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GFE Schmalkalden e.V.

Principles of Coating Technology


Part I - Basics
1.
2.
3.
4.
5.

Motivation
Tribology and Wear
Surface properties and characterization
Pre-and post-treatment
Deposition methods - Overview

Part II Deposition methods


6.
7.

Painting
Electroplating and anodic oxidation
1

Principles of Coating Technology I

GFE Schmalkalden e.V.

1.

Principles of Coating Technology I

Motivation

GFE Schmalkalden e.V.

Motivation
Some Numbers

4.5 %
>50 Mrd

of the national product of industrialized nations


are material and energy loss by wear and corrosion on
metallic parts

5%

of sales
are used for repair and maintenance (in wear intensive
industry 10-15%)

10 %

of production costs are maintenance costs

10 %

of wear parts in industrial equipment


are involved in 70% of failures and disorders

50 %

of wear loss are preventable


3

Principles of Coating Technology I

GFE Schmalkalden e.V.

Motivation

Loss of material and energy by wear and corrosion must be avoided


Preventable maintanence
to act is better than to react
Using functional material for machine function
wear and corrosion protection as design elements

Surface protection by functional coating and surface technology

Principles of Coating Technology I

Motivation

GFE Schmalkalden e.V.

Example: Production of phones


Costs () for annual production of 1 Mio units
Without
coating

BALINITcoating

tools

31.800

15.700

maintanance

17.200

Coating
total

Source: Siemens AG

800
49.000

16.500

Annual coating costs


(200 different models)
800 x 200 =

160.000

Savings per annual


(200 different models)
32.500 x 200 =

6,5 Mio

Principles of Coating Technology I

Motivation

GFE Schmalkalden e.V.

Industrial Application

Wear protection in mining

Coating of wear parts


Principles of Coating Technology I

Print roll (printing industry)

Power generation (turbine blades)


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Motivation

GFE Schmalkalden e.V.

Using coated band saw to separate submarine Kursk in 2001

Principles of Coating Technology I

Motivation

GFE Schmalkalden e.V.

Application samples of coated parts

Hip implant

Engine block
EUROFLAMM

Synchronrings

Principles of Coating Technology I

Household devices

Motivation

GFE Schmalkalden e.V.

Application samples of coated parts


Industry

Coated components

aerospace

Landing gear, airbrakes

Industrial gas turbines

Blades, abrasive coatings, cumbustion coatings

engines

Cylinder holes, wear coatings, Synchronrings

Paper, printing, steel industry

Printing and transportation rolls

Oil and gas equipment

Pump engines, seals, shafts, compressor shafts

Medicine

Implants, x-ray targets

Textile machines

rolls

Other industries

Components and parts

Consumer goods

Flat irons, writing utensils, frying pan

On-site maintenance

Steam generator, paper rolls, gas turbines

Principles of Coating Technology I

GFE Schmalkalden e.V.

2.

Principles of Coating Technology I

Tribology and Wear

10

Tribology and Wear

GFE Schmalkalden e.V.

Loss of material and energy by wear and corrosion must be avoided


Protection of the surface by coating system or surface modification
Consideration of the tribological system

Tribological system
load
velocity
intermediary

metal
mineral
Liquid
gaseous
liquid
solid
gaseous

Counter body

metal
mineral
plasic
elastomere

Base body
enviroment

liqud
gas
dust
temperarture
11

Principles of Coating Technology I

Tribology and Wear

GFE Schmalkalden e.V.


Consideration ofVerschleipaarungen
the tribological system
Verschleipaarungen
Verschleipaarungen
Determination of the wear mechnism
Solid/solid

Festkrper /
Festkrper
Festkrper //
Festkrper
Festkrper

Solid/liquid
Festkrper/
Festkrper/
Flssigkeit
Festkrper/
Flssigkeit
Flssigkeit

sliding

Mechanismus
Mechanism

sliding wear

adhesion
/ abrasion
Adhsion

Verschleiart
Verschleiart

Gleiten
Gleiten
Gleiten
rolling
Rollen
Rollen
Rollen
impact
Prallen
Prallen
Prallen
vibrations
Schwingen
Schwingen
Schwingen

Gleitverschlei
Gleitverschlei
Gleitverschlei
rolling wear
Wlzverschlei
Wlzverschlei
Wlzverschlei
impact wear
Stoverschlei
Stoverschlei
Stoverschlei
vibration wear
Schwingverschlei
Schwingverschlei
Schwingverschlei

Strmen
flowing
Strmen
Strmen
Prallen
Prallen
impact
Prallen

Kavitation
cavitation
Kavitation
Kavitation
Tropfenschlag
Tropfenschlag
droplet erosion
Tropfenschlag

Festkrper/
Strmen
Festkrper/
Gas
mit/FestSolid
gas with solid Strmen
flowing
Festkrper/
Strmen
Gas
mit
Feststoffpartikeln
Prallen
Gas
mit Festparticles
stoffpartikeln
Prallen
stoffpartikeln
impact
Prallen

