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TALAT Lecture 5105


                 Surface Treatment of Aluminium

                                  15 pages, 15 figures

                                      Basic Level

            prepared by P. M∅ller, Dansk Technisca Hoogschol, Lyngby




Objectives:

− to understand the general principles, methods, properties and applications of plating
  on aluminium




Prerequisites:

− General electrochemistry




Date of Issue: 1994
   EAA - Euro p ean Aluminium Asso ciatio n
5105              Surface Treatment of Aluminium



Table of Contents



5105    Surface Treatment of Aluminium...........................................................2
 5105.00 Introduction................................................................................................. 3
 5105.01 Non-Galvanic Methods............................................................................. 4
    Mechanical Finishes.................................................................................................4
    Organic Finishes ......................................................................................................4
 5105.02 Chemical Methods .................................................................................... 5
    Pickling and Etching ................................................................................................5
    Chemical Polishing ..................................................................................................5
    Chemical Conversion Coating .................................................................................7
    Electroless Plating....................................................................................................8
        Autocatalytic Plating .......................................................................................... 9
        Ion-Exchange Plating ......................................................................................... 9
 5105.03 Electrolytic Methods............................................................................... 10
    Electropolishing .....................................................................................................10
    Electroplating.........................................................................................................11
    Platable Metals on Aluminium ..............................................................................12
    Anodising...............................................................................................................14
 5105.04 Literature................................................................................................. 15
 5105.05 List of Figures............................................................................................ 15




TALAT 5105                                                       2
5105.00 Introduction

The processes for surface treatment of aluminium can be divided into the following
groups

            I.                 Non-galvanic methods
            II.                Chemical methods
            III.               Electrolytic methods (Figure 5105.00.01),

where the group of non-galvanic methods can be defined as surface treatment of
aluminium which does not involve chemical or electrolytic action.

The group of chemical methods can be defined as reactions taking place as a result of
chemical action, i.e. no external source of electric power is present.

The group of electrolytic methods can be defined as reactions taking place as a result of
electrochemical action, i.e. an external power supply is used.

These definitions may overlap, but can be used for a preliminary division into groups.



                            Methods of Surface Treatment for Aluminium

                                              I         Non-galvanic methods
                                                                    Mechanical finishes
                                                                    Organic finishes


                                            II          Chemical methods
                                                                   Pickling and etching
                                                                   Polishing
                                                                   Chemical conversion coatings
                                                                   Electroless plating


                                          III           Electrolytic methods
                                                                      Electro-polishing
                                                                      Electroplating
                                                                      Anodizing
                                              alu
                                                         Methods of Surface Treatment for Aluminium   5105.00.01
       Training in Aluminium Application Technologies




TALAT 5105                                                                       3
5105.01                      Non-Galvanic Methods

         •        Mechanical finishes
         •        Organic finishes

Group I can be subdivided into mechanical finishes and organic finishes.


Mechanical Finishes

Mechanical finishes cover processes such as grinding, polishing, buffing, rolling or
blasting with sand, glass or metal beads. These processes are used to remove scratches,
stains, skin from casting etc. A uniform surface, which spans from satin to mirror-
quality, is produced. The resulting surface may be post-treated, or it can be used as the
desired finish (Figure 5105.01.01).


                                                                     Mechanical Finishes
                      Methods: Grinding / polishing
                               Buffing
                               Matt finishing
                                        satin finish
                                        blasting
                               Rolling


                      Properties: Elimination of scratches, pits, tarnish etc.
                                  Production of a smooth or lustrous surface


                      Use:                                Used as pre-treatment to anodizing, organic coatings or electroplating
                                                          ( reflectors, cabinets, kitchenware etc. )
                                                          Surfaces are left unprotected


                                                    alu
                                                                              Mechanical Finishes                      5105.01.01
             Training in Aluminium Application Technologies




Organic Finishes

Organic finishes cover processes such as primers / top-coats, heavy plastic coatings,
protective coatings, powder coatings, porcelain enamelling or lacquer. These processes
are used in architecture for windows, doors, facings, panels etc. All colours of the colour
palette are possible to apply (Figure 5105.01.02). As a pretreatment to these processes,
chemical conversion coatings (chromate or chromate/phosphate) are frequently used, but
also mechanical finishes or anodising can be used as a pre-treatment to organic coating.

