Characterization of Commercially Available Polymer Blends To Predict Processability

JAPAN ADVANCED INSTITUTE OF SCIENCE AND TECHNOLOGY
MATERIAL SCIENCE SCHOOL
NGUYEN VU LE
Minor Research Project
CHARACTERIZATION OF COMERCIALLY
AVAILABLE POLYMER BLENDS TO PREDICT
PROCESSABILITY
Submitted in partial fulfillment of the requirements for the degree of Master of

School of Materials Science
Supervisor: Prof. Dr. Masayuki Yamaguchi
Japan – March 2021

ACKNOWLEDGEMENTS
I would like to extend my sincere thanks to my minor research supervisor – Prof. Dr.
Masayuki Yamaguchi – for his enthusiastic instruction throughout this research.
I also wish to express my deepest gratitude to all of the lab members in Yamaguchi’s
laboratory for their warm welcome and sincere assist during my time of doing research in
their laboratory.
Last but not least, many thanks to MITANI SANGYO CO., this work would never be done
successfully without the sponsorship from the corporation.
1
Table of Contents
I. Introduction ...................................................................................................................... 6
II. Materials and methods................................................................................................... 6
2.1 Polymer samples ..................................................................................................................... 6
2.2 Fourier Transform – Infrared Spectroscopy (FT-IR) analysis .......................................... 6
2.3 Differential scanning calorimetry (DSC) analysis ............................................................... 6
2.4 Rheology analysis ................................................................................................................... 6
2.5 Hot compression molding ...................................................................................................... 6
III. Results and discussion .................................................................................................. 7
3.1 FT-IR analysis......................................................................................................................... 7
3.2 DSC analysis ........................................................................................................................... 9
3.3 Rheology analysis ................................................................................................................. 10
IV. Conclusion ................................................................................................................... 12
Appendix ............................................................................................................................ 13
Reference ............................................................................................................................ 28
2
Table of Figures
Figure 1: FT-IR spectrum of lot No.B39928 at different pre-treatment conditions. ............ 7
Figure 2: DSC graph of lot No.B39889 with no pre-drying. ............................................... 9
Figure 3: Frequency dependence of oscillatory shear modulus for lot No.B39890 with no
pre-drying. ........................................................................................................................... 10
Figure 4: log G’ vs log G” rheometric graph of lot No.B39890 without pre-drying. ........ 11
Figure 5: FT-IR spectrum of lot No.B39889 at different pre-treatment conditions. .......... 13
Figure 6: FT-IR spectrum of lot No.B39890 at different pre-treatment conditions. .......... 14
Figure 7: DSC graph of lot No.B39889 with pre-drying at 110 oC for 5 hours. ................ 15
Figure 8: DSC graph of lot No.B39889 with pre-drying at 140 oC for 3 hours. ................ 15
Figure 9: DSC graph of lot No.B39890 with no pre-drying. ............................................. 16
Figure 10: DSC graph of lot No.B39890 with pre-drying at 110 oC for 5 hours. .............. 16
Figure 12: DSC graph of lot No.B39928 with no pre-drying. ........................................... 17
pre-drying. ........................................................................................................................... 19
Figure 16: Frequency dependence of oscillatory shear modulus for lot No.B39889 with
pre-drying at 110 oC for 5 hours. ......................................................................................... 20
pre-drying. ........................................................................................................................... 22
3
Figure 23: log G’ vs log G” rheometric graph of lot No.B39889 without pre-drying ....... 24
Figure 24: log G’ vs log G” rheometric graph of lot No.B39889 with pre-drying at 110 oC
for 5 hours............................................................................................................................ 24
for 3 hours............................................................................................................................ 25
for 5 hours............................................................................................................................ 25
for 3 hours............................................................................................................................ 26
Figure 28: log G’ vs log G” rheometric graph of lot No.B39928 without pre-drying. ...... 26
for 5 hours............................................................................................................................ 27
for 3 hours............................................................................................................................ 27
4
List of Tables
Table 1: Peak areas of the peaks at 1200 cm-1 and 1630 cm-1 and their ratios (A1200 cm-1
/A1630 cm-1) in all XYRON samples. .......................................................................................................... 8
Table 2: Melting temperatures, enthalpies of fusion, crystallization temperatures and

