MATS 64532: Surface Engineering and Materials Design

Surface Engineering Part 3

Dr Zhu Liu
Corrosion and Protection Centre
School of Materials
The University of Manchester

Contents
Lasers
Interaction of laser beam with materials
Laser surface engineering
Application examples

Laser Principles
What is a laser?
LASER: Light Amplification by Stimulated Emission of
Radiation

Features of laser beam

Coherent electromagnetic radiation
Monochromaticity (single wavelength)
Coherency
High radiance and low beam divergence
Ability to focus to a small spot size

Types of lasers: pulsed and continuous-wave (CW)

Typical Industrial Lasers for Surface Treatment

Laser

Lasant

CO2

Gas:
CO2, N2
and He

10.6 m

Solid:

Nd:
YAG
Excimer

Diode

Wavelengt
h

Operating
mode

Power

Wall plug
efficiency

CW
Pulsed

Up to
50 kW

1.06 m

Pulsed
CW

Up to
8 kW

2 3%

Gas:
ArF
KrF
XeCl

193 nm
248 nm
308 nm

Pulsed

Up to
1 kW

2%

Semicon
-ductor

810 nm
940 nm

CW

4 kW

25%

12 15%

Laser Beam Focusing

dmin: minimum focus spot size:
Laser beam

d min

Lens
f

Focus
Defocus

f
2.44
D

D: beam diameter
: laser radiation wavelength
f: focal length
For example: a CO2 laser beam
(=10.6 m), D=38 mm, f=150 mm
dmin = 102 m

Interaction of Laser Beam with Materials

LASER BEAM OPTICAL ENERGY

Depending on laser beam wavelength and

materials, there are two beam/material
interaction mechanisms:
Photothermal process
Photochemical process

Photo-thermal process
Laser wavelength: infrared or far-infrared
Materials: metals, ceramics, glass
Absorption: Interaction between the photons and electrons

Vibration of electrons Vibration of lattice Temperature rise

Heating

Melting

Boiling

Plasma forming

Laser beam optical energy: it becomes thermal energy when it

interacts with materials.

Photo-chemical Process
Laser wavelength: short wavelength - UV range

with high photon energy

Materials: polymer
Laser beam/polymer interaction: Laser wavelengths in the

UV range capable of breaking bonds of polymeric materials

during processing, without generating much thermal effect.

Influencing factors on Absorption

Wavelength [1]

Surface roughness [2]

Temperature [3]

Laser Materials Processing

The first public demonstration of laser materials processing

James Bond film, Goldfinger, 1964, filmed in England

In May, 1967, the TWI, in England, successfully cut through

tool steel (1/10 inch) using a CO2 laser.

Laser Materials Processing

Materials Removal

Cutting, drilling, Marking/Engraving,

Slotting/Grooving, Scribing, Trimming, Micromachining, Cleaning
Joining

Welding, Soldering, Brazing, Glue hardening,

Epoxy curing
Surface Treatment

Transformation hardening, Shot-peening, Melting,

Alloying, Cladding, Annealing, Particle injection, LPVD, L-CVD, L-sol-gel

Laser Surface Treatment

Shock
hardening

Vaporisation

Log(power density)

10

Glazing

Melting processes
Laser melting

Melting

Laser alloying
Cladding
Alloying
Surface melting

Heating

Laser cladding

Transformation
hardening
10-6

Non-melting processes
Laser transformation hardening
Laser annealing
Laser shock peening

Cleaning

104

10-8

10-4

10-2

100

Log (interaction time), D/v, s

Range of laser processes mapped against power
density per unit time [4]

Other laser processes

Laser physical vapour deposition
Laser chemical vapour deposition
Laser gel-gel

Processing Schematics
Beam guidance

LASER

Lens

Workpiece
CNC table

Laser Power (W):

Laser Beam Size (mm):

Scanning Velocity (mm/s):

v
Scanning
direction

Power density: 4P/D2

Interaction time, D/v

Temperature

Characteristics of LSE
Cooling rate: 104 1011 K/s

Time

Rapid heating Rapid cooling

Microstructure
Refinement of microstructures
Extended solubility of an element in another
Formation of non-equilibrium phases, like amorphous
Properties
Corrosion, wear and etc.

