Thermal Spray Coatings

For Industrial Applications

INSTM Research Unit “Roma La Sapienza”

Dept. of Chemical and Materials Engineering (ICMA)

Sapienza University of Rome

Giovanni Pulci

INSTM - Italian Consortium

on Materials Science

and Technology

Le nuove frontiere delle tecnologie al plasma - Esempi di applicazioni industriali

Consorzio Innova FVG - 24 Settembre 2018

Coatings for severe operating environment

Heavy combination of mechanical stresses and aggressive environment

Temperature

Mechanicalstress

OxidationCorrosion

Wear

Coatings for severe operating environment

Aim of presentation:

Description of case studies related to innovations and R&D in thermal spray field

R&D plays a key role for component working in critical operating conditions

R&D

Improvementof performance

Costs reduction

R&D

Introductioninto the market

Design

Existing product New product

energy

heat/energy source

material

material feed/flow

atomizing

gas or air

material spray

substrate

coating

molten particlesspray equipment

A thermal spray process can be divided into four sections:

heat/energy source (thermal energy for heating and melting)

material feed/flow

material spray (kinetic energy for propelling dispersion)

material deposition

Surface engineering by thermal spray process

Surface engineering by thermal spray processes

Surface engineering by thermal spray processes

8

• An inert gas is passed through a potential differential.

• An arc is formed between the two dipoles.

• The gas is ionized and recombines after going through a free expansion.

• The recombination effect releases heat and creates a plasma flame (“plume”).

• Powder is inserted into the flame and is propelled towards the substrate.

Plasma spraying

9

Plasma spraying

10

• Max. plume temperature ≈ 12000 °C

• Impact speed of particles 200-400 m/s

• In-flight time of particles ≈ 10-3 s

• Heating/cooling rate ≈ 107 K/s

Plasma spraying

11

• Plasma (Primary) gas flow

• Secondary gas flow

• Plasma power

• Spray distance

• Injector angle, length and size

• Carrier gas flow

• Gun spray angle

powder injection

molten particle stream

plasma

spray gun

plasma

flame or

plume

Plasma spraying

Process parameters

12

• Primary gases (Ar, N2): plasma

stability and transport properties

• Secondary lighter gases (He, H2),

enthalpy adjustment.

• N2 and H2 are diatomic gases.

These plasmas have higher

energy contents for a given

temperature than argon and

helium because of the energy

associated with dissociation of

molecules.

gas e

nerg

y c

on

ten

t [W

h/S

CF

]

N2 H2Ar

He

gas temperature [°C]

0

100

200

300

400

500

600

0 2200 4400 6600 8800 11100 13300 15500 17800 20000

dissociation

H2 2 H

dissociation

N2 2 N

Plasma spraying

Plasma gases

13

pow

de

r p

art

icle

tem

pera

ture

big particles,

high powder density

small particles,

low powder

density

flow

te

mp

era

ture

part

icle

ve

locity

Ar/H2

N2/H2 N2/H2

flo

w v

elo

city

Plasma spraying

Spray distance

14

part

icle

ve

locity

N2/H2

29 kW

20 kW(same gas comp.)

oxid

e c

on

ten

tsu

rfa

ce

ro

ugh

ne

ss

cold particles

Plasma spraying

Spray distance

15

Controlled Atmosphere Plasma Spray

chamber is backfilled after evacuation, either at

• near vacuum (1 - 10 mbar) VPS

• reduced pressure (> 50 mbar) LPPS

• standard pressure APS

• elevated pressure (up to 4 bar) HPPS

• with a substitute atmosphere (reactive (CxHy), inert (Ar)) RPS / IPS

VPS / LPPS / LVPS

➢ spraying in near vacuum or under reduced pressure conditions

➢ spray particles are unimpeded by frictional forces of the atmosphere

Plasma spraying

16

• Ceramics (high melting point)

• Al2O3, Al2O3/TiO2, Cr2O3, ZrO2 -Y2O3, La2Zr2O7, ecc.

