CEAC Summer Workshop 1999:

Functionalized Surfaces: Application and Analytical Tools

July 5-6, 1999
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Thermally Sprayed Coatings

and their Characterization
Techniques
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EMPA-Thun

St. Siegmann,
O. Brandt, M. Aeberhard Abt. 126 / SI (99)

Thermally Sprayed Coatings and

their Characterization Techniques
1. Thermal Spraying ®Coating Morphology
2. Characterization Techniques:
2.1 Destructive Test Methods:
- Coating Adhesion
- Metallographical Preparation
- Hardness Testing
- Chemical Composition (e.g. GDOS)
- Wear Testing
- Corrosion Testing
2.2 Non-destructive Test Methods:
- Coating Thickness Measurements
- Ultrasonic Testing
- Thermal Imaging Abt. 126 / SI (99)

12.02.2002 1
 History of Thermal Spraying:

Dr. Max U. Schoop

Born: April 10, 1870 in Frauenfeld (TG)
Deceased: February 20, 1956 in Zürich
(Drawing from 1920)

from: Tagungsunterlagen zum 3. Kolloquium über Hochgeschw.-Flammspritzen, Dr. K. Kirner Abt. 126 / SI (99)

Classification of Thermal Spraying (according EN 657)

Thermal spraying

Thermal Thermal
Thermal Thermal spraying by
spraying spraying
spraying by gas electric gas discharge
by beam by liquid

Molten bath Flame Detonation High velocity

Laser spraying Arc spraying Plasma spraying
spraying spraying spraying flame spraying

Powder flame Wire flame Liquid stabilised Plasma Plasma spraying

spraying spraying plasma spraying spraying in air in chambers

Abt. 126 / SI (99)

12.02.2002 2
 Different Thermal Spray Torches:
Flame Spraying Electric Arc Spraying

Detonation Gun
Spraying

High Velocity
Oxygen Fuel
Spraying Plasma Spraying

from: Stan Grainger, "Funktionelle Beschichtungen in Konstruktion und Anwendung" Abt. 126 / SI (99)

Thermal Spraying by Principle:

heat + powder = molten droplets

voids

substrate

"clamping"
v
"local alloying"
Temperature

T boiling

T melting dT/dt = 106 K/s

T substrate

RT
Abt. 126 / SI (99)
time

12.02.2002 3
 Thermal Spraying in „Reality“:
Powder Splats Coating / Substrate
1) 2)

3)

Ref 1: Edward J. Kubel Jr. in Adv. Mat. & Proc. 12/90

Ref 2: R.C. Dykhuizen in Journ. of Therm. Spr. Techn. Vol 3, No. 4 (94)
Ref 3: M. Vardelle et al. in Journ. of Therm. Spr. Techn. Vol 4, No. 1 (95) Abt. 126 / SI (99)

Thermally Sprayed Cr2O3-

Coatings (created by different processes)

flame sprayed plasma sprayed HVOF sprayed

Abt. 126 / SI (99)

12.02.2002 4
 2. Characterization Techniques

2.1 Destructive Test Methods

2.1.1. Coating Adhesion (EN 582, ISO/DIS 14916)

2.1.2. Metallographical Preparation for LM, SEM, etc.

2.1.3. Hardness Testing

2.1.4. Chemical Analysis (e.g. GDOS, and others)

2.1.5. Wear Testing

2.1.6. Corrosion Testing

Abt. 126 / SI (99)

Tensile Adhesive
Strength Test
(EN 582, ISO/DIS 14916)

Tensile testing
machine :
Frame for glueing 5 samples Epprecht: 250 kN
(left: empty, right: with samples)

Abt. 126 / SI (99)

12.02.2002 5
 Metallographical
Preparation
Investigation of:
Coating thickness, coating
morphology (structure, phases,
porosity), bonding to substrate,
micro hardness from: DVS 2310-1 Merkblatt