Organic finishes are of huge commercial importance.




TALAT 5105                                                                                4
Organic Finishes
                                                Methods :
                                                            Primers
                                                            Top coats
                                                            Heavy plastic coatings
                                                            Protective coatings
                                                            Powder coatings
                                                            Porcelain enameling

                                                Properties :
                                                           Prevents corrosion
                                                           Decorative

                                                Use :
                                                            Architectural ( windows, doors, facing etc. )
                                                            Machine parts
                                                            Cabinets

                                              alu
                                                                   Organic Finishes                     5105.01.02
       Training in Aluminium Application Technologies




5105.02                        Chemical Methods

                     •         Pickling and etching
                     •         Chemical polishing
                     •         Chemical conversion coating
                     •         Electroless plating
                               − Autocatalytic plating
                               − Ion-exchange plating

Group II can be subdivided into pickling and etching, polishing, chemical conversion
coatings and electroless plating i.e. autocatalytic and ion-exchange plating.


Pickling and Etching

Pickling and etching are primarily used as pretreatment to most other finishing
processes. During the processes deposits, oxide, scale and skin are dissolved and
removed from the surface (Figure 5105.02.01).



Chemical Polishing

Chemical polishing is a controlled dissolution of the basis metal, by which a semi- to
mirror-bright surface can be produced. Since the polished surface is vulnerable to
scratches and corrosion, it is usually combined with anodising or transparent organic
finishing. The process is used for producing reflectors and decorative components. The
best result is obtained by using pure aluminium (Al > 99,9%) (Figure 5105.02.02).


TALAT 5105                                                                   5
Pickling and Etching

                      Method:                         Surface is removed chemically
                                                      Caustic etch
                                                      Acid etch




                      Properties : Removes oxides etc.
                                                      Removes small burrs
                                                      Matt finish, especially if long time in aggressive etch




                      Use :                           Fundamental pre-treatment to most surface treatments
                                                      Difficult if alloyed aluminium is used ( special etch needed )



                                            alu
                                                                  Pickling and Etching                          5105.02.01
     Training in Aluminium Application Technologies




                                                            Chemical Polishing

                                  Method:                Surface metal is removed chemically



                                  Properties :           Bright finish
                                                         Specular reflectivity
                                                         Improve surface smoothness
                                                         Decorative surface
                                                         Uniform attack on whole surface ( also inside holes )



                                  Use :                  Substitution of mechanical polishing
                                                         Before anodizing or lacquer
                                                         Decorative components
                                                         Automotive applications ( reflectors etc. )



                                            alu
                                                                     Chemical Polishing                         5105.02.02
    Training in Aluminium Application Technologies




TALAT 5105                                                                      6
Chemical Conversion Coating

Chemical conversion coating is a controlled dissolution and formation of insoluble salts,
which reduce the risk of corrosion and improve the adhesion of organic coatings. During
the process a coloured surface is formed, ranging from pale yellow to dark brown /
black. The colour is due to light interference in the semi transparent coating so the
colour is also a measure for the coating thickness. In general the darker the conversion
layer is the thicker it is, and thereby gives a better protection.

There are three types of chemical conversion solutions: They are based on chromate, on
chromate and phosphate and chromate-free solutions (Figure 5105.02.03).



                                        Chemical Conversion Coatings (Methods)


                                  Methods:

                                                        ! With chromate
                                                            chromate processes
                                                            chromate-phosphate processes

                                                        ! Non-chromate
                                                            phosphate processes
                                                            molybdate-phosphate process
                                                            oxide processes



                                              alu
                                                            Chemical Conversion Coatings (Methods)   5105.02.03
       Training in Aluminium Application Technologies




For applications such as aerospace and military, chromate conversion coating is
extensively used. Also car components and other parts subjected to corrosion are
protected this way. Chemical conversion coatings are used either as pretreatment to
organic finishes, or it can be used alone for temporary or permanent protection against
corrosion (Figure 5105.02.04). Chemical conversion coatings based on chromate and
chromate / phosphate have a "self-curing" effect, i.e. scratches in the conversion coating
are cured by chromate migrating to the scratch.