• ZrB2, TiB2, SiC (non standard)

• Metals (refractory, oxidation control is mandatory, controlled

atmosphere)

• MCrAlY, Ni-and Mo-based alloys

• Cermets

• Cr3C2 - based (high T, generally NiCr matrix)

• WC - based (better mechanical properties, Tmax 500 °C

(decarburation), Co - CoNiCr - based matrix)

Plasma spraying

Materials

17

• Low porosity

• Lamellar microstructure, partially molten ceramic phase

Cermet Cr3C2 – Ni-Cr

Plasma spraying

HVOF deposition

Plasma Spray HVOF

• Max. jet temperature ≈ 2800 °C

• Particles impact speed 400-700 m/s

• In-flight time ≈ 10-3 s

• Heating/cooling rate ≈ 107 K/s

Applications

Wear and corrosion resistant coatings

(Mechanical, chemical, aerospace, textile industries)

- Cermet (WC, Cr3C2 or TiC in Co, Co-Cr or Ni-Cr metal matrix);

- Ceramics (Cr2O3, Al2O3-TiO2);

- Metallic (Ni or Co base, e.g. NiCrBSiC).

Thermal barrier coatings (TBC)

(Aerospace, energy industries)

- ZrO2 - Y2O3.

High temperature oxidation resistant coatings

(Aerospace, energy, chemical industries)

- Ni - Cr – Al base (e.g. NiCoCrAlY).

Biocompatible coatings

Porous Ti , hydroxy apatite (Ca10(PO4)6(OH)2

Materials and Surface Engineering Lab

Research partners and clients

Aircraft engines and power gas turbines

Max gas temperature in turbine:

900 - 1400 °C

Rise in gas temperature in turbine

Improvement of thermodynamic

efficiency

Max service temperature

of superalloy!

Turbine blades protection

High temperature and combustion products (e.g. SO2, SO3, V2O5) cause

surface damages on the Ni-base superalloy

High temperature

oxidation (T > 1000°C)

Hot corrosion

(700 – 925 °C)

(SO3 attack, sulphides

formation)

Erosion

(Solid particles in

gas stream)

Protective ceramic overlay

Thermal Barrier Coating (TBC)

Top Coat (ZrO2–6-8%Y2O3)• Thermal insulation• Erosion protection

Bond Coat (Ni/Co-CrAlY) •Enhanced adhesion•Hot corrosion resistance

TGO (a-Al2O3) • Oxidation barrier

Substrate (Ni–base superalloy) •Thermo-mechanical loading

ZrO2 permeable to O2

(through open porosity & by ionic conduction)

Thermal Barrier Coatings (TBC)

Innovative materials for gas turbines

Strategies to improve turbines performance:

use of CMC materials

Modification of substrate-coating system

Innovative materials for gas turbines

Strategies to improve turbines performance:

use of CMC materials

Modification of substrate-coating system

Innovative materials for gas turbines

Strategies to improve turbines performance:

use of CMC materials

GE Rolls-Royce – development of F136 engine (second choice for

F-35 aircraft)

3rd low pressure stage – stator in SiC/SiC

Modification of substrate-coating system

Innovative materials for gas turbines

Strategies to improve turbines performance:

use of CMC materials

Modification of substrate-coating system

Innovative materials for gas turbines

Strategies to improve turbines performance:

use of CMC materials

Problem:

- Active oxidation of SiC/SiC, expecially in presence of H2O

steam: Thermal & Environmental Barrier Coatings

Environmental Barrier Coatings

EBC deposited by APS (examples)

- HfO2-Y2O3-Gd2O3-Yb2O3

- Barium-Strontium-Alumino-Silicate (BSAS)

Innovative materials for gas turbines

Need for innovation in surface engineering

Case study: Hard chrome replacement

Hard Chrome plating is an electrolytic method of depositing chrome for

engineering applications, from a chromic acid solution.

