Injection Molding Process

Jae Wook Lee

Chemical Engineering Department
Sogang University

http://pollab.sogang.ac.kr
Plastics Injection Molding Process ...

Mass Production, Complex Geometry, High Precision

 Decaying slope
Peak cavity pressure Average holding pressure
Smoothness of holding pressure

Slope of compression Gate freeze off time

Stability point Cavity pressure

Fill-up point
during cooling stage
Slope of filling pressure
Start of injection

Melt front reaches

Induction time tranducers Residual cavity pressure

Fig. Parameters used for characterization of a standard cavity

pressure curve
 Filling
Completeness, reproduction of
mold surface, flashing,
damage to mold
Nature of surface layer
Appearance, orientation,
crystallization
Packing along flow path
Voids, sink sports, weight shrinkage,
distortion, degree of crystallinity
interior orientation,
demolding difficulties

Strain on melt
(thermal, mechanical)

A B C D E
Filling Holding pressure
Packing

Fig. The cavity pressure pattern dominantly affects quality features

 High injection speed
Late switch-over

High holding pressure

High mold temperature
High holding pressure Thick part High melt Temperature
High injection speed High hold pressure

Low melt temperature

High injection speed Low hold
pressure Thin part
Low melt temperature Strong cooling
Low mold temperature
Low mold
temperature
Low melt
Injection speed temperature

Fig. Cavity pressure patterns and molding conditions

Holding Pressure

Melt temperature
Mold temperature

Injection speed
 Shot size

Switch over point

Holding time

Mold clamping
Cushion size
 Short holding time Premature transfer Cushion runs out

Low hold pressure Standard Curve Low injection speed

High peak cavity

Mold breathing Small shot size
pressure

Fig. Conversion of abnormal patterns into a standard curve

 Governing Equations
ui ,i 0 Continuity equation.
ui
( u j ui , j ) P,i ij , j S i Momentum equation.
t
ij ( I 2 )( ui , j u j ,i ) Constitutive equation.
Boundary Conditions on Free Surface
n ( n) 0 Normal Component
t ( n) 0 Tangential Component
P

Hele-Shaw Approximation
Length/Thickness > 50
P P
Governing Equation x x y y ) 0
( S ) ( S
 Discretization of Governing Equation

2D
Classical Galerkin finite element formulation.
9-noded rectangular elements in 2D case.
Biquadratic interpolation of velocities.
Bilinear interpolation of pressure
3D
Penalty Formulation.
Trilinear interpolation of velocities.
SUPPLIER/file name : GEUSA

PC LEXAN 141 GE USA

Conductivity 0.280000 W/m/degC
Specific Heat 2232.000000 J/kg/degC
Melt Density 1017.000000 kg/cu.m PVT Specific Volume
Ejection Temperature 160.000000 deg.C
No Flow Temperature 180.000000 deg.C Temperature Pressure Specific Volume
deg.C MPa cu.cm/g
Viscosity 25.000 0.000 0.834459
141.000 0.000 0.852009
Temperature Shear Rate Viscosity 25.000 160.000 0.808354
deg.C 1/s Pa.s 194.600 160.000 0.827074
300.000 1000.000 294.500000 142.400 0.000 0.853920
320.000 100.000 225.600006 196.600 160.000 0.827368
320.000 1000.000 185.500000 147.400 0.000 0.856604
320.000 10000.000 65.099998 240.000 0.000 0.906335
340.000 100.000 132.500000 201.600 160.000 0.828974
340.000 1000.000 116.900002 240.000 160.000 0.841328
Processing Conditions:

Melt Temperature Maximum 340.00 deg.C

Melt Temperature Suggested 320.00 deg.C
Generic Mold Temperature Minimum 80.00 deg.C
Melt Temperature Absolute Maximum 360.00 deg.C
Generic Maximum Shear Stress 0.50 MPa
Generic Maximum Shear Rate 40000.00 1/s

Molding Conditions
==================
Mold temperature : 100.00 deg.C
Melt temperature : 320.00 deg.C
Injection time : 2.00 sec
Total Volume : 173.29 cu.cm
Flow rate : 86.65 cu.cm/s
Numerical Scheme for Free Surface

Lagrangian Scheme

Eulerian Scheme
( 2 D ) 0 3 M a r 1 9 9 8 2 D N O N - N E W T O N F L U ID S I M U L A T I O N

1.

