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Dharmapadmi Pradnya Kasilani - Resume 3 Nanomedicine 3 Ta 2022
Dharmapadmi Pradnya Kasilani - Resume 3 Nanomedicine 3 Ta 2022
195160100111028
Particle size
Particle science and technology deal with the production, characterization,
modification, handling, and utilization of a wide variety of particles in both dry
and wet conditions. Particles in general can be divided into two main categories,
porous and nonporous.
Porous material
The surface area depends more on the pore size. For example, a cube of
size 3cm x 3cm that has 6 surfaces, is divided into 27 cubes of size 1cm x 1cm
and each has 6 surfaces. There are 162 (6x27) surfaces after dividing into 27
cubes. The folds increase can be calculated by 162 : 54 = 3 (54 is the result of
multiplying the surface area of one side of a large cube 9 with the number of
faces of cube 6).
Absorption desorption isotherms can be used to characterize the physical
properties of solid materials, especially those used as an adsorbent. Some main
properties of porous solid material are porosity, pore structure (pore volume,
pore size, and pore size distribution and shapes), and surface area (specific
surface area, internal and external)
Porosity in the Greek word 'poros' means passage. Porosity is a pore acting
as a passage between the external and the internal surface of a solid, allowing
material such as gases and vapors to pass into, through, or out of the solid.
Almost all adsorbents for catalysis, purification, or separation possess porosity,
which enhanced surface area.
There are many types of pores:
• The open pore is a pore that is connected to the external surface of a solid
and allows the passage of an adsorbate through the solid.
• The closed pore is a void within the solid that is not connected to the
external surface and hence is isolated
• Transport pores are connecting different parts of the external surface of
the solid to the inner microporosity
• Blind pores are connected to transport pores but do not lead to any other
pore or surface
• There are other types of pores including micropores, ink bottle pores,
macropores, mesopores, pore interconnectivity/tortuosity, cylindrical
pores, slit pores, and wedge pores.
There are internal surfaces and external surfaces. The internal surface
composed of the area which surrounds the closed pores, fissures, and cracks,
penetrates deeply into the interior of the adsorbent. External surface protrusions
and superficial cracks. The total surface is an internal surface (adsorptive
properties) and an external surface. The external surface area has functional
groups playing other roles.
There are three classes of pores, micropores (<2nm), mesopores (2-50nm),
and macropores (>50nm). Micropores divide into three classes, ultramicropores
(0.5nm), micropores (0.5-1.4nm), and supermicropores (1.4-2.0nm). The
distribution of pores size may be described in terms of micro, meso, and
macropores but are not necessarily tri-modal, exhibiting three peaks of varying
ratios. A complete distribution is not always present in a material and some
samples may exhibit only some types of porosity.
Adsorption isotherms
Adsorption isotherms allow property comparisons of solid adsorbents,
provide information about the physical properties of the adsorbent, and indicate
the interaction with the adsorbate in the system, including assessment of the
surface chemistry and fundamentals involved in the adsorption process;
estimates of the surface area, pore volume, and size distribution; and efficiency
profiles for a material used in industrial processes.
All adsorption isotherms should fit at least one, or at least a combination
of two or more, of 6 types (classified by Brunauer, Deming, Deming, and Teller):
• Type I is microporous (d≤20Å)
• Type II is nonporous or microporous (d>500Å), multilayer adsorption
• Type III is no monolayer formed
• Type IV is mesoporous, silica-alumina
• Type V is mesoporous with weak adsorbate-adsorbent interaction
• Type VI is long-range solid gas interactions
There are four adsorption phenomena, adsorbent, adsorbate, adsorption,
and coverage. The adsorbent is the solid surface onto which adsorption can
occur, the substrate is also occasionally referred to as the substrate. Adsorbate
is the general term for the atomic or molecular species, which are adsorbed (or
are capable of being adsorbed) onto the substrate. Adsorption is the process in
which a molecule becomes adsorbed onto a surface of another phase (to be
distinguished from absorption which is used when describing uptake into the
bulk of a solid or liquid phase). Coverage is a measure of the extent of adsorption
of a species onto a surface, usually denoted by the lowercase Greek "θ".
There are two principal modes of adsorption of molecules on the surface,
including physical adsorption (physisorption) and chemical adsorption
(chemisorption). The only bonding of physisorption is by weak Van der Waals
(type forces). There is no significant redistribution of electron density in either
the molecule or at the substrate surface. Chemisorption is a chemical bond,
involving the rearrangement of electron density, that is formed between the
adsorbate and substrate. The bond may lie between the extremes of complete
ionic or complete covalent character.
Quantitative analysis of the adsorption process is not always easy to tell
whether the gas is inside the solid or merely at the surface because most
practical absorbents are very porous bodies with large internal surfaces. It is not
possible to determine the surface areas of such materials by optical or electron
microscopy because of the size and complexity of the pores and channels of the
material. The gas adsorption can be used to determine the accessible surface
area of most absorbents. The extent of surface coverage is normally expressed
as the fraction coverage, where θ is the result of dividing the number of
adsorption sites occupied by the number of adsorption sites available. The
fractional coverage is often expressed in terms of the volume of adsorbate
adsorbed. Vm is the volume of adsorbate corresponding to complete monolayer
coverage. The rate of adsorption, dθ/dt, is the rate of change of surface coverage
and can be determined by observing the change of fractional coverage with time.