TALAT 5105                                                                      7
Chemical Conversion Coatings ( Properties )


                                           Properties :

                                                             Coloured surface

                                                             Reacts with the surface and forms
                                                             insoluble salts of phosphates chromates or others

                                           Use :

                                                             Pre-treatment to organic finishes
                                                             Corrosion protection
                                                             Temporary or permanent protection



                                                  alu
                                                                Chemical Conversion Coatings ( Properties )   5105.02.04
           Training in Aluminium Application Technologies




Electroless Plating

Electroless plating is used for engineering and electronic parts to give increased wear-
resistance and in some cases corrosion resistance (special pretreatment) or the technique
can be used as the primary step in a conventional electroplating sequence. The process
has an excellent throwing power independent of the specimen geometry. For example
electroless nickel is used for computer hard-discs in combination with a magnetic
material such as cobalt. Many mechanical precision parts are plated with electroless
nickel to maintain strict dimensional tolerances. Composites of electroless nickel
containing silicon carbide (SiC) or teflon (PTFE) particles can increase wear resistance
and decrease the coefficient of friction, respectively (Figure 5105.02.05).

                                                            Electroless Plating ( Properties )


                    Plated metal :
                                  ! Ni, Cu, Sn, Zn, (Ag, Co )

                    Properties :
                                 ! Increased hardness and wear resistance
                                 ! Increased corrosion resistance
                                 ! Good throwing power ( uniform coating regardless of sample geometry )
                                 ! Composite plating of particles ( SiC or PTFE ) is possible
                                   to increase the wear resistance or to obtain lower surface friction

                    Use :
                                  ! Engineering parts where high precision is required
                                  ! Surfaces subjected to wear

                                                  alu
                                                                     Electroless Plating ( Properties )       5105.02.05
           Training in Aluminium Application Technologies




TALAT 5105                                                                              8
Electroless plating is deposition of metal, usually nickel or copper from an aqueous
solution by use of a reducing agent RA in the solution or by dissolution of the substrate
whereby electrons are freed. The plated metal is dissolved in the plating solution as
metal ions which plate on the surface (Figure 5105.02.06).



                                                         Electroless Plating ( Reactions )


                 Plated metal :
                                                                                                           Me n+
                        Zn, Sn, Cu, Co, Ag, Au
                                                                                                           RA



                 General reactions :

                                RA                         R + ne-
                                                                                                    Me0
                                Me n+ + ne-                          Me0


                                               alu
                                                                Electroless Plating ( Reactions )         5105.02.06
        Training in Aluminium Application Technologies




Electroless plating can be subdivided into autocatalytic plating and ion-exchange
plating.


Autocatalytic Plating
The autocatalytic plating process is driven by electrons freed by reduction of the
reducing agent RA. These freed electrons join the metal ions in the solution and form
solid metal on the surface. Because the electrons are coming from the reducing agent the
process can keep on running also after the substrate is covered, i.e. high coating
thicknesses are possible. Electroless nickel is an example of autocatalytic plating.


Ion-Exchange Plating
The other type of electroless plating is ion-exchange plating. This process is based on
oxidation (dissolution) of the aluminium substrate whereby electrons are freed so that a
reduction (deposition) of another metal coming from the aqueous solution is possible.
(Figure 5105.02.07). The metals deposited by this technique are usually zinc or tin. The
layers deposited are thin, because the deposition stops, when the aluminium is all
covered and can no more supply electrons by oxidation. The processes are used as a
pretreatment to plating (electrolytic and electroless). These ion-exchange processes are
known under the names: zincate-, stannate- or modified zincate/stannate-process. The

TALAT 5105                                                                         9
electrolytic plating processes often require this pretreatment to improve the adhesion
and to avoid the aluminium from getting dissolved in the plating bath, because
aluminium is amphoteric (dissolves in both alkaline and acid solution). When used as
pretreatment to plating correct process parameters are of great importance to the
adhesion and corrosion resistance of the plated coating. The standard ASTM B253-83
specifies the correct pretreatment process routines for aluminium (zincating etc).

