Textile International Forum and Exhibition 2014 • Taipei

Past, Present and Future of High Performance Polyimide Fibers

Qinghua ZhangQinghua Zhang

St t K L b f M difi ti f Ch Fib & P l M tState Key Lab for Modification of Chem. Fibers & Polym. Mater. College of Materials Science and Engineeirng

Donghua University, China

O 3 2014Oct 3, 2014

OutlineOutline

High performance FibersHistory of PI FibersPreparation, Structure & PropertiesPreparation, Structure & PropertiesApplicationsAcknowledgement

Organic High Perform FibersOrganic High Perform. Fibers

1960’s, aromatic polyamide lyotropic liquid crystal phenomenon was found; and 1970’s, aramid fibers were developed, Kevlar & Twaron.

1970’s, heterocyclic aromatic polymers were synthesized, including PBO, PBI, PBZT. 1990’s, PBO fibers were prepared in large scale by T bToyabo.

1970’s, DSM published its patent on gel-spinning of polyethylene; 1990’s, Dyneema was developed.

1990’s, Akzo Nobel developed a new polymer (PIPD) and M5 fiber, and the fibers were manufactured by Magellan Systems International.

Chemical structures of the polymersChemical structures of the polymersOH

Kevlar N－C CONHn

OO

n

OHNNH

PBO NN n

n

OHNN NHPIPD (M5)

O O

Polyimide (Kapton)C

CC

C

OO

N

nN O

Polyimide (Upilex) OO

OO

4

NN

O

n

O

Mechanical properties of some fibers

Density Tensile Modulus Elongation

Mechanical properties of some fibers

Fibers Density g/cm3

TensileGPa

ModulusGPa

Elongation % LOI

CF T700 1.80 4.9 230 2.1 －

Kevlar 49 1.45 2.9 124 2.8 29

Armos 1.44 4.5-5.5 145 2.8-4.0 42

Rusar 1.43 5.0 140 3 42Rusar 1.43 5.0 140 3 42

PBO 1.59 4.8-5.8 211-280 2.5 68

PI fiber(biphenyl) 1.44 3.1 128 2 40

PI fiberPI fiber(pyrimidine) 1.45 5.2 280 2 35

History of polyimide fibersHistory of polyimide fibers

1965 Dupont: PMDA+ODA/DMF, wet-spinning into water,1965 Dupont: PMDA ODA/DMF, wet spinning into water,= 1.1g/d，M=44g/d，E=6.5%

1967 Dupont: PMDA+PDA/DMAc in water or water/DMAc1967 Dupont: PMDA+PDA/DMAc, in water or water/DMAc,= 6.9 g/d, M=72 g/d，E=13%

1987 D t PMDA+ODA/PDA 15 6 /d M 570 /d E 3 3%1987 Dupont: PMDA+ODA/PDA, = 15.6g/d, M=570g/d, E=3.3%

Why did NOTNomex is enough for market?K l h d ti ?Why did NOT

Dupont further develop PI fibers?

Kevlar has good properties?More cost for PI fibers?M

Edward W M. US Patent, 1965, 3179614

pMore ……

Irwin R S, etc., US patent, 1968, 3415782; US patent, 1987, 4640972Irwin R S, etc., J. Polym. Sci. Part C, 1967, 19, 41

High strength PI fibers

1983 1986 UBE J BPDA+ODA/ hl h l D j t

High strength PI fibers

1983–1986, UBE Japan, BPDA+ODA/p-chlorophenol, Dry-jet wet-spinning, then drawn at 300–500C.

3 0 GP M 110 GP = 3.0 GPa, M = 110 GPa

1990’s, Akron USA, BPDA +PFMB/m-cresol, Dry-jet wet-spinning into H2O/methol, then drawn at ~380C. = 3.2 GPa, M > 130 Gpa

Makino H. etc, US Patent, 1983, 4370290Kaneda T etc J Appl Polym Sci 1986 32 3133 & 3151Kaneda T. etc, J. Appl. Polym. Sci., 1986, 32, 3133 & 3151Cheng SZD, etc., Polymer, 1991, 32,1803

1990’s later Russia Heterocyclic diamine1990’s later, Russia, Heterocyclic diamineintroduced into main chains of PI. = 5.8 GPa, M = 280 GPa !!! 5.8 GPa, M 280 GPa !!!No products in large scale

σ=1.0 GPa, M=91 GPa

1 5 GP M 118 GPσ=1.5 GPa, M=118 GPaσ=1.5 GPa, M=118 GPa

σ=3.0 GPa, M=130 GPa8

Sukhanova TE, Baklaginaa YuG, et al. Polymer 1999, 40, 6265.

