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Methods for surface modification

Part II
PHYSICO-CHEMICAL METHODS

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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

Chemical reactions can be classified as specific or


nonspecific.
Nonspecific reactions: leave a distribution of different functional groups
at the surface.
E.g.
- radiofrequency glow discharge in oxigen, argon, nitrogen, CO2, water
vapor
- oxidation of metal surfaces to a mixture of suboxides
- hydrolysis

Specific reactions: change only one functional group into another with
a high yield and few side reactions
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Chemical modifications of polymer


surfaces
In the treatment of polymeric surfaces, chemical
composition of polymer surfaces can be modified either
by
- direct chemical reaction with given reactive agents
in solution (wet treatment) or by
- covalent bonding of suitable molecules to the sample
surface (grafting).

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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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Wet Treatment: techniques


1.
2.
3.
4.

Etching of fluoropolymers
Oxidizing treatment based on chromic acid solutions
Hydrolysis of polyesters

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1. Etching of Fluoropolymers (PTFE, FEP)


Etching is a process of preparing the surface of a
fluoropolymer device (tubing, wire) for bonding to another
material
The chemical structure of PTFE results in a non-polar, nonwettable surface.
The etching process strips a layer of fluorine atoms from the
surface and leaves the carbon atoms with a deficiency of
electrons.
When the altered surface is exposed to the atmosphere, oxygen
and hydrogen restore some of the electrons forming a surface
that will accept bonding.
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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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Silane reaction ca be used


to modify hydroxylated
surfaces (glass, silicon,
alumina, metal oxides
and so on)

Book: BIOMATERIALS SCIENCE 1996: pag. 112

SILANIZATION: n-propyl-trimethoxysilane (nPTMS)

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Silanization: alkyl- and fluoroalkyl-silanes


Conseguences: increase of hydrophobicity

A wide range of different silanes are available, permitting many


different chemical functionalities to be incorporated on surfaces.
The advantages of silane reactions are their simplicity and stability,
which are attributed to their covalent, cross-linked, structure.
However, the link between a silane and a hydroxyl group is readily
subject to basic hydrolysis
The goal of traditional silanization is to form bonds across the interface
between mineral components and organic components.
Silanization (or siliconization) of glassware increases its hydrophobicity and
is used in cell culturing to reduce adherence of cells to flask walls.
(Wikipedia)

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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

3-Aminopropyltriethoxysilane (APTE) is one of the most widely used


silane agents for introducing amino reactive sites on the
surface(Kim, 2011; Lapin & Chabal, 2009).
In most cases, APTE is used to silanize inorganic biomaterials
surfaces to provide sites for biomolecules grafting.

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Chemical reaction: AMINOLYSIS


Aminolysis is a convenient and versatile method to introduce
-NH2 or other functional groups onto a polyester surface

a)

b)

SCHEME: mechanism of the aminolysis reaction of small molecules. R, R


and R represent alkyl groups and B represents a base molecule.
(REVIEW) RSC Advances, 2013, 3, 2509

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Chemical reaction: AMINOLYSIS


process of polyester film surfaces with 1,6-hexanediamine
= introduction of amino groups onto a surface (e.g. PolyCaproLactone)

HDA = hexanediamine (10% w/w) in


isopropanol (IPA) solution

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Polycaprolactone Membrane Modification

Through a coupling agent, i.e., glutaraldehyde, gelatin, chitosan, or collagen


can be further immobilized onto a PCL surface.
Biomacromolecules 2002, 3, 1312-1319

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PLGA: hydrolysis and aminolysis


controlled hydrolysis
to produce
carboxylic acid
functional groups and
aminolysis
to produce primary
amine groups on the
surface of PLGA

for grafting a polysaccharide


EDAC (dimethyl-aminopropyl)carbodiimide) and DMA
(dimethyladipimate) are crosslinker agents
Biomacromolecules 2004, 5, 463-473

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MORE COMPLEX! PCL-g-PDMAEMA-gelatin:


reaction of free amine and hydroxyl groups on the aminolyzed PCL film surface
with 2-bromoisobutyrate bromide (BIBB) to produce the PCL-Br surface.
Surface-initiated Atom Transfer Radical Polymerization (ATRP) of DiMethylAminoEthyl Methacrylate (DMAEMA) to produce the PCL-g-P(DMAEMA) surface,
and physical immobilization of gelatin to produce the PCL-g-P(DMAEMA)/gelatin
surface for biomedical applications

C. Li, et al., Bioconjugate chemistry, 2011, 22, 1842-1851

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Possibilities for immobilization of


biomoleculaes onto OH-rich surfaces

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SURFACE-MODIFYING ADDITIVES (SMA)


The additives of surface modification
(SMAs, Surface-Modifying
Additives), are compounds which, if
added in small quantities to a
material during the manufacture,
have the property of subsequently
migrate toward the surface, finally
emerging from it and changing its
composition.
The reasons for this phenomenon
are of energetic nature: the
migration of the additive lowers the
energy of interaction at the interface.