Cr 6+ compounds

EU classification

Need for innovation in surface engineering

Hard chrome replacement

- HIGH HARDNESS

Typical values of 850 - 1050 HV

- LOW COEFFICIENT OF FRICTION –

coefficient against steel of 0.16 (0.21 dry),

- WEAR RESISTANCE

extremely good resistance to abrasive

and erosive wear

- CORROSION RESISTANCE

extremely high resistance to atmospheric

oxidation, and a good resistance to most

oxidising and reducing agents- MACHINING

Can be successfully finished

Properties of hard chrome:

Case study

Hard chrome replacement in marine engine components

Wärtsilä aims to be the leader in power

solutions for the global marine markets

Case study

Hard chrome replacement in marine diesel engine components

Case study

Hard chrome replacement in marine diesel engine components

Case study

Hard chrome replacement in marine diesel engine components

Valves problems:

• High temperature

• Wear

• Cold and hot corrosion

Wear and cold corrosion

from sulphur compounds

Fatigue

Thermo-

mechanical fatigue

Hot-corrosion and oxidation

Creep

Case study

Hard chrome replacement in marine diesel engine VALVES

Problem:

Wear and cold corrosion in

exhaust and intake valves stem

Hard chrome on stem has a short

service-life

Case study

Hard chrome replacement in marine diesel engine valves

Ceramic-metal (cermet) HVOF coatings

Hard ceramic phase:

wear resistance

Metal matix:

toughness and corrosion

resistance

2 phases - microstructure

Cr3C2 – 25 (Ni-Cr)✓

WC-CoCrNi✓

(WC-Co)-NiCrSiFeBC ✓

Case study

Hard chrome replacement in marine diesel engine valves

Materials (Sulzer powders):

Facility:

HVOF – JP5000 gun

Wärtsilä requirements and constrain

Cermet HVOF coatings

• Thickness higher than150 µm

• Porosity as low as possible

• Hardness higher than 900 HV

• High deposition efficiency

Optimization of deposition

parameters by

Design of Experiment (DoE)

2 factors 3 levels

1) Kerosene - O2 flow

2) Spray distance

1) Low

2) Medium

3) High

32 parameter sets

Keros. (gph) – O2 (scfh)

5,5-1700 6-1850 6,5-2000

Dis

tan

ce

(mm

)

320

355

380

Phase 1- HVOF coatings optimization (DoE)

Investigated properties

• Deposition efficiency

• Porosity as a function of total flow and spray distance

• Hardness

Weighted combination of these properties

provide the “desirability function”

DESIGN-EXPERT Plot

Actual Factors:

X = O2 mass flow

Y = Distance

0.096

0.281

0.466

0.651

0.836

Des

irabil

ity

1700

1775

1850

1925

2000

320

335

350

365

380

O2 mass flow

Distance

DESIGN-EXPERT Plot

Actual Factors:

X = O2 mass flow

Y = Distance

0.096

0.281

0.466

0.651

0.836

Des

irability

1700

1775

1850

1925

2000

320

335

350

365

380

O2 mass flow

Distance

WC-CoCrNi

Properties Optimized value

Deposition efficiency

(um/pass)24,3

Hardness (HV100) 1610

Porosity (%) 3,04

Desirability 0,84

Keros. (gph) – O2 (scfh)

5,5-1700 6-1850 6,5-2000

Dis

tan

ce

(mm

)

320

355

380

Optimized

parameters

DESIGN-EXPERT Plot

Actual Factors:

X = O2 mass flow

Y = Distance

0.000

0.206

0.412

0.619

0.825

Des

irabil

ity

1700.00

1775.00

1850.00

1925.00

2000.00

340.00

355.00

370.00

385.00

400.00

O2 mass flow

Distance

(WC-Co) - NiCrSiFeBC

Properties Optimized value

Deposition efficiency

(um/pass)10,8

Hardness (HV50) 1053,5

Porosity (%) 1,79

Desirability 0,82

Keros. (gph) – O2 (scfh)

5,5-1700 6-1850 6,5-2000

Dis

tan

ce

(mm

)

400

370

340Optimized

parameters

DESIGN-EXPERT Plot

Actual Factor

X = O2 mass flow

1700.00 1775.00 1850.00 1925.00 2000.00

0.000

0.249

0.498

0.747

0.996

X: O2 mass flow

Y: Desirability

One Factor Plot

Cr3C2 – 25 (Ni-Cr)

Properties Optimized value

Deposition efficiency

(um/pass)34,3

Hardness (HV100) 1369

Porosity (%) 4,06

Desirability 0,996

Keros. (gph) – O2 (scfh)

5,5-1700 6-1850 6,5-2000

Dis

tan

ce

(mm

)

320

355

380

Optimized

parameters

Phase 1- HVOF coatings optimization (DoE)