Principles of Coating Technology I

Verschleiart
Wear
type

Mechanismus
Mechanismus

Abrasion
Adhsion

Adhsion
Abrasion
adhesion
/ fatigue
Abrasion
Adhsion
Ermdung
Adhsion

Adhsion
Ermdung
fatigue
/ adhesion
Ermdung
Ermdung
Ermdung

Ermdung
fatigue
Adhsion
Ermdung
Adhsion
Adhsion
Ermdung
Ermdung

Ermdung
fatigue
Ermdung
Ermdung

Ermdung
fatigue
Ermdung
Ermdung

Gleitstrahlverschlei
Abrasion
sliding jet wear
abrasion
Gleitstrahlverschlei
Abrasion
Gleitstrahlverschlei
Abrasion
Prallstrahlverschlei
Ermdung
impact
jet
wear
fatigue
Prallstrahlverschlei
Ermdung
Prallstrahlverschlei
Ermdung

VERSCHLP.CDR
VERSCHLP.CDR
VERSCHLP.CDR

Verschleipaarung
Wear combination Beanspruchung
loading
Verschleipaarung
Beanspruchung
Verschleipaarung
Beanspruchung

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Tribology and Wear

GFE Schmalkalden e.V.

Wear depth
Adsorption
layer
Outher
unrelated
surface layer
Inner related
surface layer

Oxide-Reaction zone

Distubtion by
forming and
modified chemical
composition

Coating wear

Corrosion
wear
Adhesive wear
Abrasive wear

Surface fatigue wear

Base material

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Principles of Coating Technology I

Tribology and Wear

GFE Schmalkalden e.V.

wear
Linear
Linearer
Verschleibetrag

Progress of wear

ion
as
r
Ab

sion
Adh

n
. Reaktio
Tribochem
g
ttun
err
z
n
he
rflc
Obe

Weg,
Zeit time
Distance,

Principles of Coating Technology I

Source: Uni Dortmund, LWT

14

Tribology and Wear

GFE Schmalkalden e.V.

Reduction of wear
Reduction of abrasion:

high hardness with adequate ductility


Hard phases in a ductile matrix

Reduction of adhesion

unrelated surface layer,


lower adhesive bonding force
material with heterogeneous structure

Reduction of fatigue:

high strength with high ductility


avoiding of stress concentrations

Reduction of thermal fatigue

high thermal strength


reduction of loading by thermal insulation layers

Reduction of tribo-oxidation: avoiding of reactive layers

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Principles of Coating Technology I

Tribology and Wear

GFE Schmalkalden e.V.

Important physical processes


Adsorption:

Accumulation of liquid oder gaseous materials


(adsorbens) on the surface of solid parts (adsorbat)
Saturation of bonding states on the surface leads to the
reduction of the fee energy (steady state)

Physical adsorption
Interaction of induced or permanent
dipoles (Van-der-Waals-forces)
Adsorption heat 4 40 kJ/mol
Process is reversible

Absorption:

Chemical Adsorption
Formation of a chemical bonding
Adsorption heat 40 400 kJ/mol
Process is not reversible

infiltration of gaes or gaseous mixtures by diffusion processes in a


condensed (solid) phase
The absorbed gas will be dissolved in a steady state at defined
temperatures and concentrations, molecules will be dissociated to
atoms

Principles of Coating Technology I

16

Tribology and Wear

GFE Schmalkalden e.V.

Important physical processes


Adhesion:

adhesive forces on the contact area of two (liquid or solid) material


Physical and chemical adhesion
Mass attraction
Mechanical clamping

Cohesion:

cohesive forces within a material or body


Primary bonding chemical bonding
Secondary bonding partial bonding, Van-der Waals Bonding

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Principles of Coating Technology I

Tribology and Wear

GFE Schmalkalden e.V.

Important physical processes


Wetting: Formation of a contact or boundary angle at the boundary between a solid and
a liquid
In the steady state the Young Equation is valid:

= + cos
, :
:
:

surface tension of the solid and the liquid


surface tension between solid and liquid
contact angle

Wetting:
< 90
No wetting:
> 90
Complete wetting: > +

Principles of Coating Technology I

18

GFE Schmalkalden e.V.

3.

Surface properties and characterization

19

Principles of Coating Technology I

GFE Schmalkalden e.V.

Surface properties and characterization

Definition of the coating deposition processes

Deposition is the application of an adherend coating of


shapeless material on a component.
Function of coatings are
Decoration
information (signals)
corrosion protection
wear protection
physical effects (diffusion barrier, flame barrier, thermal isolation,
electrical isolation, )

Principles of Coating Technology I

20

10

Surface properties and characterization

GFE Schmalkalden e.V.

