4ième SéminaireTTH &

Revêtementsinnovants

16 & 17 Octobre

Thermal Spray Thermal Spray TechnologyTechnology ::

ReviewReview of of recentrecent evolutionsevolutions, , new new opportunitiesopportunities

Lyon - Métropole

16 & 17 Octobre 2014

Dominique BILLIERESR&D Manager for Coating Solutions Business Unit

Saint-Gobain Coating Solutions

Saint-Gobain group & thermal spray

Short Introduction to thermal spray

Recent evolutions ⇨ ⇨ ⇨ ⇨ new era for TS

Evolutions in Equipment

Evolutions in Process control

2

New tools for Coating Design and Optimization

Consumables engineering

Opportunities for Thermal Spray

InnovativeMaterials

Construction Products

Building Distribution

PackagingVerallia

Saint-Gobain, one of the Top 100 Leading industrial c orp.

Operations in

64 countriesApprox. 190,000

employees2013 € bnSales 42.0

3

Flat Glass (12% of sales)No. 1 in EuropeNo. 2 worldwideOperations in 42 countriesOver 32,000 employees

High-Performance Materials (9% of sales)

No. 1 worldwideOperations in 42 countriesOver 26,000 employees

of consolidated net sales

21%

No. 1 worldwidein ductile cast iron pipe

No. 1 worldwidein plasterboard and plaster

No. 1 worldwide in insulationNo. 1 in Europe for wall facingsNo. 1 worldwide for tile adhesivesNo. 2 in the United States in siding productsManufacturing operations in 55 countriesOver 47,000 employees

25%

No. 1 in Europe building materials distribution networkNo. 1 in Europe in plumbing, heating and sanitarywareproductsOperations in 27 countries64,000 employees

45%

No. 2 worldwide bottles and jarsOperations in 14 countriesMore than 14,000employees

9%of consolidated net sales of consolidated net sales of consolidated net sales

17%17% 12%12%

11%11%

45% of the Sector’s sales in 2013

High-Performance MaterialsHigh-Performance MaterialsFlat GlassFlat Glass55% of the Sector’s sales

in 2013

Performance Plastics#1 Fluid-circuit components for intravenous therapy and ophthalmic surgery#1 Sliding fluoropolymer bearings

Ceramic Materials#1 Refractories#1 Silicon Carbide#1 Abrasive Grains#1 Scintillation#2 Proppants

Saint-Gobain GlassWorldwide leader for coated glass

Innovative Materials : Market-leading Activities

55%%

11%11%

17%17%

16%16%

22%22%Sales:

€9.1bn

4

Adfors#1 Mesh fabrics for exterior insulation#1 Drywall tapes#3 Glass veil#1 Paintable wall coverings

Abrasives#1 Bonded#1 Thin wheels#2 Coated#2 Superabrasives

#1 Sliding fluoropolymer bearings#1 Architectural fabrics for large construction projectsSekurit

Equips one out of two cars in Europe

GlassolutionsEuropean leader for processing

building glass

Coating Solutions Coating Solutions Business UnitBusiness Unit

�� Ceramic TS PowdersCeramic TS PowdersLeader position

Product Range in Thermal Spray

USAUSA� Northborough, MA� Worcester, MA

EuropeEurope� Cavaillon, FR

AsiaAsia� Shanghai, China

R&D

USAUSA� Worcester, MA

Sales Offices

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�� Plasma Plasma Spray Spray EquipmentsEquipments

�� Flame Spray :Flame Spray :� MasterJet, TopJet� Thermal Spray Flexicords� Rokide® Spray System

Leader position

�� Specialties :Specialties :� Quasicrystals, � Ekonol® polyester resin� Ceramic Suspensions

USAUSA� Northampton, MA� Huntsville, AL� Wheatfield, NY

EuropeEurope� Avignon, FR

AsiaAsia� Deng Feng, China

ManufacturingS. AmericaS. America� São Paulo, BR

EuropeEurope� Avignon, FR� Köln, DE

AsiaAsia� Shangai, China� Taiwan� Osaka, Japan� Bangalore, India

INTRODUCTION TO INTRODUCTION TO THERMAL SPRAYTHERMAL SPRAY

(inorganic ) Coating processes

Physical / ChemicalVapor Deposition

PVD / CVD

Diffusion/Conversion Coating processes

Plating Coating processes

Wet coating + firing

Thermal Spray

CladdingHardfacing

Metals

7

1 nm1 µm

10 µm50 µm

200 µm1 mm

Metals

Ceramics

Polymers

Composites

Principle of Thermal Spray

Typical microstructure

Globular PoresUnmolten particles

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Kulkarni et al., Mat. Sci. and Eng., A359 (2003) pp 100-111

Interlamellar pores

Various microstructures

Controlled Porosity ceramic coating Dense ceramic coating

Graded layer Multiphased coating

Range of materials that can be thermally sprayedMETALSMETALS Pure metals Al, Cu, Sn, Zn, Mo, Ni, W, Ta, Co, …..