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SURFACE-MODIFYING ADDITIVES (SMA)


A typical SMA designed to alter the surface
properties of a polymeric material will be a
relatively low-molecular-weight AB diblock
copolymer
E.g.
Block A: soluble in, or compatible with, the
bulk material into which the SMA is being
added
Block B: incompatible with the bulk material
and with lower surface energy
During initial fabrication, the SMA is distributed
uniformly throughout the bulk. After a period for
curing or an annealing step, the SMA will migrate
to the surface- The A block anchor the B block to
the substrate, so that the former is stable at the
interface material external environment

Example of SMA: polyurethane -A- e polydimethysiloxane -B-

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Actually , there are two types :

SMA = Surface modifying ADDITIVES


SME = Surface modifying end groups (i.e. the terminal groups of the
polymer chains of the same material)

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SURFACE-MODIFYING END GROUPS (SME)


Designed to avoid some limitations of the SMA
No need for additives to obtain desired surface properties because the active
molecules at the surface are inserted covalently at the ends of the polymer
chains
The mobility of the end groups can facilitate the self-assembly molecular
surface:

[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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RADIATION GRAFTING and


PHOTOGRAFTING
Si possono distinguere tre tipi di reazioni:

A. grafting con sorgenti di radiazioni ionizzanti


(pi comuni le radiazioni gamma con CO60 )

B. grafting con radiazioni U.V. (photografting)


C. grafting con fascio elettronico ad alta energia
In all cases they produce similar effects
The radiation breaks chemical bonds in the material to be grafted
forming free radicals, peroxides or other reactive species.
It is possible to obtain 1) modifications of chemical groups on the
surface, 2) formation of new chemical groups, or 3) surfacereactive groups may be exposed to a monomer, which is activated
with consequent propagation of a chain reaction and formation of
polymer grafted to the surface
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RADIATION GRAFTING and


PHOTOGRAFTING

The surface layers formed by radiation are fairly thick (> 1 m),
however, well bonded to the substrate

Since there are many different monomers, there are ample


possibilities to obtain various chemical structures

Using mixtures of monomers, copolymers with unique


properties balanced (eg hydrophilic / hydrophobic) may be
obtained

This type of reactions is often used for grafting hydrogels of


hydrophobic polymers

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Example: PHOTOGRAFTING
method used to modify the surface of a polymer by radiation in the field
of UV / visible

photografting on a polymer substrate with a vinyl monomer and


benzophenone as initiator
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Plasma-surface modification
(PSM)

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Plasma: principles
Irving Langmuir
(1881-1957)

THE 4TH STATE OF THE MATTER


A plasma is an ionized gas, neutral,

populated by neutral
(atoms, molecules, radicals)
and charged species (ions, electrons)
1928

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THE 4TH STATE OF THE MATTER

PLASMA = ambiente gassoso dissociato a livello atomico e molecolare.


Un plasma contiene ioni, radicali liberi, elettroni, atomi, molecole
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free electron motions

molecular motions

Traslation

Te

Tvib

Vibration

electron levels
Energy

En

Rotation

Trot
E2
E1

Traslation

Ttrasl

E0

Excitation

M.C. Tanzi Strutture Bioartificiali e Biomimetiche - aa 2015-16

Tel

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COLD PLASMAS

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APGD = Atmospheric Pressure Glow Discharges

DBD = Dielectric Barrier Discharges


M.C. Tanzi Strutture Bioartificiali e Biomimetiche - aa 2015-16

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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

The treatments at low temperature and low energy are


useful for organic deposits on polymeric substrates or
inorganic
Under high-energy, plasma can produce useful
changes on inorganic substrates.
.
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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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COLD PLASMA and methods with GAS PLASMA


The plasma used for surface modification are ionized gases at low
pressure typically at room temperature or slightly above.

They can be used to modify surfaces via


surface activation and grafting
(TREATMENT: modification or grafting of
surface functional groups)
surface ablation (ETCHING: with
effects in the order of 10 nm)
deposition of thin films (PE-CVD:
plasma enhanced chemical vapour
deposition
(thickness = maximum some m)

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PLASMA SURFACE
INTERACTIONS:

synergistic action of
active species and ion bombardment

substrate
high density

active
species
etching

low ionization degree

deposition

ion
bombardment
treatment

volatile products

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WHY NON EQUILIBRIUM PLASMAS ?


LOW TEMPERATURE PROCESSES for thermolabile materials
surface modifications, no bulk alterations
polymers, paper, textiles, ...
adaptable to any shape and material substrate
webs, inside of small tubes, powders, granules, fibers,
high density of active species
comparable with high T gases and flames
tuneable ion bombardment
dry technology, negligible impact to the environment
ATMOSPHERIC PRESSURE PROCESSES
synthesis of an entirely new class of surfaces
transfer to industrial scale
process control possible
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COLD PLASMA

(Prof. Pietro Favia)

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Plasma technologies in Plasma lab


Used for biocompatible materials
(polymers, composites, devices such as
vascular grafts, etc.)
sterilization

functionalization / modification

Plasmas are created in oxygen, hydrogen, nitrogen and


argon
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Plasma functionalization of organic


materials
Reactive particles from oxygen plasma are incorporated on the
surface forming O-rich functional groups

C-OH

C-O COOH C=O

Surface polymer
oxygen plasma

Polar groups on a polymer surface cause a dramatic increase of


surface wettability
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FUNCTIONALIZATION OF POLYMER SURFACES


Functionalization occurs by chemical interaction of plasma produced

species - ions, radicals and photons with the surface.

