유변물성 측정의 유용성

Industrial application of rheology

Introduction

• 유변학: 물질의 유동과 변형에 관한 학문

• 재료의 미세한 구조차이가 유변물성을 통 하여 증폭되어 발현

• 품질관리, trouble shooting, 제품설계 등 다양한 용도로 사용

Industrial Applications of Rheology

유변물성 측정의 유용성

• ABS (Acrylonitrile-Butadiene-Styrene) 수지의 예

• 올레핀 수지의 예

• 식품 유변학에서의 예

• 나노복합체 (clay nano composite)의 예

• 생체고분자 (biopolymer)의 예

ABS (Acrylonitrile-Butadiene-Styrene)

101.7 95.1

567 393

95.3 24.1

69 82

3100 ABS-5

103.9 93.7

582 402

96.4 26.7

42 86

3075 ABS-4

gloss VST

Flexural strength Tensile

strength Hard-

ness Impact

strength Graft

ratio Gel

content Particle

size

G’ and η* of ABS

0.01 0.10 1.00 10.00 100.00 1000.00

100 1000 10000 100000

G',VISCOSITY

ABS-4 ABS-5

관리도(G’)

G’ vs. graft ratio

20 40 60 80 100 120

10 100 1000 10000 100000

G' at w=0.1

Particle agglomeration

HDPE/PS blends

Comparison of η∗ & G'

freq. [rad/sec]

0.1 1 10 100

G' or η∗ [Pas]

10³ 10⁴ 10⁵

HDPE/PS blends

DSC (10oC/min)

Temp.(^oC)

20 40 60 80 100 120 140 160 180 200 220

W/g

-30 -20 -10 0 10 20 30

90:10 (1st) 90:10 (2nd)

HDPE/PS blends

HDPE V at 154^oC

t [sec]

0.1 1 10 100

10³ 10⁴ 10⁵ 10⁶

HDPE V at 154^oC

t [sec]

0.1 1 10 100

10³ 10⁴ 10⁵ 10⁶

Food rheology

Locust bean gum/k-carrageenan

PP/MAPP/clay

Cloisite20A 1 wt % Clay 3 wt % Clay

2θ (degree)

1 2 3 4 5 6 7 8 9 10

5 wt % Clay

Intensity

PP/MAPP/clay

Freqeuncy (rad/sec)

10^-2 10^-1 10⁰ 10¹ 10² 10³

Storage Modulus G' (Pa)

10^-1 10⁰ 10¹ 10² 10³ 10⁴ 10⁵

PP/MAPP 1wt%

3wt%

5wt%

Hyaluronic acid (GPC/MALLS)

0.0 0.5 1.0 1.5 2.0 2.5

1.0x10⁵ 1.0x10⁶ 1.0x10⁷

Differential Weight Fraction

Molar Mass (g/mol) Differential Molar Mass

0.0 0.5 1.0 1.5 2.0 2.5

1.0x10⁵ 1.0x10⁶ 1.0x10⁷

Differential Weight Fraction

Molar Mass (g/mol) Differential Molar Mass

.8





1%*

L



L



L



L



Frequency [rad/s]

0.1 1 10 100

Storage modulus G' [Pa]

0.1 1 10 100 1000

HIA0002 HIA0003 HIA0004 HIA0005

ABS수지개발 (GPC)

10 20 30 40 50

elution time (min) SAN-4

SAN-3

SAN-1

G’(storage modulus)

0.01 0.10 1.00 10.00 100.00 1000.00

frequency (rad/sec)

1E+2 1E+3 1E+4 1E+5 1E+6

G' (Pa)

220C

SAN-1

Elongational viscosity

0.01 0.10 1.00 10.00 100.00 1000.00

time(sec)

1.0E+3 1.0E+4 1.0E+5 1.0E+6 1.0E+7

elongational viscosity (Pa.s)

SV-0156T at 180 degree C

Elongational viscosity

0.01 0.10 1.00 10.00 100.00 1000.00

time(sec) 1.0E+3

1.0E+4 1.0E+5 1.0E+6 1.0E+7

elongational viscosity (Pa.s)

ST-0181 at 180 degree C

ABS

ABS

Rotational rheometer

• 시편제조상의 유의할 점

• 열안정성

• Strain sweep

• 관성 (inertia)의 영향

• 증발의 영향

• 시료의 안정성

• 기계적 영향

• 기타

Thermal stability

0.00 20.00 40.00 60.00

1E+3 1E+4 1E+5

G' (Pa)

coagulated by H2SO4

acid scavenger added 250 degree C

O2 environment N2 environment

Strain sweep

Critical strain

10^{0 101 102} 10³

10⁰ 10¹ 10²

10¹ 10²

Critical strain Critical

strain

10^{0 101 102} 10³

10⁰ 10¹ 10²

10¹ 10²

G ’ , G

[P a] Eta * [P a -s]

Strain [%]

Inertia effect

Xanthan Gum 2wt% solution_Frq. sweep

Frq. (rad/s)

1 10 100

Eta* (Pa S)

1 10 100

PP20 : Parallel Plate D=20mm

PP35: Parallel Plate D=35mm

C35/1 : Cone & Plate D=35mm, 1^o

evaporation

W/O silicone oil

0.0 300.0 600.0 900.0 1200.0 1500.0 1800.0

10¹ 10² 10³

G' () [Pa] G" () [Pa] Eta* () [Pa-s]

stability

10^{-1 100 101 102} 10³

10¹

10² 10³

10⁴

time [s]

Eta () [Pa-s] stress(t) () [Pa]

v1step rate_3_pva2%borax1%_noE

Gap 2_step rate_3__pva2%borax1%_noE

34

20 50

"U
UT "U
UT

Melt flow index (MI)

Conclusions

• 유용성

– 품질관리, trouble-shooting, design etc.

• 다양성

– Polymer, food, bio, phamaceutical, paint etc.

• 유의성

– 실험, 해석 – Experts

• Challenge

– New concept/tool