                                                             Ion-Exchange Plating


                         Principle :




                                                                                             Al 3+
                                                               Al


                                                               3e -
                                                                                             Men+



                                                   alu
                                                                      Ion-Exchange Plating           5105.02.07
            Training in Aluminium Application Technologies




5105.03                Electrolytic Methods

        •   Electropolishing
        •   Electroplating
        •   Platable metals on aluminium
        •   Anodizing

Group III can be subdivided into electropolishing, electroplating and anodising.



Electropolishing

Electropolishing is a controlled electrochemical dissolution of the basis metal by which
a semi- to mirror-bright surface can be produced. Electropolishing is a method by which
surface metal is removed by applying an external power supply and letting the sample
be the anode in the process. Actually, it is a kind of "reverse plating" where aluminium
is dissolved into the electrolyte instead of metal being plated from an electrolyte. Its
applications are much like those of the chemical polishing, but by electropolishing
corners and burrs are attacked more than the flat surfaces. The process can be
substituted by chemical polishing. Since the polished surface is vulnerable to scratches


TALAT 5105                                                                       10
and corrosion, it is usually combined with anodising or transparent organic finishing.
The process is used for producing reflectors and decorative components. The best result
is obtained by using pure aluminium (Al > 99,9%) (Figure 5105.03.01).


                                                                     Electropolishing

                                                      Principle :

                                                               Surface metal removed electrochemically

                                                      Properties :

                                                              Similar to chemical polishing, except that corners
                                                              and burrs are attacked more than surfaces
                                                              Elimination of scratches and burrs
                                                              Smoothing and brightening
                                                              High reflectivity

                                                      Use :

                                                              Reflectors
                                                              Decorative components
                                                              Often before anodizing or lacquering

                                                  alu
                                                                        Electropolishing                           5105.03.01
           Training in Aluminium Application Technologies




Electroplating

There are a number of difficulties to be considered when electroplating on aluminium:

        1. Aluminium is amphoteric, i.e. it is dissolved in both alkali and acid.
        2. The difference in potential, between the aluminium matrix and second phase
           constituents can affect the deposition reaction.
        3. The position of aluminium in the electrochemical series can lead to
           formation of immersion deposits in the plating solution.
        4. The coefficient of thermal expansion of aluminium and its alloys differs
           from most of the metals commonly deposited on it. This can lead to
           decohesion between coating and substrate when the plated aluminium part is
           subjected to high temperature elevations or to temperature shocks.
        5. The difference in atomic diameter and crystal lattice structure between the
           aluminium substrate and the metal deposited on it.
One of the major problems when plating on aluminium is the readiness by which
aluminium reacts with the air to form oxide. It is also a problem that aluminium is
amphoteric, i.e. aluminium is dissolved in both acidic and alkaline plating baths. These
problems can be overcome by removal of the oxide and electrodeposition of the metal
in the same process, or, alternatively, by using an intermediate pretreatment layer
deposited by ion-exchange plating (zincate or stannate processes as described earlier).

When the oxide is removed in the same bath as the electrodeposition takes place the

TALAT 5105                                                                           11
process is called a direct plating process. It is possible to electrodeposit copper, nickel,
silver, brass and chromium by using the direct plating method. This technique has only
limited use in the industry. The most frequent technique used is to plate an intermediate
pretreatment layer, deposited by the ion-exchange technique as described earlier.

Though plating on aluminium is a relatively expensive technique, it is increasingly
important because of the possibility of combining the low density of aluminium with the
functional properties of the deposit. Good results can be obtained with a suitable
combination of metal and process (Figure 5105.03.02).