Example: H abstraction by O atom enables attaching O atoms as a


peroxy site
Increase surface energy increase wettability.
Process treats the top few layers.

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PRIMER ON SURFACE CHEMISTRY


Polypropylene structure

Functional groups are created when treated in O2 containing plasmas:

Alkoxy

EUJapan_0307_20

R-O

Carbonyl

R=O

Alcohol

R-OH

Peroxy

R-OO

Acid

O=R-OH

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PE-CVD deposition of functional polymer coatings


ACRYLIC ACID and ALLYLAMINE
two valid candidates to deposit functional coatings
H

OH
H

Acrylic Acid

NH2
H

Allylamine

PLASMA functionalization with COOH or -NH2 of biomedical


surfaces for

DIRECT
CELL-GROWTH

BIOMOLECULE
IMMOBILIZATION
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favia@chimica.uniba.it
M.C. Tanzi Strutture Bioartificiali e Biomimetiche - aa 2015-16

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

surface & material


diagnostics & tests

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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PLASMA PARAMETERS: external and internal


internal PARAMETERS
external PARAMETERS
imposed from the operator

output from diagnostics


Fragmentation degree of the feed

Pressure

Density of neutrals

Feed composition, flow rate, leaks

Distribution energy (EEDF) and


density (ne) of electrons

Field frequency, power density


Reactor configuration, materials,
electrode geometry
Substrate position
(e.g. glow vs. afterglow)
.

Ionization degree
Residence time of the species
Process homogeneicity
Positive-ion bombardment, sputtering

Deposition, etching, treatment rate


Contaminations
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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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rotating reactor for granules

top view

RF

side view

Internal wing system to keep granules


stirred during the process
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LAB SCALE PLASMA REACTOR FOR TUBES

processes (deposition, treatment) inside catheters, tubes 54


M.C. Tanzi Strutture Bioartificiali e Biomimetiche - aa 2015-16

HYDROPHILIC TEXTILE
CF4 plasma treated

untreated

WCA
1223

Volume (l)

Volume (l)

water adsorbtion kinetics

Time (s)

10

15

20

Time (s)

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25

30

35

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HYDROPHOBIC PBT WNW


O2 plasma treated

untreated

WCA
1424

Volume (l)

Volume (l)

water adsorbtion kinetics

Time (s)

10

10

20

30

Time (ms)

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40

50

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PE-CVD

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XPS analysis of PTFE PLASMA-deposited

Nothing to do with: -[CF2-CF2]- !!


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COMMERCIAL
BIOMEDICAL SURFACES
FROM GLOW DISCHARGES
cell/tussue culture PS plates

hydrophilic, cell-adhesive surfaces

contact lenses

hydrophilic gas-permeable contact lenses


confortable for long wear

pacemakers

protective coating on wires

micro-fluidic devices

etched channels, hydrophilic/phobic surfaces


at the microscale

wound healing bandages

transfer of autologous cells

from culture to the skin of the patient


.
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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

M.C. Tanzi Strutture Bioartificiali e Biomimetiche - aa 2015-16

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Grafting di molecole bioattive

Grafting di peptidi,
polisaccaridi, enzimi, proteine
per ottenere specifiche e
selettive reazioni cellulari

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(B.D. Ratner)
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RF Glow Discharge Plasma Deposition of Tetraglyme:

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Ultra-low fibrinogen adsorption:


plasma deposition apparatus for tetraglyme coating of tubes

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Impiantazione ionica (Ion beam implantation)


The ion beam method injects accelerated ions with energies ranging from
101 to 106 eV (1 eV = 1.6 x 10~19 joules) into the surface zone of a
material to alter its surface properties
The accelerated ions have another chance to penetrate into the material
ions of almost all the elements of the periodic table may be implanted
Generally used for metals and inorganic solids, but not only
Application: change of hardness, slipperiness (lubricity), toughness,
corrosion resistance, conductivity, bioreactivity
Examples: implantation of
iridium on Ti-6Al-4V to increase the resistance to corrosion
nitrogen on Ti to reduce wear

boron and carbon of stainless steel to increase the fatigue strength

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Some considerations for the ion implantation process

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Ion Beam Treatments


Ion assisted vs ion implantation
Ion implantation is a process in which
ion beam is introduced directly to the
surface
Ion assisted treatment is to target
species which will then form a coating
on the surface
Apparatus includes ion gun and closed
system
Plasma-based techniques combining the advantages of conventional plasma
and ion beam technologies are effective methods for medical implants with
complex shapes.
In particular, modification of the surface energetics of the materials can
improve the adhesion strength, surface and coating properties, and
biocompatibility
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