Materials for surface modification

Processes for surface modification

mechanical (e.g. shot peening)

Pure metals (chromium, zinc, gold, )

thermal (partial laser hardening)

Alloys for special applications (e.g.


corrosion)

thermo-mechanical (e.g. hot isostatic

pressing

Anorganic, non-metallich (enamal,


ceramics)

Thermo-chemical (e.g. nitriding)

Organic (pintings, polymers)

Compounds

21

Principles of Coating Technology I

Surface properties and characterization

GFE Schmalkalden e.V.

Coating application fields

optics

Heat
insulating

High
Temperature
protection

Bearring

Coating of
new parts

decoration

Repair
coatings
Oxidation
protection

Principles of Coating Technology I

Bioactivities
Wear
protection

Corrosion
protection

Elcetrical
properties

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Surface properties and characterization

GFE Schmalkalden e.V.

Relevant surface properties


primary

secondary

Chemical composition

elasticity

Phase composition

hardness

Structure and microstructure

strength, fatigue strength

Residual stress

friction and sliding properties

Surface roughness

corrosion resistance

wear resistance

optical properties (colour, coverage)

electrical / thermal conductivity

Important: characterization of the properties


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Principles of Coating Technology I

Tribology and Wear

GFE Schmalkalden e.V.

key property: coating adhesion

Adhesion > coating strength

Adhesion < coating strength

adhesion is influenced by

Surface energy

Material properties (e.g. strength,


conductivity, )

adhesion mechanism:

Mechanical clamping

Adhesion

Diffusion

Surface material interaction


Bonding mechanism
Residual stresses (High residual
stresses lead to coating delamination

Principles of Coating Technology I

Chemical bonding
Electrostatical forces

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12

Surface properties and characterization

GFE Schmalkalden e.V.

Methods for measurements

Measurement of coating properties

coating thickness
coating adghesion strength
Hardness
Wear resitance at diferent loads
Friction coefficient
corrosion properties
Thermal properties
Mechanical properties (ductility,
elasitcity, stresses,
Electrical properties (conductiviy,
resistance,
Optical properties (color, brillance, )
Surface roughness

Metallographic investigations

Corrosion behaviour

Wear behaviour

Thermal behaviour

Mechanical behaviour

Optical behaviour

Destructive and nondestructive tests


are possible
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Principles of Coating Technology I

Surface properties and characterization

GFE Schmalkalden e.V.

Methods for measurements


Mechanical values of coating
Bond strength test (<80 MPa)
bending test
test of fatigue strength
thermal shock test

cupping test
measurement of residual stresses
creep behaviour

Metallographic evaluation
structure and microstructure
phase boundaries
pores and pore distribution

micro- / macro- hardness


Interface coating / substrate
roughness

corrosion behaviour
salt-spray test, thermal test, current density potential test
Wear behaviour
Taber-Abraser-Test; pin on disc test; vibrational wear
.

Extremely high number of other tests with or without standards


Principles of Coating Technology I

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13

Surface properties and characterization

GFE Schmalkalden e.V.

Measurement examples
Measurement of coating thickness d
- Simple and cheap procedure
- Fast measurement
- Destructive method
parameters:
grinding time
ball diameter
Preparation of a calotte grinding
-

friction pair coating / ball)


Measurement of the diameter
of the grinded calotte

27

Principles of Coating Technology I

Surface properties and characterization

GFE Schmalkalden e.V.

Measurement examples
Measurement of wear behaviour
- Destructive method
- Pin-On-dic method
- Determination of the friction and
the wear coefficient
Methode
Ball with defined load
Interaction with a coated surface
Friction between ball and surface
Measurement of Wear trace;
Determination friction coefficient :(FR = FN * R)
Parameter:
Normal force
Rotational speed
Speed
Trace diameterLaufspurdurchmesser
Friction length
rotation
Friction time
Principles of Coating Technology I

[N]
[s-1 ; m-1]
[m/s ; m/min]
[mm]
[m]
[min]
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14

GFE Schmalkalden e.V.

Surface properties and characterization


Measurement examples

Measurement of coating hardness

Micro harndess messurement


Measurement of the indentation of an
indenter (diamond pyramide) with
difined load
Determination of hardness by relation of
geometriy and load

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Principles of Coating Technology I

GFE Schmalkalden e.V.

Surface properties and characterization

Measurement of coating adhesion strenth

Scratch-Test
Diamond indenter will be moved with a defined
load along the coated surface
At critcal load: coating delamination or crack
formation
Determination and evaluation of the scratch

Measurement examples

Diamond
indenter

Depth
sensor
Acoustic
emission
sensor

Moving direction of the probe

Principles of Coating Technology I

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15

Surface properties and characterization

GFE Schmalkalden e.V.

Measurement examples

Measurement of roughness

Mechanical method (tactile scanning)


Measuring sensor are moved with
constant speed along the surface
Recording of the different roughness
values

Ra= 0.2 - 0.45 m

Ra= 0.07 - 0.15 m


31

Principles of Coating Technology I

GFE Schmalkalden e.V.

4.