1.6
24

0.
1.

8 1.84

1.9
0 .6 44
44
4

1 .0 4
0 .4 9
0 .2 4
0 .1 6 8
0 .0 8
 Results of Numerical Simulation
( Newtonian Case)
6

FF 0.010959 14788.2
0.9375 0.084375 0.010228 13666.4
4 0.875 0.07875 0.009497 12544.6
0.8125 0.073125 0.008766 11422.8
0.75 0.0675 0.008035 10300.9
0.6875 0.061875 0.007305 9179.13
0.625 0.05625 0.006574 8057.31
0.5625 0.050625 0.005843 6935.5
0.5 0.045 0.005112 5813.69
3 0.4375 0.039375 0.004381 4691.88
0.375 0.03375 0.003650 3570.06
0.3125 0.028125 0.002920 2448.25
0.25 0.0225 0.002189 1326.44
0.1875 0.016875 0.001458 204.625
0.125 0.01125 0.000727 -917.188
0.0625 0.005625
2

0
0 0.5 1 1.5 0 0.5 1 1.5 0 0.5 1 1.5 0 0.5 1 1.5
F Uz Ur P
 MF/FLOW3D Fill Pattern Prediction
Filling Pattern Prediction
Actual Predicted

Click to play

(Glass Model)
Actual Predicted
Packing Pressure Prediction

Predicted vs. actual packing pressure

Mold filling
Mold filling(different gate position)
Weld Line
Minimizing weld lines
1. Locate weld lines closer to a gate
to make them strong.
2. It is important to have enough pressure
to get good packing.
3. P rovide venting at the weld line.
4. Increase part thickness at the weld line
5. Increase melt temperature more flow.
6. Increase injection pressure and speed.
Shrinkage
causes the post mold dimensions of plastic parts to differ from
the mold cavity dimensions

Warpage
causes the post mold shape of plastic parts to differ from the
mold cavity shape - results from nonuniform shrinkage

w=hpart or w=dpart
Shrinkage is not a material property!

It depends on...
Material properties
--- PVT data, Thermal properties, etc.
Part geometry
--- Thickness, mold constraints, etc.
Manufacturing
--- Temperature, pressure, flow, etc.

Shrinkage is a system property!

A good predictor of shrinkage must consider

all three factors.
Prediction of shrinkage
Nonuniform shrinkage due to pressure gradient
The Application of Artificial Neural Network for
the Prediction of Mechanical Property
in Injection Molding Process

Jung Gon Kim, Hern Jin Park* ,Jae Wook Lee

Department of Chemical Engineering

Sogang University, Seoul, Korea
*SKI Inc. , Suwon, Korea
Sogang University
ntroduction

Processing Parameters Engineering Properties

1. Injection rate 1. Impact Strength

2. Mold Tmep. 2. Yield Strength
3. Injection Pres.
Injection Machine
3. Modulus Neural Network
4. Holding Pres. 4. Tensile Strength
Etc. Etc.

Thermomechanical History

1. Pressure
2. Temperature
Test Geometry 3. Vol.shrinkage
4. Shear stress
Etc.
MOLDFLOW
Thermomechanical History

1. Pressure
Another Geometry 2. Temperature
Traditional method 3. Vol.shrinkage
4. Shear stress
Predicted Engineering Properties Etc.
Method to train 1. Impact Strength
2. Yield Strength
3. Modulus
Method to predict 4. Tensile Strength
Etc.

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 input hidden output
neurons neurons neurons
1 1 1

design
i j k responses
variables

L M N

1 1

threshold
neurons

Fig. Structure of an Artificial Neural Network.

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 Rule

- Least Mean Squared Error

i At t, Wij(t)
j
neuron neuron
Ep (opj tpj)2
j
W ij ( t 1) Wij ( t ) Wij x pi (o pj t pj )
E Ep
pj o pj t pj
p

- Chain Rule
Learning parameter (0 , 1)
E p E p o pj
o pj Objective value pj x pi
Wij o pj Wij
t pj Output value

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 Method to avoid Local Minimum

- Momentum Parameter ()

