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HIGH TEMPERATURE POLYIMIDE MATRIX COMPOSITES · PDF file 3 Polyimide resin as high temperature matrix Epoxy Bismaleimide 5250-4, 5270-1 Less than 230 ℃ SKYBONDⓇ 700, 703, 705 PMR-15

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  • 1

    HIGH TEMPERATURE POLYIMIDE MATRIX COMPOSITES

    Tsuyoshi Ozaki, Composites Research and Development Koji Moriuchi and Shinichi Sakane, IST Corporation

    Satoshi Uehara and Takashi Yokoyama, Super Resin Inc.

  • 2

    Fiber reinforced plastic matrix composites

    Very attractive materials

    * Light-weight structures

    * Especially for aerospace applications

    Some of the aerospace parts such as engine components require high heat resistance of more than 200 ℃.

  • 3

    Polyimide resin as high temperature matrix

    Epoxy

    Bismaleimide 5250-4, 5270-1 Less than 230 ℃

    SKYBONDⓇⓇ 700, 703, 705

    PMR-15 More than 300 ℃

    Very attractive matrix for high temperature composites

    High heat resistance

    Polyimide

    Less than 200 ℃

  • 4

    Major disadvantage of polyimide matrix resin

    * The difficulty in polyimide curing process

    * Imidization and curing happened simultaneously. ⇒ High voids of more than 3 % ⇒ Derade the mechanical and thermal performance

    SolventSolvent

    ImpregnationImpregnation LaminationLaminationHeatHeat

    DryingDrying CuringCuring

    HeatHeat

    WaterWaterSolventSolvent

    ImpregnationImpregnation LaminationLaminationHeatHeat

    DryingDrying CuringCuring

    HeatHeat

    WaterWater (Imidization)

  • 5

    IST’s SKYBONDⓇⓇ 8000 and SKYBONDⓇⓇ 800

    IST has developed new polyimide resins to solve the problem. 2 solutions are proposed.

    (1) SKYBONDⓇⓇ 8000 for RTM (Resin Transfer Molding)

    Citraconic endcapped imide oligomer

    (2) SKYBONDⓇⓇ 800 for two stage autoclave process

    Citraconic endcapped amic acid oligomer

    N NR’ RR

    OO

    n

    O O

    N N

    O OO O

    N NR’ RR

    OO

    n

    O O

    N N

    OO OOO O

    N NR’ RR

    O

    O

    O

    O OH

    OO HO

    n

    O O

    OH N N

    HO N NR’ RR

    O

    O

    O

    O OH

    OO HO

    n

    O O

    OH N N

    HO

  • SKYBONDⓇⓇ 8000 for RTM

    6

  • 7

    Resin Transfer Molding (SKYBONDⓇⓇ 8000)

    SKYBONDⓇⓇ 8000 (Citraconic endcapped imide oligomer )

    (1) Solvent free (imidized powder)

    (3) Can be cured at >300 C

    without volatiles

    (2) Low melt viscosity (of less than 1.0 Pa・s)

    N NR’ RR

    OO

    n

    O O

    N N

    O OO O

    m

    N NR’ RR

    OO

    n

    O O

    N N

    OO OOO O

    m

    N NR’ RR

    OO

    n

    O O

    N N

    O OO O

    N NR’ RR

    OO

    n

    O O

    N N

    OO OOO O

    0 100 200 300 400

    1E+1

    1E+2

    1E+3

    1E+4 1E+5

    1E+6

    Temperature (℃)

    Vi sc

    os ity

    ( P)

    0 100 200 300 400

    1E+1

    1E+2

    1E+3

    1E+4 1E+5

    1E+6

    Temperature (℃) 0 100 200 300 400

    1E+1

    1E+2

    1E+3

    1E+4 1E+5

    1E+6

    0 100 200 300 400

    1E+1

    1E+2

    1E+3

    1E+4 1E+5

    1E+6

    0 100 200 300 400

    1E+1

    1E+2

    1E+3

    1E+4 1E+5

    1E+6

    Temperature (℃)

    Vi sc

    os ity

    ( P)

    Temperature Scan with 10℃/minFig.1

    1.0 Pa・s

  • 8

    SKYBONDⓇⓇ 8000 molding & cure condition

    Carbon Fabric 1) G30(0/90)n Volume Fraction 48-50 % Injection Temp. 240 ℃ Cure Temp. 335 ℃

    200

    250

    300

    350

    0 100 200 300 400

    335 ℃ x 4 h cure

    Ramp Step 1 C/min

    Injection & Hold Step

    Time (min)

    Te m

    p. (℃

    )

    Table 1. Molding condition

    Fig.1 Cure cycle

    1) Desized at 400 C for 1hr

  • 1.40 (0.29)48.5 (0.45)50.1 (0.38)40.7 (0.39)1.50 (0.00)Ave. (Std. Dev.) 1.648.849.741.01.503

    1.648.050.440.31.502

    1.148.850.240.81.51Sample1

    Voids (%)Resin Volume (%)Vf (%)Resin (wt%)Density (g/cc)

    1.40 (0.29)48.5 (0.45)50.1 (0.38)40.7 (0.39)1.50 (0.00)Ave. (Std. Dev.) 1.648.849.741.01.503

    1.648.050.440.31.502

    1.148.850.240.81.51Sample1

    Voids (%)Resin Volume (%)Vf (%)Resin (wt%)Density (g/cc)

