Linear and Non Linear Rheological Measurements on TA Instruments. Physical description of Polymers Strain Sweep -LAOS 0.0 π 0.5 π 1.0 π 1.5 π 2.0 π-8000-6000-4000-2000 0 2000

  • View
    233

  • Download
    4

Embed Size (px)

Text of Linear and Non Linear Rheological Measurements on TA Instruments. Physical description of Polymers...

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Linear and Non Linear Rheological

    Measurements on Rubber

    Polymers and Compounds

    Thomas Rauschmann

    Copyright TA Instruments, USA

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Standard Test: Mooney

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    0.0

    16.0

    32.0

    48.0

    64.0

    80.0

    0.0 1.6 3.2 4.8 6.4 8.0

    Mo

    on

    ey-V

    isko

    sit

    t [M

    U]

    Zeit [min]

    SCARABAEUS GMBH - info@scarabaeus-gmbh.de - Tel.:+49 (0) 6403/9034-0

    Polymer C1

    Polymer C1

    Polymer B1

    Polymer B1

    Polymer A1

    Polymer A1

    SCARABAEUSMooneyprfung

    Entwicklung

    Mooney Viscosity Mooney Relaxation Mooney Scorch

    Shear rate 1.6 s-1 (2 rpm)

    0,01 0,1 1 10 100

    0,01

    0,1

    1

    .

    shear rate,

    vis

    cosity

    ML1+4

    Standard Test: Mooney

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    TA Instruments - RPA

    Zeit

    -1.5

    -1

    -0.5

    0

    0.5

    1

    1.5

    0 5 10 15 20 25 30 35 40

    1

    2

    Zeit

    1

    -3

    -2

    -1

    0

    1

    2

    3

    0 5 10 15 20 25 30 35 40

    2

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Zeit

    -1.5

    -1

    -0.5

    0

    0.5

    1

    1.5

    0 5 10 15 20 25 30 35 40

    1

    2

    Frequency:

    RPA 0.00150.0 Hz

    Step 0.001Hz

    RPA Rheometer

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Effect of Branching on G, G, * and tangent

    1000

    10000

    100000

    1000000

    10000000

    0.01 0.1 1 10 100 1000

    Frequency (Rad/s

    Eta

    * (P

    a.s

    )

    Branched

    Linear

    Mooney shear rate

    range

    0.1

    1

    10

    100

    1000

    0.01 0.1 1 10 100 1000

    Frequency (Rad/s)

    G' &

    G"

    (kP

    a)

    0

    1

    2

    3

    4

    5

    6

    7

    8

    9

    Tan

    gen

    t D

    elt

    a (

    -)

    or Tan

    High performance EPDM polymers based on a new technology of controlled Long Chain Branching H.J.H.

    Beelen, IRC97, Nrnberg.

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    LCB and MWD (linear) effect on Tangent

    0

    0.5

    1

    1.5

    2

    2.5

    3

    0.01 0.1 1 10 100 1000

    Frequency (Rad/s)

    Ta

    ng

    en

    t D

    elt

    a (

    -)B50

    B100

    Star-IIR

    Mix4

    Weight % B15 B30 B50 B100 B200Mix 1 90.7 0 0 0 9.3

    Mix 4 10.9 21.9 36.4 22 8.8

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Correlation between * and Mooney viscosity ML(1+4) EPDM polymers

    1000

    10000

    100000

    1000000

    10000000

    0.01 0.1 1 10 100 1000

    *

    (Pa

    .s)

    Angular frequency (Rad/s)

    Polymer 1-2

    Polymer 2-2

    Polymer 3-2

    Polymer 4-2

    Polymer 5-2

    Polymer 6-2

    Polymer 7-2

    Mooney shear rate

    range

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    EPDM (ML(1+4)@125 C 65 5 MU

    0

    0.2

    0.4

    0.6

    0.8

    1

    1.2

    1.4

    1.6

    0.01 0.1 1 10 100 1000

    Ta

    ng

    ne

    t

    (-)

    Angular frequency (Rad/s)

    Polymer 1-2

    Polymer 2-2

    Polymer 3-2

    Polymer 4-2

    Polymer 5-2

    Polymer 6-2

    Polymer 7-2

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Zeit

    1

    -3

    -2

    -1

    0

    1

    2

    3

    0 5 10 15 20 25 30 35 40

    2

    Strain:RPA 0.005360.0

    Step 0.01

    RPA Rheometer

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Why Non linear viscoelasticity ?

    PIPKIN Diagram

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    RPA Rheometer

    0

    100

    100

    200

    200

    300

    300

    400

    400

    1 10 100

    Schubmodul G' [kPa]

    Amplitude [%]

    SCARABAEUS GMBH - info@scarabaeus-gmbh.de - Tel.:+49 (0) 6403/9034-0

    Scarabaeus GmbHMe- und Produktionstechnik

    SIS V 50

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Physical description of PolymersStrain Sweep - LAOS

    0.0 0.5 1.0 1.5 2.0

    -8000

    -6000

    -4000

    -2000

    0

    2000

    4000

    6000

    8000

    -1200

    -1000

    -800

    -600

    -400

    -200

    0

    200

    400

    600

    800

    1000

    1200

    PIB, =0.1 Hz, 0=1000%, T=140C

    [P

    a]

    t [Pa]

    [%

    ]

    " S

    tad

    ler

    FJ,

    Le

    yg

    ue

    A,

    Bu

    rhin

    H,

    Ba

    illy

    C (

    20

    08

    ) T

    he

    po

    ten

    tia

    l o

    f la

    rge

    am

    plitu

    de

    osc

    illa

    tory

    sh

    ea

    r to

    ga

    in a

    n in

    sig

    ht

    into

    th

    e

    lon

    g-c

    ha

    in b

    ran

    chin

    g s

    tru

    ctu

    re o

    f p

    oly

    me

    rs.