Steps:
1. Sectioning
2. Embedding (organic binder, event. vacuum infiltration)
3. Grinding (e.g. SiC 180 to 1200)
4. Polishing (6, 3, 1, 1/4 µm)
5. Cleaning
6. Event. sputtering for interference layer contrast (e.g. ZnSe, ZnTe)
7. Electrolytic -, chemical etching
8. Investigation (LM, SEM) Þ Interpretation
Abt. 126 / SI (99)

Hydroxyapatite Coatings for

Biomedical Applications:

atmospheric vacuum
plasma sprayed plasma sprayed

Abt. 126 / SI (99)

12.02.2002 6
 Hardness Testing
w ISO 4516 Metallic and related coatings; Vickers and Knoop
microhardness tests
w ISO 6506 Metallic materials; Hardness test; Brinell test
w ISO 6507-1 Metallic materials - Vickers hardness test - Part 1:
Test method
w ISO 6507-2 Metallic materials - Vickers hardness test - Part 2:
Verification of testing machines
w ISO 6507-3 Metallic materials - Vickers hardness test - Part 3:
Calibration of reference blocks
w ISO 6508 Metallic materials; Hardness test; Rockwell test
(scales A - B - C - D - E - F - G - H - K)

Abt. 126 / SI (99)

Example of Microhardness Test

on a Thermally Sprayed Coating

HV » 0.1891 x F/d2

Abt. 126 / SI (99)

12.02.2002 7
 Chemical Analysis

w X-Ray Fluorescence Analysis (XRF)

w Glow Discharge Optical Spectroscopy (GDOS)
w Mass Spectrometry (MS)
w Energy Dispersive X-Ray Analysis (EDX)
w Electron Probe Micro Analysis (EPMA)
w Transmission Electron Microscopy (TEM)
w and many others ...
Abt. 126 / SI (99)

Glow Discharge Optical Emission

Spectroscopy GDO(E)S
...Optical Emission Spectroscopy
Glow Discharge ...

Abt. 126 / SI (99)

12.02.2002 8
 I

Abt. 126 / SI (99)

Concentration
1.0 ppm 100 ppm 1% 100%
0.1 nm
Surface

1 nm
Information Depth

10 nm

100 nm

1 µm
Bulk

10 µm

Abt. 126 / SI (99)

12.02.2002 9
 Comparison of Different Methods
Eigenschaften AES SIMS ESCA ESMA SNMS GDOS

erfassbarer 1 - 100 0,3 - 103 1 - 100 Querschliff 0,5 - 104 1 - 105

Tiefenbereich in nm ohne ohne ohne
Zerstäubung Zerstäubung Zerstäubung
Informationstiefe in 1-6 0,5 - 1 0,5 - 10 1000 1-2 mit
nm Zerstäubung
1 - 100
Tiefenauflösung in 2 nm 10 nm 0,5 nm 0,1 nm 10 7 - 12
% der abgetragenen ohne mit ohne
Tiefe Zerstäubung Zerstäubung Zerstäubung
Tiefenprofilanalyse 1 - 2 µm mit > 10 µm mit 1 µm mit Querschliff Zerstäubung in Zerstäubung in
technischer Zerstäubung; Zerstäubung; Zerstäubung; die Tiefe die Tiefe
Schichten oder Querschliff Querschliff 5 - 10 µm 40 - 150 µm
Querschliff mater. abh.
laterale Auflösung 0,2 µm 0,3 µm 200 µm 1 µm 20 µm 2,5 - 8 mm
Simultananalyse keine keine keine keine keine max. alle
Elemente
typische element- teilweise bis 0,1 - 1 0,1 - 10-3 0,1 - 10-4 10-2 - 10-4
Nachweisgrenzen abhängig 10-4
in % 0,1 - 5
Nachweis leichter > 0,1 atom % alle alle ohne H nicht unter alle alle
Elemente und Z ³ 3 einschliesslich 0,1 % einschliesslich einschliesslich
H H H
Quantitative nicht sehr nur in ±5% leichte Quantifizierung Quantifizierung
Messung genau homogener verschiedene Elemente
Matrix Elemente schwierig bis
unmög.
AES = Auger Electron Spectroscopy Ref. H. Böhm, Oberflächen Werkstoffe, Nr.4/94
SIMS = Secondary Ion Mass Spectroscopy
ESCA = Electron Spectroscopy for Chemical Analysis
ESMA = Elektronenstrahl Mikroanalyse = EPMA = Electron Microprobe Analysis
SNMS = Secondary Neutral Mass Spectroscopy Abt. 126 / SI (99)
GDOS = Glowdischarge Optical Spectroscopy

