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UV CURABLE

COATINGS

By: Adesh Katariya

plast.adesh@gmail.com

UV COATING TECHNOLOGY

UV curing has now been established as an


alternative curing mechanism to thermal
hardening,contrary to the past, where it was only
considered for the curing on temperature
sensitive substrates, like wood, paper and
plastics.

UV CURABLE COATING USED FOR


decorative appearance,(colour, gloss)
protective barrier. (against mechanical, biological
and chemical attack etc. )

MAJOR END APPLICATIONS OF UV


COATINGS

BASIC PRINCIPLE OF UV CURING

UV curing technology uses the energy of photons


of radiation sources in the short wavelength
region of the electromagnetic spectrum in order
to form reactive species, which trigger a fast
chain growth curing reaction.

ELECTROMAGNETIC SPECTRUM
RANGE

UV-A, UV-B, and UV-C radiation, is mainly used


for this technology.

ENERGY CALCULATION IN UV
CURING
The energy content of a photon is defined by the
equation
E = h = hc/,
where is the frequency and is the wavelength
(nm).
This equation tells us, that the shorter the
wavelength, the higher the energy of a photon.

INTERACTION OF UV PROCESS
DESIGN PARAMETERS

COMPONENTS OF UV COATINGS

Reactive resins containing a plurality of polymerizable


double bonds, which govern mainly the desired
properties of the final coating;

Copolymerizable, monomeric diluents, which are


responsible for the reduction or adjustment of the
viscosity of the formulation, a function taken by the
solvent in conventional formulations;

Photo initiators or a photo initiating system containing


photoinitiator and photosensibilizer or coinitiators;

Additives, like surface active additives, slip additives,


fillers, pigments, light stabiliser, etc.

TYPES OF UV CURING

CHEMISTRY OF RADICAL UV
COATINGS
The chemistry involved in the radical initiated
UV induced crosslinking can be divided into the
three steps,
1. Initiation
2.
Propagation
3.
Termination

IMPORTANCE OF PHOTO-INITIATOR
Although the UV energy applied in photo curing
may cleave CC and CH bonds, the commonly
used monomers do not produce sufficient amounts
of initiating species, which is due to low absorbance
and poor cleavage efficiency. Thus, photoinitiator is
required to initiate photo curing reaction of
Coating .

WHAT HAPPENS , WHEN UV LIGHT


HIT PI

Absorption of a photon by the photoinitiator Molecule

Excitation of an electron into higher singlet states

By intersystem crossing (ISC) an electron spin inversion


leads to the excited triplet state.

Molecule posses two unpaired electrons, rather than from


the singlet state.

From the triplet state two main reactions can lead to


initiating species, the intramolecular scission of an -bond,
or the intermolecular abstraction of a hydrogen atom.

THE QUANTUM YIELD OF


INITIATION
The number of growing chains per photon
absorbed reflects the importance of the processes
leading to initiation over all the indicated
processes of deactivation.

THE EFFICIENCY OF THE PHOTOINITIATION

The efficiency of the photo-initiation is a function


of different quantum yields, since several side
reactions can occur in every step. Thus, the
overall yield of initiation is a complex function of
different quantum yields, represented
exemplarily in Slide .

JABLONSKY-TYPE DIAGRAM FOR


PHOTOINDUCED RADICAL PHOTOINITIATION.

LIGHT IS ABSORBED BY A MOLECULE


WHAT HAPPENS?

The electronic configuration changes.


This leads to an initial geometry of the excited
state which is usually not the energy minimum.
During excitation the electron spin remains unchanged.
Spin inversion during excitation is forbidden by
quantum mechanics and therefor unlikely.

Note: The Franck-Condon principle says that the heavy atom nuclei do not change their
positions

RIGHT AFTER THE EXCITATION


SEVERAL THINGS MAY HAPPEN.
1) Vibronic relaxation brings the molecule
quickly into the new energy minimum
structure for the excited state. Energy is
released into the solvent.
2) Intersystem crossing leads to triplet states by spin
inversion.
3) Emission of light and return to the ground state
(luminescence, fluorescence, phosphorescence).
4) Quenching of the exited state: Energy is
transferred to another molecule.
5) Radiation less deactivation. Molecule goes back to
ground state by vibrational (thermal) deactivation
(no light emission). The energy goes to the
solvent/environment of molecule.

SCIENCE BEHIND RADIAL UV


CURING
First law of Photo-Chemistry
Second Law of Photo-Chemistry
Excitation state and Radiation Energy
Role of Photon into Radical Formation

THE FIRST LAW OF PHOTOCHEMISTRY,


THE GROTTHUSS-DRAPER LAW:
The law was first proposed in 1817 byTheodor
Grotthussand in 1842, independently, byJohn
William Draper.
According to this law, light must be absorbed by a
compound in order for a photochemical reaction
to take place.

THE SECOND LAW OF PHOTOCHEMISTRY,


THE STARK-EINSTEIN LAW:
Each

photon of light absorbed by a chemical system,


only one molecule is activated for subsequent reaction.
Named after German-born physicistsJohannes
StarkandAlbert Einstein
The photon is a quantum of radiation, or one unit of
radiation. Therefore, this is a single unit of EM radiation
that is equal to Planck's constant (h) times the
frequency of light. This quantity is symbolized by , h,
or .
The photochemical equivalence law is also restated as
follows: for everymoleof a substance that reacts, an
equivalent mole of quanta of light are absorbed.

The formula is:


where NAisAvogadro's number.

RADIATION ENERGY MUST MATCH ENERGY


DIFFERENCE OF GROUND AND EXCITED STATE

FORMATION OF RADICALS

CONT..
The

ejected electrons, known


asphotoelectrons, carry information about
their pre-ionized states.
For example, a single electron can have
akinetic energyequal to the energy of the
incident photon minus theelectron binding
energyof the state it left. Photons with
energies less than the electron binding
energy may be absorbed orscatteredbut
will not photo ionize the atom or ion.

PHOTO-GENERATION :ALPHA
-CLEAVAGE

PHOTO-GENERATION : H-ABSTRACTION
TheNorrish

reactioninorganic
chemistrydescribes thephotochemical
reactionstaking place
withketonesandaldehydes.
The reaction is named afterRonald
George Wreyford Norrish

PROPAGATION

Propagation is the key step to very efficient


curing, since it is a chain reaction where for
instance one produced radical can add more than
1000 monomer units within a fraction of a
second.

PROPAGATION AND TRANSFER

TERMINATION

RISKS IN UV COATING CURING

Irradiation. Low-pressure mercury lamps have their main


output at 254 nm. This light severely damages cells, eyes
and skin. Shield reactors; turn lamps off before checking
the reaction. Never look into the beam of a high power
LED; the lights very high intensity damage your eyes.

Ozone generation: Short wavelength light may generate


ozone from oxygen. Perform reactions always in a well
ventilated fume hood.

Lamps: Most lamps operate at high temperature and at


high vapor pressure. Never move or touch lamps during
operation. Never switch of the cooling right after
switching of the lamp!

Thank you