Principles of Coating Technology I

Pre-and post-treatment

32

16

Pre- and Posttreatment

GFE Schmalkalden e.V.

Process steps during coating deposition


1.

Pre-treatment
cleaning
Surface activation
roughening

2.

Coating deposition
Determination of coating technology and parameters
Surface protection

3.

Post-treatment
Homogenization of the coating
Additional improvement of the properties

4.

Measurement of coating quality g


Mechanical values
metallographic values
Wear and corrosion
33

Principles of Coating Technology I

Pre- and Posttreatment

GFE Schmalkalden e.V.

Pre- Treatment
Cleaning

- removal of dirt
- removal of oils and greases
- removal of paints

Blasting

- roughening
- decontamination
- activation

Blasting materials

- sand (improper due silkose)


- corund (Al2O3)
- grit
- pellets
- carbides

Ultrasonic assited claning

- removal of blasting residues

Principles of Coating Technology I

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Pre- and Posttreatment

GFE Schmalkalden e.V.

Post- Treatment
Objective:

homogenization of the coating or the surface near areas to improve the


properties (e.g. corrosion resitance, wear resistance)

reduction of porosity

Smoothing of the surface

Improvement coating adhesion

Reduction of residual stresses

Improvement of coating hardness and ductility

Closing of cracks

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Principles of Coating Technology I

Pre- and Posttreatment

GFE Schmalkalden e.V.

Post- Treatment
Thermal Post-Treatment:

flame (z.B. acetylen/ oxygen)


arc (tungsten inertgas weld method)
Laser beam
Electron beam
induction

Thermo-mechanical

hot isostatic pressing (HIP)

Mechanical

final expanding
hammering
shot peening
simultaneous spraying and peening

Principles of Coating Technology I

36

18

GFE Schmalkalden e.V.

Pre- and Posttreatment

Thermal Post-Treatment
Fuly or partial remelting of the surface with and energy source (flame, laser beam, ) for
-

Smoothing of rough surfaces

Dissolving of unwantet phases

Creation of additional hard phases

Hardening of thin layers

Example: Laser remelting


Laserstrahl
Laser beam

Coated
part
Bauteil

Bewegungsrichtung
Moving
direction of the probe

Requirements and parameters:


Avoiding of cracks due to different
thermal expansion coefficients
Pre-heating possible
Adjustment of process parameters
Feed rate
Laser power
Laser focus point
Shielding gas

37

Principles of Coating Technology I

GFE Schmalkalden e.V.

Pre- and Posttreatment

Thermal Post-Treatment
Heat treated Ti-coating with reaction zone

Electron beam surface remelted NiCrAl


coating

Laser remelted TiMo coating


Principles of Coating Technology I

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Pre- and Posttreatment

GFE Schmalkalden e.V.

Thermal Post-Treatment
modification of the adhesive strength by different thermal post treatment processes
- Remelting without reaction zone: adhesive strength is reduced
- Remeling with reactive zone: increasing of adhesive strength
> 65

Adhesive tensile strength [MPa]

80
57
70
60
38,5

glue
coating

50
40
30

Probe

20
10
0
wie gespritzt
As sprayed

umgeschmolzen mit
remelted
fusion
Aufmischung

umgeschmolremelted
zen mit
Reaction
Reaktzone
ions-

zone

coating

Adhesive tensile strength


According to DIN EN 582

substrate

39

Principles of Coating Technology I

GFE Schmalkalden e.V.

Pre- and Posttreatment

Thermo-mechanical Post-Treatment
Hot isostatic pressing (HIP)
-

Material will be loaded with high temperature and high pressure in one process step

Pressure carrier is inert gas

HIP will be used for compacting of poros structures (eg sintering of ceramics)
Processes during HIP
diffusion
creeping
Modification dring hip
Structural compacting, removal of pores
Phase formation within the coating
Grain growth wihin coating

Principles of Coating Technology I

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Pre- and Posttreatment

GFE Schmalkalden e.V.

Thermo-mechanical Post-Treatment
Hot isostatic pressing (HIP) - Example
Production of metal matrix composites (MMC)
-

Twisting of fibres on a base body

Deposition of the metalic matrix

Hot isostatic pressing

Using for brake drums, cylinder sleeves, drive shafts


Sttzkrper
(geschliffen)

Verbundwerkstoff

Faser

Spritzpistole

41

Principles of Coating Technology I

Pre- and Posttreatment

GFE Schmalkalden e.V.

mechanical Post-Treatment
Shot peening
Objective of mechanical post-treatment
compacting
Reduction of surface roughness
Characteristics of shot peening
Ball shaped blasting material off metal, ceramic, glass
Process similar to sand blasting
Velocity of blasting material 15-150 m/s
Simultaneous shot peening
Compacting of the whole coating
Optimization of corrosion resistance
Induction of residual compressive stresses

Thermal sprayed Ni20Cr coating


before and after shot peening
Principles of Coating Technology I

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21

GFE Schmalkalden e.V.

