Green Manufacturing

Cellulosic nanocrystals from biomass waste for

thermoplastics for automotive applications

Student: Alexandru RISTEA

Master: IAMD I
 Table of Contents
1.Introduction

2.About CNCs
2.1 Core properties
2.2 Health and Safety
2.3 Sustainability
3. Processing of Cellulose Nanocrystals
4. Properties of CNCs
5. Applications of CNCs
6. Conclusion
1.Introduction

Green generally refers to materials, technologies, and products that

have less impact on the environment and/or are less detrimental to human

health than traditional equivalents

Green Manufacturing : the methods of manufacturing that minimize

waste & pollution and conserve resources. The review of literature on Green

manufacturing gives different Green designs based on environment

management system, energy conservation, development of cleaner

products, waste and pollution reduction. The literature is also available that

advocate green manufacturing as an instrument for sustainable

infrastructure. New concepts like green accounting are emerging that reflect

the true welfare by incorporating the cost of ecological damages and

resource depletion.

The cases of Indian and foreign industries covered under the paper, unveil some

new aspects like green supply chain and value chain transition as in corrugated

cardboard industry, role of public policy in commercialization of green technology as

observed in US wind and gas turbine projects. The cases of varied approaches to

green manufacturing with conventional objectives of cost reduction, resource

conservation and pollution control have been covered from different chemical and

automobile sectors. The extension of green manufacturing to buildings and

architecture opens new avenues where green manufacturing can foray.

 2. About CNCs - Cellulosic nanocrystals from biomass waste for thermoplastics
for automotive applications

CNCs are produced from wood by-products like sawdust and woodchips, but are
stronger than carbon fiber and Kevlar. Not only that, but CNCs are significantly cheaper
to produce. The problem is that they swell with water, so you'd need some kind of stain,
paint, or other coat to keep them dry. Still, we dream about seeing more of this stuff.

Fig.1

CNC are not all made equal. The CNC produced by CelluForce is called
CelluForce NCCTM and has specific properties and are especially easy to disperse.
CelluForce NCCTM is the base material that CelluForce uses in all its products. This
base material can be modified and tailored to suit the specific needs in various
applications.

Fig. 2

Production and incorporation of cellulosic nanocrystals (also known as cellulose

whiskers) derived from several sources such as pineapple, curaua, banana and coir into
thermoplastics matrix composites for automotive applications. They described the work,
which could lead to stronger, lighter, and more sustainable materials for cars and other
products, at the 241st National Meeting & Exposition of the American Chemical Society
(ACS) in Anaheim.

Cellulose nanocrystals are the crystalline domains of cellulosic sources. They have
the potential to improve, among others, the mechanical, optical, and dielectric properties
of these polymeric matrices, and have been of significant research interest for a number
of years.

Some of these nano-cellulose fibers are almost as stiff as Kevlar, but unlike Kevlar
and other traditional plastics, which are made from petroleum or natural gas, nano-
cellulose fibers are completely renewable

The properties of these plastics are incredible. They are light, but very strong
30% lighter and 3-to-4 times stronger. We believe that a lot of car parts, including
dashboards, bumpers, side panels, will be made of nano-sized fruit fibers in the future.
For one thing, they will help reduce the weight of cars and that will improve fuel
economy
 So far, focusing on replacing automotive plastics. But in the future, the industry
may be able to replace steel and aluminum automotive parts using these plant-based
nanocellulose materials

Besides weight reduction, nano-cellulose reinforced plastics have mechanical

advantages over conventional automotive plastics, Leo added. These include greater
resistance to damage from heat, spilled gasoline, water, and oxygen. With automobile
manufacturers already testing nano-cellulose-reinforced plastics with promising results,
he predicted they would be used within two years.

Cellulose is the main material that makes up the wood in trees and other parts of
plants. Its ordinary-size fibers have been used for centuries to make paper, extracted
from wood that is ground up and processed. In more recent years, scientists have
discovered that intensive processing of wood releases ultra-small, or nano cellulose
fibers, so tiny that 50,000 could fit inside across the width of a single strand of human
hair. Like fibers made from glass, carbon, and other materials, nano-cellulose fibers can
be added to raw material used to make plastics, producing reinforced plastics that are
stronger and more durable.