Laser Transformation Hardening

Laser beam

Substrate
Traverse direction

Temperature, K

1800

Ac3
1000

Ac1

200
Time

Laser Transformation Hardening for

Large Area Coverage
Re-heated region back tempering

Hardness

Overlapping effect

Softer and harder regions due to back tempering

Beneficial effect on wear performance

Features of Laser Transformation Hardening

Advantages:

Selective hardening
Better fatigue properties
Self-quenching
Less thermal distortion than others
Suitable for complex geometry
No post-treatment required
Limitations:

High capital cost and low efficiency for large area treatment
17

LTH Application Examples

Controller shaft (100Cr6, 0.45mm hardened depth. 850Hv) [5]

Application Examples

Laser hardening of
saw tooth

Enhanced wear performance:

Bearing
Wear areas
Seal areas
Gears
Cams
Engine components
Cutting, bending, forming
edges

Laser hardening of
a steel bottle-opener

Laser Surface Melting

Laser
input

Solidification microstructure
Dendritic structure
Cooling rate controls microstructural#
size; the faster the cooling rate, the finer
the microstructure is.

Laser Surface melting - LSM

Refinement of microstructures
Extended solubility of an element in another
Formation of non-equilibrium phases, like amorphous
Classification of LSM
Thick-layer melting:

Thin-film melting:

Melt depth: 20 200 m

Melt depth: 1 20 m

Cooling rate: 104 106 K/s

Cooling rate: 107 1011 K/s

Applications

Pre-treatment
Anodising of

aluminium alloys

Surface protection
Wear
Corrosion
Other properties

Post-treatment
Weld-decay
HVOF coatings

LSM Application Examples

AISI 304 austenitic stainless steel
Poor pitting corrosion resistance - compositional heterogeneity
such as an MnS inclusion, segregates or precipitates.
LSM: significant improve pitting corrosion resistance
Main reasons:
1) dissolution/refinement of large
scale sulphide inclusions due to
rapid cooling rate cooling rate - < 1m;
2) the formation of duplex
austenite/ferrite structure. S
has a higher solubility in ferrite
than in austenite.

Post-treatment: Laser melting of weldments

Example 1: Weld decay of austenitic stainless steel
Applying thick-layer melting to
HAZs to eliminate sensitisation,
to restore corrosion resistance of
austenitic stainless steels, using
high-power CO2, Nd:YAG or
HPDL.
Example 2: Friction stir weldment of aluminium alloys
Applying thin-film melting to
HAZs and TMZs to eliminate
various precipitations, to restore
corrosion resistance of Al alloys,
using a high-power Excimer
laser.

Example 3: Laser de-sensitised 316 austenite stainless steel:

Poor IGC resistance sensitised microstructure: Cr rich M 23C6 and
Cr-depleted regions along the grain boundaries.
LSM modifies the microstructure and eliminate IGC.
i) dissolution of M23C6

carbides during melting;

ii) no re-occurrence of M23C6

carbides after solidification

iii) homogenisation of Cr-

depleted regions.

* Importance: laser welding of stainless steels does not introduce weld decay

LSM Application Examples

Example 4: LSM of AA2014 and AA2024 alloys
As-received

Materials

Main second phases

As-received

AA 2014-T6 Al2Cu
CO2 laser-melted

AA 2024-T3

Cu in -Al
solution
after LSM

CO2 LSM
Al2Cu

Al2CuMg

Al2CuMg,
Al2Cu

0.14 2.6 wt.%

(depending on
cooling rate)

LSM Application Examples

Results of corrosion tests

Materials

Pitting potential, mV (SCE)

Improvement?

As-received

Laser-melted

AA 2014-T6

-730

-560

AA 2024-T351

-640

-680

Why?

