Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Part II
PHYSICO-CHEMICAL METHODS
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M.C. Tanzi Strutture Bioartificiali e Biomimetiche - aa 2015-16
CHEMICAL REACTION
There are hundreds of chemical reactions that can be used to modify the
chemistry of a surface. Chemical reactions are intended those reactions
performed with reagents that react with atoms and molecules at the
surface, but do not overcoat those atoms or molecules with a new layer
Specific reactions: change only one functional group into another with
a high yield and few side reactions
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Wet Treatment
Wet treatments were the first surface modification
techniques used to improve surface properties of
polymers (hot chromic acid was used to oxidize
polyolefins)
The effectiveness of the treatment depends on the
interaction of the different modification mechanisms
Polymer surfaces are rarely homogeneous
When the surface composition is constant throughout
the surface, amorphous and crystalline domains are
present on it
Wet treatment is not homogeneous on the surface.
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Etching of fluoropolymers
Oxidizing treatment based on chromic acid solutions
Hydrolysis of polyesters
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3. Hydrolysis
The attack of a nucleophilic agent, such as a base, on an electrondeficient carbon atom, has been exploited in several different
classes of polymers in order to improve their surface properties.
Hydrolysis of PET by hot sodium hydroxide attack is the oldest and most used
technique which increases the number of hydrophilic groups, improves the
moisture-related properties
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Surface Functionalization
The aim of the functionalization of polymer surfaces
is to create well-defined functional groups ( )
In this way one can create surfaces with controlled
properties or controlled chemical reactivity.
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Surface Graftng
In surface grafting, the aim is to achieve chemical
modification of the surface by the covalent bonding of
new molecules
on top of the substrate
Fundamental step in grafting is the creation of reactive
groups ( ) on the substrate surface.
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Surface Grafting
It can either be done chemically or by irradiation (ionizing
radiation, UV light and glow discharge).
Sometimes the grafting-coupling technique is followed but it
is more common to contact the activated surface with a
suitable monomer, so that a growing chain starts from the
activated site
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Silanization:
trichlorosilanes
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Silanization: aminosilanes
Aminosilanes are useful because they can be used to directly or
indirectly (through a linker) immobilize biomolecules on biomaterials
surface, which are important for subsequential cell or tissue
responses
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a)
b)
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[R.S. Ward,
1995]
It can vary both the chemical structure that the molecular weight of the
terminal groups to direct the surface properties
In addition, the use of mixed end groups (e.g: hydrophilic-hydrophobic) in a
same polymer produces amphiphilic structures as desired
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The surface layers formed by radiation are fairly thick (> 1 m),
however, well bonded to the substrate
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Example: PHOTOGRAFTING
method used to modify the surface of a polymer by radiation in the field
of UV / visible
Plasma-surface modification
(PSM)
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Plasma: principles
Irving Langmuir
(1881-1957)
populated by neutral
(atoms, molecules, radicals)
and charged species (ions, electrons)
1928
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molecular motions
Traslation
Te
Tvib
Vibration
electron levels
Energy
En
Rotation
Trot
E2
E1
Traslation
Ttrasl
E0
Excitation
Tel
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COLD PLASMAS
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PLASMA TREATMENTS
There are two types of plasma treatment:
Cold Plasma and Hot Plasma
Hot plasma treatments can be utilized in melting of a
powder to be used for deposition of coatings
Eg. the deposition flame-spray procures the injection of a metal powder of
high purity, finely divided on the substrate. The molten particles, or
partially melted, hit the surface and will solidify quickly
COLD PLASMAS
ENERGY INPUT
E.M. field (DC / AC)
shock wave
laser
heat
GAS
FEED
ACTIVE SPECIES
electrons (0 - 10 eV)
ions
atoms
radicals
molecules
plasma
in different
states
UV VIS radiation
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PLASMA SURFACE
INTERACTIONS:
synergistic action of
active species and ion bombardment
substrate
high density
active
species
etching
deposition
ion
bombardment
treatment
volatile products
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COLD PLASMA
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functionalization / modification
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C-OH
Surface polymer
oxygen plasma
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Alkoxy
EUJapan_0307_20
R-O
Carbonyl
R=O
Alcohol
R-OH
Peroxy
R-OO
Acid
O=R-OH
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OH
H
Acrylic Acid
NH2
H
Allylamine
DIRECT
CELL-GROWTH
BIOMOLECULE
IMMOBILIZATION
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The REACTORS
pulse
generator
DC
AC (KHz - MHz GHz)
AF RF
MW
power supply
0.001-10 Torr
matching
network
Atm
pressure
gauge
gas
feed
PLASMA REACTOR
plasma
diagnostics
(vacuum) chamber
many sources and
configurations possible
pumping
system
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LOW PRESSURE
GLOW DISCHARGES
PARALLEL PLATE
PLASMA REACTOR
RF generator
13.56 MHz
gas
optical window
(spectroscopy)
PLASMA
pressure gauge
50 - 1000 mTorr
pump
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Pressure
Density of neutrals
Ionization degree
Residence time of the species
Process homogeneicity
Positive-ion bombardment, sputtering
SUBSTRATE POSITION
glow vs afterglow
RF
plasma
Preglow
no treatment
Glow
active species
ion bombardment
crosslinking
high rates
fragmentation
Afterglow
no electrons
no ions
long living species
mild treatments
selectivity
structure retention
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top view
RF
side view
HYDROPHILIC TEXTILE
CF4 plasma treated
untreated
WCA
1223
Volume (l)
Volume (l)
Time (s)
10
15
20
Time (s)
25
30
35
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untreated
WCA
1424
Volume (l)
Volume (l)
Time (s)
10
10
20
30
Time (ms)
40
50
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PE-CVD
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COMMERCIAL
BIOMEDICAL SURFACES
FROM GLOW DISCHARGES
cell/tussue culture PS plates
contact lenses
pacemakers
micro-fluidic devices
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FUNCTIONALIZING
POLYMER/MEMBRANES
IN PLASMA PROCESSES
stable engineered interfaces
for cell culture
membrane
synthesis
functionalization
PE-CVD/treatment
plasma diagnostics
surface analysis
stability
ageing
.
coupling
a biomolecule
cell culture
bioreactor
surface analysis
biological tests
stability, ageing
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Grafting di peptidi,
polisaccaridi, enzimi, proteine
per ottenere specifiche e
selettive reazioni cellulari
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(B.D. Ratner)
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