Leo said that pineapple leaves and stems, rather than wood, may be the most
promising source for nano-cellulose. Another is curaua, a plant related to pineapple that
is cultivated in South America. Other good sources include bananas; coir fibers found in
coconut shells; typha, or cattails; sisal fibers produced from the agave plant; and fique,
another plant related to pineapples. It takes just one pound of nano-cellulose to produce
100 pounds of super-strong, lightweight plastic, the scientists said.

Similar plastics also show promise for future use in medical applications, such as
replacement materials for artificial heart valves, artificial ligaments, and hip joints, Leo
and colleagues said.

2.1 Core properties

The core properties of CelluForce NCCTM allows its use in diverse applications
leading to new or improved products and processes. The creativity and vision of
CelluForce's dedicated technical staff and clients has led to innovations in various
industrial sectors.

The core properties that can be used to improve products are as follows:
 Self-assembles

The crystals that comprise CelluForce NCCTM interact with one another based on their
size, charge and shape. Since nanoparticles are at a scale where they are in constant
motion, the resulting energy allows the particles to self-organise.

Liquid crystals
Due to the CelluForce NCCTM crystals spindle shape, they can form liquid crystals: a
state where there are domains of order within a fluid. As the fluid is concentrated, the
spindles self-orient and form layers of crystals where each layer is oriented in the same
direction. At a particular concentration, there is a phase separation into a phase where
the domains exist and a phase where they do not. As the fluid is further concentrated,
more of the fluid becomes organised until a film with only an ordered structure remains
on a given surface.

Packing
This ordered structure creates a hard, smooth and tightly packed film. The packing is
particularly tight for CelluForce NCCTM because the crystals contain a twist, allowing
the spindles to interlock. Due to the chirality of CelluForce NCCTM, the twists in each
crystal are in the same direction, resulting in even more effective packing

Stronic

CelluForce NCCTM is an inherently strong material because of its high crystallinity.

Each crystal has a stiffness that is of the order of 150 GPa and a tensile strength that is
of the order of 10 GPa. These numbers are comparable to those of Kevlar as well as
hard metals and their alloys. Many crystals are also inherently hard and incompressible
and CNC is not an exception.

The crystals of CNC, however, are nanometric and are not strongly interconnected
except in the structures laid down by nature from which they are isolated or when they
are aggregated or incorporated into matrices and films.
 The challenge is to use CNC to impart greater stiffness, tensile strength, hardness
and incompressibility to materials and therefore harness the power of what nature has
provided. This challenge, which is now being met in various ways, is to ensure that the
nanometric particles can be controlled in the way that they are distributed and that they
are compatible with matrices to which they are part or to which they adhere.

Thixotropic

Fluids containing CelluForce NCCTM are shear thinning, meaning they decrease
in viscosity with the application of shear. This property provides the basis for several
types of application. The degree of shear thinning is dependent on the rigidity, charge
and shape of the crystal. These parameters amplify the effect of a small amount of
CelluForce NCCTM by changing the effective particle diameter and can be affected and
tuned by the interplay of other components of the system.

Methods of preparation that affect the rigidity, charge and shape of the crystal will
also affect the rheology. For example, using methods that result in a carboxylated or
uncharged crystal product will not yield the same properties as CelluForce NCCTM. The
ongoing uniformity and purity of the product is also critical to obtaining consistent
rheological properties. By the nature of the process used to make it, CelluForce NCCTM
is both uniform and contaminant-free.

Active

Hydroxyl Groups

Like all cellulose, CelluForce NCCTM is comprised of a linear, long-chain glucose

polymer that is rich in oxygen, particularly hydroxyl groups. These hydroxyl groups
develop the hydrogen bonds that give the CNC its inherent strength while providing a
reactive surface of hydroxyl groups on two of the crystals facets. Though not all of the
hydroxyl groups are equally reactive and accessible, they adequately allow a multitude
of reactions. The hydroxyl groups are also the reason why CNC, unlike carbon
nanotubes and other materials, is inherently hydrophilic.