LSM Application Examples

+

AA 2024: Al2CuMg is anodic to Al solid solution

Potential

Al2Cu (2014)

Increase of Cu
- Al solution
Al2CuMg (2024)

Increased Cu in -Al solution

AA 2014: Al2Cu is cathodic to Al solid solution

shifts corrosion potential to more

positive direction
AA 2024: reduce resistance to
pitting corrosion
AA 2014: improve resistance to
pitting corrosion

LSM Application Examples

CO2 LSM reduces pitting corrosion resistance of AA2024-

T351 alloy
Thinking of how we can completely eliminate second phases
Cooling rate determined by type of lasers
Excimer laser: UV wavelength, ns pulse width
Expected:
Higher cooling rate
Elimination of 2nd phase particles
No-precipitation after solidification

Excimer Laser Surface Melting of Aerospace

AA2024-T351 and AA2050-T8 alloys
Thin-film melting
Melt depth: 510 m
No visible inter-

metallics within the melt

layer observed
AA2024-T351

Excimer LSM of AA2024

XRD analysis showing

complete dissolution of secondphase intermetallics after a
certain number of laser pulses
per area.

Excimer Laser Surface Melting of Aerospace

AA2024-T351 and AA2050-T8 alloys
AA2024-T351 in deareated 3.5% NaCl
solution:
1. Significant reduction of passive

current density (Ipass);

2. The higher the number of laser pulses,
the lower the Ipass.
AA2050-T8 in deareated 3.5% NaCl solution:
1. Laser-treated surface exhibited passive

behavior
2. Significant reduction of passive current
density (Ipass);
3. The higher the number of laser pulses, the
lower the Ipass.

Excimer LSM of Magnesium alloys

Electrochemical potentials

Excimer LSM of Magnesium alloys

Significant improvement of corrosion performance by Excimer LSM

As-received

Excimer LSM

Excimer LSM

Potential Applications of LSM

Example 1:
Pre-treatment of AA2024 alloy for anodising
Example 2:
Post-treatment of HVOF MMC coatings

Pre-treatment for Anodizing of AA2024

Anodising
Problems (due to the presence of 2nd phase particles)
1. Defects within the
anodised layer, affecting
corrosion performance
2. Reduction of anodising
efficiency

Pre-treatment for Anodizing of AA2024

Anodising at 12 V in 0.56 M H2SO4

Improvement:
1. Elimination of defects
2. Increasing anodising

efficiency

Pre-treatment for Anodizing of AA2024

Treatment

Ecorr
(V)

Epit
(V)

Passive
current
density
(A/cm2)

As-received

-0.70

-0.51

0.1E-5

Asreceived

-0.76

-0.61

0.2E-7

10-pulses

-0.74

-0.60

0.8E-9

25-pulses

-0.60

-0.37

0.3E-9

50-pulses

-0.56

-0.31

0.2E-9

Anodising

Anodising of LSM AA2024:

1. Reduction of Ipass
2. Increasing number of
pulses results in lower
Ipass, and more positive
pitting potential
3. No delamination

Laser modification of HVOF MMC coatings

60WC/Co-base alloy

Fully melting: Pore-free,

Fusion-bond, New phases
at interface

Partially melting (HT) via

diffusion: New phases at
interface

Laser modification of HVOF MMC coatings

Immersion test

Corrosion resistance

Wear resistance

Example: Sealing (Re-melting) of Ceramic TBCs for

gasturbine blades:
Plasma sprayed coatings: pores, micro-cracks, rough surface

Before laser treatment

After laser treatment

Laser Surface Alloying

Process as shown below: Metal film A + Metal substrate B

Reference 10

Produce a NEW material, which is different from A and B.

Two types of laser surface alloying processes

1) Thin film alloying:

Laser: short pulse, short wavelength, such as Excimer laser
Thin film: < 1 m, such as: 50 nm Pd (or Ni) on Ti foil
Mixing mechanism: diffusion of mass transfer
2) Thick layer alloying:
Laser: continuous-wave, IR wavelength, such as CO 2 and YAG.
Thick layer: 0.1 to a few mms
Mixing mechanism: convective (due to Marangoni effect)

Two types of laser surface alloying processes

Reference 10

CO2 laser (CW, Power of

kW, interaction time >50 s)
Homogenous alloying
distribution by convection

Pulsed laser (such as

Nd:YAG laser, Excimer
laser with pulse width of 20
ns)
Concentration profile along
the depth by liquid state
diffusion mainly.

