Lecture 6

Surface Energy

• Interface
– boundary between 2 layers

protein adsorption to materials

blood coagulation/thrombosis due to material contact

cellular response to materials

• At the surface (interface) there are intermolecular forces and intramolecular

forces of attraction and repulsion.

Surface Electrical Properties

• surface may become charged by

– adsorption of ionic species present in sol’n or preferential adsorption
of OH-
– ionization of -COOH or -NH2 group
 Electric Double Layer

• it is a structure that appears on the surface of an object when it is placed into

a liquid.
• The DL refers to two parallel layers of charge surrounding the object.
• The first layer, the surface charge comprises ions adsorbed directly onto the
object due to chemical interactions.
• The second layer is composed of ions attracted to the surface charge via the
coulomb force, electrically screening the first layer.
• This second layer is loosely associated with the object, because it is made of
free ions which move in the fluid under the influence of electric attraction
and thermal motion .

Surface Energy and the Contact Angle


LV

SV SL
We denote the solid–vapor energy as , the solid–liquid interfacial energy as and the liquid–vapor
energy (i.e. the surface tension) as simply , we can write an equation that must be satisfied in equilibrium
(known as the Young Equation):
The contact angle can also be used to determine an interfacial energy (if other
interfacial energies are known). This equation can be rewritten as the Young-Dupre
equation:

where W is the adhesion energy per unit area of the solid

Critical Surface Tension, gc

The critical surface tension is the surface tension of a liquid that would
completely wet the solid of interest.

Lecture 7: Revision sheet and solved problems

Lecture 8: Mid Term Exam
Lecture 9
Surface Modification for Biomaterials Applications

The cellular response to the material should be evaluated by performing in vitro

and in vivo experiments.–Cell adhesion–Cell motility–Protein or enzyme
production–Gene expression–Cell death or toxicity
- Surface Modification Techniques
-Biological Surface Modification Techniques
-Surface Patterning Techniques
a-- Protein Adsorption
Factors affecting adsorption:
• Surface energy
• Surface hydrophobicity
• Surface charge
• Important Definitions:
• Hydrophobic: water fearing
• Hydrophilic: water loving
• Adsorption: adhesion to solid surface
• Absorption: penetration of molecules into bulk
Surface Tension
  Adding molecules that prevent adsorption is called steric
hindrance.
for example : polyethylene glycol (PEG) attaches to the surface
(hydrophobic) preventing protein adhesion
 Surface modification with no overcoat, and laser methods for surface
modification make surface locally attractive for adhesion of desired
species
Methods of surface coating: Plasma Discharge

Charged particles are attracted to the sample surface, which acts as the
cathode. Particles may be positive or negative ions, free radicals,
 electrons, atoms, molecules or photons. Often used to add OH or NH2
groups to surface as a precursor to further modification
Plasma Discharge
• Advantages:
– Coatings are conformal
– Free of voids/pinhole defects
– Easily prepared
– Sterile when removed from reactor
– Produce low amount of leachable substances
– Demonstrate good adhesion to substrate
– Allow unique film chemistries to be produced
– Easily characterized
• Disadvantages
– Chemistry within reactor may be undefined
– Equipment often expensive
– Uniform reaction within long, narrow pores may be difficult
– Care must be taken in sample preparation to prevent
contamination
Vapor Deposition: Physical (PVD)
Physical Vapor Deposition (PVD) may be from evaporation or
sputtering. Sometimes a plasma is used to create high energy species that
collide with target .
Vapor Deposition: Chemical (CVD)
In Chemical Vapor Deposition (CVD) a reactive gas is passed over the
substrate to be coated, inside of a heated, environmentally controlled
reaction chamber. In this case , CH4 gas is introduced to create a
diamond-like coating.
Physiochemical coatings
Physiochemical coatings are used to coat biomaterials with biologically
active molecules. These methods include solution coatings and Langmuir-
Blodgett films.
Coatings are amphiphilic, having a hydrophilic head and hydrophobic
tail. This causes the heads to remain in the water and the tails to extend
above the surface. The molecules at the head may be tailored to enable
crosslinking with other molecules or to the biomaterials surface

Study more modification methods from refrance

 Lecture 10, 11
Nanotechnology
What is Nanotechnology?

• Lycurgus cup,4th century AD (now at the British Museum, London).

• Depicts King Lycurgus of Thrace being dragged to the underworld
• When illuminated from outside, it appears green. However, when
illuminated from within the cup, it glows red.
 Size-Dependent Properties
If you cut a block of gold into smaller & smaller pieces, it would still look
like gold. Not true of gold at the nanoscale, where properties change.