Ni alloys NiAl, NiCrAlY, NiCr (bondcoats)NiCrFeSi (Self fluxing alloys)Superalloys (Inconels, Hastelloys,…)

Cu alloys CuNiIn, CuAlFe,

Co Alloys Superalloys, Triballoy (CoCrMoSi), CoCrNiW, Stellite, …..

Fe alloys Steels, stainless steels, …

Various SnPb,

CERAMIC OXIDESCERAMIC OXIDES Zirconia based ZrO2-Y2O3, ZrO2-MgO, ZrO2-CaO, ZrO2-CeO,…ZrSiO4 (zircon)

Alumina based Al2O3, Al2O3-3 to 50% TiO2, Spinel Al2O3-MgO, MulliteAlumina based Al2O3, Al2O3-3 to 50% TiO2, Spinel Al2O3-MgO, Mullite

Chromia based Cr2O3, Cr2O3-TiO2-SiO2,

Other oxides TiO2, Y2O3, HfO2, NiO, …

CARBIDES AND CERMETSCARBIDES AND CERMETS Tungsten carbide based WC12%Co, WC17%Co, WC10Co4Cr, WC15Ni, …

Chromium carbide based Cr3C2-25%NiCr, Cr3C2-Ni, Cr3C2-FeCrAlY, …

Various B4C, ZrC, HfC, TiC, TaC, …..

NITRIDES, BORIDES, ..NITRIDES, BORIDES, .. Various TiN, ZrN, ZrB2,

VARIOUS BLENDSVARIOUS BLENDS Abradables AlSi-Polyester, Ni-Graphite, ….

Cermets oxide + metals Al2O3 -NiAl, Al2O3 -Al, ZrMgO3-NiCr, …

POLYMERSPOLYMERS High performance polymers PEEK, PPS, PA, …

Wide range of possible substrates

Coating on Graphite Coating on CFC CompositeCoating on Alumina

Coating on anodized aluminum

Coating on SiCAND OF COURSE …

ON ALL METALS

Functionalities that Coatings can bring

Hardness

Thermal barrier for high temperatures

Wear resistance

Electrical insulation or conductivity

Low friction coefficientLow friction coefficient

Changing surface emissivity

Very rough and wear resistant coatings

Anti-corrosion protection (galvanic effect)

Oxidation protection

…

Thermal spray processes & Equipments

HVOFHVOF

PLASMA PLASMA

FLAME FLAME SPRAYSPRAY

Electrical energy

Combustion energy

PLASMA PLASMA SPRAYSPRAY

TWIN ARC TWIN ARC SPRAYSPRAY

Mapping (T ; V) of Thermal spray processes

Tem

pera

ture

(103

K)

10

15

Plasma Spray

15

Gas

Tem

pera

ture

5

Particle velocity (m/s)1000750500250

HVOF

Cold Spray

Powder

Flame

TwinWire Arc

WFS

Flexcord,

Rokide HVAF

Thermal spray penetration in the industryAerospace engines since 1960-1970s

High quality standards

Quality control through heavy laboratoryanalysis « full control »

Nuclear Industry since 1970sHigh quality standards

Quality control through heavy laboratoryanalysis « full control »

Semiconductor industry (wafer treatment

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Semiconductor industry (wafer treatmentchambers) since 1990s

High quality standards

Quality control through heavy laboratoryanalysis « full control »

Traditionnal industry (Paper & printing, Mechanics): since 1960-70s

…BUT still limited use in Automotive Industry, Very high volume consumption goods

Key challenges faced by thermal spray in the past

Become a 100% reliable / predictable technology

Not dependent on some « experts » to deliverthe expected result

Pluggable in an automated line

Manageable with SPC only

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Manageable with SPC only

Become a recognized « technology brick » for the technical design teams

Consider the coating as part of the design of a system…not the last minute lifeline in case of need only

RECENT EVOLUTIONS RECENT EVOLUTIONS IN THERMAL SPRAY IN THERMAL SPRAY

⇨ ⇨ ⇨ ⇨ ⇨ ⇨ ⇨ ⇨ NEW ERANEW ERA

Evolutions in Spray Equipments

High reliability components (mass flowmeters, transistor power supply, etc…)

PLC with management of pre-defined Recipes & access control

Closed loop control of all spray Closed loop control of all spray parameters

Touch screen displays

Interfacing with surrounding PLCs, Robot, etc…

Remote control

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Evolutions in Process ControlProcess parameters doesn’t allow to predict coatingquality : Relation between Process parameters and Coating properties is not bijective

In the past : eyes, experience, feeling, trials and e rrors.