Mixing Mechanism Marangoni Effect

Thermal gradient intensive

convection (thermo-capillary
flow) rapid homogenisation
within the melt pool

It suggests that the convection speed is several orders of magnitude

higher than the scanning speed, leading to extremely rapid
homogenisation.

Selection of Materials for LSA

Thermal Properties between alloying
elements and substrate
Difference of melting temperatures between

alloying element and substrate material

Vaporisation temperature
Vapour pressure
Thermal conductivity
Examples:
Difficult case:

alloying Zn into Cu

Features of Laser Surface Alloying

Advantages:
Most of elements can be added;
Chemical composition of alloying layer is fully controllable;
Extended solubility;
Localised treatment;
Fine microstructure and less segregation;
Gas alloying: much thicker compared to PVD, CVD or
other conventional methods.
Limitations:
Some loss of the volatile elements;
Variation of alloying element distribution

Example: Excimer laser micro-alloying

Ti foils (50 m thickness) employed as electron-transparent

window materials in the electron beam treatment of flue gases

Environment: a complex mixture of ions, radicals, and excited
species, and sulphuric acid at 80 C.
Currently, Ni, Pd (15 500 nm) can be deposited by PVD to
prolong life time, but with a problem of detachment during
services.
Possible solution: Laser surface alloying of Ni or Pd into Ti foils,
without thermal distortion.
Laser selected to be the best-suited: Excimer laser (248 nm, 20 ns
pulse width)

After immersion tests in H2SO4 at 80C

Ni alloyed

Ti foil

Material

Weight loss,
gm-2d-1

Ti foil

45.1 + 0.50

Ni alloyed

0.62 + 0.02

Pd alloyed

0.42 + 0.01

Pd alloyed

Excimer laser micro-alloying:

significant improvement of
corrosion resistance in H2SO4 at
80C
no spallation occurred
No thermal distortion
No vacuum required

Different form of LSA

Laser gas alloying TiN on Ti6Al4V and Ti for improvement of

corrosion resistance and wear resistance

Treated depth: 200 m

http://www.opticsjournal.net/OEPNNews.htm?id=PT111108000072z6C9E

Laser Cladding
Dilution (Dl): percentage of clad
contamination by substrate
materials.
A2

A1

HAZ

A2
Dl
A1 A2

Advantages of Laser Cladding

Limited and controllable heat input:

Low dilution
Minimal thermal distortion
Minimal heat affected zones (HAZs)

Bonding strength
Fusion bond
No spallation

Coating microstructure

No porosity
No cracks
Fine microstructure
Homogeneous elemental distribution (less segregation)

Process
High process stability
Robust, easily automated process
High reliability in production

Applications of Laser Cladding

Repairing (reconditioning):

Surface protection
against:

Damaged parts

Wear
Corrosion
Thermal

Worn
Corroded
Mechanicallydamaged
To salvage the parts

To prevent critical systems

breakdown, and increase
product lifecycle.

Manufacturing 3-D
components

Laser Cladding
1) Cladding of high performance materials onto low cost
substrates
Example 1: Laser cladding of 50Nb-50Ti alloy on the tip of
airfoils (Ti-6A1-4V alloy) - excellent oxidation resistance at
1000C in air;
Example 2: Laser cladding for extending the solid solubility
limits of rare-earth additions (e.g. yttrium, rhenium hafnium and
cerium) in nickel-based superalloys to improve their resistance
to oxidation at elevated temperatures.
Example 3: Laser cladding of Al, or Al alloys on Mg for
significantly enhances the corrosion resistance, along with wear
resistance.

