สไลด์ กลุ่มที่ 15

Advisor : Assist. Prof. Dr. Chanchai Thongpin Co-advisor : Assist. Prof. Dr. Bussarin Ksapabutr

Researchers : Ms. ChayaneeKasemsook Student ID : 09530074

Mr. Triwat TalbumrungStudent ID : 09530146

Mr. Worawit Sangtean Student ID : 09530379

Present :: 3 April 2014 :: 1

Out line

Introduction

Project Objectives

Project scope

Materials and Experimental

Results and Discussion

Conclusion

Faculty of Engineering and Industrial Technology, Silpakorn UniversityFaculty of Engineering and Industrial Technology, Silpakorn University 2

INTRODUCTION


PLA is thermoplastic aliphatic polyester derived from renewable resourceds, such as corn starch.

Polylactic acid, PLA

High stiffness & strength Crystillinity High brittle Low toughness

Main Main propertiepropertiess

INTRODUCTION


INTRODUCTION


Chemical structure of NBR

NBR, a synthetic rubber which is a copolymer between acrylonitrile (ACN) and butadiene.

Nitrile butadiene

rubber, NBR

High abrasion resistance Low gas permeability Oil and Chemical resistance High thermal aging Poor weather resistance

Main Main propertiepropertiess

INTRODUCTION


Vulcanization :: Peroxide vulcanizationAdvantage1)No problem of chemicals bloom.2)Reaction is faster at higher temperatures.3)Resistance deformation of rubber after compression (at high temperatures).4) Heat resistant.

Dicumyl peroxide

Peroxide vulcanization

INTRODUCTION


Organo Montmorillonite

Low cost and easy to find.Compatibility with PLA. Reinforcement in rubber and PLA. Improve mechanical and thermal property.

Low cost and easy to find.Compatibility with PLA. Reinforcement in rubber and PLA. Improve mechanical and thermal property.

http://www.nishikawa-rbr.co.jp/english/technology/techno_5423.htm

PLAhttp://www.indiamart.com/unichemimpex/rubber-products.html

NBR & NBR compound

Toughness PLA

INTRODUCTION




http://www.indiamart.com/unichemimpex/rubber-products.html

http://www.indiamart.com/unichemimpex/rubber-products.html

Project Objectives

1. To investigate mechanical, thermal property and

morphology of PLA/NBR blends and PLA/NBR compounds.

2. The effect of Organic Montmorillonite (OMMT)Cloisite® (30B) on mechanical, thermal property and morphology of PLA/NBR blends and PLA/NBR compounds.


Using NBR rubber (acrylonitrile 50%) masticated with two roll mill for 60 min and

PLA (grade 3052 D). Study the effect of NBR content in

PLA/NBR (95:5, 90:10 85:15, 80:20, 75:25 70:30 %w/w) on toughness

of PLA.

In peroxide vulcanization, dicumylperoxide will be used as curing agent.

Using Organo Montmorillonite (OMMT) Cloisite® (30B) added in polymer blends.


Project Scope

Materials and Experimental



1. Polylactic acid (PLA) >> 3052 D from NatureWorks produced

2. Nitrile Butadiene Rubber (NBR)>> 50% acrylonitrile content from LG Chem

3. Dicumylperoxide (DCP)>> from Sigma-Aldrich

4. Organic Montmorillonite (OMMT)>> Cloisite®30B from ROCKWOOD ADDITIVE

Materials


Universal testingMachine


Differential scanning calorimetry (DSC)


Thermo gravimetric Analyzer (TGA)


Scanning electron microscopy (SEM)Scanning electron microscopy (SEM)

Prepare samples by Compression

molding 170 oC pressure 1000 psi



Part IPart I Study PLA/NBR BlendsStudy PLA/NBR Blends Preparation of NBR blends.

Masticate NBR by two roll mill for 60 min

ratio of PLA: NBR (95:5, 90:10, 85:15, 80:20 ,75:25, and 70:30)

Preparation of NBR blends.



Preparation of PLA.

PLA dried at 50°C for 24

hours

Preparation of PLA.

PLA dried at 50°C for 24

hours

Experimental

Mix in internal mixer

at 170oC 70 rpm


at 170oC 70 rpm

Testing

Testing

Faculty of Engineering and Industrial Technology, Silpakorn UniversityFaculty of Engineering and Industrial Technology, Silpakorn University

Experimental












Testing

Testing







Preparation of PLA.

PLA dried at 50 °C for 24 hours

Preparation of PLA.