enthalpies of crystallization of all XYRON samples in 3 pre-treatment conditions. ............ 10
Table 3: G’ values at G” = 10000 Pa and G’ plateau values of all XYRON samples with 3
pre-treatment conditions............................................................................................................................ 12
5
I. Introduction
The dimension of plastic products is significantly important at the injection molding
process. In general, it is necessary for the material’s dimension to be identical regardless of
the production lot. In this research, we examined Mitani Sangyo’s polymer samples,
XYRON, which is a blended material containing polyamide 66 (nylon 66) and
polyphenylene oxide. There was an irregularity in the dimension of the company’s
products, and it seems to be dependent on lot numbers and pre-drying protocols. Therefore,
various analysis methods were employed in order to understand the variation of the
dimension, such as the crystallization point, the degree of crystallization, and the
viscoelastic properties.
II. Materials and methods

2.1 Polymer samples
XYRON materials were used as granule form. Samples from 3 lot numbers, No.B39928,
No.B39889, and No.B39890, were chosen with different drying conditions such as no pre-
drying, drying at 110 oC for 5 hours, and drying at 140 oC for 3 hours.
2.2 Fourier Transform – Infrared Spectroscopy (FT-IR) analysis

The functional groups and the crystallinity of the polymer material were determined by
PerkinElmer Spectrum 100 FT-IR spectrometer. Before each measurement, polymer
samples were compressed into 100 µm thick films at 320 oC. The absorption signal was
collected in a wavenumber range from 380 cm-1 to 4000 cm-1.
2.3 Differential scanning calorimetry (DSC) analysis

In order to find thermodynamic information, such as melting point, crystallization point,
etc., a PerkinElmer DSC 8500 differential scanning calorimeter was employed. A
particular sample was molded into a 100 µm thick film before conducting the
measurements. The temperature was set to rise from 25 oC to 300 oC at 20 oC/min and kept
at the desired temperature for 1 minute. After that, the sample chamber was cooled down
to room temperature at -20 oC/min
2.4 Rheology analysis

The rheology investigation was performed by a AR 2000 EX rheometer at 290 oC using
1mm thick films.
2.5 Hot compression molding

Prior to hot-compression, polymer samples were vacuum-dried at 90 oC for 3 hours. Later,
the samples were transferred into the mold and pre-heated with the hot-press for 1 minute
at 320 oC, followed by an applied pressure of 10 MPa for 5 minutes at the same
6
temperature. Finally, the films were allowed to be cooled down to room temperature for 5
minutes. PTFE sheets were employed to prevent sample adhesion on the molding plates.
III. Results and discussion

3.1 FT-IR analysis
No pre-drying
no 1200 cm-1
110 oC x 5h
110 1630 cm-1
140 oC x 3h
Absorbance (a.u)
3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
Figure 1: FT-IR spectrum of lot No.B39928 at different pre-treatment conditions.
For nylon 66, peak signals at wavenumbers of 936 cm-1 and 1200 cm-1 are assigned for the
crystalline phase.[1] The infrared bands at 924 cm-1 and 1136 cm-1 are the representatives
for the amorphous phase.[1] Moreover, the absorption at 1630 cm-1 can be used as a
reference signal to evaluate the crystallinity of this polymer material.[1] Therefore, area
ratios between the peaks of 1200 cm-1 and 1630 cm-1 in all infrared spectrums were
recorded. The results in Table 1 showed that there was no significant difference in the
crystallinity in all XYRON samples irrespective of lot numbers as well as of different pre-
drying conditions.
7
Table 1: Peak areas of the peaks at 1200 cm-1 and 1630 cm-1 and their ratios (A1200 cm-1
/A1630 cm-1) in all XYRON samples.
Pre-drying Peak area Area ratio

Lot No.
conditions 1200 cm-1 1630 cm-1 (A1200 cm-1 /A1630 cm-1)
B39889 No pre-drying 6.6 8.7 0.76
110 oC x 5h 4.8 7.2 0.66
140 oC x 3h 5.8 9.5 0.61
B39890 No pre-drying 7.4 10.7 0.69
110 oC x 5h 5.5 7.8 0.71
140 oC x 3h 6.5 8.6 0.76
B39928 No pre-drying 5.6 7.6 0.74
110 oC x 5h 7.2 9.7 0.74
140 oC x 3h 3.3 4.0 0.84
8
3.2 DSC analysis
-220
Crystallization point
-210
EXO
-200
Crystalline onset point
-190
Heat flow (mW)
-180
-170
Melting onset point Melting point