Laser cladding of WC-Co MMC

for wear protection

Laser cladding of print roller shaft

Substrate material....................................................Mild Carbon Steel

Cladding material ............................................Hoganas C22 Hastelloy
Laser type................................................... Coherent Highlight 4000L
Laser power................................................................................. 4 kW
Spot size ........................................................................... 0.5 x 12 mm
Travel Speed ........................................................................0.6 m/min
Powder Feed Rate .................................................................. 25 g/min
Step Size...................................................................................... 8 mm
Clad Thickness ......................................................................... 0.5 mm
Ref.: Cladding with High Power Diode Lasers, http://www.coherent.com/downloads/CladdingWithHPDDL_WhitepaperFinal.pdf

Laser Cladding of Shaft Journal

Substrate material ......................................................High Alloy Steel

Cladding material .............................................................. Inconel 625
Laser type ................................................... Coherent Highlight 1000F
Laser power ................................................................................. 1 kW
Spot Size......................................................................................2 mm
Process Speed .....................................................................0.75 m/min
Ref.: Cladding with High Power Diode Lasers, http://www.coherent.com/downloads/CladdingWithHPDDL_WhitepaperFinal.pdf

Laser Cladding of Roller Teeth Mock Up

Substrate material ..................................................... Mild carbon steel

Cladding material .............................................Deloro 60 clad powder
Laser type ................................................... Coherent Highlight 1000F
Laser Power................................................................................. 1 kW
Spot Size......................................................................................2 mm
Process Speed .....................................................................0.35 m/min
Clad Thickness ........................................................................1.2 mm
Ref.: Cladding with High Power Diode Lasers, http://www.coherent.com/downloads/CladdingWithHPDDL_WhitepaperFinal.pdf

Laser Cladding of Boiler Tubes

A layer of Inconel 622 deposited onto a carbon steel A210

boiler tube, which was then bent 1D and 4D without
cracking.
Ref.: Laser Cladding, http://www.alspi.com/lasercladding.htm

Laser Cladding Application Examples

2) Repairing (re-generating, re-conditioning) of damaged
(corroded), high value components
Conventional methods: arc welding, flame spraying.
Disadvantages: high thermal input, distortion, postdeposition machining.
Laser cladding technique:
Well-controlled, high accuracy (no post machining), low
thermal input less distortion (less dimensional change)

Restoring of the airfoil profile

Restoration of
damaged blisks

Reconditioning of worn bores

Video Shows on Laser Cladding

1. Laser Cladding Multi Axis
http://www.youtube.com/watch?v=zAOsqDc6fgk&feature=related
2.Laser Cladding wire feeding, The University of Manchester.

E:\Wire feed Laser Deposition.wmv

3. Laser Cladding
http://www.youtube.com/watch?v=Yrg86Gqmdc8&NR=1

Laser-assisted Thermal Spray

Thermal sprayed coating with defects

Defects-free
Metallurgical bond
Higher processing

efficiency

Laser-assisted sprayed coating with

defects-free and metallurgical bond

Shot Peening
A method of cold working metals in which

compressive stresses are induced in metal surface

layer by the impingement of a stream of shot at
high velocity under controlled conditions
How does it work?

Laser Shock Peening

Mirror

Laser
pulse

Plasma

Protective
coating

Target

Shock wave

Water

Mechanism:

Generation of plasma within a overlay

Pressure on surface (GPa) shock wave plastic
deformation - compressive residual stress
No melting

Laser Shock Peening

To generate 1-3 mm residual

compressive stress zones

To improve fatigue lives of

components

Applications
Improvement in

resistance to stress
corrosion-cracking,
Improvement in fatigue
properties: Aircraft
construction: fastener holes;
aircraft gas turbine components

Advantages of LST over Conventional

techniques for Corrosion Protection
Dense surface layer with no porosity (cf. spraying )
Fusion bond in laser cladding (cf. spraying, roll bonded,

electrodeposition)
Localised treatment with less HAZ than diffusion technique
No vacuum required (cf. electron beam, PVD, CVD)
No fundamental restriction on component shape
Novel, superior microstructure, such as microcrystalline or
amorphous)
Possibility of limited areas to be treated
Chemical cleanliness
Remote, non-contact, easy to automate

Applicability of LST in Industries

Large area coverage
Disadvantages:
Advantages:

Low efficiency
Localised treatment with minimum
HAZ

Economic considerations
High capital investment
Case-by-case consideration

Lack of technology transfer

Lack of experienced personnel

Comparison between Laser and Other

(Conventional) Techniques

Laser shot peening and shot peening

Laser cladding and thermal spray
Laser alloying and ion implantation
Laser CVD (pyrolytic and photolytic) and CVD

In terms of:

Adherence of coating and substrate

Features of coatings (density, porosity, microstructure)
Treated depth
Level of compressive stress
Level of solid solubility

Laser Assisted PVD Pulsed Laser Deposition

Target: Just about anything!
(metals, semiconductors,
polymers ).
Laser: Typically excimer
(UV, 10 nanosecond pulses)
Vacuum: Atmospheres to
ultrahigh vacuum
Mechanism: photon interaction to create an ejected plume of

material from any target. The ejection of material to occur due to

rapid explosion of the target surface due to super-heating.