Optimized coatings

WCN

WSF

CRC

Phase 2- optimized coatings characterization

Corrosion tests Wear tests

Phase 2- optimized coatings characterization

Corrosion tests

1 hour immersion test – boiling 5% H2SO4 solution

8,29 6,26 0,065

191,02

0

50

100

150

200

CRC WSF WCN HC

Mas

s lo

ss (

mg

/cm

2 )

Corrosion test - mass lost

Not protective

Phase 2- corrosion tests

Hard chrome

No surface damage

detectable

Phase 2- corrosion tests

WCN coatings

0,42

0,49

0,14 0,13

0,02 0,030,07 0,08

0,230,27

0,16

0,22

0,01 0,01 0,01 n.c.0,00

0,10

0,20

0,30

0,40

0,50

0,60

Wear

(m

m3)

Senza attacco corrosivo

Con attacco corrosivo

As sprayed

Post corrosion attack

Phase 2- optimized coatings characterization

Wear tests - Load: 91 N

- Sliding distance: 2000 m

- Speed: 1 m/s

Phase 3- coating selection for valve deposition

WC-CoCrNi:

- Highest hardness

- Lowest wear rate

- Lowest corrosion rate

- Good density

- High deposition efficiency

- WC-CoCrNi coating was selected

- Coated valves tested for 3 years on a

Wartsila test engine

Innovative coatings for hot corrosion

Case study: Hot corrosion on marine diesel engines valves

Aggressive environment produced by high impurity contents within

the fuel: V, Na, S.

Innovative coatings for hot corrosion

Multiphase cermet coatings: CrystalCoat

Innovative coatings for hot corrosion

Multiphase cermet coatings: CrystalCoat

Metal alloy SiO2 Basalt Oxide Other silicates

CRYSTALCOAT

Innovative coatings for hot corrosion

Case study: Hot corrosion on marine diesel engines valves

Aim: development of innovative thermal spray coatings

alternative to Crystal Coat

Commercial

(non standard)

tested solutions

Development of

innovative

solutions

✓ Cr3C2 – NiCr

✓ Cr3C2 – NiCrAlY

✓ Cr3C2 – CoNiCrAlY

✓ Cr3C2 – self fusing alloy

✓ Mullite – nano SiO2 – NiCr

Phase 1- coatings optimization (DoE)

Innovative coatings for hot corrosion

2 factors 3 levels

1) Kerosene - O2 flow

2) Spray distance

1) Low

2) Medium

3) High

32 parameter sets

Keros. (gph) – O2 (scfh)

5,5-1700 6-1850 6,5-2000

Dis

tan

ce

(mm

)

320

355

380

• Thickness higher than150 µm

• Porosity as low as possible

• High deposition efficiency

Optimization of deposition

parameters by

Design of Experiment (DoE)

Very low porosity (< 1 %)

Ceramic phase dispersed in multiphase metallic matrix

Example: optimization of Cr3C2 - self fusing alloy

Optimized coating

Innovative coatings for hot corrosion

✓ Mullite – nano SiO2 – NiCr

Powder agglomeration – spray drying

Nano-SiO2 cover completely

the spray dried agglomerates

Innovative coatings for hot corrosion

✓ Mullite – nano SiO2 – NiCr

Coating deposition

Coatings retain the

nano-structure

100 h

50 h

5 h

Innovative coatings for hot corrosion

Hot corrosion tests

• Temperature: 750 °C• Environment: Na2SO4 – V2O5 molten salt• Exposure time: up to 100 h

Oxide scale

evolution

Innovative coatings for hot corrosion

Hot corrosion tests

Nanostructured coating

25 h

Innovative coatings for hot corrosion

Hot corrosion tests

Comparison between nanostructured and self fusing coatings

Nano 25 hCr3C2 – self fusing alloy 25 h

Thinner oxide scale in nano-coating

0

10

20

30

40

50

60

70

80

90

0 20 40 60 80 100 120

Thic

kne

ss [μ

m]

Time [h]

Scale growth kinetics

Carbide-NiCr Carbide-MCrAlY/2 Carbide-Self flux

Carbide-MCrAlY/1 Cer-nano/oxide-NiCr

Corrosion kinetics

Faculty of EngineeringSapienza University of Rome

giovanni.pulci@uniroma1.it