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10
INCORPORATIONOFDEVULCANIZEDRUBBER
IN A TIRE RUBBER COMPOUND
INATIRERUBBERCOMPOUND
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M.Meysami,S.Zhu,andC.Tzoganakis
DepartmentofChemicalEngineering
UniversityofWaterloo
W t l
Waterloo,Ontario,Canada
O t i C d
Outline
Introduction
I t d ti
Experimental
20
10
RecycledTires/RubberCrumb/
Vulcanization & Devulcanization
Vulcanization&Devulcanization
BackgroundandObjectives
Process/Materials/Characterization
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Introduction
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World:1.6billions
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Annualgeneration
ofScraptires:
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USA:299millions
USA:
299 millions
Canada:30millions
References:
ScrapTireMarketinTheUnitedStates,RubberManufacturerAssociation,Nov2006,page15
Sangari,S.S.;Kao,N.;Bhattacharya,S.N.;Pavel,DandSilva,K.MechanochemicalDevulcanisationof
Elastomers,RubberDiv.ACS,Oct.,2001
Schnekenburger,Michael,TireRecyclinginCanada1999,RubberDivision,ACS,PaperNo.166,Set.21
24,1999
Introduction
Tire Recycling
TireRecycling
Statisticsin2005fortheUSAshowthatnearly87%ofscraptiresintheU.S.were
usedinendusemarket.
Statisticsshowthatthereisaneightfoldincreaseinpercentageofconsumingof
S i i h
h h
i
i h f ld i
i
f
i
f
scraptiresbyendusemarketannuallysince1990.
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Introduction
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TDF(tirederivedfuel)applicationconsumedabout52%oftotalscraptireinU.S
( i d i d f l)
li i
d b
2% f
l
i i
S
CivilengineeringmarketisanotherbigconsumerofscraptiresinU.S(16%)
12%isconsumedbygroundrubberproducts
Introduction
20
Ambientgrindingprocess
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GroundRubber:ProductionMethods
Cryogenicgrindingprocess
Cryogenic grinding process
Extrusion
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Wetgrindingprocess
Introduction
RubberCrumbApplications
Rubber Crumb Applications
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SportSurfaces
20
Geotechnical/ AsphaltApplications
RubberandPlasticProducts
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AutomotiveIndustry
AdhesivesandSealants
Construction
ShockAbsorptionandSafetyProducts
Introduction
RubberVulcanization
Rawrubberissoftandstickymaterialwitha
l t il t
lowtensilestrengthandelasticity
th d l ti it
Atomicbridgescomposedofsulphurorcarbon
carbonbondslinkthepolymerchainstogether
Thevulcanizedrubberisathermosetmaterial
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Introduction
RubberDevulcanization
Devulcanizationreferstoaprocessinwhichthecrosslinkbondsinthevulcanized
rubber cleave totally or partially
rubbercleavetotallyorpartially.
Thedevulcanizedrubberisabletoberevulcanizedandutilizedagainlikeavirgin
rubber
bb
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Introduction
Ad
Advantagesofbreakingthe3Dnetwork:
t
f b ki th 3D t
k
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(Devulcanized Rubber)
Re
Re Compoundable
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Re Processable
Re Vulcanizeable
Introduction
D l i ti M th d
DevulcanizationMethods
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Mechanical
Ultrasonic
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Chemical
Microwaves
Microorganisms
Introduction
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ThermoMechanicalDevulcanizationProcess
withSupercriticalCO2
Nochemicalagents
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Acontinuousdevulcanizationprocesswhichiscarriedoutina
twinscrewextruder
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scCO
CO2 actsasaplastisizerandfacilitatestheprocess
t
l ti i
d f ilit t th
USpatent7,189,762
Introduction
Devulcanization Mechanism
Crosslink
V l
Vulcanized
i d rubber
bb
CO2
SY
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SY
ScCO2diffusesandswellstherubbernetwork
Elastic constant (k) for S S bonds is about 1/30 that for C C bonds
Elasticconstant(k)forSSbondsisabout1/30thatforCCbonds
SelectivecleavageofSSbondsoccurs
Experimental
p
Control Panel
Valve
20
50 rpm
200 C
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Thermocouples
Gear
box
Valve
10
Feeder
Extruder
Pressure
Transducers
Syringe
Pump
CO2
Cylinder
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Experimental
p
Experimental
p
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Screwconfiguration
Inthefirstzonethecrumbrubberisheatedtothedevulcanization temperature
p
KneadingelementsafterinjectionofCO2givetheCO2andrubbercrumbagood
mixingandenoughshearingandstretching
Experimental
p
20
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Particlesize:
P
ti l i
60mesh
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RubberCrumb(EdgeRubberco.)