5.

Deposition methods - Overview

43

Principles of Coating Technology I

Deposition methods - Overview

GFE Schmalkalden e.V.

Classification of Deposition methods

Deposition
from liquid or
pasty state

Deposition
from solids or
powders

Painting
Hot dipping

Powder
coating with
polymers or
metalls

Principles of Coating Technology I

Deposition by
welding

Deposition by
soldering

Deposition
from gaseous
or voporized
state

PVD / CVD

Deposition
from ionized
state by
electrolytical
or chemical
deposition
Galvanic
methods
Anodic
methods

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Deposition methods - Overview

GFE Schmalkalden e.V.

Important methods
Deposition by welding
Fusion welding (autogenously, metal inert gas, tungsten inert gas plasma welding with wire or
powder, submerged , laser welding )
Pressure welding (roll cladding or explosive plating)
Deposition by brazing
fusion soldering (with gas, metal inert gas, plasma, oven)
Deposition from gaseous or voporized state
Physical Vapor Deposition
Chemical Vapor Deposition
Combination of PVD and CVD methods
Deposition from ionized state
Galvanic methods with and without an external current generator
anodic methods
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Principles of Coating Technology I

Deposition methods - Overview

GFE Schmalkalden e.V.

Important thermochemical methods


method
Aufkohlen
Carbonitrieren
Nitrieren
Nitrocarburieren
Oxidieren
Oxinitrieren
Sulfidieren
Sulfonitrieren
Sulfonitrocarburieren
Borieren
Vanadieren
Chromieren
Chromvanadieren
Niobieren
Alitieren
Silizieren
Stannieren
Manganieren

Principles of Coating Technology I

Diffused element
C
C, N
N (H)
N, C (O, H)
O
N, O
S
N, S
N, C, S
B
V
Cr
Cr, V
Nb
Al
Si
Sn
Mn

Media
Gas, Paste, Pulver, Salzbad
Gas, Plasma, Salzbad
Gas, Plasma
Gas, Plasma, Pulver, Salzbad
Gas, Salzbad
Gas
Salzbad
Gas (Plasma)
Salzbad (Plasma)
Gas, Paste, Plasma, Pulver
Pulver, Salzbad
Gas, Pulver, Salzbad
Pulver
Pulver
Gas, Pulver, Salzbad
Pulver
galv. berzug
Pulver

temperature [C]
800 - 1050
600 - 930
350 - 550
350 - 600
150 - 550
~ 500
200
~ 600
570 - 580
800 - 1000
850 - 1100
900 - 1200
1000
1000 - 1100
~ 1200
930 - 1200
580
1000 - 1100

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23

Deposition methods - Overview

GFE Schmalkalden e.V.

Typical coating thickness of some methods

CVD / PVD

0,001 - 0,1 mm

chemical Ni

0,03 - 0,3 mm

galvanic Cr

0,01 - 0,5 mm

thermal spraying

0,05 - 3 mm

build up soldering

0,1 - 1 mm

build up welding

2 - 20 mm

roll cladding

2 - 12 mm

PVD
TiNcoating

Thermal spraying
APSAl2O3
50 m

6 mm

Built-up-welding

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Principles of Coating Technology I

Deposition methods - Overview

GFE Schmalkalden e.V.

Typical coating thickness of some methods


Hot dipping
Roll cladding
Build-up welding
Arc spraying
Plasma spraying
Flame spraying
Chemical Ni
galvanic Ni
galvanic Cr
plasmapolymerisation
CVD / PECVD
Ion plating
sputtering
vaporation
-5

10

-4

10

Principles of Coating Technology I

-3

10

-2

-1

10
10
1
Coating thickness [mm]

10

100
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Deposition methods - Overview

GFE Schmalkalden e.V.

Substrate temperature (C)

coating thickness and substrate temperature of some methods


1000

CVD

Build-up welding

800

Thermal
Thermal spray
spraying
600

PVD
400

Chemical methods
200

II
0

0.1

10

100

1000

10000

Coating thickness (mm)


(II = Ion implantation
Principles of Coating Technology I

49

GFE Schmalkalden e.V.

Part II Deposition methods


6. Painting
7. Electroplating and anodic oxidation

Principles of Coating Technology I

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Painting

GFE Schmalkalden e.V.


Pre-tratment
pre-treatment is normally ncessary
Using of mechanical or chemical oricesses
Chemical:

Mechanical:
Brushing

Etching

Blasting

lubricating

Painting systems are based on:


Water
Alcohole
Organic solvents (Trichlorethylen, Toluol, )

51

Principles of Coating Technology I

Painting

GFE Schmalkalden e.V.


Mostly used industral method of painting: spray painting
- Spaying of the material by high pressure, high velocity or elcectrostatic fields
- Ball shaped droplets are accelerated toward to the substrate
Compressed air spraying
- Using nozzle with defined geometry
- High velocity of paint droplets
- Formation of a droplet jet

Airless-nozzle Finespray-nozzle
Principles of Coating Technology I

Spritzlackieren
52

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GFE Schmalkalden e.V.