New development since 2000’s : in-flight diagnostics to capture (T, V) state of the particles

Powerful tool for Process development and for Process

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Powerful tool for Process development and for ProcessControl in production

Evolutions in Process Control

A good plasma doesn’t mean a good coating !

ControlVision (laser backlight ⇨ ⇨ ⇨ ⇨ shadowgraphy)

R&D / Process development - 1 st order process maps

Process maps for plasma spraying of yttria-stabilized zirconia: An integrated approach to design, optimization and reliabilityA.Vaidya, V. Srinivasan, T. Streibl, M. Friis,W. Chi, S. Sampath

Materials Science and Engineering A 497 (2008) 239–253

Coating design – 2 nd order process maps

Process maps for plasma spraying of yttria-stabilized zirconia: An integrated approach to design,

optimization and reliabilityA.Vaidya, V. Srinivasan, T. Streibl, M. Friis,W. Chi, S.

SampathMaterials Science and Engineering A 497 (2008) 239–253

• Zone I: low stiffness and low thermal conductivity regime.• Zone II: moderate compliance and moderate thermal conductivity regime.• Zone III: stiff, higher thermal conductivity regime.

Application of 2 nd order Process maps : Thermal Barrier coatings (YSZ)

Process maps for plasma spraying of yttria-stabilized zirconia: An integrated approach to design, optimization and reliabilityA.Vaidya, V. Srinivasan, T. Streibl, M. Friis,W. Chi, S. Sampath

Materials Science and Engineering A 497 (2008) 239–253

Other diagnostics

Heat flux measurements with Calorimeter

Enthalpic probe to determine plasma enthalpy

In-Situ Coatings Properties : beam (substrate) deflection during spraying and after cooling → Evolving stresses and residual stresses

Temperature

Deflexion

Manufacturing processes of ceramic powders for TS

Feed fine powders

1-3 µm

Fusion & Crushing

Feed fine powdersor precursors

Agglomeration& sintering

Crystal growth SpecialAgglomeration & plasma fusion

Spray-drying + flash fusion

Typical sizes requested for Thermal spray : from d50 = 15 µm to d50 = 80 µm

Sintering

Hollow & spherical particles

Agglomeration

Firing

Consumables engineering

Tight control of PSD from batch to batch ⇨ ⇨ ⇨ ⇨

process reliability

20

25

Spherical shape preferred for process consistency

Particles morphology & density control

Full traceability

27

0

5

10

15

20

0 50 100 150 200 250 300

Full traceability

Consumables engineering - example

Optimum Morphology for the product & the coating features

Perfect powder morphology (easy-to-melt) for extremely

28

for extremely dense coatings

Yttria(Tm=2700°C) very dense coating >99%)

OPPORTUNITIESOPPORTUNITIESFOR THERMAL SPRAYFOR THERMAL SPRAY

Thermal Spray made its (r)evolution

Thermal Sprayed Coatings can be designedprecisely , from material & process to properties

…and should be part of the designing processof any system, as a technological brick available for designers

Opportunities still large in several industries where this technology is not used

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Thermal spray enlarge its scope : suspension thermal spray

Physical / ChemicalVapor Deposition

PVD / CVD

Diffusion/Conversion Coating processes

Plating Coating processes

Wet coating + firing

Thermal Spray

CladdingHardfacing

Suspension Thermal Spray

31

1 nm1 µm

10 µm50 µm

200 µm1 mm

Metals

Ceramics

Polymers

Composites

Mega-trends create opportunities for coatingsLightening of components in transportation

Lightweight alloys, composites, can’t fulfill all required functionnalities

Friction performance

Wear resistance

Electrical surface properties

Corrosion protectionCorrosion protection

Environmental & Safety regulationsHard Chrome plating replacement

Energy production mix evolutionGas turbines

Nuclear

SOFC

Solar thermal CSP32

4ième SéminaireTTH &

Revêtementsinnovants

16 & 17 Octobre

Merci pour votre attention

Thank you for your attention

Lyon - Métropole

16 & 17 Octobre 2014

Dominique BILLIERESR&D Manager for Coating Solutions Business Unit

Saint-Gobain Coating Solutions