PLA dried at 50 °C for 24 hours Mix in

internal mixer

at 170oC 70 rpm


at 170oC 70 rpm

Part IIPart II Study PLA/NBR CompoundStudy PLA/NBR Compound

14

Dicumyl peroxide (DCP) 1 phr

Dicumyl peroxide (DCP) 1 phr













Select appropriate ratio for PLA/NBR

blends and PLA/NBR

compounds

Select appropriate ratio for PLA/NBR

blends and PLA/NBR

compounds Mix in internal mixer

at 170oC 70 rpm


at 170oC 70 rpm

Testing

Testing

Experimental

XRDXRD

15

Part IIIPart III Study the effect of clay on properties of PLA/NBR blends and PLA/NBR compoundsStudy the effect of clay on properties of PLA/NBR blends and PLA/NBR compounds

Cloisite®30B


Results and Discussion

16


PART IPART IMorphology of

PLA/NBR Blends

Figure 1 Morphology of PLA/NBR blends in 5, 10, 15, 20, 25 and 30% NBR

NBR 20

NBR 30

NBR 5

NBR 10

NBR 15

NBR 20

NBR 25

NBR 30


Figure 2 DSC Thermogram of neat PLA and PLA/NBR blends in first heating

PART IPART I Thermal properties of PLA/NBR Blends

Crystallization

1 st Heat

TgTcc Tm 160.5

7159.0

3160.06

159.05

159.05

159.00159.05160.02

149.57150.02

150.54

155.40148.50

150.58

148.42

149.57



Crystallization

Table 1 Crystallization behavior of PLA/NBR blends in different weight contents of NBR and pure PLA in first heating


Figure 3 DSC Thremogram of neat PLA and PLA/NBR blends in first heating


Crystallization

2nd Heat Tg

Tcc Tm

15

95.115

94

9

16

02.1

15

96.5

16

00.1

159.56159.60160.06

15

05.815

06.3

15

16.3

15

16.8

14

96.115

11.3

15

05.8

15

06.3


Crystallization

Table 2 Crystallization behavior of PLA/NBR blends in different weight contents of NBR and pure PLA in second heating



Degradation

Figure 4 TGA Thermogram of neat PLA and PLA/NBR blends


Virgin PLANeat PLA

PLA95/NBR5

PLA90/NBR10

PLA85/NBR15

PLA80/NBR20

PLA75/NBR25

PLA70/NBR30



Degradation

Figure 5 DTG Thermogram of neat PLA and PLA/NBR blends

Virgin PLA

Neat PLA

PLA95/NBR5

PLA90/NBR10

PLA85/NBR15

PLA80/NBR20

PLA75/NBR25

PLA70/NBR30

280ºC 350ºC

(316.98)(306.21)(326.40)

(329.80)(335.89)(331.04)(320.28)

(320.35)


Formula

Degradation temperature (°C) Peak area

OnsetInflecti

onEnd

At 10% degradatio

n(%)

PLA virgin

294.61 316.98332.1

6298.18 94.24

PLA neat

293.46 306.21324.9

8291.84 94.29

NBR 5 284.74 326.40335.0

2291.26 88.49

NBR 10 288.65 329.80349.9

5294.28 83.07

NBR 15 303.18 335.89346.0

9292.25 74.89

NBR 20 296.64 331.04342.1

3292.26 78.16

NBR 25 292.02 320.28329.0

7280.89 67.35

NBR 30 303.73 320.35327.2

6282.81 61.94


Degradation

Table 3 Degradation data of PLA/NBR blends in different weight contents of NBR and pure PLA by TGA


PART IPART I Mechanical properties

Figure 6 Stress-Strain curve of PLA virgin and PLA/NBR blends in different weight content of NBR

PART IPART I Mechanical propertiesStress-Strain

Curve


PART IPART I Mechanical propertiesMorphology after Tensile

Testing

NBR 20

NBR 30

Figure 7 Morphology of PLA/NBR blends in 5, 10, 15, 20, 25 and 30% NBR after tensile testing

NBR 5

NBR 20

NBR 25

NBR 30

NBR 5

NBR 10

NBR 15

NBR 20

NBR 30

NBR 25

PART IPART I Mechanical properties Modulus

Figure 8 Modulus of PLA virgin and PLA/NBR blends in different weight content of NBR


PART IPART I Mechanical propertiesMaximum

Tensile Strength

Figure 9 Maximum Tensile Strength of PLA virgin and PLA/NBR blends in different weight content of NBR