Rubber Crumb (Edge Rubber co.)
scCO2 (Praxair)
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Experimental
p
Typicaldevulcanized samples:
a)
Samplesofdevulcanized rubberinstrandshape
b)
Devulcanized rubberribbonsexitingthedie;
c)
Samplesofdevulcanized rubberinribbonshape
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Tire Tread :
Tread is the wear resistance component of the tire in contact with
the road
It must provide traction,
traction wet skid,
skid and also minimum noise
generation and low heat buildup
A blend of natural rubber, polybutadiene (BR),and styrene
butadiene rubber (SBR), compounded with carbon black, silica, oils,
and vulcanizing chemicals
Why devulcanized rubber incorporation ?
Lowering the cost of raw material
Recycling of scrap tires
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C
Crosssectionofahighperformancepassengertire
i
f hi h
f
i
Experimental
p
Compoundingrecipeforsamples
p
g
p f
p
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Ingredients
Control
10%
20%
30%
TreadMB
194phr
p
174phr
p
155phr
p
135phr
p
Devulcanizedrubber
20phr
39phr
59phr
OBTS
1.25phr 1.25phr 1.25phr 1.25phr
PVI
03 h
0.3phr
03 h
0.3phr
03 h
0.3phr
03 h
0.3phr
Sulfur
1.95phr 1.95phr 1.95phr 1.95phr
Experimental
p
10
Sample preparation
Samplepreparation
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The
Thevirgintirecompoundanddevulcanizedrubberwerefirstmixedina
virgin tire compound and devulcanized rubber were first mixed in a
Banburymixer
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Thencuringchemicalswereaddedduringmillingthecompoundonatwo
rollmill
AppropriatecuringtimewasdeterminedusingtheMDRtestdata
Sampleswerepressedandcuredintostandardtestingspecimensusinga
hotpress
Experimental
p
Characterization
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Mooneyviscosity
CuringProperties(MH,Ts
i
i (
)
2,T90)
Tensileproperties(Tensilestrength,Elongationatbreak,
Modulus)
Tearstrength
Hardness (shore A)
Hardness(shoreA)
Heataging(72hr@70C)
y
(
p)
Hysteresis(heatbuildup)
Cutandchip(%ofmassloss)
10
45
40
20
35
30
25
20
15
10
0
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50
10
20
30
40
AslightincreaseforMooneyviscositycanbeobservedwhenthepercentof
g
f
y
y
p
f
devulcanized rubberinvirginrubbercompoundincreases
PresenceofremainedcrosslinkbondscouldbethereasonfortheMooney
viscosityincreasing
y
g
10
1.2
0.8
20
Time (Min)
0.6
0.4
10
20
Tc90
30
40
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0.2
Ts2
Scorchtime(Ts2)andoptimumcuretime(Tc90)donotchangebyincorporationof
( )
p
(
)
g y
p
f
devulcanized rubberintoatiretreadcompoundupto30%.