W ij ( t 1) pj o pj Wij ( t )
y value

A - Noise Factor (NF)

pj o pj (1 NF Rndf )
o new old

x value

A : Global Minimum

B : Local Minimum

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 1.25
Calculation of the output value
1.00
net pi Wij o pj i
.75 i

o pi f i ( net pi )
Output

.50

.25 = 0.5
= 1.0 - Squashing Function
= 2.0
0.00
= 4.0
1
fi
-.25
-15 -10 -5 0 5 10 15
1 exp( net pi )
Input

Fig. Plot of Sigmoid Function

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Material

- Poly styrene (PS)

< GPPS-25sp supplied by LG-Chem. In Korea>
Tg = 97.11oC MI = 3.3g/10min 1.05g/cm3

- Pre-drying Condition
At 80oC for 24 hours in Convection oven

Mechanical Test
- Impact Strength
< CEAST Impact Tester>
Tested 5 samples at least
- Shear Modulus
< TA Instrument DMA 983>
Heating rate = 2oC/min from 10 to 70oC , Frequency = 1Hz

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 Mechanical Test
1
1 2 3 2
3
4

5
6 5 4 6
7
8

(a) Location of Impact Strength (a) Location of Shear Modulus

Fig. Schematic representation of the methodology used to predict the mechanical

properties of injection molded parts

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Apparatus
- Injection Molding Machine
< Allrounder 220M 250-75 ARBURG>
25 ton clamping force, 2.08oz capacity, 25mm screw with 20 L/D
mold temperature controller (RG-150, Regloplas Co.)
- Mold Geometry
Two 100mm x 50mm x 3mm plates

Table Injection Molding Condition

Condition Value
Injection Temperature (oC) 220 280
Injection Pressure (MPa) 90 100
Mold Temperature (oC) 60
Packing Pressure (MPa) 80
Packing Time (sec) 10
Cooling Time (sec) 30
Filling Time (sec) 0.8 1.4
Clamp Opening Time (sec) 2

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Computer Simulation
- MOLDFLOW
< Used MF/VIEW, MF/FLOW, MF/COOL>
Work Station = Indogo 2, Impact

Thermomechanical History Calculated from the Results of

Injection Molding Simulation.
Node Value Element Value
Pressure (MPa)
Temperature (oC)
Instant Temperature (oC)
Vol. Shrinkage (%)
Max. Shear Stress (MPa)
Apparent Density (kg/m3)
Top Temperature (oC)
Bottom Temperature (oC)
Different Temperature (oC)

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Plot of Cavity and Mold Cooling-Line at MOLDFLOW Simulation

(a) Mesh of Cavity (b) Geometry of Mold

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MOLDFLOW Simulation for Node Value

(a) Pressure (b) Temperature

(c) Instant Temperature

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MOLDFLOW Simulation for Element Value(1)

(a) Volume Shrinkage (b) Max Stress

(c) Apparent Density

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MOLDFLOW Simulation for Element Value(2)

(d) Top Temperature (e) Bottom Temperature

(f) Different Temperature

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 Results
5 5


4 4


3 3
Pattern error

Pattern error

2 2

1 1

0 0

0 25 50 500 1000 0 25 50 500 1000

Iteration number Iteration number
(a) Shear Modulus (b) Impact Strength

Fig. Plot of Simulated Pattern Error Curve for Learning

Parameter

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 Results
2.5 2.5

2.0 2.0


Pattern error

Pattern error
1.5 1.5

1.0 1.0

.5 .5

0.0 0.0

0 25 50 500 1000 0 25 50 500 1000

Iteration number Iteration number
(a) Shear Modulus (b) Impact Strength

Fig. Plot of Simulated Pattern Error Curve for Momentum

Parameter

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 Results
5
5
NF = 0
NF = 0
4 NF = 0.1
4 NF = 0.1
NF = 0.2
NF = 0.2
NF = 0.4
NF = 0.4
3

Pattern error
3
Pattern error

2
2

1
1

0
0

0 25 50 500 1000
0 25 50 500 1000
Iteration number
Iteration number
(a) Shear Modulus (b) Impact Strength

Fig. Plot of Simulated Pattern Error Curve for Noise Factor

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 Results
950 20.0

900 17.5
Shear modulus [MPa]

Impact strength [J/m]

850 15.0

Real data (set=7) Real data (set=5)

800 3-layer (72-36-8) 12.5 3-layer (54-27-6)
4-layer (72-50-20-8) 4-layer (54-34-17-6)
5-layer (72-60-40-15-8) 5-layer (54-40-20-10-6)