Painting

nozzle geometries
Compressed air nozzle
- Using compressed air
- High velocity differenz destroyed paint surface
Airless nozzle
- High pressure of the paint
- Expansion of the paint after the nozzle exit
- Priniple is used in sprays
Electrostatic nozzle
- Mechanical nebulization of the paint
- Electrostatic acceleration of the paint to the substrate
- Extremly low paint losses

Principles of Coating Technology I

GFE Schmalkalden e.V.

53

Painting

Dipping
-

Using a dipping bath


Dipping of the components into the bath until a fully wetting
Hardening of the paints at the air or in a stove
Hot dipping processes are use for mass production

Cathodic hot dipping

Principles of Coating Technology I

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Painting

GFE Schmalkalden e.V.


Modifications of dipping process

Electrical hot dipping

Conventional hot dipping:


only wetting of the surface
no additional solvents

Paint particles
in aqueous solvent
Surface of the Component

Electrical hot dipping


Chemical modification of the paint paint droplets
Coagulation of paint droplets on the surface
Hardening by heat treatment

Paint droplets
coagulated on the
surface
Surface of the Component

Paint surface after


hardening

Advantages of the dipping process

Good automatable
Complete painting of the components
(cavities, beadings,)
Low consumption of paint

Surface of the Component

Disadvantages of the dipping process

Irregular paint surface possible


High investment costs
High quantity of paint necessary (dipping bath)

55

Principles of Coating Technology I

Painting

GFE Schmalkalden e.V.


Hot dipping
dipping of e metallic part in a molten metal bath
Formation of solid or liquid reaction products at the boundaries
After removing: solidification of the adhere pint layer
Pre treatment of the hot dipping process

Modifications of hot dipping process

Librication in an alcalic bath


Etching with salt acid or sulfurid acid for a
metallic surface
Purging of the surface to remove formed salts
Tratment with fluxes of zinc chloried or
aluminum chloride
Precision cleaning and drying

Zinc coating (450 530 C)


(galvanizing)
Hot dip tinning (300C)
Aluminum coating (700C)
Lead coating (380 C)

Principles of Coating Technology I

56

28

Painting

GFE Schmalkalden e.V.


Hot dipping zinc coating
Corrosion improvement by formation of oxidic and carbonatic passivation layers

Wet zinc coating


Removal of etched parts without drying
Flux is floated on the bath surface
Parts are dived through flux
Hot-dip galvanizing
Diffucion between iron and zinc
Formation of an alloy layer of iron and zinc
(intermerallic fe-Zn phases)
Deposition of a pure zinc layer during
removal of parts

57

Principles of Coating Technology I

Painting

GFE Schmalkalden e.V.


Powder coating
Processing of solvent-free, dry and fre-flowing powder of metals or plastic
Plastics:
Epoxy resin (EP)
Epoxy /polyester resin (EP/PES)
Polyester resin (PES)
Polyacrylic resin (PAC)
Polyuretan PUR)
Polyethylen (PE)
Polyamide (PA)
Ethylen-Vinylalkohol-Copolymerisat
Thermosetting resing
plastomere

Principles of Coating Technology I

Pre treatment of the powder coating process


different pre-treatment processes
depending on application and material
Degreasing
Etching
Phosphatizing (steel parts)
Chromating (aluminum parts)
Blasting with corund

58

29

Painting

GFE Schmalkalden e.V.


Powder coating - Powder spray coating

Up to 100 % of material will be used

Coating thickness 40 - 120 m

Specific paint sprayer with


continously powder feeding and
deed unit

Processing gas: compressed air

Electrodes generating a potential


difference between sprayer and
grounded part

High-voltage generator with


powder feeder

Poder recycling
unit

Continous oven

Podwer spray
chamber
chain conveyor

Powder particles (10 bis 80 m) will


be charged and accelerated by
compressed air and electrostatic
potential

Pre treatment unit


give in

Condenstation of the particles on the


surface

give out

59

Principles of Coating Technology I

Painting

GFE Schmalkalden e.V.


Powder coating whirl sintering

Coating thickness 200 - 500 m (in


special cases 1000 m)

Component are pre-heated to


sintering temperature

Dipping the component into the


whirl sintering bath

Wetting of the component by


floating powder particles

After short dipping melting of the


particles to a solid coating

Cooling on air or in water (on air lead


to a smoother surface)

Useful for small components and


large number of pieces

Good automation

Principles of Coating Technology I

Powder
cloud

Porous
Intermediate
layer

air

60

30

Painting

GFE Schmalkalden e.V.


Powder coating rotation sintering

Shake or rotation sintering

Internal coatings in pipes

Pre-heating to sinter temperature

Filling with powder

Processing time 7- 10 s

Homogenous layer by heating and


shaking

pipes

give out

Powder
deposition

Heating

cooling

Smoothing

61

Principles of Coating Technology I

Painting

GFE Schmalkalden e.V.