Figure 10 Modulus of PLA virgin and PLA/NBR blends in different weight content of NBR


% Elongation at Break


PART IIPART II Morphology of PLA/NBR compounds

Figure 11 Morphology of PLA/NBR compounds in 5, 10, 15, 20, 25 and 30% NBR

NBR 5

NBR 10

NBR 15

NBR 15

NBR 20

NBR 25

NBR 20

NBR 30


Figure 12 DSC Thermogram of neat PLA and PLA/NBR compounds in first heating

PART IIPART II Thermal properties of PLA/NBR Compounds

Crystallization

1 st Heat

Tg

Tcc Tm160.5

7159.0

31589.5

15

90.1

15

89.0

15

89.0

15

84

215

89.1

147.97148.44

148.42

148.50

155.40

14

95.8148.52

149.55



Crystallization

Table 4 Crystallization behavior of PLA/NBR compounds in different weight contents of NBR and pure PLA in first heating


Figure 13 DSC Thermogram of neat PLA and PLA/NBR compounds in first heating


Crystallization

2nd Heat Tg

Tcc Tm159.5

1159.4

91596.1

15

94.8

15

95.1

15

89.6

15

90.114

89.6

14

95.3

15

04.814

98.8

149.61

155.40

15

00.315

00.215

00.4


Crystallization

Table 5 Crystallization behavior of PLA/NBR compounds in different weight contents of NBR and pure PLA in second heating



Degradation

Figure 1 4 TGA Thermogram of neat PLA and PLA/NBR compounds


Virgin PLA

Neat PLA

PLA95/NBR5

PLA90/NBR10

PLA85/NBR15

PLA80/NBR20

PLA75/NBR25

PLA70/NBR30



Degradation

Figure 1 5 DTG Thermogram of neat PLA and PLA/NBR compounds

Virgin PLA

Neat PLA

PLA95/NBR5

PLA90/NBR10

PLA85/NBR15

PLA80/NBR20

PLA75/NBR25

PLA70/NBR30

290 - 350ºC

430 - 475 ºC

(316.98)

(306.21)

(340.15)(333.17)(326.32)(331.04)(333.96)(329.50)



Degradation

Table 6 Degradation data of PLA/NBR compounds in different weight contents of NBR and pure PLA by TGA

Formula

Degradation temperature (°C)Peak area

OnsetInflecti

onEnd

At 10% degradatio

n(%)

virgin PLA 294.61 316.98

332.16 298.18 94.24

neat PLA 293.46 306.21

324.98 291.84 94.29

NBR 5 + DCP 296.81 340.15

350.10

289.70487.55

NBR 10 + DCP 297.76 333.17

342.91 295.63 82.42

NBR 15 + DCP 294.41 326.32

341.78 294.41 83.81

NBR 20 + DCP

296.64 331.04342.1

3292.26 78.16

NBR 25 + DCP

304.68 333.96

341.70

291.4269.71

431.89 440.05

472.20 15.80

NBR 30 + DCP

308.95 329.50

335.62

288.6062.57

432.84

439.21

475.84 15.01



Figure 16 Stress-Strain curve of PLA virgin and PLA/NBR compounds in different weight content of NBR

PART IIPART II Mechanical propertiesStress-Strain

Curve


PART IIPART II Mechanical propertiesMorphology after Tensile

Testing

Figure 17 Morphology of PLA/NBR compounds in 5, 10, 15, 20, 25 and 30% NBR after tensile testing

NBR 5

NBR 5

NBR 10

NBR 15

NBR 20

NBR 25

NBR 30

PART IIPART II Mechanical properties Modulus

Figure 18 Modulus of PLA virgin and PLA/NBR compounds in different weight content of NBR


PART IIPART II Mechanical propertiesMaximum

Tensile Strength

Figure 19 Maximum Tensile Strength of PLA virgin and PLA/NBR compounds in different weight content of NBRFaculty of Engineering and Industrial Technology, Silpakorn UniversityFaculty of Engineering and Industrial Technology, Silpakorn University 41

PART IIPART II Mechanical properties

Figure 20 Modulus of PLA virgin and PLA/NBR compounds in different weight content of NBR




PART III.IPART III.I Morphology of PLA/NBR Blends with OMMT

Figure 21 Morphology of PLA/NBR blends in 20, 25 and 30% NBR with OMMT

NBR 20

NBR 25

NBR 30

NBR 20

NBR 25

NBR 30


PART III.IPART III.I Morphology of PLA/NBR Blends with OMMT

Figure 22 Morphology of PLA/NBR blends in 20, 25 and 30% NBR with OMMT

5º


Figure 23 DSC Thermogram of neat PLA and PLA/NBR blends with OMMT in first heating