PI fibers in ChinaPI fibers in China

1960 1970 PI fib d l d b Chi 1960s–1970s, PI fiber developed by China As an anti-radiation fiber

2000 PI fib d l d b f t i i 2000 -, PI fiber re-developed by means of wet-spinning and dry-spinning by CIAC, Donghua Univ., Sichuan Univ. High strength & modulus High strength & modulus Anti-radiation fiber

PI (PMDA-ODA) fibers have been produced in large scale PI (PMDA-ODA) fibers have been produced in large scale with 1000 t/a in Jilin and Jiangsu, by wet-spinning and dry-spinning technology.p g gy Tensile, 3–5 cN/dtex; fineness: 1–3 dtex,

Preparation of PIF: two-step methodPreparation of PIF: two-step method

OO

OO

ONH2 NH2+Synth. Sol.

Dianhydride＋Diamide

OO

DMAC / DMF / NMPPolyamic acid solutionPAA the precursor

y

Spinning

OO

ONH

NH

OHOH

PAA, the precursor

OO

Heating 200～400℃PAA (precusor) fiber

ImidizationOO

ONNHigh perform. PI fiber

Imidization,Drawing

OOHigh perform. PI fiber

BPDA-AAQ/PDA

T：2.80 GPaM：115 GPa

BPDA/BIA BPDA/BIA/ODA BPDA/BIA/DABA/T：2.24 GPaM：102 GPa

/ /T：2.0 GPaM：100GPa

/ /T：2.3 GPaM：140GPa

Copolyimides: BPDA-BIA-DABACopolyimides: BPDA-BIA-DABA

OO

OO

O

O

O

O

C

O

N

H

NH2H2NN

NNH2

H2N

H

+ + mn (m+n)

DABABIA BPDA

C N

N

NN

C

CHO

O

C OH

O

C C NO O

CONHH

HH

mn

DMAcN2

ice bath

NCHO

O

C OH

OCHO

OC OH

O

Hm

BPDA/(BIA/DABA) co-PAA

NN

O

O

O

O N

NN N CONH

O O

O mH O On mH

BPDA/(BIA/DABA) co-PI

WAXD patterns of the PI fibers with various diamine molar ratios (BIA/DABA):WAXD patterns of the PI fibers with various diamine molar ratios (BIA/DABA): (A) 10/0, (B)9/1, (C) 7/3, (D) 5/5, (E) 3/7 and (F) 0/10.

Modification to improving propertiesModification to improving properties

Yin, Zhang*, et al. Composites: Part B, 2014, 58, 430

Dry-spinning and simulationDry-spinning and simulation

Dianhydride & diamine Spinning solution

PAA l ti

Synthesis

yPump

SpinneretPAA solution

Spinning@200CHot air

PAA fibersp g@

Precursor fibers

Polyimide fibersCyclization 350C

ecu so be s

Hot air

PIF d tDrawing @ 400C

Hot airPIF products Hot air

Take up roll

Simulation of dry spinning process. M d l difi d t fit f ti f PAA/DMA t

Continuity equation

Models modified to fit formation of PAA/DMAc system.

)exp()(4 2

212

10,0

0, VRzD

wwww PSSSSS

AVVRCdVAVdF 2)(

Momentum equation

gAVVRCdz

AVdz zaaf 2)(

Energy equation

)]()([20yyMkHTTh

RdzdTVC ssyvazp

Energy equation

... dV.

Viscoelastic constitutive equationModified White-Metzer model

03)21)(21( AF dz

Changes of parameters along the spinline are simulated.

400 Filament velocity

g p g p

250

300

350

400

m/s

)

400

y

0.7

0.8C

Solvent content in filaments

Tension of filaments

100

150

200

250

Velo

city

(cm

100

200

300

400

0.4

0.5

0.6

0 3

0.4

0.5

0.6

0.7

0.8

ion

of D

MAC

1 2

1 4

1 6 w ith a ir d ra g w ith o u t a ir d ra g

Tension of filaments

0 .0 5 3 5

0 0 1 /

Mass flow rate

0 200 400 600 800 10000

50

100V

0 40 80 1200

0.1

0.2

0.3

0 20 40 60 80 100 1200.0

0.1

0.2

0.3

Mas

s fra

ct

4

6

8

1 0

Tens

ion

(N)

0 .0 5 1 5

0 .0 5 2 0

0 .0 5 2 5

0 .0 5 3 0at

ion

degr

eew = 0 .0 1 g /s

w = 0 .0 2 g /s w = 0 .0 3 g /s

240

260 Temperature of filaments

Spinline (cm)0 200 400 600 800 1000

0.0

Spinline (cm)0 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 00

2

4

S p in lin e (c m )0 0 4 9 5

0 .0 5 0 0

0 .0 5 0 5

0 .0 5 1 0

Imid

iza

1 80

200

220em

pera

ture(o C

)

9 0

100

110

120

130

pera

ture

(o C)

0 2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 00 .0 4 9 5

S p in lin e (cm )

1 20 240 3 60 480 600 720 840 960

140

160

Te

0 20 40 60 80 100 120

70

80

Tem

p

S p in line (cm )

S p in line (cm )

Products

纱线 高温滤袋纱线 高温滤袋

Jiangsu Aoshen New Materials Co.

