Naturally Occurring Nanomaterials

Sarah Cooper
NaturalNano, Inc.

“Nanomaterials” is an interesting moniker. “Materials” is self explanatory, but the

“Nano” prefix is open to interpretation, particularly where funding is at stake. Nano can
refer to the fundamental particle size, to the distance across which phenomena occur, or
to the scale of a fundamental feature such as grain boundary.

Since we’re engineers and not philosophers, let’s start by setting some ground rules on
what constitutes nano in a real sense. As most of you know, Nano refers to the 10-9 scale;
a nanometer is 10-9 meters, which is approximately one millionth of a human hair or the
width of three atoms. Generally, Nano is only an economically significant term in the
cases where the nanoscale is a critical point at which novel unique properties arise.

Despite the increased excitement surrounding the nanoscale, nanomaterials have been
around for millions of years. Mother Nature is the penultimate nanomanufacturer.
The recent attention is a result of advancements in characterization tools and techniques
enabling manipulation and control of nanoscale goings on. As we’ve probed the nano-
universe, it’s become apparent that properties developed at the nanoscale are often quite
different from those at larger scales. For instance, the same aluminum foil that you might
use to wrap up leftovers, when broken down into nanoparticles, becomes a potential
alternative lightweight rocket fuel.

This isn’t a particularly surprising result when you consider that such a nanoparticle is
only ~50 atoms wide. At that scale there exists a greater ratio of surface atoms to internal
atoms. Surface atoms are higher energy and therefore have slightly different and in some
cases radically different properties from their internal neighbors. The properties of the
nano-particle are therefore dominated by the surface atoms rather than the internal atoms
at the nanoscale.

Man likes to think of himself as the great inventor of progress, but as is so often the case
Mother Nature beat us to the punch. At the most basic level, nature has created a
plethora of inorganic and organic nanomaterials in the forms of nanotubes, nanodots,
nanowires, and even nanomachines. From minerals that curl into nanotubes to protein
mechanical pumps, the variety is astounding.

Let’s take Halloysite clay nanotubes as an example. Halloysite is aluminosillicate clay

that forms as volcanic feldspars weather, a process that involves the intercalation of water
through the native bed dissolving the sulfur in the volcanic mass making for a highly
acidic environment. The acids dissolve a large part of the mineral content of the native
feldspar, eventually leaching out nearly everything except the silica and alumina content.
The process also opens a greater degree of free space within the initial bed. As the ore
moves closer to a pure aluminosillicate, the clay begins to arrange into a laminar structure
of alumina-silica bi-layers held together by an intercalated water layer. The Silica layer
is tetrahedrally bound, where as the alumina layer is octahedrally bound, producing a
lattice mismatch and resulting curling force that, given enough room to move, will curl
the laminar platelet structure into a tube, much like rolling up a burrito or a newspaper.
Nature’s manufacturing is Man’s benefit. Platelet nanoclays, such as the montmorillonite
and smectites sold by Southern Clay Mining Co. and Nanocor, have already found
commercial application in structural composites within Nylon 6 and others. Clay
nanotubes with easier processing provide property enhancement in-line with the best
platelet nanoclay fillers and include additional functionalities. NaturalNano is
developing technologies such as metal coated tubes for RF shielding coatings and
electrically conductive thin films, as well as tubes filled with active ingredients for
extended release, long lasting perfumes as an example.

In addition to inorganic nanostructures, nature provides a vast array of organic

nanoparticles as well. When bamboo is burnt it reveals a network of carbon nanothreads,
for which several Taiwanese companies have shown applications such as yarn in sports
wear, shoe pads, and other textiles. The nano-yarns in textiles improve thermal insulation
and moisture modulation, while maintaining ventilation. Mother Nature even created the
first carbon nanotube and the first buckyball (carbon fullerene) as an end product of the
combustion process of various fossil fuels. Chances are if you drive a diesel fueled car,
the scum on the inside of your tailpipe contains at least a few carbon nantubes. Mother
Nature’s production of well-ordered carbon structures may appear far from commercial
scale, but in fact there are groups exploring volcanic ash for large sources of naturally
occurring buckyballs.

In addition to combustion by-products, organic nanostructures form in petroleum and

natural gas deposits as diamondoids or nano-scale diamond structures. ChevronTexico,
Inc. spun out MolecularDiamond Technologies in 2002 to look into the commercial
applications of the diamondoids which had been stockpiled as a waste product.
Diamondoids, although originally a nanomaterial looking for an application, have been
investigated for use in optical films, polymerization monomers, pharmaceutical
development, and wear resistant coatings. With variety of diamondoid structures and
warehouses of material, commercial products are mainly a matter of time.

The combination of Nature’s production capacity with the unique functionalities of

nanomaterials makes for an exciting engineering opportunity in the design of products
and processes that can effectively take advantage the benefits of nanomaterials. The
application and opportunity space appears to be limited only by the 24 hours in a day.