PART III.IPART III.I Thermal properties of PLA/NBR Blends

Crystallization

1 st Heat

PLA70/NBR30

TgTcc

Tm160.5

7

159.03

15

8.89

158.00

157.99

148.50

155.40



Crystallization

Table 7 Crystallization behavior of PLA/NBR blends with OMMT in different weight contents of NBR and pure PLA in first heating


Figure 24 DSC Thermogram of neat PLA and PLA/NBR blends with OMMT in first heating


Crystallization

2nd Heat Tg Tcc

Tm

159.51

159.49

159.0515

90.51 5895

14

95.7

149.56

149.57

149.61

151.68


Crystallization

Table 8 Crystallization behavior of PLA/NBR blends with OMMT in different weight contents of NBR and pure PLA in second heating



Degradation

Figure 2 5 TGA Thermogram of neat PLA and PLA/NBR blends with OMMT


PLA75/NBR25



Degradation

Figure 26 DTG Thermogram of neat PLA and PLA/NBR blends with OMMT

300 - 350ºC

400 - 530 ºC

(316.98)

(306.21)

(337.47)

(339.12)

(330.23)



Degradation

Table 9 Degradation data of PLA/NBR blends with OMMT in different weight contents of NBR and pure PLA by TGA

Formula


OnsetInflecti

onEnd

At 10% degradatio

n(%)

virgin PLA 294.61 316.98

332.16 298.18 94.24

neat PLA 293.46 306.21

324.98 291.84 94.29

NBR 20316.17 337.47

349.34

297.4568.99

435.00 453.15522.9

3 9.31

NBR 25318.44 339.12

349.03

299.0766.63

408.37 455.41532.5

6 9.60

NBR 30309.26 330.23

338.96

290.2259.75

400.49 452.77515.3

1 12.21



Figure 27 Stress-Strain curve of PLA virgin and PLA/NBR blends with OMMT in different weight content of NBR

PART III.IPART III.I Mechanical propertiesStress-Strain

Curve


PART III.IPART III.I Mechanical propertiesMorphology after Tensile

Testing

Figure 28 Morphology of PLA/NBR blends in 20, 25 and 30% NBR with OMMT after tensile testing

NBR 20

NBR 25

NBR 30

NBR 20

NBR 30

NBR 25

PART III.IPART III.I Mechanical properties Modulus

Figure 29 Modulus of PLA virgin and PLA/NBR blends with OMMT in different weight content of NBR


PART III.IPART III.I Mechanical propertiesMaximum

Tensile Strength

Figure 30 Maximum Tensile Strength of PLA virgin and PLA/NBR blends with OMMT in different weight content of NBR


PART III.IPART III.I Mechanical properties

Figure 31 Modulus of PLA virgin and PLA/NBR blends with OMMT in different weight content of NBR




PART III.IIPART III.II Morphology of PLA/NBR Compounds with OMMT

Figure 32 Morphology of PLA/NBR compounds in 20, 25 and 30% NBR with OMMT

NBR 20

NBR 25

NBR 30

NBR 25

NBR 20

NBR 30


PART III.IIPART III.II Morphology of PLA/NBR Compounds with OMMT

Figure 3 3 Morphology of PLA/NBR compounds in 20, 25 and 30% NBR with OMMT

5º


Figure 34 DSC Thermogram of neat PLA and PLA/NBR compounds with OMMT in first heating

PART III.IIPART III.II Thermal properties of PLA/NBR Compounds

Crystallization

1 st Heat

PLA70/NBR30

neat PLA

PLA80/NBR20

PLA75/NBR25

Tg Tcc

Tm

160.57

159.03

15

8.55

158.05

158.50

149.50

155.40



Crystallization

Table 10 Crystallization behavior of PLA/NBR compounds with OMMT in different weight contents of NBR and pure PLA in first heating


Figure 35 DSC Thermogram of neat PLA and PLA/NBR compounds with OMMT in first heating


Crystallization

2nd Heat

neat PLA

PLA80/NBR20

PLA75/NBR25

PLA70/NBR30

Tg Tcc

Tm

159.51

159.4915

95.115

8.501 5850

149.61

151.68

PART III.IIPART III.II Thermal properties of PLA/NBR Blends

Crystallization

Table 11 Crystallization behavior of PLA/NBR compounds with OMMT in different weight contents of NBR and pure PLA in second heating



