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The Effect of Chitin Fiber Morphology on Mechanical Strength Heather Johnson and J.D. Mendez Indiana University – Purdue University Columbus, Division of Science, 4601 Central Ave., Columbus, IN 47203 Chitin is an extremely abundant natural with many amazing properties. Chitin is already used in the agriculture, medical, cosmetic and water treatment industries. 1 In the field of biomedicine, chitin has been found to be able to clot blood and heal wounds faster, and it is non-toxic. 2 Even though it is used commercially in a wide range of applications, most of the commercial supply of chitin comes from one source, shrimp shells. Different sources such as crawfish and insects have large quantities of chitin but the difference between the sources is not well understood. 3 Acknowledgements This material is based upon work supported by the Office of Student Research at IUPUC, the Indiana Academy of Science as well as the Federal Work-Study program. We also sincerely thank Matt Ferrell and the Purdue College of Technology for their assistance with mechanical testing, and Caroline Miller for the help with the TEMs. Selected References 1. Ding, F. Y.; Deng, H. B.; Du, Y. M.; Shi, X. W.; Wang, Q., Emerging chitin and chitosan nanofibrous materials for biomedical applications. Nanoscale 2014, 6 (16), 9477-9493. 2. Sahoo, D.; Sahoo, S.; Mohanty, P.; Sasmal, S.; Nayak, P. L., Chitosan: a New Versatile Bio-polymer for Various Applications. Des. Monomers Polym. 2009, 12 (5), 377-404. 3. Hajji, S.; Younes, I.; Ghorbel-Bellaaj, O.; Hajji, R.; Rinaudo, M.; Nasri, M.; Jellouli, K., Structural differences between chitin and chitosan extracted from three different marine sources. Int. J. Biol. Macromol. 2014, 65, 298-306. 4. Dufresne, A., Comparing the mechanical properties of high performances polymer nanocomposites from biological sources. J. Nanosci. Nanotechnol. 2006, 6 (2), 322- 330. 5. Fernandez, J. G.; Ingber, D. E., Unexpected Strength and Toughness in Chitosan- Fibroin Laminates Inspired by Insect Cuticle. Adv. Mater. 2012, 24 (4), 480. Introduction Results – TEM (Cicada) Results – Mechanical Testing Conclusions Future Work Sources of Chitin and the Extraction Process Source material, washed and ground Three separate agitate/drain/wash cycles 100°C in NaOH Room temperature in HCl Room temperature in bleach Desiccate for 48 hours Weigh final product Characterize O HO NH CH 3 O OH O O OH NH CH 3 O HO O n Results – Aspect Ratio Deacetylation Process O HO NH CH 3 O OH O O OH NH CH 3 O HO O n O HO NH 2 OH O O OH NH 2 HO O n Chitin Chitosan NaOH Chitin is a mechanically strong material due to the high degree of hydrogen bonding however, this means it is also insoluble in common solvents. Deacetylation improves solubility but decreases the mechanical properties. Cicada – the numbers above show the widths of the fibers As many as 1 billion cicadas can be found per square mile every 17 years Almost 69 thousand lbs of lobster were caught in Maine in 2005. LA Crawfish production was 81.9 million lbs in 2005. The shells are discarded as waste. 500 nm The fiber circled above is about 340 nm long and 24 nm wide. 500 nm The fiber circled above is about 460 nm long and 23 nm wide. There does see to be some differences in the fiber size and shape of the different source materials. However, more TEM scans are needed of the crawfish, lobster, and shrimp to confirm this. The mechanical testing suggests that the chitin could potentially strengthen PVA composites but too much can have a detrimental effect. 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 0% 5% 10% 15% 20% 25% Young's Modulus (GPa) Percent Chitin/Chitosan PVA/Chitin Composites 0.00E+00 2.00E+07 4.00E+07 6.00E+07 8.00E+07 1.00E+08 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 Stress (Pa) Strain Typical Stress-Strain Curve (5% Chitin/Chitosan) By controlling the degree of acetylation, it should be possible to make it soluble without sacrificing all of the mechanical strength. The aspect ratio is a measure of how long and skinny a fiber is. For example; a circle would have an aspect ratio of 1. The chitin fibers in the cicada sample have an average aspect ratio of 31.7 +/- 8.1. The higher the aspect ratio, the lower concentration needed for percolation. = 100 nm Chitin/chitosan fibers were combined with poly(vinyl alcohol) (PVA), a common plastic By adding a mechanically strong filler, the goal was to increase the mechanical properties of the composite 4,5 The top figure is a typical stress- strain curve for one of the composites The sample was pulled until it broke and the force was measured Most samples did not show an increase in Young’s Modulus expect at 5% loading Large error means the results are inconclusive Lobster Shrimp 100 nm 100 nm Preliminary tests show that the source material has a significant impact on the chitin fiber aspect ratio; mechanical testing needs to be done to see if this difference affect composite formation The ratio in chitin to chitosan samples needs to be varied to determine how this change will affect solubility and fiber formation
Transcript
Page 1: The Effect of Chitin Fiber Morphology on Mechanical Strength ·  · 2018-01-30range of applications, ... Sasmal, S.; Nayak, P. L., Chitosan: a New Versatile Bio-polymer for Various

The Effect of Chitin Fiber Morphology on Mechanical StrengthHeather Johnson and J.D. Mendez

Indiana University – Purdue University Columbus, Division of Science, 4601 Central Ave., Columbus, IN 47203

Chitin is an extremely abundant natural with many amazing properties.