-160
-150
-140
200 250 300
Temperature (oC)
Figure 2: DSC graph of lot No.B39889 with no pre-drying.
The DSC analysis was employed to investigate the enthalpy of fusion, the enthalpy of
crystallization, the melting points, the crystallization points, and their on-set points, of all
XYRON samples. The results from the DSC analysis showed no significant differences in
the properties between samples of different lot numbers and between samples pre-treated
with different drying protocols. In general, the enthalpy values of all 9 samples were
determined at around 40 J/g for the fusion and -32 J/g for the crystallization. Furthermore,
the melting point and the crystallization point were identified roughly at 259 oC and 225
o
C, respectively. The detailed data for each XYRON sample are listed in Table 2.
9
Table 2: Melting temperatures, enthalpies of fusion, crystallization temperatures and
enthalpies of crystallization of all XYRON samples in 3 pre-treatment conditions.
Onset Tm Tmelting ∆Hf Onset Tc Tc ∆Hc
Lot No. Conditions
(oC) (oC) (J/g) (oC) (oC) (J/g)
B39889 No pre-drying 242.9 258.9 41.9 228.9 225.7 -32.6
110 oC x 5h 245.6 260.1 39.0 229.4 226.4 -32.2
140 oC x 3h 245.2 258.01 35.9 227.6 223.4 -31.4
B39890 No pre-drying 243.7 258.8 42.0 228.7 225.6 -32.7
110 oC x 5h 245.8 258.6 36.1 229.7 226.8 -31.2
140 oC x 3h 243.6 259.2 41.8 228.1 225.1 -31.9
B39928 No pre-drying 244.7 260.6 43.0 229.1 225.9 -31.9
110 oC x 5h 244.1 259.7 41.1 228.4 225.5 -33.1
140 oC x 3h 244.1 258.7 38.8 227.4 224.1 -34.1
3.3 Rheology analysis
4.8
4.4
290 oC
4.0
log [G’(Pa)], log [G”(Pa)]
3.6
3.2
log G’
log G'
2.8 log G
log G”
2.4
-0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4
log [ω (s-1)]
pre-drying.
10
4.8
BB39890 no pre-drying
log G” = log G’
log [G’(Pa)] 4.4
4.0
3.6
3.2
3.2 3.6 4.0 4.4 4.8
log [G”(Pa)]
Figure 4: log G’ vs log G” rheometric graph of lot No.B39890 without pre-drying.
Unlike the results from DSC graphs and FT-IR spectra, rheology analysis described clear
changes in their viscoelastic properties between samples from different lot numbers, and
between samples pre-dried with different conditions. As in Table 3, the storage elastic
modulus at the frequency where G” is 100 kPa, was high for pre-treated samples compared
with those without pre-drying. It suggested that pre-drying treatment leads to crosslinking
reactions. Moreover. G’ seemed to be a plateau in the low frequency region. The values
were high after pre-drying. These results indicated that the pre-drying has to be performed
carefully.
11
Table 3: G’ values at G” = 10000 Pa and G’ plateau values of all XYRON samples with 3
pre-treatment conditions.
Pre-drying G’ value at
Lot No. G’ plateau (Pa)
conditions G” = 105 Pa (kPa)
B39889 No pre-drying 5.50 626