                                                                     Electroplating

                                       Methods :
                                                       Direct plating
                                                       Anodic preparation
                                                       Zinc immersion
                                                       Tin immersion
                                                       Hard chromium

                                      Properties added by electroplating ( examples ) :
                                                       Wear resistance, corrosion resistance, electrical
                                                       properties, weldability, solderability, etc.

                                      Use :
                                                      Portable computers, telephones etc.
                                                      Computer harddisk
                                                      General engineering applications like machine elements etc.


                                                    alu
                                                                            Electroplating                          5105.03.02
             Training in Aluminium Application Technologies




Platable Metals on Aluminium

As an example of the plating techniques, gold is deposited on aluminium for an
aerospace application. The process is:

         •   Zincate / stannate
         •   electrolytic copper deposit, 5µm
         •   electrolytic nickel deposit, 10µm
         •   electrolytic gold deposit, 5µm

By using the above process sequence it is possible to eliminate the difficulties when
plating aluminium that were listed earlier. The copper deposit has an excellent ability to
absorb stress resulting from differences in the coefficient of thermal expansion. The
nickel deposit eliminates the risk of galvanic corrosion by forming a dense and pit-free
layer. The nickel layer is also necessary to prevent diffusion of copper into the gold. The
gold is the desired top coating and by depositing 5µm a pit-free layer is obtained, i.e. no
corrosion of the underlaying layers is possible. The gold layer is 100% resistant to
corrosion and has the desired electrical and thermal characteristics.



TALAT 5105                                                                             12
The above described gold-plating is tested by the following test sequence:

         •   10 temperature-shocks (quick) from -55°C to +125°C.
         •   200 temperature cycles (slow) from -55°C to +125°C.
         •   240 hours at 95% relative humidity at 40°C.
         •   High temperature storage at 125°C for 1000 hours.

After this test cycle no visible or electrical changes can be allowed.

Other more common applications of plated aluminium coatings are machine elements
and many leight weight components. The metals that are platable on aluminium either
directly or by use of an intermediate zincate or stannate layer are many. The most
common ones are chromium, nickel, silver, gold tin, zinc and copper (Figure
5105.03.03).


                                               Chemical Conversion Coatings (Methods)


                                         Methods:

                                                               ! With chromate
                                                                   chromate processes
                                                                   chromate-phosphate processes

                                                               ! Non-chromate
                                                                   phosphate processes
                                                                   molybdate-phosphate process
                                                                   oxide processes



                                                     alu
                                                                   Chemical Conversion Coatings (Methods)   5105.02.03
              Training in Aluminium Application Technologies




The obtainable properties by plating aluminium are changed wear resistance and
friction. Thermal conductivity, solderability and electrical resistance are main properties
in many electronics. The commercially most common reason for surface treatment are
decorative or corrosion resistance related (Figure 5105.03.04).




TALAT 5105                                                                             13
Properties of Electrolytic Plated Metals on Aluminium



                                                                     Cr    Ni     Cu Ag       Sn   Pb     Cd   Zn   Au    Rh
                                Wear                                  "    "                                              "

                                Friction                                                "     "           "
                                Thermal                                           "     "

                                Electrical                                        "     "     "                     "     "

                                Decorative                            "    "            "     "                     "     "

                                Corrosion                             "    "                  "     "     "    "    "

                                Solderability                                     "           "     "     "         "




                                                             alu
                                                                          Summary of Properties and Use             5105.03.04
                   Training in Aluminium Applicat ion Technologies




Anodising

Anodising is a commonly used method for surface treatment of aluminium. This is due
to a number of properties offered by this technique. Depending on the process condi-
tions the following properties can be obtained:
        •   Corrosion resistance
        •   Decorative surfaces
        •   Surfaces in almost any colour on the palette, except white
        •   Hard and wear resistant surfaces
        •   Electrical and thermal insulation
        •   The surface can be used as a base for organic finishing and for plating
The anodising technique is expected to have an increasing advantage over many other
surface treatment processes, because the technique does not require toxic chemicals,
heavy metals etc., and the anodised aluminium is easily recycled (Figure 5105.03.05).