Chitin is already used in the agriculture, medical, cosmetic and water treatmentindustries.1 In the field of biomedicine, chitin has been found to be able to clot blood andheal wounds faster, and it is non-toxic.2 Even though it is used commercially in a widerange of applications, most of the commercial supply of chitin comes from one source,shrimp shells. Different sources such as crawfish and insects have large quantities ofchitin but the difference between the sources is not well understood.3

AcknowledgementsThis material is based upon work supported by theOffice of Student Research at IUPUC, the IndianaAcademy of Science as well as the Federal Work-Studyprogram. We also sincerely thank Matt Ferrell and thePurdue College of Technology for their assistance withmechanical testing, and Caroline Miller for the help withthe TEMs.

Selected References

1. Ding, F. Y.; Deng, H. B.; Du, Y. M.; Shi, X. W.; Wang, Q., Emerging chitin and chitosan nanofibrous materials for biomedical applications. Nanoscale 2014, 6 (16), 9477-9493.

2. Sahoo, D.; Sahoo, S.; Mohanty, P.; Sasmal, S.; Nayak, P. L., Chitosan: a New Versatile Bio-polymer for Various Applications. Des. Monomers Polym. 2009, 12 (5), 377-404.

3. Hajji, S.; Younes, I.; Ghorbel-Bellaaj, O.; Hajji, R.; Rinaudo, M.; Nasri, M.; Jellouli, K., Structural differences between chitin and chitosan extracted from three different marine sources. Int. J. Biol. Macromol. 2014, 65, 298-306.

4. Dufresne, A., Comparing the mechanical properties of high performances polymer nanocomposites from biological sources. J. Nanosci. Nanotechnol. 2006, 6 (2), 322-330.

5. Fernandez, J. G.; Ingber, D. E., Unexpected Strength and Toughness in Chitosan-Fibroin Laminates Inspired by Insect Cuticle. Adv. Mater. 2012, 24 (4), 480.

Introduction Results – TEM (Cicada)

Results – Mechanical Testing

Conclusions

Future Work

Sources of Chitin and the Extraction Process

• Source material, washed and

ground

• Three separate agitate/drain/wash

cycles

• 100°C in NaOH

• Room temperature in HCl

• Room temperature in bleach

• Desiccate for 48 hours

• Weigh final product

• Characterize

O

HO

NH

CH3

O

OH

O

O

OH

NH

CH3

O

HO

O

n

Results – Aspect RatioDeacetylation Process

O

HO

NH

CH3

O

OH

O

O

OH

NH

CH3

O

HO

O

n

O

HO

NH2

OH

O

O

OH

NH2HO

O

n

Chitin Chitosan

NaOH

• Chitin is a mechanically strong material due to the high degree of hydrogen bonding however, this means it is also insoluble in common solvents.

• Deacetylation improves solubility but decreases the mechanical properties.

Cicada – the numbers above show the widths of the fibers

As many as 1 billion cicadas can be found per square

mile every 17 years

Almost 69 thousand lbs of lobster were caught in Maine in 2005.

LA Crawfish production was 81.9 million lbs in 2005. The shells are discarded as waste.

500 nm

The fiber circled above is about 340 nm long and 24 nm wide.

500 nm

The fiber circled above is about 460 nm long and 23 nm wide.

• There does see to be some differences in the fiber size and shape of the different source materials. However, more TEM scans are needed of the crawfish, lobster, and shrimp to confirm this.

• The mechanical testing suggests that the chitin could potentially strengthen PVA composites but too much can have a detrimental effect.

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

0% 5% 10% 15% 20% 25%

Youn

g's

Mod

ulus

(GP

a)

Percent Chitin/Chitosan

PVA/Chitin Composites

0.00E+00

2.00E+07

4.00E+07

6.00E+07

8.00E+07

1.00E+08

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8

Stre

ss (P

a)

Strain

Typical Stress-Strain Curve (5% Chitin/Chitosan)

• By controlling the degree of acetylation, it should be possible to make it soluble without sacrificing all of the mechanical strength.

• The aspect ratio is a measure of how long and skinny a fiber is.

• For example; a circle would have an aspect ratio of 1.

• The chitin fibers in the cicada sample have an average aspect ratio of 31.7 +/- 8.1.

• The higher the aspect ratio, the lower concentration needed for percolation.

𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑅𝑅𝑅𝑅𝐴𝐴𝑅𝑅𝑅𝑅 =𝑙𝑙𝐴𝐴𝑙𝑙𝑙𝑙𝐴𝐴𝑙𝑤𝑤𝑅𝑅𝑤𝑤𝐴𝐴𝑙

100 nm

• Chitin/chitosan fibers were combined with poly(vinyl alcohol) (PVA), a common plastic

• By adding a mechanically strong filler, the goal was to increase the mechanical properties of the composite4,5

• The top figure is a typical stress-strain curve for one of the composites

• The sample was pulled until it broke and the force was measured

• Most samples did not show an increase in Young’s Modulus expect at 5% loading

• Large error means the results are inconclusive

Lobster Shrimp

100 nm 100 nm

• Preliminary tests show that the source material has a significant impact on the chitin fiber aspect ratio; mechanical testing needs to be done to see if this difference affect composite formation

• The ratio in chitin to chitosan samples needs to be varied to determine how this change will affect solubility and fiber formation

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