110 oC x 5h 5.89 705
140 oC x 3h 6.03 682
110 oC x 5h 5.75 691
140 oC x 3h 6.03 714
110 oC x 5h 5.50 613
140 oC x 3h 5.50 578
IV. Conclusion
In summary, from the results of plateau modulus, and G’ values at constant G”, the
viscoelastic properties of XYRON samples were dependent on lot numbers. Furthermore,
we also found that the pre-drying made the polymer blends rubbery. The inconsistency in
viscoelastic characteristics tremendously influences the processability of the polymer
material, for instance, the flow pattern in the mold and the degree of volume filling.[2]
Hence, each manufacturing stage of the material must be carefully examined.
12
Appendix
A. FT-IR spectrums
No pre-drying
No pre-drying
110oC 5h
110 oC x 5h
140oC
140 C x 3h
o 3h
Absorbance (a.u)
3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
13
No
No pre-drying
pre-drying
110oC x 5h
110
Absorbance (a.u) 140 oC x 3h
140
3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
14
B. DSC graphs
a. Lot No.B39889
-220
-210
-200
-190
Heat flow (mW)
-180
-170
-160
-150
-140
200 250 300
Temperature (oC)
Figure 7: DSC graph of lot No.B39889 with pre-drying at 110 oC for 5 hours.
-220
-210
-200
-190
Heat flow (mW)
-180
-170
-160
-150
-140
200 250 300
Temperature (oC)
15
b. Lot No.B39890
-220
-210
-200
-190
Heat flow (mW)
-180
-170
-160
-150
-140
200 250 300
Temperature (oC)
-220
-210
-200
-190
Heat flow (mW)
-180
-170
-160
-150
-140
200 250 300
Temperature (oC)
16
-220
-210
-200
-190
Heat flow (mW)
-180
-170
-160
-150
-140
200 250 300
Temperature (oC)
c. Lot No.B39928
-220
-210
-200
-190
Heat flow (mW)
-180
-170
-160
-150
-140
200 250 300
Temperature (oC)
17
-220
-210
-200
Heat flow (mW) -190
-180
-170
-160
-150
-140
200 250 300
Temperature (oC)
-190
-180
-170
Heat flow (mW)
-160
-150
-140
-130
-120
200 250 300
Temperature (oC)
18
C. Rheology graphs
a. Graphs of frequency dependence of oscillatory shear modulus
1. Lot No.B39889
4.8
4.4 290 oC
4.0
3.6
3.2
log G’
log G'
2.8 log G
log G”
2.4
-0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4
log [ω (s-1)]
pre-drying.
19
4.8
4.4
290 oC
4.0
3.6
3.2
log
log G’
G'
2.8
log
log G”
G
2.4
-0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4
log [ω (s-1)]
pre-drying at 110 oC for 5 hours.
4.8
4.4
290 oC
4.0
3.6
3.2
log G’
log G'
2.8
log G”
log G
2.4
-0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4
log [ω(s-1)]
20
2. Lot No.B39890
4.8
4.4
290 oC
4.0
3.6
3.2
2.8 log G’
log G'
log G”
log G
2.4
-0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4
log [ω (s-1)]
4.8
4.4 290 oC
4.0
3.6
3.2
logG'G’
log
2.8
log
logGG”
2.4
-0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4
log [ω (s-1)]
21
3. Lot No.B39928
4.8
4.4
290 oC
4.0
3.6
3.2
2.8 logG'
log G’
log
logGG”
2.4
-0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4
log [ω (s-1)]
pre-drying.
4.8
4.4
290 oC
4.0
3.6
3.2
2.8 log
logG’
G'
logG”
log G
2.4
-0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4
log [ω (s-1)]
22
4.8
4.4 290 oC
log [G’(Pa)], log [G”(Pa)] 4.0
3.6
3.2
2.8
logG'G’
log
log
logGG”
2.4
-0.8 -0.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4
log [ω (s-1)]
23
b. Rheometric graph of log G’ vs log G”
1. Lot No.B39889
4.8
B39889no
B39889 nopre-drying
pre-drying
log G” = log G’
4.4
log [G’(Pa)]
4.0
3.6
3.2
3.2 3.6 4.0 4.4 4.8
log [G”(Pa)]
Figure 23: log G’ vs log G” rheometric graph of lot No.B39889 without pre-drying
4.8
B
B39889 110 oC x 5h
log G” = log G’
4.4
log [G’(Pa)]
4.0
3.6
3.2
3.2 3.6 4.0 4.4 4.8
log [G”(Pa)]
for 5 hours.
24
4.8
B
B39889 140 oC x 3h
log G” = log G’
4.4
log [G’(Pa)]
4.0
3.6
3.2
3.2 3.6 4.0 4.4 4.8
log [G”(Pa)]
for 3 hours.
2. Lot No.B39890
4.8
B39890
B 110 oC x 5h
log G” = log G’
4.4
log [G’(Pa)]
4.0
3.6
3.2
3.2 3.6 4.0 4.4 4.8
log [G”(Pa)]
for 5 hours.
25
4.8
BB39890 140 oC x 3h
log G” = log G’
4.4
log [G’(Pa)]
4.0
3.6
3.2
3.2 3.6 4.0 4.4 4.8
log [G”(Pa)]
for 3 hours.
3. Lot No.B39928
4.8
BB39928 no pre-drying
log G” = log G’
4.4
log [G’(Pa)]
4.0
3.6
3.2
3.2 3.6 4.0 4.4 4.8
log [G”(Pa)]
Figure 28: log G’ vs log G” rheometric graph of lot No.B39928 without pre-drying.
26
4.8
B
B39928 110 oC x 5h
log G” = log G’
4.4
log [G’(Pa)]
4.0
3.6
3.2
3.2 3.6 4.0 4.4 4.8

