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Nanoporous materials
1 Introduction
Porous materials are like music: the gaps are as important as the filled-in bits. The presence
of pores (holes) in a material can render itself all sorts of useful properties that the
corresponding bulk material would not have. The definition of pore size according to the
International Union of Pure and Applied Chemistry (IUPAC) is that micropores are smaller
than 2 nm in diameter, mesopores 2 to 50 nm and macropores larger than 50 nm. However
this definition is somewhat in conflict with the definition of nanoscale objects. Nanoporous
materials are a subset of porous materials, typically having large porosities (greater than 0.4),
and pore diameters between 1- 100 nm. In the field of chemical functional porous materials,
it is better to use the term "nanoporous" consistently to refer to this class of porous materials
having diameters between 1 and 100 nm. For most functional applications, pore sizes
normally do not exceed 100 nm anyway.
Introducing porosity in to a nanostructure material can alter some of its properties
significantly. In general, a porous material has a porosity volume fraction between 20 to 95%.
Depending on the connectivity of the pores, these materials can further subdivided into open
pore and closed pore materials. Open pore- Pores are interlinked with each other spreading
from the interior of the material to its surface. Closed pore- Pores are isolated from each
other. Open porous materials have their potential applications in various fields like
adsorption, catalysis etc. Closed porous materials are used for structural and thermal
insulating materials.
Nanoporous materials contain pores having a volume fraction more than 40% and the pore
size varies from 1 to 100 nm. Because of high volume fraction of pores, manoporous
materials exhibit low density compared to that of the parent material, hence they are also
referred as Nanofoams. Metallic nanofoams inherit the metallic character of their parent
metal such as high thermal and electrical conductivity, ductility, strength etc. along with
display properties due to high surface area to volume ratio and strength to density ratio.
SEM image showing nanoprous Gold after dealloying Ag from Au26%Ag74% (at. %)
The ligament diameter and pore size decreases with its corresponding applied dealloying
potential.
Mean-field phase diagram for conformationally symmetric diblock melts. Phase are
Lamellar (L), Gyroid (G and G), Cylindrical (C and C) and Spherical (S and S).
Dashed lines denote extrapolated phase boundaries, and the dot denotes the mean-field
critical point. Red color represents A monomer and Black represents B monomer
The well-known thermodynamically stable ordered structures of block copolymers are body
centered cubic spheres, hexagonal cylinders and bicontinuous or double Gyroid structure. In
contrast to all other phases gyroid structure has some superior properties as listed below:
(i) both the polymer phases are continuous throughout the entire domain, and
(ii) extremely high specific surface area can be obtained.
Obtaining a gyroid structure from a system of block copolymer comprising of gyroid phase
consists of three sequential processes. This process is known as template directed synthesis.
This procedure is aimed at selective removal of the Gyroid phase without affecting
the polymer which comprises the matrix phase.
The process to be employed for getting a successful removal of the gyroid phase
depends on the chemical nature of both the polymers which comprise the block
copolymer.
For metal gyroid there are two most commonly used technologies: electrochemical
and electroless plating.
In case of electrochemical plating an external current is applied across the two
opposite free surfaces.
In case of electroless plating, the template is immersed in an electroless plating bath.
Metal deposition in such process is carried out by autocatalytic method. This process
certainly does not require any external current source.
After successful replication of the metal gyroid the polymer template is removed by
any of the various processes available, such as dissolution, UV degradation, pyrolysis
etc.