    Fig.4 Microscopy of Cross Section

    Fig.3 Ultrasonic C-scan- Poor

    Good

    Small amount of voids compared with conventional polyimide composites

    ASTM D3171

    Table 2. Summary of the Acid Digestion

    Void content of SKYBONDⓇⓇ 8000 RTM FRP

    9

    Calculated void content by digestion method

  • 10

    Flexural Strength of SKYBONDⓇⓇ 8000 FRP

    0

    20

    40

    60

    80

    100

    120

    Stress Modulus

    R et

    en tio

    n R

    at e

    (% )

    23℃ 180℃ 200℃ 220℃ 230℃ 240℃ 250℃

    Stress 856.4 MPa Modulus 48.1 MPa

    n = 5 error bar = σ

    Test Temp. (℃)

    0

    20

    40

    60

    80

    100

    120

    Stress Modulus

    R et

    en tio

    n R

    at e

    (% )

    23℃ 180℃ 200℃ 220℃ 230℃ 240℃ 250℃

    Stress 856.4 MPa Modulus 48.1 GPa

    n = 5 error bar = σ

    Fig.5 Flexural strength of SKYBONDⓇⓇ 8000 Test Temp. (℃)

    > 60 %

    Only a small reduction

    Good retention

  • SKYBONDⓇⓇ 800 for two stage autoclave process

    11

  • 12

    Two stage cure autoclave process

    Conventional Imidization stage and curing stage would overlap.

    Imidization stage Curing stage 1st 1st -- StageStage 2nd 2nd -- StageStage

    Cure laminatesCure laminatesRemove volatiles Remove volatiles (solvent/water)(solvent/water)

    Two stage cure for autoclave process

  • 13

    SKYBONDⓇⓇ 800 for two stage autoclave process

    SkybondⓇⓇ 800 (Citraconic endcapped amic acid oligomer)

    N NR’ RR

    O

    O

    O

    O OH

    OO HO

    n

    O O

    OH N N

    HO N NR’ RR

    O

    O

    O

    O OH

    OO HO

    n

    O O

    OH N N

    HO

    150 ℃ to 220 ℃

    1st :Imidization stage

    Imidization was completely

    separated from curing stage

    Laminates can be cured

    without influence of water

    N NR’ RR

    OO

    n

    O O

    N N

    O OO O

    N NR’ RR

    OO

    n

    O O

    N N

    OO OOO O

    N NR’ RR

    OO

    n

    O O

    N N

    O OO O

    m

    N NR’ RR

    OO

    n

    O O

    N N

    OO OOO O

    m

    > 300 ℃

    2nd : Curing stage

    Very unique resin for molding of composite laminates

    having such a ‘two-stage’ cure cycle.

    with NMP solvent

  • DSC (Differential scanning calorimetric analysis) of SKYBONDⓇⓇ 800

    14

    Fig.6 DSC thermograms of SKYBONDⓇⓇ 800 powder after it is dried

    Metho d: imidization dt 1 .0 0 s 30 .0 -40 0 .0°C 3 .00 °C/min Synchro nizatio n enabled

    Sa mple: SK8 00 PAA powder.., 9 .0 4 00 mg

    Co ntent 12 .0 8e+0 3 % no rma lized -12 0 .76 J g^-1 Onset 13 4 .17 °C Pea k 16 2 .63 °C Left L imit 11 0 .34 °C Rig ht L imit 23 2 .81 °C

    m W

    0

    5

    10

    m in

    °C50 100 150 200 250 300 350

    0 20 40 60 80 100

    ^ e x o

    S T A R e S W 9 . 2 0L a b : M E T T L E R

    Imidization Crosslink

    Endothermic

    220 ℃ 335 ℃165 ℃

    Temperature

    H ea

    t f lo

    w

    Exothermic

  • Imidization ratio of SKYBONDⓇⓇ 800

    15

    Table 3   Imidization ratio of SKYBONDⓇ 800

    Conditions 1) Ratio 2)

    1376 cm-1

    /1500 cm-1

    Imidization ratio (%)

    150 ℃ -1 hr 0.740 0

    150 ℃ -1 hr, 220 ℃ -30 min 1.000 71

    150 ℃ -1 hr, 220℃ -1 hr 1.036 81

    150 ℃ -1 hr, 220℃ -2 hrs 1.080 93

    150 ℃ -1 hr, 220 ℃ -1 hr and 335 ℃ -4hr 1.106 100

    1) Atmospheric pressure

    2) 1376 cm-1: C-N streching of imide group

    2) 1500 cm-1: C-N streching of para-benzene group

  • Tg of SKYBONDⓇⓇ 800 neat resin

    16 Fig.7 DMA of SKYBONDⓇⓇ 800 neat resin

    2 stage cured film

    296 ℃

  • Tensile properties of SKYBONDⓇⓇ 800 neat resin

    17

    Table 4 Tensile properties of SKYBONDⓇ 800 neat resin

    Properties 23 ℃ 250 ℃ Measurement

    Tensile strength 96 MPa 52 MPa ASTM D638

    Tensile modulus 2.6 GPa 1.5 GPa ASTM D638

    Elongation 5.6% 4.8% ASTM D638

    Help to make the composite tougher than other brittle resin matrix like BMI.

    About 5% elongation

  • SKYBONDⓇⓇ 800 FRP with two stage cure process

    18

  • 0

    100

    200

    300

    400

    500

    600

    0 2 4 6 8 10 12

    Time (hrs)

    Te m

    pe ra

    tu re

    ( ℃

    )

    -12

    -8

    -4

    0

    4

    8

    12

    P re

    ss ur

    e (k

    gf /c

    m 2 )

    Pressure : 1

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