Thermal PVD

Laser PVD

the laser-induced expulsion

produces a vapor
produces a plume of material with
composition
stoichiometry similar to the target. It
dependent on the
is generally easier to obtain the
vapor pressures of
desired film stoichiometry for multielements in the target
element materials using PLD than
material
with other deposition technologies.
Faster and higher quality coatings

Laser/Sol-gel Technique
TiO2 Structure and Applications

500-600C

Rutile

Anatase

Anatase absorbs light at 380-390

nm (4-10% of solar spectrum)
*J. Lian et al. Thin Solid Films 516 (2008) 33943398
*K. HASHIMOTO et al. Jpn. J. Appl. Phys., Vol. 44, No. 12 (2005)
*U. Diebold, Sur. Sci. Rep., 48(2003) 53-229

3.0eV

3.32eV

Photo-catalysis in TiO2
During UV excitation*

hv E

TiO 2 g eTiO hTiO

2

Oxygen in Air

Surface recombination

e O2 hv O2 (ad )

3.2e
V

O (ad ) H HO (ad )
Water/Moisture in Air
h H 2O hv HO (ad ) H

Ox. ()

+
+

TiO2

Red. ()

TiO2 + h e + h+

+ +
Volume recombination

Red. (O2)

Ox. (H2O)

h O2 (ad ) 2 O(ad )
h OH OH

Eventually, powerful redox radicals further interact with organic contaminates by

decomposing them into CO2 and other volatile species.
*A.L. Linsebigler et al. Chem. Rev., 1995, 95 (3), 735-758

Mechanism of Disinfection of Bacteria by TiO2

Improving Efficiency of TiO2

Control e-/h+ recombination
Red Shift into visible spectra1,2

Additives, dopants into TiO2;

Rare Earths (La, Ce, Nd)
Noble metal ions (Ag, Au, Pt)
Non-metal anions (N, C, S)

Ag2+ + 2e- Ag0

Ag+2

- - -

Ag+2

+ +
TiO2
+ +

Noble metals are inert, can sustain for longer time, Au,

Ag and Pt nanoparticles are found to red shift the

absorption of pure TiO2 into the visible spectrum.
Ag ions/Ag nanoparticles interact with protein, leading

to inactivation of protein and death of bacterial cells.

1. P. Periyat et. al. J. Sol-Gel Sci. Tech. 43 (2007) 299-304
2. Shah, et al J. Appl. Phys. Lett. 83, 4143 (2003)

Comparison of various techniques for TiO2 film

generation

Our new technique

Sol-gel/Laser-induced Technique (SGLIT)

Sol-gel TiO2 films amorphous

Excimer laser - to crystallise sol-gel TiO2 films into
anatase (or rutile)
Ag-TiO2 films
Conventional Sol-gel techniques

Our SGLIT technique:

Step 1: sol-gel TiO2 film

Step 2: furnace annealing
Step 3: Ag ion adsorption
Step 4: UV illumination

Step 1: sol-gel TiO2 film

Step 2: Ag ion adsorption
Step 3: Laser irradiation

Experimental Procedure
Stage 1: Preparation of TiO2 sol-gel coatings on glass
Stage 2: Adsorption of Ag ions
Stage 3: Excimer laser processing of coatings
Mask - raw beam

XY table

TiO2 coated glass

Excimer laser operating parameters

Film
Ag-TiO2

Fluence, mJ/cm2

Repetition rate,

Number of pulses

85-100

Hz
15

50-200

Characterisation and Tests

Materials Characterization
XRD phase analysis
SEM/EDX film morphology/elemental analysis
XPS Ag state
TEM more detailed micro/nanostructural analysis

