# Presentation: 880127

**Ecocomposites Reinforced with Cellulose Nanoparticles: ****           An Alternative to Existing Petroleum Based Polymer Composites**
-  **EPA Grant Number:** R830897  1/15/2004-1/14/2007
-           WT Winter, Cellulose Res. Inst., SUNY-ESF, Syracuse, NY, 13210
** **

- Philadelphia 8-18-2004

- CRI@ESF

## Drivers for This Program

**Sustainability**
**Use renewables**
** ****safely and responsibly**
**Nanotechnology**
**       ****surface, surface, surface**
**Policy /Regulation**
**Biomass R&D Act of 2000**
**Farm Bill 2002, Title IX**

- Biorefinery

** ****Willow Project**

- Products
- Bioplastic, Biofuels, Nanoparticles for reinforced bioplastics

## Driver: UN Agenda 21

- 4.19. ... society needs to develop effective ways of dealing with the problem of disposing of mounting levels of waste products and materials. Governments, together with industry, households and the public, should make a concerted effort to reduce the generation of wastes and waste products by:
-  Encouraging recycling in industrial processes and at the consumer level;
-  **Reducing wasteful packaging** of products;
-  Encouraging the **introduction of more environmentally sound products**.

## Why Biodegradable?

- Sustainable
- Regulations
-     on disposal

- X

## Nanoparticles

- At least 1 dimension < 100 nm (10-7 m) - NSF
- 2 Advantages of Nanotechnology
**Speed** of light:  3 x 1010 cm/sec * 10 -9 s/ns
**1 ns = 30 cm** (1 foot) mostly useful in electrical applications
- Increased **specific surface area**
- Influences catalysis, adhesion

## Nanocomposites

**Particulate composites**:
- Matrix
- Particulate Phase
- Reinforcing particles have at least one dimension (i.e. length, width, or thickness) on the nanometer scale

**Why small?**

- Surface area:

- 125 x (1 x 1 x 6) = 750 = 5 x 150

- 5 x 5 x 6 = 150

**In proceeding from a ********m to nm scale the specific surface area increases by 3 orders of magnitude**

## Surface Area vs. Aspect Ratio

**Surface Area vs. Aspect Ratio**

- Cellulose Nanocrystals:
- Length: 100 –  several m
- Diameter: 3 – 20 nm
- Aspect Ratio:
- 10 – 10,000

- Montmorillonite Clay:
- Length: 1 nm
- Diameter: 200 – 400 nm
- Aspect Ratio:
- 0.005 – 0.0025 (200 – 400)

## Cellulose Morphology

***Fiber (cell)***
***White pine tracheids – Helm, Va Tech***

**Wood Cell Schematic**

**Microfibril**
**Hanna, ESF**

## Parenchyma Cells

- Predominant cell type in fruit
- Primary cell wall tissue
- Rays in woody tissue

## Microfibril size

**Cotton              Wood      Sugar Beet**

**Algae                                 Tunicate**

## Biomass from Fruit and Sugar Processing 

- Sugar Beets
- 27Mt/yr USDA 2002
- 1 ton beets >110 lb pellets

- 4.3 Mt/yr- USDA 2002
- 40% > juice

- 12.4 Mt/yr USDA 2002

## Composition of Orange ByproductWeight % 

## Composition of Apple PomaceWeight %

- Chiellini (2001) *Biomacromol *2:1029-1037

## Sugar Beet Pulp Cellulose 

**20% cellulose, 25-30% hemicellulose and 25-35% pectin, sucrose, proteins, lignin, fat**
**Individual microfibrils 2 - 4 nm in diameter**

## Nanoparticle Samples 

**Sources Utilized**
- Apple Pomace
- Bagasse
- Chitin
- Orange Pulp
- Sugar beet
- Tunicate
- Wheat
- Wood

**Derivatives Made**
- Acetates
- Maleates
- N-Acetyl (chitin)
- Trimethylsilyl
**Derivatives Planned**
- Amino
- Carboxylate
- Fatty acid