                                                                                Anodizing

                                Principle:
                                        Controlled oxidation of the aluminium metal surface, forming
                                        aluminium oxide ( alumina )

                                Properties :
                                        Increased wear resistance and hardness
                                        Corrosion protection
                                        Colourable to many colours
                                        High coefficient of heat emission and electrical isolating
                                        Improved adhesion for organic coatings
                                        Corner defects due to brittleness

                                Use :
                                                               Architectural (house facing, window frames etc. )
                                                               Cars and aerospace ( structural, decorative, engine parts )
                                                               Domestic, holloware, pots and pans

                                                       alu
                                                                                 Anodizing                              5105.03.05
             Train ing in Aluminium Application Technologies




TALAT 5105                                                                                   14
5105.04      Literature

Wernick, S., Pinner, R. & Sheasby, P.G.: The Surface Treatment and Finishing of
Aluminium and its alloys, 5th edition,

Hübner, W. & Speiser, C.T.: Die Praxis der anodischen Oxidation des Aluminiums,
3rd edition,

Montgomery, D.C.: Light Metals Finishing Process Manual, AESF 1990



5105.05 List of Figures



Figure No.   Figure Title (Overhead)

5105.00.01   Methods of Surface Treatment for Aluminium

5105.01.01   Mechanical Finishes
5105.01.02   Organic Finishes

5105.02.01   Pickling and Etching
5105.02.02   Chemical Polishing
5105.02.03   Chemical Conversion Coatings: Methods
5105.02.04   Chemical Conversion Coatings: Properties
5105.02.05   Electroless Plating: Properties
5105.02.06   Electroless Plating: Reactions
5105.02.07   Ion-Exchange Plating

5105.03.01   Electropolishing
5105.03.02   Electroplating
5105.03.03   Platable Metals on Aluminium
5105.03.04   Summary of Properties and Use
5105.03.05   Anodizing




TALAT 5105                                 15

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TALAT Lecture 5105: Surface Treatment of Aluminium