log [G”(Pa)]
for 5 hours.
4.8
B39928 140 oC x 3h
B
log G” = log G’
4.4
log [G’(Pa)]
4.0
3.6
3.2
3.2 3.6 4.0 4.4 4.8
log [G”(Pa)]
for 3 hours.
27
Reference
[1] N. Vasanthan, J. Chem. Educ. 89 (2012) 387 – 390.
[2] J. E. Galve, Polymer. 11 (2019) 1063.
28

Characterization of Commercially Available Polymer Blends To Predict Processability

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JAPAN ADVANCED INSTITUTE OF SCIENCE AND TECHNOLOGY

MATERIAL SCIENCE SCHOOL

Minor Research Project

Submitted in partial fulfillment of the requirements for the degree of Master of

Supervisor: Prof. Dr. Masayuki Yamaguchi

Japan – March 2021

Figure 1: FT-IR spectrum of lot No.B39928 at different pre-treatment conditions. ............ 7

Figure 2: DSC graph of lot No.B39889 with no pre-drying. ............................................... 9

Figure 5: FT-IR spectrum of lot No.B39889 at different pre-treatment conditions. .......... 13

Figure 6: FT-IR spectrum of lot No.B39890 at different pre-treatment conditions. .......... 14

Figure 9: DSC graph of lot No.B39890 with no pre-drying. ............................................. 16

Figure 12: DSC graph of lot No.B39928 with no pre-drying. ........................................... 17

Table 2: Melting temperatures, enthalpies of fusion, crystallization temperatures and

II. Materials and methods

2.2 Fourier Transform – Infrared Spectroscopy (FT-IR) analysis

2.3 Differential scanning calorimetry (DSC) analysis

2.4 Rheology analysis

2.5 Hot compression molding

III. Results and discussion

3000 2500 2000 1500 1000 500

Figure 1: FT-IR spectrum of lot No.B39928 at different pre-treatment conditions.

Pre-drying Peak area Area ratio

Melting onset point Melting point

Figure 2: DSC graph of lot No.B39889 with no pre-drying.

3.3 Rheology analysis

3.2 3.6 4.0 4.4 4.8

Figure 4: log G’ vs log G” rheometric graph of lot No.B39890 without pre-drying.

B39889 No pre-drying 5.50 626

3000 2500 2000 1500 1000 500

Figure 5: FT-IR spectrum of lot No.B39889 at different pre-treatment conditions.

3000 2500 2000 1500 1000 500

Figure 6: FT-IR spectrum of lot No.B39890 at different pre-treatment conditions.

Figure 9: DSC graph of lot No.B39890 with no pre-drying.

Figure 12: DSC graph of lot No.B39928 with no pre-drying.

Heat flow (mW) -190

a. Graphs of frequency dependence of oscillatory shear modulus

log [G’(Pa)], log [G”(Pa)] 4.0

3.2 3.6 4.0 4.4 4.8

3.2 3.6 4.0 4.4 4.8

3.2 3.6 4.0 4.4 4.8

3.2 3.6 4.0 4.4 4.8

3.2 3.6 4.0 4.4 4.8

3.2 3.6 4.0 4.4 4.8

3.2 3.6 4.0 4.4 4.8

3.2 3.6 4.0 4.4 4.8

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