## Crystal and Microfibril Preparation

**acid (HCl, H****2****SO****4****)**
**concentrations ( 65%)**
**temperature (40****°****C****)**
**hydrolysis time (1 – 2 h)**
**acid-to-substrate ratio (0.1 – 0.5 mol/g)**

**Hydrolysis (for nanocrystals):**

**Extraction, Bleaching:**

**Dewax- Soxhlet**
**Mill **
**Alkali solution**
**Sodium chlorite**
**homogenize**

**Notes:**
20g in 400mkl toluene/200ml ethanol 6h @115-118c

## Bacterial Cellulose

***Acetobacter xylinum***
**Ribbons: rectangular cross-section of 50 x 0.8 nm**

## Apple Pomace /Cellulose XRD 

- As received:
- After bleaching, dispersion and re-drying

- 2******(deg)**

- I

- Cellulose I
- Size from
- Line broadening
- ~ 3 nm

## Are Parenchymal Celluloses Unusual?? 

- Dinand *et al., Cellulose ***9: **7–18, 2002.

- After 10% NaOH

- After 9% NaOH

- After 12% NaOH

- The sudden and essentially complete disappearance of microfibril structure is dramatically different from the gradual loss of microfibril size found in secondary wall mercerization

## CPMG

**n and d2 are variables and act as a T****2**** filter which allows the selective removal of signals associated with short T****2**** values (rigid components, crystal interior).**

## HR vs CP MAS NMR 

**HR vs CP MAS NMR **

## Parenchyma Fibers Have Pectin Rich Surfaces

- No evidence of methylation in CP/MAS

- 1H  CPMG HR/MAS NMR

- 13C CP/MAS NMR

- Raw apple pomace  Purified Cellulose

- Methyl groups (pectin) reside on the mobile surface seen by HR/MAS, not in the interior.

- n=10,
- d2=1500 s

- 1 ms contact

## Possible interactions at the filler matrix interface

## Dynamic Mechanical Analysis

- Different Reinforcing Mechanisms ????

## Scale Up

- June 2004: Purchased a 22 l
-  reactor to make nanoparticles
-  in larger quantities
- July 2004: First run
- 65% H2SO4 @ 40° C for 2h
- 400 gm wood pulp
- Final yield = 280 g (70% conversion)

**Problems / Challenges**
- Separation of particles from acid
- Acid recycling?
- Minimizing   reaggregation
- TEBOL(t-BuOH) ppt

**What’s Ahead**

- Reactive Extrusion - Can we improve the association by covalent links from particles matrix molecules?

- Biodegradability Plastic (GreenPla®???)
-     - Currently review ASTM and other standards.

** ****? ? ? ?**

## Conclusions

- Cellulose Nanoparticles can be made from almost any kind of biomass,
- The properties of the particles may vary with source due to species dependent differences in mean particle size,
- Scale up of our preps, now in progress, will permit more widespread testing,
- New techniques are needed to characterize surface chemistry and interactions,
- Reactive extrusion may provide a route to stronger composites. (speculation at this point),
- An acid free or reduced process may come from treating the nanoparticles as a coproduct of ethanol production from biomass.

## Acknowledgements

**Funding  **
**Eastman Chemical Co  **
** ****XEROX Foundation**
**USDA NRI and McIntire Stennis  **
**and **
**the EPA which is enabling  continuation of this work**

**Time, Effort, Ideas**
** ****Dr. Deepanjan **
**        ****Bhattacharya,**
**Prof. Avik Chatterjee,**
**Mr. Chad Denton,**
**Mr. Jake Goodrich,**
**Ms. Hoa Nguyen**
**Prof. Maren Grunert Roman,  **
**Dr. Qing Sun,**
**Prof. Arthur Stipanovic,**
**Ms. Yae Takahashi**

## Edwin C. Jahn Chemistry

**Edwin C. Jahn Chemistry**
**Laboratory**

**www.esf.edu/cellulose**

***Cellulose Research Institute***

**Notes:**
Jahn Lab