  • 1. TALAT Lecture 5105 Surface Treatment of Aluminium 15 pages, 15 figures Basic Level prepared by P. M∅ller, Dansk Technisca Hoogschol, Lyngby Objectives: − to understand the general principles, methods, properties and applications of plating on aluminium Prerequisites: − General electrochemistry Date of Issue: 1994  EAA - Euro p ean Aluminium Asso ciatio n
  • 2. 5105 Surface Treatment of Aluminium Table of Contents 5105 Surface Treatment of Aluminium...........................................................2 5105.00 Introduction................................................................................................. 3 5105.01 Non-Galvanic Methods............................................................................. 4 Mechanical Finishes.................................................................................................4 Organic Finishes ......................................................................................................4 5105.02 Chemical Methods .................................................................................... 5 Pickling and Etching ................................................................................................5 Chemical Polishing ..................................................................................................5 Chemical Conversion Coating .................................................................................7 Electroless Plating....................................................................................................8 Autocatalytic Plating .......................................................................................... 9 Ion-Exchange Plating ......................................................................................... 9 5105.03 Electrolytic Methods............................................................................... 10 Electropolishing .....................................................................................................10 Electroplating.........................................................................................................11 Platable Metals on Aluminium ..............................................................................12 Anodising...............................................................................................................14 5105.04 Literature................................................................................................. 15 5105.05 List of Figures............................................................................................ 15 TALAT 5105 2
  • 3. 5105.00 Introduction The processes for surface treatment of aluminium can be divided into the following groups I. Non-galvanic methods II. Chemical methods III. Electrolytic methods (Figure 5105.00.01), where the group of non-galvanic methods can be defined as surface treatment of aluminium which does not involve chemical or electrolytic action. The group of chemical methods can be defined as reactions taking place as a result of chemical action, i.e. no external source of electric power is present. The group of electrolytic methods can be defined as reactions taking place as a result of electrochemical action, i.e. an external power supply is used. These definitions may overlap, but can be used for a preliminary division into groups. Methods of Surface Treatment for Aluminium I Non-galvanic methods Mechanical finishes Organic finishes II Chemical methods Pickling and etching Polishing Chemical conversion coatings Electroless plating III Electrolytic methods Electro-polishing Electroplating Anodizing alu Methods of Surface Treatment for Aluminium 5105.00.01 Training in Aluminium Application Technologies TALAT 5105 3
  • 4. 5105.01 Non-Galvanic Methods • Mechanical finishes • Organic finishes Group I can be subdivided into mechanical finishes and organic finishes. Mechanical Finishes Mechanical finishes cover processes such as grinding, polishing, buffing, rolling or blasting with sand, glass or metal beads. These processes are used to remove scratches, stains, skin from casting etc. A uniform surface, which spans from satin to mirror- quality, is produced. The resulting surface may be post-treated, or it can be used as the desired finish (Figure 5105.01.01). Mechanical Finishes Methods: Grinding / polishing Buffing Matt finishing satin finish blasting Rolling Properties: Elimination of scratches, pits, tarnish etc. Production of a smooth or lustrous surface Use: Used as pre-treatment to anodizing, organic coatings or electroplating ( reflectors, cabinets, kitchenware etc. ) Surfaces are left unprotected alu Mechanical Finishes 5105.01.01 Training in Aluminium Application Technologies Organic Finishes Organic finishes cover processes such as primers / top-coats, heavy plastic coatings, protective coatings, powder coatings, porcelain enamelling or lacquer. These processes are used in architecture for windows, doors, facings, panels etc. All colours of the colour palette are possible to apply (Figure 5105.01.02). As a pretreatment to these processes, chemical conversion coatings (chromate or chromate/phosphate) are frequently used, but also mechanical finishes or anodising can be used as a pre-treatment to organic coating. Organic finishes are of huge commercial importance. TALAT 5105 4
  • 5. Organic Finishes Methods : Primers Top coats Heavy plastic coatings Protective coatings Powder coatings Porcelain enameling Properties : Prevents corrosion Decorative Use : Architectural ( windows, doors, facing etc. ) Machine parts Cabinets alu Organic Finishes 5105.01.02 Training in Aluminium Application Technologies 5105.02 Chemical Methods • Pickling and etching • Chemical polishing • Chemical conversion coating • Electroless plating − Autocatalytic plating − Ion-exchange plating Group II can be subdivided into pickling and etching, polishing, chemical conversion coatings and electroless plating i.e. autocatalytic and ion-exchange plating. Pickling and Etching Pickling and etching are primarily used as pretreatment to most other finishing processes. During the processes deposits, oxide, scale and skin are dissolved and removed from the surface (Figure 5105.02.01). Chemical Polishing Chemical polishing is a controlled dissolution of the basis metal, by which a semi- to mirror-bright surface can be produced. Since the polished surface is vulnerable to scratches and corrosion, it is usually combined with anodising or transparent organic finishing. The process is used for producing reflectors and decorative components. The best result is obtained by using pure aluminium (Al > 99,9%) (Figure 5105.02.02). TALAT 5105 5