Optical Properties of Gold

Bulk gold appears yellow in color while, Nanosized gold appears red in color
 The particles are so small that electrons are not free to move about as
in bulk gold (the energy gap between conduction and valence bands
increases with decreasing size)
 Because this movement is restricted, the particles react differently with
light
Optical Properties of Zinc Oxide (ZnO)
 Large ZnO particles
- Block UV light
- Scatter visible light
- Appear white
 Nanosized ZnO particles
- Block UV light
- So small compared to the wavelength of visible light that they
don’t scatter it
- Appear clear
Optical Properties - TiO2 and ZnO
• Scattering of visible light (whitening effect) is influenced by particle size
and the difference between the refractive index of the pigment and the
surrounding media.
• Maximum scattering occurs when size equals 1/2 the wavelength and
particles are uniformly dispersed (Mie theory).
Mention method of preparation nano-particles

For Lycurgus cup, The colors originates from metal nanoparticles

embedded in the glass. At places, where light is transmitted through the
glass it appears red, at places where light is scattered near the surface,
the scattered light appears greenish.
This is due to: Suspensions of spherical gold particles with various
diameters (150, 100, 80, 60, 40, 20 nm) in water. The difference in colors
is due to different scattering and absorption behaviour of small and large
gold particles.
• Gold nanoparticle can be suspended in water to make a colloidal gold,
used for centuries as a medical treatment . [ ‫مصطفى السيد‬.‫]د‬
Lecture 11
Physical Properties of nanoparticles
Physical Properties Change: Melting Point of a Substance
Melting Point (Microscopic Definition)
 Temperature at which the atoms, ions, or molecules in a substance
have enough energy to overcome the intermolecular forces that
hold them in a “fixed” position in a solid
 Surface atoms require less energy to move because they are in
contact with fewer atoms of the substance

Melting Point of Small Objects

- The smaller a solid object gets, the larger the percentage of its
atoms residing at the surface. If it keeps shrinking, eventually it's
practically all surface.
- Inside a crystalline solid the atoms are constrained by the crystal
lattice, but at the surface the atoms have more freedom to move.
- As the temperature increases, they begin to vibrate; when the
vibration of the surface atoms reaches a certain percentage of the
bond length between them, melting begins and then starts to
propagate through the solid
 At the macroscale At the nanoscale
The majority …almost all on the …split between the
of the atoms inside of the object inside and the surface
are… of the object

Changing an …has a very small …has a big effect on

object’s effect on the the percentage of
size… percentage of atoms atoms on the surface
on the surface
The melting …doesn’t depend on … is lower for smaller
point… size particles
 Surface to Volume Ratio Increases
• As surface to volume ratio increases
- A greater amount of a substance comes in contact with surrounding material
- This results in better catalysts, since a greater proportion of
the material exposed
for reaction
• Mixing two or more chemically dissimilar materials------Composites
• The goal is to achieve properties that are otherwise unreachable in individual
components
• Some advantages: High strength/light weight, low cost, environmentally
resistant, electrically and thermally conductive
• Natural Composites:
• Wood: mixture of flexible cellulose fibers and stiffer lignin
• Bone: mixture of soft collegen (protein) and brittle apatite (mineral)
• Combine strong, stiff, or electrically or thermally conductive, or
magnetic particles/fibers/layers with adhesive, soft, relatively ductile
plastics. -----polymer+ composite
• Nano-Products in medicine
• FeO nanoparticles injected into tumor site.
• Alternating magnetic field (similar to MRI) heats up nanoparticles, destroying
tumor from inside with minimal damage to surrounding tissue
• Nanosensor
• Particles that are smaller than the characteristic lengths associated with the
specific phenomena often display new chemistry and new physics that lead to
new properties that depend on size
• When the size of the structure is decreased, surface to volume ratio increases
considerably and the surface phenomena predominate over the chemistry and
physics in the bulk
• The reduction in the size of the sensing part and/or the transducer in a sensor
is important in order to better miniaturise the devices
• Science of nano materials deals with new phenomena, and new sensor devices
are being built that take advantage of these phenomena
• Sensitivity can increase due to better conduction properties, the limits of
detection can be lower, very small quantities of samples can be analysed,
direct detection is possible without using labels, and some reagents can be
eliminated.
• A nanosensor probe carrying a laser beam (blue) penetrates a living cell to
detect the presence of a product indicating that the cell has been exposed to a
cancer-causing substance

Next lecture : tissue engineering

 Lecture 12
Tissue Engineering

Tissue engineering

Tissue engineering is a field whereby damaged or missing tissue is replaced

or facilitated in its regeneration.

Tissue engineering is based on isolating

cells from an individual and expanding
them in culture. These cells are then
seeded on a biocompatible, porous and
biodegradable carrier, called “scaffold”,
where they start to proliferate and
secrete their extracellular matrix.