750 10.0
1 2 3 4 5 6 7 8 1 2 3 4 5 6
Sample location Sample location

Fig. Predictions of Shear Modulus and Impact Strength of Injection

molded parts on layer number of ANN

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 Results
950 950

900 900
Shear modulus [ MPa ]

Shear modulus [ MPa ]

850 850

Real data (set=7)

Real data (set=12)
800 = 0, = 0.02, NF = 0 800
= 0, = 0.02, NF = 0
= 0.1, = 0.001, NF = 0.1
= 0.1, = 0.001, NF = 0.1

750 750
1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8
Sample location Sample location

Fig. Predictions of Shear Modulus of Injection molded parts

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 Results
20.0 22.5

20.0
17.5
Impact strength [ J/m ]

Impact strength [ J/m ]

17.5

15.0

15.0
Real data (set=5)
Real data (set=10)
12.5 = 0, = 0.02, NF = 0
12.5 = 0, = 0.02, NF = 0
= 0.1, = 0.001, NF = 0.1
= 0.1, = 0.001, NF = 0.1

10.0 10.0
1 2 3 4 5 6 1 2 3 4 5 6
Sample location Sample location

Fig. Predictions of Impact Strength of Injection molded parts

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 Conclusions

1. The Impact strength and Shear modulus within a part is more dependent of the
thermomechnical histories than the others are.

2. The accuracy of predicted results doesnt get any better even though the number of
hidden layer increases.

3.In order to guarantee the global minimum and to approach to the minimum as soon
as possible, in the neural network, not only learning parameter but also momentum
parameter and noise factor should be applied.

4. In case of impact strength, except 9 thermomechanical histories, another history

seems to be influenced.

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Parts Weight Prediction
Using On-Line Variables

In Ho Shin, Jung Gon Kim, Jae Wook Lee

Department of Chemical Engineering
Introduction

Injection Molding Process

Mass Production
In a Discontinuous Manner
Quality Consistency is a Crucial Issue

Mold T
Holding P, t Cavity Parts
Injection P, T P, T Quality
Material
Theory

Factorial Design (FD)

y f(x) Linear y bo b1 x1 b2 x2 residual

Interaction y bo b1 x1 b2 x2 b12 x1 x2 residual

Quadratic y bo b1 x1 b2 x2 b11 x12 b22 x22 b12 x1 x2 residual

Exp. No. Factor Response

x1 x2 x1 x2
1 1 1 +1 A
2 +1 1 1 B
22 3 1 +1 1 C
4 +1 +1 +1 D
Theory

Modified Factorial Design (mFD)

h f(g) g1 Mean of P/T from a Shot

g2 Peak of P/T from a Shot
g3 Integrated Area of P/T from a Shot

(+)

h
()

() g (+)
Theory

Modified Factorial Design (mFD)

R e sp o n se
( ) (+ )
F a cto r 1 a e
F a cto r 2 b f
F a cto r 3 c g
F a cto r 4 d h

Factor 1 Factor 2 Factor 3 Factor 4 Response

Case 1 0.25(a+b+c+d)
Case 2 + 0.25(e+b+c+d)
Case 3 + 0.25(a+f+c+d)

Case 15 + + + 0.25(a+f+g+h)
Case 16 + + + + 0.25(e+f+g+h)
Theory

Artificial Neural Network (ANN)

input output
W ij xi
value value

input hidden output

neurons neurons neurons
1 1 1

factors i j k responses

L M N

1 1

threshold
neurons
Experiments

Material
Polypropylene by Honam Petrochemical Corp. (SFR 170-G)

Injection Molding Machine

Arburg Allrounder 220M 75 (25-ton clamping, 25mm screw)
Regloplas RG-150

Machine Settings
Nozzle Temperature (oC, 200/220, x1)
Mold Temperature (oC, 50/70, x 2 )
Holding Pressure (bar, 550/850, x 3 )
Injection Speed (ccm/s, 45/55, x 4 )
} 24 = 16
16 + 1 = 17
Experiments

Cavity Transducers
Two Pressure Transducers (Kistler 6157BB, 9221A)
One Pressure-Temperature Transducer (Kistler 6190A)

50mm P1-T1

100mm P2
40mm

P3 (indirect)
10mm
Experiments

Data Acquisition
GPIB (National Instruments AT-MIO-16X)
Sampling Rate of 20/sec
Three LVDT Signals (Nozzle, Screw, Mold)