Powder coating powders and powder properties
properties

unit
yes
no

yes
no

Powder type
PA
EP
yes
yes
no
yes

yes
320-360
yes
1
70
105-110
2,5 x 10-5
0,35
2,3
0
good
bad

yes
270-360
yes
1
80
70-150
8 x 10-5
0,15
0,98
0,2
moderate
moderate

yes
270-360
yes
1
95
186
12 x 10-5
0,29
2,4
0,8-1,5
moderate
moderate

PE
Pre treatment: blasting
Etching / phosphatizing
(without passivation)
Adhesion layer
Processing temperature
Post treatmend
Minimal sheet thickness
Shore hardnees
Melting tange
Thermal expansion
Heat conductivity
Spez. heat
Water absorption (24 Std. RT)
Chemical stability
Weather resistance

Principles of Coating Technology I

C
mm
C
K-1
W/Km
kJ/kgK
%

PVC

yes
200
yes
95
4 x 10-5
0,15
1,7
0,3-1,5
moderate
bad

EVAL
yes
yes
yes
180-360
no
0,5
85
105-108
13 x 10-5
0,28
1,9
0,2
good
good

62

31

GFE Schmalkalden e.V.

7.

Electroplating and anodic oxidation

63

Principles of Coating Technology I

GFE Schmalkalden e.V.

Electroplating and anodic oxidation

electroplating
Anode

Electroplating (wtih external energy source)

Using an electrolytic bath

Part will be used as cathode (metallic layer)

Metallic ions of electrolyte are transfered


by the external electrical field to the
cathode

Metallic ions are reduced to metal atoms

Oxidation of the remianing of anions on


the anode

Anode is composed from coating material

Kathode

Metallionen

Non-uniform coating thickness at cavities and on


edges due to concentration of electical field lines

Current free electroplating

Ion exchange method (exchange of ion between anode and solved ions)

Reduction method (deposition of solved ions by reduction of the electrolyte)

Contact method (short time contact by an ignobly material)

Principles of Coating Technology I

64

32

GFE Schmalkalden e.V.

Electroplating and anodic oxidation

electroplating

Metals (steel, copper and copper alloys, zinc, aluminum and aluminum alloys

Plastics

ceramics

Electrical non conductive material must be pre-coated with a conductive coating (e.g. Au, Cu, Al)

Pre-tratment is nessecary

Removal of rust and scale salts, lubricants, oils, soaps, paints

Removal of coarse conatamination: etching, grinding, burning

Removal of fine contaminations: olishingdegreasing, deoxidation

65

Principles of Coating Technology I

GFE Schmalkalden e.V.

Electroplating and anodic oxidation

electroplating: some basics


ions

Positve or negative charged particles

Formation of ions by dissoziation of electrolytes

Cations: metallic ions (Na+) ; anion: acid radicals (Cl-)

Complex ions

Ions of more atoms

Reaction on the anode

Dissolvabel anode: anode will be oxidized

Insolvabe abbode: parts of the electrolyte will be aoxidized; formation of gases

Principles of Coating Technology I

66

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Electroplating and anodic oxidation

GFE Schmalkalden e.V.


Electroplating: some basics
electrolyte

Electrolytes are acid or alcalic liquid or non-liquid solvents with ions

acid: metal sulfates or chlorides

Alcalic: complex cyanides or metal oxygen combinations


Components of the electrolyte

Metal carrier (salts)

Conducting salts (for high current densities)

Buffer materials (for constant pH value)

Wetting agents ( for dissolving dirt)

Brightener (organic materials for a more unifcorm and fain grained coating)

Defoaming agent

Supenser (to influence electical fields)

Complex creator (to mask unwanted metals

67

Principles of Coating Technology I

Electroplating and anodic oxidation

GFE Schmalkalden e.V.


Electroplating: some basics
Cathodic deposition:

Faraday equation to determine deposition rate

Deposition rate can be used to control deposition rate

I t MG
zF

mth

theoretical deposit mass

Mg

atomic mass of the metal

current

ionic charge

time

Faradya constant (96.496 C/mol)

Coating characterisitics

nonunifom coating thickness distribution

Specification of minimum thickness necessary

Reduction of surface roughness by deposition: higher


deposition rate within holes

Principles of Coating Technology I

mth

a)

b)

c)
Grundwerkstoff
Beschichtung

68

34

Electroplating and anodic oxidation

GFE Schmalkalden e.V.


Methods of deposition
Bath electroplating

for large components

Expensive equipment

High current for deposition

Exampe of
bath electroplating

Trommel or cavity electroplating

For mass production (loose material)

Rotating boxes (trommel shape)

cathodic current supply by the loose material

No bright surface possible


69

Principles of Coating Technology I

GFE Schmalkalden e.V.