Preparation: One-step methodPreparation: One-step method

S th S l

Dianhydride＋DiamideO

O

ONH2 NH2+O

O

Polyimide Solution

Synth. Sol.

p-chlorophenol,

OO

spinning

p chlorophenol,m-cresol, PPA, etc.

Polyimide fiber

Drawing & post-

O

ONN

O

High perform. PI fiber

Drawing & posttreatment

OO

Synthesis of soluble polyimidesSynthesis of soluble polyimides

C CO O

CC

O O H3C CH3C

NC C

NC

O OC

NCC

NC

O O

CN

C

O

CN

CNCC

NO

O OO

OC

CCOO

O

m-cresolp-chlorophenolC

NCC

NC

O O CF3

n

Horio M, et al. J. Appl. Polym. Sci, 1986, 32, 3133 & 3151.

OO F3C

Cheng ZDS, et al. Polymer 1991, 32, 1804 & 1003, 34, 3209; & Macromol. Chem. Phys. 1994, 195, 2207.

P84: soluble PI (BTDA-MDI-TDI)P84: soluble PI (BTDA-MDI-TDI)

P84 developed by Lenzing in 1980’s Evonic &P84 developed by Lenzing in 1980 s, Evonic & Degussa now, is the first commercial PI fiber.

Prepared by wet-spinning methods.p y p g

Fabricated into heat-resistant filter bags. Glass fiber is usually blended with P84 to reduce the price.

Mechanical properties: 2.2 dtex sample, =3.8 cN/dtex, LOI~38，Tg~315℃，260－280oC

N N

OO O CH3

CH2 n BTDA-MDI-TDI

21From http://www.p84.com/

O OBTDA MDI TDI

Soluble PI and fibersSoluble PI and fibers

CF3O O

O3

CF3

NH2H2Nm +N

NH2NNH2

H

n + OO

O O

m+n

NMPisoquinolin

190 oC

CF O OO O O

O

CF3

CF3

NN

O Om

N

N

H

NN

O O n

Code m/n NMP DMAC DMF DMSO THF CHCl3 m-cresol Toluene CCl4PI-85/15 ++ ++ + + - + + - -

PI-75/25 ++ ++ + + - +- + - -

PI-50/50 ++ ++ + + +- +- + - -

PI 40/60PI-40/60 ++ ++ + +- +- +- +- - -

++: soluble at room temperature; +: soluble on heating; +-: partly soluble on heating; -: insoluble.

FTIR & NMR confirm Thermal treated fiber

the polyimide structures

As-spun fiber

1150

723

1374

1780

1667

g, hk

j

a

b

d, f

i

4000 3000 2000 1750 1500 1250 1000 750 500

1723

Wavenumber (cm-1)

8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2 7.0

e

ppm

bc

i

m

ATR-FTIR spectra of PI-50/50

14 13 12 11 10 9 8 7 6

ppm

N-H

m1H NMR of PI-50/50

ppm

CF3OO

ON

NN

OO O

b cd

e g h i

CF3

NN

OO

N

Hm O O n

a fk

j

mFig. 2. 1H NMR spectra of co-PI-3 fiber.

PI/NMP exhibits i t i hanisotropic phase

POM of the PI/NMP systems with yvarious content (25 C).

POM of PI/NMP solutions at various temperature (a,10 wt%; b, 13 wt%).