Anti-bacteria Tests (S. Aureus and E.Coli):

under UV illumination
under normal light
under dark room

XRD Structural Analysis

TiO2 films
Sol-gel Ag-TiO2: amorphous
Excimer laser crystallize Ag-

TiO2 film into:

single anatase
Anatase with minor Rutile,
depending on laser operating
conditions.
Ag-TiO2 films

Film

Structure

As-dried

amorphous

Pure TiO2 (Laser)

Mainly Anatase,
+ minor Rutile

Ag-TiO2 (Laser)

Only Anatase

Ag-TiO2 (Furnace+UV) Only Anatase

Ag stabilised anatase -TiO2
No information on Ag

XPS Chemical Analysis of Ag NPs on TiO2

50 pulses @ 85 mJ/cm2

200 pulses @ 85 mJ/cm2

Formation of Ag in metallic state, indicating Excimer laser irradiation

capable of converting Ag ions into metallic Ag (not Ag oxide)

Grain size and Ag nanoparticle size

Grain size of TiO2 (Laser-treated) > Grain size of TiO 2 (Furnace-treated)

Particle size of Ag (Laser-treated) < Particle size of Ag (Furnace + UV treated)

Surface Morphology
Laser treatment

Amorphous TiO2 matrix

Ag Nps

Mesoporous,
rough surface
with Ag NPs
uniformly
distributing
on the
surface.

Furnace treatment
Anatase TiO2 matrix

Smooth, and pore-free after furnace sintering at 700C for 1 hr and immersion

in Ag ions, and adsorbed Ag ions being irradiated by UV lamp for 4-5 hrs.

TEM Analysis nanostructure details

After Laser Irradiation @

85mJ/cm2, 50 pulses

FCC Ag
After Laser
Anatase

Hexagonal Ag
Hexagonal and cubic Ag NPs were generated after laser irradiation.
Nanocrystallised depth is 150 nm out of 350 nm in total thickness.

UV-Visible Spectroscopy
Photo-absorption studies

Ag-TiO2 (Laser)

Ag-TiO2 (Furnace)

Ag-TiO2 (as-dried)

Laser-treated surface exhibits a red-shift and a strong absorption peak at 518 nm,

which is believed to be due to the surface plasmonic effect from Ag nanoparticles.

Furnace-treated did show a small peak at 410 nm.

Anti-Bacterial Drop Test

Two types of bacteria are tested.
1.Gram-positive bacterium: a thick, multilayered cell wall.

Typical example: Staphylococcus Aureus (S. Aureus).

2. Gram-negative bacterium: Gram negative cell walls are

more complex than Gram positive cell walls, both structurally
and chemically.
Typical example: Escherichia coli (E.Coli)

Gram Negative Bacteria - E. Coli

Under UV (365 nm) light Illumination

Initial concentration used

to plate: 2x104 CFU/ml

Laser-prepared Ag-TiO2 killed E.Coli up to 100% after 30 min,

while the furnace-annealed partially kill the bacteria with constant

remain.

Gram Negative Bacteria - E. Coli

Under Dark and Normal Light conditions

Normal Light

Dark Room

Under both conditions, laser-prepared Ag-TiO2 killed 100% E.Coli

after 60 min, while the furnace-treated failed to kill completely.

Gram Positive Bacteria - S. Aureus

Under Dark and Normal Light Conditions

Laser-prepared Ag-TiO2 killed S. Aureus up to 100% after 60

min, under both dark and normal light conditions.

Conclusions

Excimer laser irradiation has two functions of 1) nanocrystallisation; and 2) reduction of Ag ions, being one-step
process of generating Ag-TiO2 films.

Film characteristics: meso-porous, rough surface morphology

with enlarged surface area, anatase, uniform distribution of Ag
NPs.

Laser-generated Ag-TiO2 showed red-shift in solar spectrum

and enhanced photo-absorption.

Laser-generated Ag-TiO2 has improved efficiency of killing

both E.Coli and S. Aureus bacteria compared with furnacetreated Ag-TiO2.

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