; two of them are non-deformed (A) and one is
dynamically stressed (B). The adhesion is determined on shredder by means of
special fixing jaws. The test result is given in average adhesion value of
dynamically non-stressed and stressed part of the sample and adhesion loss
calculated by usage of this formula (43), [20]:
adhesion loss =
A B
.100 [%]
A
(43)
110
Fig. 19: Testing piece and its dynamic/impulse stress during Henley test
Fig. 20: Operation principle of DMA DMA will add oscillation force causing
mostly sinusoidal loading applied on the sample, which creates sinusoidal
deformation. Measurement of material response to loading will discover the phase
shift between applied force and real deformation behavior in tested material and
values of module, viscosity and absorption can be calculated. (applied stress =
aplikovan zaaenie (naptie); material response = materilov odozva, phase lag
= fzov oneskorenie; amplitude = amplitda)
Applied force is called stress (). When material is put under load, deformation ()
will be expressed. These data are traditionally achieved from mechanical tensile
111
Fig. 21: Stress-deformation curve gives the force into connection with deformation.
Ratio of stress (loading) to deformation is module (E) as the extent of the material
stiffness or its resistance to deformation. Youngs modulus slope of the initial
linear part of the stress-deformation curve is normally used as indicator of the
material behavior.
Fundamental measured values from DMA analysis are force and changed
dimensions of tested material. These values are used for calculation of modules; the
module type depends on type of dynamical loading (i.e. shearing, tensile, bending
and pressure stress etc.) and viscosity value that characterizes creep material
resistance.
One of DMA advantages is that we can achieve module every time and application
of sinusoidal curve gives us analysis during the whole length of temperature,
frequency, deformation and time scope. Module measured by means of DMA is not
exactly the same as Youngs modulus of classical stress-deformation curve (Fig.
22). The Youngs modulus is slope of stress-deformation curve in its initial linear
area. In case of DMA, the complex modulus E*, elastic modulus E and imaginary
(loss) modulus E are calculated from material response of the sinusoidal behavior.
These different modules allow us better characterize the material as we can better
explore the material ability to return back or stored (retained - elastic) energy (E) to
its energy loss ability plastic component (E), and ratio of these effects (tan
delta), which is also called absorption [21].
112
Fig. 22: Mutual relation between modules E*, E, E, tan delta and *
Materials also show some types of creep behavior and it is valid also for those
materials we think of as solid and rigid. Such materials have final viscosity very
high and generally we can state that if we wait sufficiently long time thus
everything flows. These times are sometimes so long that it is not possible to
measure them, but creep tendency can be calculated. This example illustrates the
fact that the question of rheology is not if the subjects creep, but how long will
they creep [21].
One example for utilization of DMA to explore the material properties is
development of graphic dependency of the elastic modulus on temperature (in case
we scan the sample under constant heating or cooling speed), where we can notice
modulus change under low temperatures. This transition is marked as glass
transition (Tg) and it is also called alpha-transition (T). Tg or T can be awarded to
partial chain motions. Except of the glass transition it is possible to scan also so
called beta-transition (T) which is accredited to other changes in molecular
motions. -transition is often connected with side chains or motions of groups and
may be in relation with polymer stiffness [21]. Idealized DMA temperature analysis
is shown on Fig. 23.
Fig. 23:
Idealized DMA temperature analysis (melting = mknutie; Rubbery
Plateau = kauukov plat; glass transition = sklen prechod; local motions =
loklne pohyby; bend and stretch = ohyb a pretiahnutie; side groups = bon
skupiny; gradual main chain = iaston hlavn reazec; large scale chain = dlh
stupovit reazec; chain slippage = preklzovanie reazca)
113
(44)
Fig. 24: Zero shear plateau one of the main utilizations of frequency data for
molecular weight estimate. The zero shear plateau can be used for calculation of
polymer molecular weight by means of the above stated formula in case of known
material constant factor k and molecular weight (MW) is higher than critical value
(Mc).
114
By the way, many types of DMA offered on the market allow creep and relaxing
testing. Creep (flowing) is one of the most fundamental tests of material behavior
and it is directly applicable for the final product properties. Creep-relaxing testing is
also very strong analytic tool. These experiments allow to state material response to
the constant loading and its behavior after removal of this loading. Creep-relaxing
testing allows to achieve inside view - how the material will respond when loaded
with constant load [21].
We should remember that creep is not a dynamical test the constant loading is
applied during creep step and it is removed for next relaxation step (Fig. 25).
Fig. 25: Creep relaxing testing Creep-relaxing experiments allow stating such
balanced properties as modulus Ee and viscosity e. These values allow forecasting
of material behavior under imitative conditions of real usage in practice.
(irrecoverable creep is lost forever = nenvratn teenie je plne straten; rate of
strain = rchlos deformcie; retardation time is a measure of recovery =
retardan as je mierou zotavenia)
The units that allow dynamical-mechanical testing, so called DMA (or DMTA)
apparatuses are offered by many companies on the market. Equipment Qualimeter
Eplexor 500N supplied by Gabo company is shown on the next figure:
115
Different types of jaws can be used for individual testing types, some of them are
shown on following figures:
pressure jaws
116
tension jaws
117
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
118