    In

    : T

    he

    23

    5th

    AC

    S n

    ati

    on

    al

    me

    eti

    ng

    , p

    oly

    me

    r p

    rep

    rin

    ts A

    CS

    , vo

    l4

    9. N

    ew

    Orl

    ea

    ns,

    LA

    , U

    SA

    , p

    p 1

    21

    1

    22

    "

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Physical description of PolymersStrain Sweep - LAOS

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Henri Burhin, Polymer Process Consult, 2012

    Physical description of PolymersStrain Sweep - LAOS

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    LAOS Sensitivity to branching content

    A (Branched) 2.5% branched in linear H (Linear)

    G'1/G'5 6,91 6,09 3,74

    A3/A5 -2,97 -3,44 -3,00

    E1 3,91 5,32 4,00

    E2 -3,97 -4,44 -4,00

    E3 4,94 5,93 5,00

    G'1/G'5-E3 1,97 0,16 -1,27

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    EPDM polymers ML(1+4), 125 C 65 5 MU

    0

    0.2

    0.4

    0.6

    0.8

    1

    1.2

    1.4

    1.6

    0.01 0.1 1 10 100 1000

    Ta

    ng

    ne

    t

    (-)

    Angular frequency (Rad/s)

    Polymer 1-2

    Polymer 2-2

    Polymer 3-2

    Polymer 4-2

    Polymer 5-2

    Polymer 6-2

    Polymer 7-2

    -300000

    -200000

    -100000

    0

    100000

    200000

    300000

    -8 -6 -4 -2 0 2 4 6 8

    Sh

    ea

    r st

    ress

    (P

    a)

    Shear rate (s-1)

    Polymer 6-2

    Polymer 7-2

    Polymer 5-2

    Polymer 4-2

    Polymer 3-2

    Polymer 2-2

    Polymer 1-2

    -2

    0

    2

    4

    6

    8

    10

    12

    Polymer 7-2 Polymer 6-2 Polymer 5-2 Polymer 4-2 Polymer 3-2 Polymer 2-2 Polymer 1-2

    mean

    LCB

    In

    de

    x (

    G'1

    /G'5

    -E

    3)

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    RPA Rheometer Tan Delta

    LCB Index:BR1: 3.7BR2: 2.2

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Strain-Sweep / tan @ 1000%aging @ 150C, 400%

    2.7

    4

    53.7

    6

    0

    10

    20

    30

    40

    50

    60

    BR 1 BR 2

    Tan Delta

    percentage differencesbefore and after aging

    0.000

    0.500

    1.000

    1.500

    2.000

    2.500

    3.000

    3.500

    4.000

    4.500

    BR 1 BR 2

    Tan Delta

    before aging

    after aging

    2 types of BR with:45MUcis-1,4 Content % > 96

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Strain-Sweep / LCB @ 1000%

    aging @ 150C, 400%

    14.45

    101.74

    0

    20

    40

    60

    80

    100

    120

    BR 1 BR 2

    LCB Index

    percentage differencebefore and after aging

    0

    1

    2

    3

    4

    5

    6

    7

    8

    BR 1 BR 2

    LCB Index

    before aging

    after aging

    2 types of BR with:45MUcis-1,4 Content % > 96

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Strain-Sweep / tan @ 1000% aging @ 150C, 400%

    2.74

    53.76

    14.45

    101.74

    0

    20

    40

    60

    80

    100

    120

    BR 1 BR 2

    dif

    fere

    nce b

    efo

    re/a

    fter

    ag

    ing

    [%

    ]significant differences in LCB Index

    Tan Delta

    LCB Index

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Practical example, linear and branched Polymer

    Keltan 6950 Nordel 5565

    Mooney ML 1+4 [MU] 65 65

    Ethylen [%] 48 50

    ENB content [%] 9 7.5

    Distribution medium medium

    Degree of branching Branched Linear

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Practical example, linear and branched Polymer

    Frequency Sweep

    Shear - thinning

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Practical example, linear and branched Polymer

    Frequency Sweep

    Mooney

    Low

    Frequency

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Physical description of Polymers

    Strain Sweep - LAOS

    High Strain

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Physical description of PolymersStrain Sweep - LAOS

  • TAINSTRUMENTS.COMTAINSTRUMENTS.COM

    Recipe of Compounds

    Keltancompound

    Nordelcompound

    phr phr

    EPDM (LCB) 100

    EPDM, linear 100

    Fast Extrusion Furnace (FEF) carbon black 95 95

    Chalk 50 50

    Paraffinic Oil 65 65

    ZnO 6 6

    Stearic acid 1 1

    Drying agent 9 9

    Antiaging agent 0,5 0,5

    Sulfur and accelerator 4,5 4,5