Dong, Zhang*, et al. J Polym Sci B: 2014, 52, 450

Morphology of co-PI fibers produced from coagulation bath of H2O (a), H2O/NMP=95/5 (v/v) (b), and H2O/NMP=90/10 (c)2 ( ) ( ), 2 ( )

40

crystallinity orientation

0.90

12.3o16.1o

30

35

linity

(%)

0.80

0.85

Preferred o

=2 5

=3.0

=3.5

20

25

Cry

stal

l

0.75

orientation=1.5

=2.0

=2.5

1.5 2.0 2.5 3.0 3.5

20

Draw ratio

0.70

0 4

10 20 30 40 50

as-spun fiber

2/ degree

2.0

2.5 As-spun fiber HT fiber,=1.5 HT fiber, =2.0 HT fiber, =3.0 HT fiber, =3.5

0.3

0.4

co-PI-1 co-PI-2 co-PI-3 co-PI-4

(B)

1.0

1.5

Tens

ile (G

Pa)

0.2

Ta

n

0 5 10 15 20 25 300.0

0.5

T

0.1

0 5 10 15 20 25 30 Strain (%) 100 200 300 400 500

Dong, Zhang*, et al. J Mater Sci, 2013, 48, 7594

PI/Graphene composite fibersPI/Graphene composite fibers

M difi ti t i i d lModification to improving modulus

Dong, Zhang*, et al. Polymer, 2013, 54, 6415

PI/Graphene composite fibersPI/Graphene composite fibers

2.5 ed

c1.5

2.0

2.5gt

h (G

Pa) (C)(A)

1 5

2.0 b

0.5

1.0

Tens

ile s

tren

(GPa

)

a

1.0

1.5

120

140

GPa

)

0.01.0wt%0.8wt%0.5wt%0.3wt%pure PI

T

(B) Sres

s (

PI

0.560

80

100

's m

odul

us (G a. pure PI

b. PI/GO-ODA 0.3 wt%c. PI/GO-ODA 0.5 wt%d. PI/GO-ODA 0.8 wt%

0 1 2 3 4 50.0

0

20

40

1.0wt%0.8wt%0.5wt%0.3wt%pure PI

Youn

g

Strain (%)

e. PI/GO-ODA 1.0 wt%

( )

Thermal stabilityDynamical and thermal properties

Thermal stability

Content ofGO-ODA

Tg (C) in DMA

T5d (C) in TGA

Tmax (C) in TGA

Pure PI 356 585 638

0.3 wt% 360 593 650

0 % 369 602 6 10.5 wt% 369 602 651

0 8 wt% 374 604 6530.8 wt% 374 604 653

1.0 wt% 378 606 654

Properties of PI fibers

Stability Radiation-M h i l

Properties of PI fibers

Properties Kevlar 49 BPDA-ODA PI fiber

Stability RadiationResistantMechanical

Properties Kevlar 49 BPDA ODA PI fiber

Tensile, GPa 2.9 3.0

M d l GP 120 128Modulus, GPa 120 128

Limited Oxygen Index, % 29 50

Stability in air @300C Remain 60% for 15 h Remain 90% for 15 h

Stability in vapor@200C Remain 35% for 8 h Remain 65% for 8 h

Stab. in 40%H2SO4@85C Remain 60% for 40 h Remain 95% for 200 h

Stab. in 10%NaOH@85C Remain 50% for 50 h Remain 60% for 1 h

UV Xe@80-100 C Remain 30% for 8 h Remain 90% for 24 h

Applications of heat-resistant PIFApplications of heat resistant PIF

PI fibers have high thermal stability anti-corrosion of chemicals andPI fibers have high thermal stability, anti corrosion of chemicals, and environmental stability.They are extensively used in filter at high temperature and protection, y y g p p ,such as filter bags to reduce dust pollution.P84 developed by Lenzing in 1980’s, Evonic & Degussa now, the only commercial PI fibers, is fabricated into heat-resistant filter bagsHigh price ($60/kg) limits applications in large scale.

Applications of high-strength polyimide fibers in structure materialspolyimide fibers in structure materials

A i ti & Aviation & aerospace Defense & safety Bulletproof equipment Speed vehicles Sport equipment Ocean DevelopmentOcean Development

AcknowledgementAcknowledgement National Science Foundation of China (NSFC 51233001, 51173024 ) High-tech Development Plan (863 Plan) – High-Performance FibersHigh tech Development Plan (863 Plan) High Performance Fibers

Donghua University(Former China Textile University)

S ff 3 000Staff: ~ 3,000Undergraduate ~20,000 Graduate: ~ 6,000

Shanghai

TaiwanHong Kong

College of Mater Sci & EngCollege of Mater. Sci. & Eng.State Key Lab of Modif. Chem. Fibers & Polym Mater.Ministry Key Lab of High Perform. Fibers & ProductsEngineering Research Center of Adv. Glass Tech.Innovation Center for Adv. Fibers & Tech. (111 Plan)

Depart Polymer Science and EngineeringDepart. Polymer Science and EngineeringDepart. Inorganic Materials and EngineeringDepart. Composite Materials and TechnologyDepart. Composite Materials and Technology

Staff 130; Profs. 40undergraduates 250/aundergraduates 250/a Master 180/a Ph.D. candidates 45/a

Thank You