Mean
Peak
Integrated Area
Results

Temperature Profiles

Peak and Average of T1 Integrated Area of T1

85 640

620
80
600

Integrated Temperature [oC sec]

75 580
Temperature [oC]

560
70
540

65 520
4 mean
10 mean case 4
17 mean 500
case 10
60 4 paek
case17
10 peak 480
17 peak

55 460
10 20 30 40 50 10 20 30 40 50
Part Number Part Number
Results

Variational Noise
Shot-By-Shot Variation of Parts Weight

C a s e 17

10.0
W e i g h t [g]

9.9
0 25 50 75 100 125 150 175 200
Part Number
Results

Developed Response Model of FD

y 9.9400 0.0520x1 1.9870e 3 x2 6.2510e 4 x3 6.9990e 4 x4 4.0750e3 x1x2

2.6180e4 x1x3 2.0620e3 x1x4 1.4630e3 x2 x3 9.3720e4 x2 x4 1.4500e3 x3x4
Results

Four Factors Having the Highest R2 of mFD

0.9248 0.9337
10.15

10.10 10.10

10.05 10.05
Weight [g]

Weight [g]
10.00
10.00

9.95
9.95

9.90
9.90

9.85
9.85

9.80
1 2 2 3
Peak Points at P3 Peak Points at P2
Results

Four Factors Having the Highest R2 of mFD

0.9009 0.8775

10.10 10.15

10.10
10.05
10.05
Weight [g]

Weight [g]
10.00
10.00
9.95
9.95
9.90
9.90

9.85 9.85

9.80 9.80
1 2 1 2 3 4 5 6 7 8 9
Peak Points at P1 Intrgrated Areas of P2
Results

Developed Response Model of mFD

h 9.9870 0.0310g1 0.0310g 2 0.0320g 3 0.0360g 4 6.2150e7 g1g 2 8.1250e7 g1g 3

2.9780e 6 g 1g 4 5.4400e 6 g 2 g 3 2.8890e 6 g 2 g 4 3.0240e 6 g 3 g 4
Results

ANN Training

standard feed-forward back-propagation network

4 input neurons / 4 hidden neurons / 1 output neuron
700 training data sets and 150 testing data sets
learning rate was 0.5
momentum factor was 0.8
trained for half and an hour (100000 iterations)
final sum squared error was 0.0011
Results

Case 4 Case 10

10.08 10.08

measured measured
FD FD
mFD mFD
10.04 ANN 10.04 ANN
Weight [g]

Weight [g]
10.00 10.00

9.96 9.96

20 30 30 40
Part Number Part Number
Results

Case 12 Case 16

10.12

measured
measured
FD
10.08 FD
10.04 mFD
mFD
ANN
ANN

10.04

Weight [g]
Weight [g]

10.00
10.00

9.96
9.96

9.92
40 50 20
Part Number Part Number
Results

Case 4 Case 12

10.08 10.08

measured measured
FD FD
mFD mFD
ANN 10.04
10.04 ANN
ANN2 ANN2

Weight [g]
Weight [g]

10.00
10.00

9.96
9.96

20 30 40 50
Part Number Part Number
Conclusions
Conventional factorial design is not capable of monitoring
shot-by-shot variation of the process at all.

On the contrary, modified factorial design, which does utilize on-line

variables, successfully traces constantly varying parts weight.

Meanwhile, artificial neural network, which is based on non-linear

function inside each neuron, yields the most reliable predictions.

Adjustment of training parameters, such as learning rate, noise and

momentum factor, will affect the performance of ANN.

Two-stage-strategy is believed to be of practical value for the

optimization of injection molding process.
Rheo-Kinetic Analysis of Shear Induced Crystallization
of Semicrystalline Polymers

Jung Gon Kim, Hyun Seog Kim and Jae Wook Lee

Department of Chemical Engineering

Sogang University, Seoul, Korea

Sogang University
 Introduction
Stress Temperature
a
Injection Molding b
c
Non-isothermal, Semi-Batch Process d
Gate

a wide variety of
Thermal and Deformation Histories
Tmelt

Structural Gradient Tmold

in the injection molded parts
Time Time Time Time
a b c d

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 Effects on Crystallization Behavior
Thermal History Deformation History
Temperature Shear Rate
Heating / Cooling Rate Shear Stress
Heating / Cooling Time Shearing Time