Acidic Groups

CelluForce NCCTM surface is also comprised of acidic groups attached to its

surface which allows for reaction with a variety of bases. Though many traditional
products (such as cellulose acetate, carboxymethylcellulose and cellulose ethers) take
advantage of the reactivity of cellulose, CelluForce NCCTM allows for the bonding of a
variety of hydrophobic structures. This makes the material compatible with a wide range
of solvents and polymer matrices.

Photonic

Structural colour

CelluForce NCCTM forms solids with structural colour. As the ordered CelluForce
NCCTM fluid becomes a solid, its colour is created by the interaction of light with the
layered structures that are developed. Many animals and plants use structural colour
rather than pigments or dyes to create vibrant, iridescent and durable displays.

Layers
As the layers develop, the charge that is on the crystal surfaces keeps the layers
separated. The chiral twist in the crystals that make up a given layer results in a helical
structure of layers wherein the orientation of the crystals in each layer is offset. This
helix has periodic layers of crystals with the same orientation.

Periodicity
The periodicity of CelluForce NCCTM is of the order of the wavelength of light, which in
turn is reflected and amplified through constructive interference. Because only one
helical twist exists in the layers, the reflected light is polarised. The layer periodicity can
be tuned by the addition of salts, by ultrasound and by the strength of the magnetic
field. The observed colour is also affected by the viewing angle. Under polarised light,
even the dynamic, layered structures within the fluids can be observed as birefringent
patterns.

The only reinforcing material that is stronger than cellulose nanocrystals is a carbon
nanotube, which costs about 100 times as much

2.1 Health and Safety

Because CelluForce NCCTM can be added to so many products, CelluForce is
continuously striving to ensure its safe use. Though some questioning regarding
nanoparticles is understandable, Cellulose NanoCrystals, unlike many other
nanomaterials, are of natural origin.

Numerous human health and safety tests have shown that CelluForce NCCTM is
benign. For example:

Upon evaluation of its potential acute toxicity to mammals, three separate tests on
oral, inhalation and dermal effects determined that CelluForce NCCTM falls into the
least toxic classification in the Globally Harmonized System of Classification and
Labelling of Chemicals.

An array of in vitro and in vivo test studies on our products potential to cause
deleterious cellular effects and whole body, sublethal effects revealed CelluForce
NCCTM to be within acceptable limits.
 As a result, CelluForce NCCTM has been added to Canadas Domestic Substance
List allowing its unrestricted production and sale. CelluForce NCCTM has also received
regulatory clearance for use in US and Europe.

2.3 Sustainability
CelluForce NCCTM is committed to an active and responsible approach to
sustainability that:

Lowers the total environmental impact of our activities

Minimizes our environmental footprint

Guides the designs of our plant, manufacturing of our products and

operation of our facilities

Finally, in an ecotoxicological characterization conducted by CelluForce, tests on

nine aquatic species show CelluForce NCCTM to have low toxicity potential and low
environmental risk to aquatic life.

3. Processing of Cellulose Nanocrystals

Although there are many variants of the process to isolate CNCs from a given
cellulose source material, this process generally occurs in two primary stages. The first
stage is a purification of the source material (plants, tunicates, algae, bacteria, etc.) to
remove most of the non-cellulose components in the biomass. These include lignin,
hemicellulose, fats and waxes, proteins, and inorganic contaminants. The second stage
uses an acid hydrolysis process to deconstruct the purified cellulose material into its
crystalline components. This is accomplished by preferentially removing the amorphous
regions of the cellulose microfibrils [3,8]. The resulting whisker-like particles (320 nm
wide, 502000 nm long) are ~100% cellulose, are highly crystalline (62%90%,
depending on cellulose source material and measurement method), and have been
referred to in the literature as cellulose nanocrystals (CNCs), nanocrystalline cellulose
(NCC), and cellulose nanowhiskers (CNW) to name a few. The variations in CNC
characteristics are strongly linked to the cellulose source material and the acid
hydrolysis processing conditions Subsequent chemical treatments can be carried out to
alter
the CNC surface chemistry.
 CNCs are a particularly attractive nanoparticle because they have low
environmental, health, and safety risks, are inherently renewable, sustainable, and
carbonneutral like the sources from which they are extracted, and have the potential to
be processed in industrial-scale quantities at low cost.