10
9.5
8.5
8
20
MH (lb-in)
7.5
7
6
0
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6.5
10
20
30
40
AveryslightincreaseatthebeginningcanbeobservedfortheM
y g
g
g
f
H valueandthenit
startstodecrease
96
83
10
87
80
20
60
40
20
120
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0
0
10
20
30
40
Tensilestrengthdecreasesasdevulcanized
g
rubbercontentincreases
Samplewith30%devulcanized rubbershowsan83%retentionoftensilestrength
94.7
10
100
85.5
80.4
20
80
60
40
20
0
0
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Elongationatbreak
g
10
20
30
40
Elongationatbreakdecreasesasdevulcanized
g
rubbercontentincreases
Samplewith30%devulcanized rubbershowsan80.4%retentionofelongationat
break
Modulus 200%
Modulus 300%
10
140
130
20
110
100
90
80
70
60
50
0
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Reten
ntion (%)
120
10
20
30
40
Modulusincreasesasthecontentofdevulcanized rubberincreasesinthetiretread
compound
10
110
100
90
20
80
70
60
50
40
0
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Retention
n of Tear strength (%)
120
10
20
30
40
Tearstrengthincreasesby7%atthebeginning(when10%devulcanized
g
y
g
g(
rubberis
added)andthenstartstodecrease
Compoundcontaining30%devulcanized
Compound
containing 30% devulcanized rubbershowsaround95%retentionof
rubber shows around 95 % retention of
tearstrength
60
62
20
55
50
45
40
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35
30
63
10
62
65
10
20
30
Additionofdevulcanized rubberdoesnotchangethehardnessoftiretread
compound
Elongation
10
16
-16
-10
-16
16
-18
3.4
10
20
30
-15
-20
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-5
5
E
Elongation (%)
10
20
-8
Tensile (%)
15
10
20
Tensilestrengthincreasesaround10%afteragingforthecontrolcompound,this
valueforthecompoundshavingdevulcanized rubberisaround3%
Elongationatbreakdecreasesby8%forcontrolcompoundwhileforsamples10&
20thisvalueis16%.Forsamplehaving30%devulcanized rubberelongation
decreasesby18%afteragingprocess
Tan delta
30
0.5
0.45
10
0.35
15
10
0.25
0.2
0.15
0.3
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0
0
10
Tan
20
04
0.4
20
Hy
ysteresis (C)
25
0.1
20
30
Specimensweresubjectedtoadynamicloadfor25minat148Cusinga
flexometer
Hysteresis(heatbuildupunderdynamicstress)decreasesascontentof
devulcanized rubberincreasesintiretreadcompound
Tan (damping)doesnotshowadistinguishabletrendandfluctuatesfrom0.332
to0.408
10
14.2
13
14
12 11
11.7
20
Ma
ass Loss (%)
16
10
8
6
2
0
0
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10
20
30
40
Thistestshowstheserviceperformanceoftiretreads
Percentofmasslossinacutandchiptestincreasesasthepercentofdevulcanized
rubber increases in a tire tread compound
rubberincreasesinatiretreadcompound
Concluding
g remarks
Devulcanization of ground tire rubber crumbs under stress in the twin screw
extruder with supercritical CO2 is a continuous, costeffective, and environmentally
friendly process
20
Devulcanizedrubberobtainedfromourdevulcanizationprocesswasincorporated
Devulcanized
rubber obtained from our devulcanization process was incorporated
inavirgintirecompoundandtheresultsshowthatbyadditionupto30%of
devulcanizedrubbertheMooneyviscosity,Hardness,tearstrengthandcuring
properties does not change significantly. Tensile strength and elongation at break
propertiesdoesnotchangesignificantly.Tensilestrengthandelongationatbreak
decreaseupto15%and20%,andheatbuildupimproves.
Theseresultsshowthatdevulcanizedrubbercanbeincorporatedinatire
compound in order to lower the price without significant deterioration of
compoundinordertolowerthepricewithoutsignificantdeteriorationof
compoundproperties.However,additionalexperimentsarerequiredtofurther
optimizethetirecompoundproperties.
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Current Efforts
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Optimizationthepropertiesofthetiretreadand
Optimization the properties of the tire tread and
devulcanizedrubbercompound
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Incorporationofdevulcanizedrubberina
conveyorbeltcompound
DevulcanizationofEPDMscraprubber
PreparationofTPVmaterialbyusingthe
d l i d bb
devulcanizedrubber
Acknowledgements
g
20
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FinancialsupportfromNSERCandC4/OntarioMinistryof
/
ResearchandInnovation'sOntarioResearch
Commercialization Program is gratefully acknowledged
CommercializationProgramisgratefullyacknowledged
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Airboss
Airbossrubbercompoundingassocciationforusingtheir
rubber compounding assocciation for using their
facilitiesisgreatlyappreciated