Typical Applications of GDOS:

• Quality control for different coating systems
(e.g. car industry)
• Galvanic coatings
• Thin films (Semiconductor industry)
• Paintings
• Thermal Spraying
• Diffusion zones
• and many others ...
Abt. 126 / SI (99)

12.02.2002 10
 Quantitative Calibration of Si
Content in Different Matrices
45
40 Aluminum
35 Cast iron
Concentration (%)

30 Steel
Brass
25
20
15
10
5
0
Intensity (Volt)
Abt. 126 / SI (99)

TiN + TiCN on Steel

100

90
Steel
80

Fe
Konzentration in %G

70
N
60
Ti
50

40
Ti
30 N
20

10
C
0
0.0 2.0 4.0 6.0 8.0 10.0 12.0
Tiefe in µm
Abt. 126 / SI (99)

12.02.2002 11
 Paintings on Tinplate

Abt. 126 / SI (99)

Advantages
GDOES
... is a quantitative chemistry analysis method
... for conductive and non conductive materials (RF)
... for high concentration range (ppm ...100 %)
... offers good resolution in depth (nm)
... offers good integration in lateral size (spot diameter)
... offers fast response (1 ... 10 µm/Min.)
... up/down to 100‘s of microns
... analysis of all elements (H...U) simultaneously
... keeps substrate temperature low
... needs no wet chemistry
Abt. 126 / SI (99)

12.02.2002 12
 Some Wear Testing Standards
ASTM G 32: Test Method for Cavitation Erosion Using Vibratory
Apparatus (1992)
ASTM G 65: Test Method for Measuring Abrasion Using the Dry
Sand/Rubber Wheel Apparatus (1994)
ASTM G 73: Liquid Impingement Erosion Testing (1993)
ASTM G 75: Test Method for Determination of Slurry Abrasivity
(Miller Number) and Slurry Abrasion Response of
Materials (SAR Number) (1995)
ASTM G 76: Conducting Erosion Tests by Solid Particle Impingement
Using Gas Jets (1995)
ASTM G 99: Test Method for Wear Testing with a Pin-on-Disk
Apparatus (1995)
Abt. 126 / SI (99)

Abt. 126 / SI (99)

12.02.2002 13
 aus: DIN 50320 Verschleiss; Begriffe, Systemanalyse von Verschleissvorgängen, Gliederung des Verschleissgebietes

Abt. 126 / SI (99)

ASTM G 32 - 92:
Test Method for
Cavitation
Erosion Using
Vibratory
Apparatus

Bestimmung der
Kavitations-
erosion an
vibrierenden
Proben
Abt. 126 / SI (99)

12.02.2002 14
 ASTM G 65 - 94:
Test Method for Measuring
Abrasion Using the Dry
Sand/Rubber Wheel
Apparatus

Richtlinien für die

Durchführung von
Abriebversuchen mit
Trockensand und
rotierendem Gummirad
Abt. 126 / SI (99)

ASTM G 75 - 95:
Determination of Slurry
Abrasivity (Miller Number)
and Slurry Abrasion
Response of Materials
(SAR Number)

Bestimmung der
Schleifwirkung von
Schlamm nach dem
Nummernsystem von
Miller Abt. 126 / SI (99)

12.02.2002 15
 100

Volumetric
material loss
tested 10

according to
ASTM G 75 1

as a function
of materials
hardness 0,1
100 1000 10000

Ref. WF-Project, O. Brandt, St. Siegmann

Abt. 126 / SI (99)