4. Properties of CNCs

The important properties of CNCs can be described under three main categories,
which are briefly discussed as follows.

Mechanical properties

The limitations in measuring the mechanical properties of nanomaterials along

multiple axes have made the quantitative evaluation of the tensile modulus and strength
of CNC extremely challenging. In addition to this, different factors such as anisotropy,
defects in the nanocrystals, percentage crystallinity, dimensions of the samples, and so
on can also affect the results. Theoretical calculations and indirect experimental
measurements using atomic force microscopy (AFM), X-ray diffraction analysis, inelastic
X-ray scattering, Raman scattering, etc were used to calculate the elastic properties of
CNC.46 The theoretical tensile strength of CNCs was found to be in the range of 7.5
7.7 GPa, which is much more than that of steel wire and Kevlar. In another study, the
elastic modulus of the CNC obtained from tunicates was determined using AFM,
whereby the AFM tip was used to perform a three-point bending test. The elastic moduli
of CNCs were found to be ~150 GPa.47 Using AFM, the transverse elastic modulus of
CNCs was also determined by comparing the experimental forcedistance curves with
three-dimensional finite elemental calculations. This measurement proved that the
transverse modulus of an individual CNC lies in the range of 1850 GPa. The
deformation micromechanics analysis of tunicate cellulose whiskers using Raman
spectroscopy proved that the calculated modulus of tunicate CNC is ~143 GPa.

Liquid crystalline nature of CNCs

Under suitable conditions and at critical concentrations, all asymmetric rod-like or

plate-like particles spontaneously form ordered structures, leading to the formation of a
nematic phase. Rod-like CNCs, when dispersed in water, self-align to form chiral
nematic phases with liquid crystalline properties. Their stiffness, aspect ratios, and the
ability to align under certain conditions make them ideal for exhibiting liquid crystalline
behavior. However, cellulose crystallites are known to have a helical twist down the long
axis, similar to a screw, which can either lead to a chiral nematic or a cholesteric phase
of stacked planes aligned along a perpendicular axis depending on the concentration. 46
Various factors such as size, charge, shape, dispersity, electrolyte, and external stimuli
can also affect the liquid crystallinity of CNC. The liquid crystallinity of nanocrystals
coupled with the birefringent nature leads to interesting optical phenomena. The type of
acid used for hydrolysis can also affect the liquid crystalline nature. CNC obtained by
sulfuric acid hydrolysis often possesses a negatively charged surface, which promotes
uniform dispersion in water due to electrostatic repulsions. Even though the interactions
between nanocrystals are strong, highly sulfonated CNC is readily dispersible and this
leads to the development of lyotropic behavior. Sulfuric acid- and phosphoric acid-
derived CNCs normally give chiral nematic structure, whereas hydrochloric acid-derived
CNCs with postreaction sulfonation give rise to a birefringent glassy phase.