Relative pressure (P/P0) is a convenient way to study adsorption isotherm,
a scale from 0 to 1 (completely saturated). The gas adsorption mechanism
occurred at specific P/P0. The free gas and the adsorbed gas are in dynamic
equilibrium. The fractional coverage of the surface depends on the pressure of
the overlying gas. The variation of θ with pressure at a chosen temperature is
called the adsorption isotherm. For example, a plot amount of gas adsorbed on
the adsorbent or substrate equilibrated with the gas pressure at constant
temperature (iso = same).
a. The Langmuir isotherm
Based on the assumptions, adsorption cannot proceed beyond
monolayer coverage, all sites are equivalent and the surface is uniform,
and the ability of a monocule to adsorb at a given site is independent of
the occupation of neighboring sites.
b. The BET isotherm
The BET theory was developed by Stephen Brunauer, Paul Emmett,
and Edward Teller in 1938. The first letter of each publisher's surname
was taken to name this theory. The BET theory was an extension of the
Langmuir theory, developed by Irving Langmuir in 1916.
The Langmuir theory relates the monolayer adsorption of gas
molecules, also called adsorbates, onto a solid surface to the gas pressure
of a medium above the solid surface at a fixed temperature to 2.3.1, where
θ is the fractional cover of the surface, P is the gas pressure and α is a
constant.
The Langmuir theory has a few flaws that are addressed by the BET
theory. The BET theory extends the Langmuir theory to multilayer
adsorption with three additional assumptions: gas molecules will
physically adsorb on a solid in layers infinitely, the different adsorption
layers do not interact, and the theory can be applied to each layer.
Surface area
Surface area can be defined based on a model and assumptions. For
example, nitrogen gas can be used as a probe to determine the surface area.
Several atoms or gas of a probe covered a layer (monolayer) (Vm) on a surface of
an adsorbent with mass m, and if the cross-section or surface of the probe is A.
Hysteresis classification by IUPAC, including:
• Hysteresis loop type H1
The adsorption and desorption branches are almost vertical and
approximately parallel. Characteristic of porous materials consisting of
agglomerates or packing of uniform spheres and tidy, also characteristic
of materials with pores of cylindrical geometry with uniform pore size.
• Hysteresis loop type H2
General characteristic of materials with "bottleneck" pores or materials
with an interconnected network of pores also occurs in materials with
non-uniform size and shape. For example, is inorganic oxides.
• Hysteresis loop type H3
Characteristics of porous material consist of aggregates of plate-like
particles that give rise to slit-shaped pores. For example, mesoporous
activated carbon.
Nonporous materials
Characterizations of nonporous materials are depending on techniques
and theories such as size (particle size distribution), surface area, density
(absolute, apparent, bulk, etc.), shape, volume, etc.
Sampling is subjected to errors due to the bias of the operator cult to
obtain a sample that represented the whole population (i.e. representative).
Sampling has to be done a few times and statistical analysis has to be made. The
properties of particles are divided into three basic important, shape, size (volume,
surface area, and diameter), and density. Composition is density (for bulk or
particles), conductivity (for solid particles), and Chemical properties. The shape
is a sphere, cubic, and nonspecific shape (difficult to classify). The size is divided
into, surface area, surface area or volume, and rate of setting. Sphere-d is the
only 1d that can be used to explain the structure. Cubic-1 is the only 1d that
can be used to explain the structure. Cuboids- I, w, h is 1d to explain the
structure. No specific shape is difficult to describe.
The USP definitions of shape parameters are divided into acicular, flakes,
plate, lath, and equant. An acicular is a slender, needle-like particle of similar
width and thickness columnar long, thin particle with a width and thickness
that are greater than those of an acicular particle. Flake is a thin, flat particle of
similar length and width. A plate is a flat particle of similar length and width
but with greater thickness than flakes. Lath is a thin, blade-like particle. Equant
is particles of similar length, width, and thickness; both cubical and spherical
particles are included. In practice, the particle is not discrete usually
aggregated/agglomerated into more complex structures.
Degree of associations involve lamellar stacked plates, aggregate (mass of
adhered particles), agglomerate (fused or cemented particles), conglomerate
(mixture of two or more types of particles), spherulite (radial cluster), drusy), and
particle covered with tiny particles.
Particle conditions are edges, optical, and defects. Edges include angular,
rounded, smooth, sharp, and fractured. Optical includes color, transparent,
translucent, and opaque. Defects include occlusions and inclusions.
Surface characteristics involve cracked (partial split, break, or fissure),
smooth (free of irregularities, roughness, or projections), porous (having
openings or passageways), rough (bumpy, uneven, not smooth), and pitted (small
indentations). There are three basic important properties of particle size, shape,
and density.
Shape factor
Spherecity (Φ) is the surface area of a sphere having the same volume as
the particle/s.a. of the particle. Φs={d(v)/d(s)}2, with powdered material is 0,6<
Φs<0,8 and polished sphere is Φs≤0,95. O(s)= 6V(p)/d(p)S(p), with dp as eq
diameter of the sphere, Sp is sa for a particle, and Vp is the volume of a particle.
The shape of particles controlled the flowability, compactibility (powdered
materials), interaction with fluid, and absorpability (for pigments).