Degradation

Figure 3 6 TGA Thermogram of neat PLA and PLA/NBR compounds with OMMT


PLA80/NBR20

PLA75/NBR25

PLA70/NBR30



Degradation

Figure 37 DTG Thermogram of neat PLA and PLA/NBR compounds with OMMT

PLA80/NBR20

PLA75/NBR25

(316.98)

(306.21)

(326.30)

(322.00)

(319.41)



Degradation

Table 12 Degradation data of PLA/NBR compounds with OMMT in different weight contents of NBR and pure PLA by TGA

Formula


OnsetInflecti

onEnd

At 10% degradatio

n(%)

virgin PLA 294.61 316.98

332.16 298.18 94.24

neat PLA 293.46 306.21

324.98 291.84 94.29

NBR 20

294.62 326.30337.4

3286.54

67.93

403.90 442.21468.4

28.12

NBR 25

289.91 322.00330.1

3280.05

64.26

401.07 446.36470.0

714.6

NBR 30

290.87 319.41330.0

2278.44

59.63

408.9 445.94472.6

619.18



Figure 38 Stress-Strain curve of PLA virgin and PLA/NBR compounds with OMMT in different weight content of NBR

PART III.IIPART III.II Mechanical propertiesStress-Strain

Curve


PART III.IIPART III.II Mechanical propertiesMorphology after Tensile

Testing

Figure 39 Morphology of PLA/NBR compounds in 20, 25 and 30% NBR with OMMT after tensile testing

NBR 20

NBR 25

NBR 30

NBR 20

NBR 25

NBR 30

PART III.IIPART III.II Mechanical properties Modulus

Figure 40 Modulus of PLA virgin and PLA/NBR compounds with OMMT in different weight content of NBR


PART III.IIPART III.II Mechanical propertiesMaximum

Tensile Strength

Figure 41 Maximum Tensile Strength of PLA virgin and PLA/NBR compounds with OMMT in different weight content of

NBRFaculty of Engineering and Industrial Technology, Silpakorn UniversityFaculty of Engineering and Industrial Technology, Silpakorn University 69

PART III.IIPART III.II Mechanical properties

Figure 42 Modulus of PLA virgin and PLA/NBR compounds with OMMT in different weight content of NBR



Conclusion



PLA/NBR blendsPLA/NBR blends

1. NBR resulted to PLA increase crystallinity2. NBR resulted to PLA increase Td

3. NBR resulted to PLA/NBR blends Increase elongation at breakDecrease modulusDecrease maximum tensile strength

4. NBR was disperse phase in PLA matrix


PLA/NBR compoundsPLA/NBR compounds

1. DCP resulted to PLA decrease crystallinity2. DCP resulted to PLA increase Td

3. DCP resulted to PLA/NBR compounds Increase elongation at breakDecrease modulusDecrease maximum tensile strength

4. DCP improved miscibility between PLA and NBR


PLA/NBR blends + OMMTPLA/NBR blends + OMMT

1. OMMT resulted to PLA increase crystallinity.2. OMMT resulted to PLA increase Td.

3. OMMT resulted to PLA/NBR blends Decrease elongation at breakDecrease modulusDecrease maximum tensile strength


PLA/NBR compoundsPLA/NBR compounds

1. OMMT resulted to PLA increase crystallinity.2. OMMT resulted to PLA increase Td.

3. OMMT resulted to PLA/NBR compounds Increase elongation at breakDecrease modulusDecrease maximum tensile strength

ConclusionConclusion Thermal properties Tg


Figure 4.43 Tg of PLA/NBR blends in different weight content of NBR


ConclusionConclusion Thermal properties Tm1

Figure 4.44 Tm1 of PLA/NBR blends in different weight content of NBR


ConclusionConclusion Thermal properties Tm2



ConclusionConclusion Thermal properties %Xc

Figure 4.46 %Xc of PLA/NBR blends in different weight content of NBR


ConclusionConclusion Thermal properties Td


ConclusionConclusion Mechanical properties Modulus


Figure 4.48 Modulus of PLA/NBR blends in different weight content of NBR

82

ConclusionConclusion Mechanical propertiesMaximum

Tensile Strength


Figure 4.49 Maximum tensile strength of PLA/NBR blends in different weight content of NBR

ConclusionConclusion Mechanical properties% Elongation

at Break


Figure 4.50 Maximum tensile strength of PLA/NBR blends in different weight content of NBR

สไลด์ กลุ่มที่ 15

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