Rheological properties

Rheological parameters of CNC are influenced by properties such as liquid

crystallinity, ordering, and gelation properties. Dilute CNC suspensions show shear
thinning behavior, which shows concentration dependence at low rates. At higher
concentrations, in which the suspensions are lyotropic, they exhibit anomalous
behavior. The main reason for such behavior is that the rod-shaped nanocrystals tend to
align at a critical shear rate. As the shear rate reaches a critical point, the chirality of the
CNC suspension breaks down in favor of a simple nematic structure. In addition, the
relaxation time constant depends on the aspect ratio, and CNCs with higher aspect
ratios stay aligned for longer times even after shear. The type of acid used for hydrolysis
can also influence the rheological properties of CNC suspensions. Sulfuric acid-treated
crystals show some shear thinning that is independent of time, while HCl-derived
crystals show much higher shear thinning behavior, anti-thixotropy at lower
concentrations and thixotropy at higher concentrations.
5. Applications of CNCs
CNC is a suitable nanomaterial for a wide range of applications, such as enzyme
immobilization, synthesis of antimicrobial and medical materials, green catalysis,
biosensing, synthesis of drug carrier in therapeutic and diagnostic medicine, etc. These
nanomaterials offer several potential advantages as drug delivery excipients due to their
properties such as smaller size, hydrophilicity, biocompatibility, etc. Due to their very
large surface area and possibility of acquiring negative charge during hydrolysis, large
quantities of drugs can be bound to the surface of these materials with the potential for
optimal control of dosing. In one such report, CNCs prepared from softwood were used
to bind ionizable drugs such as tetracycline and doxorubicin, which could be released
rapidly over a 1-day period. The abundant surface hydroxyl groups present in
nanocrystals provide sites for surface modification with a range of chemical groups.
Surface modification can be used to modulate the loading and release of drugs that do
not normally bind to cellulose, such as nonionized or hydrophobic drugs. CNC-based
aerogels are also receiving growing interest in biomedical and pharmaceutical
applications due to their open pore structure and high surface area, which can provide
enhanced drug bioavailability and better drug-loading capacity. Highly porous
nanocellulose aerogel scaffolds were reported to attain sustained drug release, which
also revealed new possibilities as carriers for controlled drug delivery.

Its properties and many potential forms allow many uses, including:

Manufacturing of improved construction products

Recyclable interior and structural components for the transportation industry

Innovative bioplastics

Reinforced composites

Films for optical switching

Biocomposites for bone replacement

Paint additives

Electrically conductive membranes

 Electronic paper printers

Encapsulated quantum dots for crystalline semiconductors

The utilization of CNCs for various applications can be of two broad types: one
type involves the use of functionalized or nonfunctionalized as-synthesized CNC, and
the other one involves the use of polymer nanocomposites wherein CNC acts as a
reinforcing agent. As a result of their distinctive properties, as-synthesized CNCs have
the potential for being used in various and diverse applications ranging from products
such as nanopaper, barrier films, and pH sensors, to stabilization of oil/water interfaces,
to production of Pickering emulsions with outstanding stability, etc, but CNC-containing
polymer nanocomposites has many more applications.

A polymer nanocomposite is a multiphase material wherein the polymer phase is

reinforced with a nanomaterial. These polymer nanocomposites exhibit unique
properties because of their nanometric size and the increased surface area of the
reinforcing material. CNC is used as the load-bearing constituent in many polymer
nanocomposite systems as it can produce significant improvements in mechanical
properties even at very low volume fractions. Furthermore, its high aspect ratio, good
dispersion in hydrophilic systems, and the capability to form percolated network-type
architecture within the polymer matrix make it a widely preferred reinforcing component.
In the area of polymer nanocomposites, CNCs are also used as model nanofillers with a
defined morphology to impart sufficient strength and modulus. Both natural and
synthetic polymers are used for the fabrication of nanocomposites. Several natural
polymers, such as starch, chitosan, natural rubber, cellulose acetate butyrate,
carboxymethyl cellulose, hydroxypropyl methylcellulose, gelatin, and soy protein, are
used in the preparation of nano-composites. Similarly, several synthetic polymers such
as polyvinyl alcohol (PVA), polyvinyl chloride, polyethylene, polycaprolactone,
polypropylene, and polyurethane are also used.

The main challenge in achieving excellent performance lies in attaining

homogeneous dispersion of nanocrystals within the polymer matrix and a good matrix
filler interaction. Good dispersibility of the CNCs in the polymer matrix is a prerequisite
to make polymer nanocomposites with better properties, as a nonhomogeneous
dispersion of the filler in the polymer matrix decreases the final mechanical properties of
the nanocomposite material. CNCs can form stable colloidal dispersions in water and
hence they are best suited for water-soluble or water-dispersible polymers such as
latexes. However, stable cellulose nanoparticle dispersions in nonpolar solvents can
also be obtained by using either surfactants or surface chemical grafting. Among these,
the use of the polymer grafting method is better in some cases due to the presence of
the covalent linkage between the compatibilizer and the nanocrystal. In addition, if the
grafted chains and the matrix are the same, better compatibilization can be obtained
due to the formation of a co-continuous phase.