Erosion Test Equipment

Erosionskammer
Hochdruck-
pumpen-
anschluss

Mischkopf
Abb.2

Pneumatischer
Schliesser
Proben-
halterung
mit Ver-
formungs- Vertikale
Bedienpult einrichtung Führung
Abb. 8

Höhen-
verstellung Horizontale
vergl. Führungs-
Pulverförder Abb. 6 schiene
Absetzbecken

Ref. L. Kirchhoff, O. Brandt

Abt. 126 / SI (99)

12.02.2002 16
 ASTM G 99: Pin-on-Disk Tribometer
(compatible with DIN 50324)

Rotation speed: 0.03 to 500 rpm

Forces: 1 to 60 N
Standard loads: 1, 2, 5, 10 N
Disk dimensions: r = 60 mm,
h = 15 mm

Abt. 126 / SI (99)

Some Technical Corrosion Tests

prEN 4437: Test Method of Salt Spray

(Fog) Testing

EN ISO 6988: Sulfur dioxide test with general

condensation of moisture

ASTM B 368: Acetic Acid-Salt Spray (Fog)

Testing (CASS Test)

Abt. 126 / SI (99)

12.02.2002 17
 Corrosion
Testing

Fig: O. Brandt

Abt. 126 / SI (99)

Results from Corrosion Tests

Same coating material:

porous (atmospheric dense (vacuum plasma
sprayed) and showing sprayed)
interface corrosion
Abt. 126 / SI (99)

12.02.2002 18
 2. Characterization Techniques

2.2. Non-destructive Test Methods

2.2.1. Coating Thickness Measurements

2.2.2. Chemical Composition (see also 2.1.4)

2.2.3. Ultrasonic Testing

2.2.4. Thermal Imageing

Abt. 126 / SI (99)

Standards for Coating Thickness Measurements

1. ENV 1071-2
Determination of coating thickness by the cap grinding method
2. ISO 1463
Measurement of coating thickness; Microscopical method
3. ISO 2064
Definitions and conventions concerning the measurement of thickness
4. ISO 2177
Measurement of coating thickness; Coulometric method by anodic
dissolution
5. ISO 2178 Measurement of coating thickness; Magnetic method
6. DVS 2303-1 Non-destructive testing of thermally sprayed coatings, thickness
measurements
7. ISO 2360 Measurement of coating thickness; Eddy current method
8. ISO 2808 Paints and varnishes - Determination of film thickness
9. ISO 3497 Measurement of coating thickness; X-ray spectrometric methods
10. ISO 3543 Measurement of thickness; Beta backscatter method
11. ISO 3868 Measurement of coating thicknesses; Fizeau multiple-beam
interferometry method; Mehrstrahlinterferometer-Methode nach Fizeau
12. ISO 3882 Review of methods of measurement of thickness
13. ISO 4518 Measurement of coating thickness; Profilometric method
14. ISO 9220 Measurement of coating thickness; scanning electron
microscope method
Abt. 126 / SI (99)

12.02.2002 19
 Ultrasonic Testing on Coatings
(by principle)

from: Krautkrämer, Zerstörungsfreie Werkstoffprüfung mit Ultraschall, Einführung in die Grundlagen

Abt. 126 / SI (99)

Ultrasonic Picture of Coating

and Adhesion Defects
Gradient:
metal /
ceramic

metallic
inclusions

ceramic ground
layer

roughness
defect

corrosion

substrate
Ultrasonic picture Optical picture
(from back side) (from top side) Abt. 126 / SI (99)

12.02.2002 20
 Thermal Imaging
on Thermally
Sprayed
Coatings
(by principle)

Ref. DACS / IBF

Abt. 126 / SI (99)

Investigation by Thermal Imaging

Optical picture Thermographic picture

Ref. EMPA Ref. DACS / IBF

Abt. 126 / SI (99)

12.02.2002 21
 Conclusions: Characterization
Industry: Research:
as much as as much as
necessary possible

Many standardized test methods available

• for coating development
• for coating quality assurance
• for characterizing coating failure
but still needs
better predictability of coating reliability
Abt. 126 / SI (99)

12.02.2002 22