Combined
Analysis

Rheo-Kinetic Analysis

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 Material
Polymer Resins
- Poly buthylene terephthalate (PBT)
< SKYTON 1100A supplied by SKI in Korea >
Tg = 36 oC Tmo = 227 oC

- Poly propylene (PP)

< SJ-170 supplied by Honam Petrochemical in Korea >
Tg = -10 oC Tmo = 165 oC

- Pre-drying Condition
PBT ; at 120 oC for 2 hours, PP ; at 80 oC for 4 hours

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 Experimental
Rheological Measurement
of Shear-Induced Crystallization Behavior
Rheometrics RMS 800
< with 2Kg-force transducer & plate-plate attachment >
After melting at 250 oC for 10 minutes,
Quenching to crystallizing temperature and then shearing.
Monitoring the shear stress due to shear-induced crystallization
True shear rate was obtained by single-point correction method

Preparation of Sheared Polymer Samples

Taking the sheared samples at true shear rate region (at rs* = 0.75)

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 Single-Point Correction Method
1.0
M.M.Cross and A.Kaye, Polymer,
28, 435 (1987).
0.8 M.S.Carvalho, M.Padmanabhan and
C. Macosko, J. Rheology, 38, 1925 (1994).
Power-law
rR

rsorsrs*oR
0.6
fluid

Newtonian
0.4
fluid rsrs* R
0.2 rs* = rs/R = [4/(3+n)]1/(n-1)
rs*

0.0
rs* = 0.75 - 0.785
0.0 0.2 0.4 0.6 0.8 1.0
for n from 0 to 1.2
r/R

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 Memory effects in the crystallization

A.Ziabiki and G.C.Alfonso, Colloid & Polym. Sci., 272, 1027 (1994)

The memory of previous structures manifests itself in the distribution of

atomic clusters which determines the initial number of crystal nuclei and
the initial rate of thermal nucleation.

Crystallization rate depends on original structure of the sample and its

thermo-mechanical histories.

Measurements of Crystallinity
Dupont 9900 DSC system
Heating rate 10 oC/min from 30 oC to 250 oC

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 Crystallization Kinetics
Dupont 9900 DSC system
< with Mechanical Cooling Accessory >

- Isothermal Kinetics
After melting at 250 oC for 10minites,
Quenching to crystallizing temperature

- Non-Isothermal Kinetics
After melting at 250 oC for 10minites,
Cooling rate 2, 5, 10, 15 oC/min from 250 oC to 30 oC.

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 Analysis
Kinetic Experiment
Isothermal Kinetics
(Unsheared & Sheared
(JMA equation)
Samples)

k(T) vs. , t1/2

Non-Isothermal k(T,) Half-time Analysis

Kinetics (Hoffman-Laurizen
(Kamal & Nakamura equation)
equation)

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- Isothermal Kinetics
Johnson-Mehl-Avrami equation

Xr = 1 - exp( - k t n )

Here, Xr : relative crystallinity

k : rate constant
n : JMA constant

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- Half-time Analysis

Hoffman-Laurizen equation

(1/t1/2) = (1/t1/2)oexp(-U*/R(T-Too ))exp(-C3/TTf)

Here, R : gas constant

T : Tmo - T
f : 2T/(T+Tmo)
T oo : Tg - 30K
U* : universal constant
C3 : folding constant of polymer chain

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- Non-Isothermal Kinetics

Nakamura equation

T
Xr = 1 - exp[ - ( K(T) dT/R)n], K(T) = k(T)1/n
To

Kamal equation

T
Xr = 1 - exp[ - k(T) n ((To - T)/R)n-1 dT/R]
To

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 Time dependent shear stress of PP at various temperatures.
8000
. -1
= 1.0s
The shear stress of PP is steeply
6000
increased with time after showing
o
130 C o oscillatory fluctuation at the early
Shear stress [Pa]

140 C
state.
o
150 C
4000
The reason may be that the cluster
is repeatedly formed and destroyed
2000
at the early shearing state before
the formation of clusters above the
critical size.
0
0 400 800 1200 1600 2000
Time [sec]

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 Time dependent shear stress of PP at various shear rates.