Electroplating and anodic oxidation

Cathodic nickel deposition


Substrate materials:

Steel

Zinc and zinc alloys

Copper and copper alloys (often adhesion layer for nickel coatings)

electrolytes

Matt nickel (WATTS-electrolytes) (coating


hardness 155 -200 HV)

Bright nickel
(coating hardness 380 480 HV)

Electrolyte composition influences coating


properties (structure, hardness, optics)

Exampe of
Hard nickel cylinder
Principles of Coating Technology I

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Electroplating and anodic oxidation

GFE Schmalkalden e.V.


Cathodic chrome deposition
Coating properties

Application

High hardness

Decorative coatings (thickness < 2 mm)

High wear and corrosion resistance

Reduced friction coefficient

Functional coatings on barrels, cylinders, forms,


(tickness up to 500 mm, with microcracks)

Reduced affinity to adhesion

High gloss

Used cylinder

Chrome plated
cylinder
High gloss chrome cylinder
71

Principles of Coating Technology I

Electroplating and anodic oxidation

GFE Schmalkalden e.V.


Cathodic chrome deposition
Substrate materials:
Steel

Aluminum

Cast steel

Nickel

Copper and copper alloys

High stiftness of the substrate necessary (due to the


brittleness of chromim)

electrolytes

Chromimtrioxide CrO3 (acutely poisonous)

Anorganic acid as catalyzer(H2SO4, HF)

Cr3+ ions

Wetting agent
Hard chrome coating: higher CrO3 content
Bright chrome: lower CrO3 content

Principles of Coating Technology I

72

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GFE Schmalkalden e.V.

Electroplating and anodic oxidation

Cathodic zinc deposition


applications

Corrosion protection on plates, bands, pipes, small parts,

On iron based materials cahodic corrosion protction

Non-decorative coating (no brightness possible)

Coating properties

Process modifications

thin and uniform coatings

Fine coating microstructure

Sealing of chlinch connections

Limited possibility for bright surfaces

For large components and baths

No pre-treatment necessary

No influence on the substrate

Hot-dip galvanizing

Spray galvanization

Flexible application on site (repair)

73

Principles of Coating Technology I

GFE Schmalkalden e.V.

Electroplating and anodic oxidation

Electroplating of plastics
Generation of conductive surfaces necessary by

Electroless metal plating without external power

Graphite dust coating

Electro-paint

applications

Thin coatings (thickness < 0,5 mm) for gloss


properties

Thick coatings (thickness ~10 mm) show higher


strength

Bad adhesion properties (coating delamination


due residual stresses possible)

Adhesion optimization by mechanical or


chemical treatment

Uniform coating thickness at edges and within


cavities

Principles of Coating Technology I

Metallionen +
Reduktionsmittel

74

37

GFE Schmalkalden e.V.

Electroplating and anodic oxidation

Electroplating methods

Reduction of a solved metal (electrolyte)

Oxidation of an ignoble metal potential difference


between solvent and metal is the driving force

Potential difference influences coating structure

Fe
-

ee

2+

Cu

CuSO4

Dipping method

ignoble metal will be coated

Inner shortcut

Fe2+

Stromfluss
Kontakt- material

Fe
Contact method

e-e

Ignoble metal as electron donator

Current by outher contact of disssolving and coated


metal

Fe2+ 3+
2Al
Cu2+ 2+
Cu
Cu2+ SO42-

75

Principles of Coating Technology I

GFE Schmalkalden e.V.

Al
eeeeee

Electroplating and anodic oxidation

Electroless nickel depsotion

Reduction of a Ni2+ ions by solved reducing agents (elcetron donator)

Reducing agents: natriumhypophospite, natriumborhydrite

Inclusion of phosphor (max. 13 %) and Boron (max. 6 %) in nickel coatings


possible

Deposition conditions

Using acid baths

Working temperature 80-95C

Addionally using of NaOH, nickel salt and


reducing agents

Principles of Coating Technology I

76

38

GFE Schmalkalden e.V.

Electroplating and anodic oxidation

Electroless nickel depsotion


Applications

High wear and corrosion


resistance for steel copper
and copper alloys

Higher contur accuracy

Chemical stability

Properties

Amorphous or fine crystalline structure with moderate


hardness

Dispersion hardening by heat treatment

With higher phosphor content :

Higher electrical resistivity, ductility and corrosion


resistance

Lower hardness and wear resistance


77

Principles of Coating Technology I

GFE Schmalkalden e.V.

Electroplating and anodic oxidation

Advantages and disadvantages

Thin layer

only metallic layers

Coatings with multilayer and graded structure possible

Dense coatings depending on coating material)

High effort of pre-treatment (etching)

Lower adhesion at local loads (egg-shell effect)

During deposition inclusion of hydrogen into the substrate heat treatment necessary

Limited possibility to deposit very complex geometries

Limited contour accuracy at deposition with external current sources

Principles of Coating Technology I

78

39

GFE Schmalkalden e.V.

Principles of Coating Technology I

79

40

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