With the help of the chemical grafting method, various functional molecules such
as fluorescent molecules, DNA, etc can also be attached on the surface of CNCs, which
can be used for anchoring in a biological environment. It is also possible to disperse
cellulose whiskers in an organic solvent without either addition of a surfactant or any
chemical modification. Moreover, in some cases, better dispersion of CNCs leads to the
formation of a percolated network of nanocrystals within the polymer matrix, which also
contributes to enhancement in the properties of polymer nanocomposites.

These types of nanocomposites are used for making biomimetic foams, toughened
paper, flexible panels for flat panel displays, water repellents, and high-security papers.
They are also useful for various biomedical applications such as wound healing
patches, tissue engineering scaffolds, and hydrogels for clinical and pharmacological
applications, etc. Considering the biocompatibility of CNC and the possibility of chemical
modifications such as fluorescent labeling, CNCs are potentially useful in the field of
biomedical applications such as biosensors, bioprobes, fluorescence bioassays,
bioimaging applications, and so on. Fluorescently labeled CNCs enable the use of
fluorescence techniques to study the interaction between CNCs and living cells in
vivo.91 CNCs are also capable of forming highly functional nanocomposites for
applications such as ultrathin film-coating materials. CNC can also be used for
stabilizing nanoparticles of specific functionality for specific applications. CNC-
containing polymer nanocomposites is also used for developing membranes, fibers,
textiles, batteries, supercapacitors, electroactive polymers, and sensors and actuators
that utilize electromechanical responses. One future area of application wherein CNC-
containing polymer nanocomposites can make an impact is in the field of biodegradable
packaging materials. The incorporation of CNC can significantly improve the mechanical
performance, thermal stability, and barrier and optical properties due to its improved
crystallinity and better interfacial interaction. Biodegradable nanocomposite films with
superior properties can also find their applications in food and biomedical packaging
areas, in which lower permeability to moisture, gases, aroma, and oil are very much
needed. In one research investigation, PVA-based barrier membranes containing
different amounts of CNCs have been reported. These membranes containing up to 10
weight percentage of CNCs have been found to reduce the water vapor transmission
rate. The presence of highly crystalline nanocrystals can increase the tortuosity of water
vapor within the polymer, leading to a slower diffusion process and, hence, lower
permeability. The barrier properties are enhanced if the filler is less permeable and has
good dispersion in the matrix along with a high aspect ratio. However, many scientific
and technological challenges have to be addressed in several areas, such as optimizing
suitable processing technologies for reducing the production cost, establishing the
compatibility between products and packaging materials, meeting several packaging
legislations, etc, before achieving a truly biodegradable packaging material that satisfies
both industry requirements and consumer expectations.

6. Conclusion
CNC is unique among a range of other nanostructured materials due to its benefits such as being a
renewable, sustainable, nontoxic, and biocompatible nanomaterial. Due to its nanometric dimensions,
large aspect ratio, and excellent mechanical and chemical properties, CNC has many potential
applications in many areas, including materials science, electronics, and medicine. The emerging
industrial extraction processes to obtain CNC in large quantities need to be optimized to achieve greater
yield and quality. So far, most of the research has focused on characterizing the morphological,
mechanical, optical, and liquid crystalline properties of CNC, but exploring various surface modification
processes to manipulate the functionality of CNC without affecting its inherent properties will be the
main focus of future research. This approach will make CNC attractive for use in a wide range of
industrial applications, such as high-performance biodegradable material science, electronics,
biomedical engineering, drug delivery, catalysis, etc. Innovations in this area may lead to versatile
nanomaterials with improved properties. In polymer nanocomposite systems, attaining uniform
dispersion and distribution of CNC in a polymer matrix is still a challenging issue, as aggregation or
agglomeration is commonly encountered. A tailor-made chemical modification process is necessary to
incorporate CNC into different polymer matrix systems effectively. Innovations in nanotechnology related
to renewable nanomaterials such as CNC are anticipated to provide technologically advanced products
that are not harmful to the environment.
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