8000
T = 140oC

The increasing behavior of shear

6000 stress of PP is pronounced with the
Shear stress [Pa]

2.0 s
-1 increase in shear rate at constant
1.0 s
-1 crystallizing temperature.
4000
The induction time for crystalliza-
tion occurs at an earlier point in
-1
2000 0.5 s time for higher shear rate and
lower temperature.

0
0 200 400 600 800 1000 1200
Time [sec]

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 Time dependent shear stress of PBT
at various temperatures and shear rates

10000 10000
. T = 215oC
= 1.0s-1

Shear stress [Pa]

Shear stress [Pa]

210oC
4.0 s-1

1000 1000 2.0 s-1

215oC

220oC 1.0 s-1

225oC

230oC

100 100
0 200 400 600 800 1000 1200 1400 0 200 400 600 800 1000
Time [sec] Time [sec]

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 DSC melting area and shear stress for sheared PBT sample
600 54

550 T = 215oC
.
= 1 s-1 52
500

Melting area [J/g]

The melting area of sheared PBT
Shear stress [Pa]

450 sample significantly increases

50 with the shearing time, and it
400
shows similar trend to shear
350 stress data.
48
300
The increase of shear stress is due
250
46 to the formation of crystal.
200

150
0 200 400 600 800 1000
Time [sec]

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 DSC thermogram at isothermal temperatures

0.8 0.7

0.6 0.6
187oC

0.5
0.4
Heat flux [W/g]

Heat flux [W/g]

0.4
0.2
191oC
0.3
193oC
0.0
0.2 195oC
197oC
-0.2 199oC
tc 0.1
201oC

-0.4 0.0
10 11 12 13 14 15 16 0 2 4 6 8 10 12 14
Time [min] Time [min]

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 JMA analysis of isothermal crystallinity data for PBT

424.57Pa
The isothermal JMA analysis of
3382.60Pa
PBT samples is carried out in the
0
ln(-ln(1-Xr))

range of relative crystallinity

between 20 and 80%.

The results show that as the shear

-1 unsheared
stress increases, the rate constant
increases.
1445.10Pa

-2
-1 0 1 2
ln t

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 JMA constants and rate constants of sheared PBT as a function of
the applied shear stress

2.7

2.6 0

2.5
JMA constant

-1

ln k
2.4
-2
2.3

-3
2.2

2.1 -4
0 2000 4000 6000 8000 10000 12000 0 2000 4000 6000 8000 10000 12000
Shear stress [Pa] Shear stress [Pa]

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 Linear regression of unsheared PBT isothermal kinetics
for Half-time analysis

U* = 6066.8 J/mol
0
(1/t1/2)o = 23.3164 min-1
ln(1/t1/2)+U*/R(T-Too)

-1 C3 = 65090.3325 K2.

-2 The half-times can be extrapolated

to lower temperatures and rate
-3
constant can be calculated using
k = ln2/(t 1/2)n

-4
4e-5 6e-5 8e-5 1e-4
o
1/T(Tm -T)f

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 Half-time of isothermal kinetics for sheared PBT samples

3 From the isothermal kinetics, the

207oC half-time of sheared PBT sample
with different histories lies on a
199oC
single line as a function of shear
log(t1/2) [sec]

2
stress.
193oC

.
Half time is strongly dependent on
T=215 C, =1s-1
o
the applied shear stress rather than
.
1 T=215oC, =2s-1
.
T=215oC, =4s-1 the shear rate, the shearing time
.
T=210oC, =1s-1 and the crystallization
.
T=210oC, =2s-1 temperature.
.
T=210oC, =4s-1
0
2 3 4
log(shear stress) [Pa]

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 (1/t1/2)o and C3 of sheared PBT samples with different histories

5 7.0

6.5
ln(t1/2)o [sec]

C3 x 10-4
6.0
.
T = 215oC, =1s-1 .
T=215oC, =1s -1
. .
3 T = 215oC, =2s-1 T=215 C, =2s-1
o
.
T = 215oC, =4s-1 .
T=215oC, =4s-1
. 5.5
T = 210oC, =1s-1 .
T=210oC, =1s-1
.
T = 210oC, =2s-1 .
T=210oC, =2s-1
.
T = 210oC, =4s-1 .
T=210oC, =4s-1
2 5.0
5 6 7 8 9 10 5 6 7 8 9 10
ln(shear stress) [Pa] ln(shear stress) [Pa]