Properties of Ideal /Scaffolds characteristics

The following characteristics must be considered when designing a scaffold for

tissue engineering.
a. Biocompatibility
 Biocompatibility is the ability of the scaffold to perform in a specific application without
eliciting a harmful immune or inflammatory reaction. For a scaffold to positively interact
with cells and with minimal disruption to the surrounding tissue, it should have an
appropriate surface chemistry to allow for cellular attachment, differentiation and
proliferation.[ surface roughness ]Cells primarily interact with scaffolds via chemical
groups on the material surface or topographical features.

b. Biodegradability

Biodegradation is the dissolution of the scaffold by the cellular and enzymatic

reactions. This occur when the scaffold is exposed to a biological environment, either
in vivo or in vitro, a different mechanisms may be involved in either setting .
In vivo, scaffolds are degraded during the foreign body response against the
scaffold, a process which may involve an immune response, release of enzymes, and
deposition of replacement extra-cellular matrix. Understanding the foreign body
response to a given biomaterial is a key step in developing a clinical therapy . In vitro,
scaffold degradation is dependent upon the cell type and medium content.
Degradation products should be non-toxic. If there is toxic products , it should have
a degradation rate slow enough for the body to manage .

c. Mechanical Properties

The scaffold provides structural integrity in 3D. It, also provides mechanical stability to
support the growing tissue during in vitro and/or in vivo growth phases . This mechanical
stability is required to meet the specific requirements of the tissue to be regenerated at the
defect site. These requirements allow for handling by the clinician, are able to withstand
the mechanical forces imposed on it during the implantation procedure and survive under
physiological conditions. After implantation, the scaffold has a minimal level of
biomechanical function improve mechanically until normal tissue function is restored and
fully integrated with the surrounding host tissue.
d. Scaffold Architecture

Scaffold with Porous structures allow for optimal interaction with cells. The scaffold pore
architecture is characterised by pore size and shape, pore interconnectivity, degree of
porosity and surface area. These characteristics determine cell interactions with the
scaffold. It leads to a molecular transport (movement of nutrients, wastes and biological
chemicals e.g. growth factors) within the scaffold. Scaffold pore size determines the cell
seeding efficiency [50]. Very small pores prevent the cells from penetrating the scaffold.
Very large pores prevent cell attachment due to a reduced area. Cell migration within a
scaffold is determined by degree of porosity and pore interconnectivity.

A scaffold with an open and interconnected pore network (>80 %), and a high degree of
porosity is ideal for the scaffold to interact and integrate with the host tissue . But, with
increasing porosity, mechanical properties decrease. In manufacturing scaffold, a
compromise between different properties according to application requirements is required.

Zeta potential [mV] Stability behaviour of the colloid

from 0 to ±5, Rapid coagulation or flocculation
from ±10 to ±30 Incipient instability
from ±30 to ±40 Moderate stability
from ±40 to ±60 Good stability
more than ±61 Excellent stability

Process Advantage Disadvantage

Thermally High porosities (_95%) Long time to sublime solvent
induced phase Highly interconnected pore (48 hours) Shrinkage issues
separation structures Small scale production
(TIPS) Anisotropic and tubular pores Use of organic solvents
possible Limited range of pore size
Control of structure and pore size
by varying preparation conditions

Solvent and Controlled porosity Controlled Structures are isotropic

particle interconnectivity (if particles are Use of organic solvents
leaching sintered) Poor interconnectivity
control of porosity structure Limited membrane
thickness(3mm)

Solid free-form Porous structure can be tailored to Resolution needs to be improved

host tissue to the micro-scale
Protein and cell encapsulation Some methods use organic
possible solvents
 Good interface with medical
imaging
Polymeric Graded porosity structures possible Mechanical properties is an
Sponge method Controlled pore size issue
High porosity
High interconnection
Emulsion Independent control of porosity and Problem with residual solvent,
templeting pore size Residual progens
Superior compressive strength Less than 200μm
Foaming- No organic solvents Non-porous external surface or
pressure High interconnection Closed pore structure may be
processing produced
Electro- use of solvents that may be
spinning toxic need high voltage
 The need for TE

Required for application

requirements

Scaffold Cell

Biomaterial as raw
material

Ceramics% Polymer % Composite %

Scaffold
processing

Combination Emulsion Leaching Foaming Phase Electospinning Proto-

separation type

Scaffold evaluation

Imaging methods Traditional methods

U. S. SEM U-CT Mercury InfraRed

Porosimetry Spectroscopy

Lecture 13, 14: Revision, Quizz, Report presentation for each group
Thanks and Good Luck