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 Comparison of extrapolated reciprocal half-times of PBT
with experimental results

0.08

0.07
3382.60Pa
0.06 The results of half-time analysis
are in good agreement with the
0.05
1445.10Pa experimental data.
1/t1/2 [sec-1]

0.04

0.03 The shear stress increases both

424.57Pa
the crystallization kinetics and
0.02
the onset of crystal melting
0.01 temperature.
0.00 unsheared

250 300 350 400 450 500 550

Temperature [K]

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 Envelope of time-temperature-transition of PBT
500

475
The half-time of high shear stress
Temperature [K]

450 unsheared is shorter than that of low shear

424.57Pa
921.88Pa stress.
1445.10Pa
425 2099.36Pa
5249.80Pa
10175.60Pa
As the shear stress increases, the
400 TTT envelope broadens.

375

350
10 100 1000
t1/2 [sec]

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 Determination of crystallization rate constant of PBT

14
1091.46Pa
12 2099.36Pa
5249.80Pa
10 10175.60Pa
The results are obtained from
unsheared Hoffman-Laurizen equation
8 and the isothermal kinetics data
k(T)

6 at different shear stresses.

4 As the shear stress increases,

2
the crystallization rate constant
significantly increases.
0

450 475 500

Temperature [ K ]
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 Prediction of the extent of non-isothermal crystallization
using Nakamura equation
Unsheared Sheared [5249.8Pa]
o
2 C/min (Exp.) 2oC/min (Exp.)
o
5 C/min 5oC/min
1.0 o 1.0 10oC/min
Relative crystallinity

10 C/min

Relative crytallinity
15oC/min 15oC/min
2oC/min (Pred.) o
2 C/min (Pred.)
o
5 C/min
o
5oC/min
10 C/min
o
10oC/min
15 C/min 15oC/min
0.5 0.5

0.0 0.0

450 475 500 525 550 450 475 500 525 550
Temperature [ K ] Temperature [ K ]

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 Prediction of the extent of non-isothermal crystallization
using Kamal equation
Unsheared Sheared [5249.8Pa]

2oC/min (Exp.) 2oC/min (Exp.)

5oC/min 5oC/min
1.0 10oC/min
1.0 10oC/min
Relative crystallinity

Relative crytallinity
15oC/min 15oC/min
2oC/min (Pred.) 2oC/min (pred.)
5oC/min 5oC/min
10oC/min 10oC/min
15oC/min 15oC/min
0.5 0.5

0.0 0.0

450 475 500 525 450 475 500 525

Temperature [ K ] Temperature [ K ]

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 Summary
The increase of melting area shows a similar trend to shear stress data.
From this
result, we can deduce that the increase of shear stress is due to the formation of
crystal.
When shear stress is applied to a polymer melt, crystal is formed at a higher
temperature and at a shorter time than a quiescent one.

The shear stress of PP is increased with time showing oscillatory fluctuation,

but in the case of PBT the oscillatory fluctuation is not significant.
This phenomenon might be expected that the cluster is repeatedly formed and
destoryed in the shearing field before it grows up to the critical cluster size.

The induction time of crystallization reduces as shear rate increases and also
temperature decreases.

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 The shear stress can reduce the dimension of the crystal growth from 3 dimensional
spherulite to 2 dimensional lamellar morphology in case of PBT.

The half-time of sheared samples is strongly dependent on the applied shear stress
rather than the shear rate, the shearing time and the crystallization temperature.

The results of non-isothermal kinetics of unsheared and sheared PBT accord with
Kamal equation rather than Nakamura equation.

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 Time dependent shear stress of PBT
at various shear rates

10000
o
T = 210 C

4.0 s-1
Shear stress [Pa]

-1
2.0 s
1000
-1
1.0 s

100
0 100 200 300 400 500
Time [sec]

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 Dependence of the isothermal crystallization peak time
on melt annealing temperature and time

8 9

7 8

6 7

Peak time [min]

Peak time [min]

5
6
4
5
o
3 T1 = 180 C
o
4 T1 = 200 C
PP1, Tc = 124oC o
2 T1 = 220 C
o
PP2, Tc = 127 C T1 = 240oC
3
1 PP3, Tc = 126 C
o
T1 = 260oC

0 2
420 440 460 480 500 520 540 0 100 200 300 400 500

Melt temperature [K] Isothermal time [min]

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