  • 6. Pickling and Etching Method: Surface is removed chemically Caustic etch Acid etch Properties : Removes oxides etc. Removes small burrs Matt finish, especially if long time in aggressive etch Use : Fundamental pre-treatment to most surface treatments Difficult if alloyed aluminium is used ( special etch needed ) alu Pickling and Etching 5105.02.01 Training in Aluminium Application Technologies Chemical Polishing Method: Surface metal is removed chemically Properties : Bright finish Specular reflectivity Improve surface smoothness Decorative surface Uniform attack on whole surface ( also inside holes ) Use : Substitution of mechanical polishing Before anodizing or lacquer Decorative components Automotive applications ( reflectors etc. ) alu Chemical Polishing 5105.02.02 Training in Aluminium Application Technologies TALAT 5105 6
  • 7. Chemical Conversion Coating Chemical conversion coating is a controlled dissolution and formation of insoluble salts, which reduce the risk of corrosion and improve the adhesion of organic coatings. During the process a coloured surface is formed, ranging from pale yellow to dark brown / black. The colour is due to light interference in the semi transparent coating so the colour is also a measure for the coating thickness. In general the darker the conversion layer is the thicker it is, and thereby gives a better protection. There are three types of chemical conversion solutions: They are based on chromate, on chromate and phosphate and chromate-free solutions (Figure 5105.02.03). Chemical Conversion Coatings (Methods) Methods: ! With chromate chromate processes chromate-phosphate processes ! Non-chromate phosphate processes molybdate-phosphate process oxide processes alu Chemical Conversion Coatings (Methods) 5105.02.03 Training in Aluminium Application Technologies For applications such as aerospace and military, chromate conversion coating is extensively used. Also car components and other parts subjected to corrosion are protected this way. Chemical conversion coatings are used either as pretreatment to organic finishes, or it can be used alone for temporary or permanent protection against corrosion (Figure 5105.02.04). Chemical conversion coatings based on chromate and chromate / phosphate have a "self-curing" effect, i.e. scratches in the conversion coating are cured by chromate migrating to the scratch. TALAT 5105 7
  • 8. Chemical Conversion Coatings ( Properties ) Properties : Coloured surface Reacts with the surface and forms insoluble salts of phosphates chromates or others Use : Pre-treatment to organic finishes Corrosion protection Temporary or permanent protection alu Chemical Conversion Coatings ( Properties ) 5105.02.04 Training in Aluminium Application Technologies Electroless Plating Electroless plating is used for engineering and electronic parts to give increased wear- resistance and in some cases corrosion resistance (special pretreatment) or the technique can be used as the primary step in a conventional electroplating sequence. The process has an excellent throwing power independent of the specimen geometry. For example electroless nickel is used for computer hard-discs in combination with a magnetic material such as cobalt. Many mechanical precision parts are plated with electroless nickel to maintain strict dimensional tolerances. Composites of electroless nickel containing silicon carbide (SiC) or teflon (PTFE) particles can increase wear resistance and decrease the coefficient of friction, respectively (Figure 5105.02.05). Electroless Plating ( Properties ) Plated metal : ! Ni, Cu, Sn, Zn, (Ag, Co ) Properties : ! Increased hardness and wear resistance ! Increased corrosion resistance ! Good throwing power ( uniform coating regardless of sample geometry ) ! Composite plating of particles ( SiC or PTFE ) is possible to increase the wear resistance or to obtain lower surface friction Use : ! Engineering parts where high precision is required ! Surfaces subjected to wear alu Electroless Plating ( Properties ) 5105.02.05 Training in Aluminium Application Technologies TALAT 5105 8
  • 9. Electroless plating is deposition of metal, usually nickel or copper from an aqueous solution by use of a reducing agent RA in the solution or by dissolution of the substrate whereby electrons are freed. The plated metal is dissolved in the plating solution as metal ions which plate on the surface (Figure 5105.02.06). Electroless Plating ( Reactions ) Plated metal : Me n+ Zn, Sn, Cu, Co, Ag, Au RA General reactions : RA R + ne- Me0 Me n+ + ne- Me0 alu Electroless Plating ( Reactions ) 5105.02.06 Training in Aluminium Application Technologies Electroless plating can be subdivided into autocatalytic plating and ion-exchange plating. Autocatalytic Plating The autocatalytic plating process is driven by electrons freed by reduction of the reducing agent RA. These freed electrons join the metal ions in the solution and form solid metal on the surface. Because the electrons are coming from the reducing agent the process can keep on running also after the substrate is covered, i.e. high coating thicknesses are possible. Electroless nickel is an example of autocatalytic plating. Ion-Exchange Plating The other type of electroless plating is ion-exchange plating. This process is based on oxidation (dissolution) of the aluminium substrate whereby electrons are freed so that a reduction (deposition) of another metal coming from the aqueous solution is possible. (Figure 5105.02.07). The metals deposited by this technique are usually zinc or tin. The layers deposited are thin, because the deposition stops, when the aluminium is all covered and can no more supply electrons by oxidation. The processes are used as a pretreatment to plating (electrolytic and electroless). These ion-exchange processes are known under the names: zincate-, stannate- or modified zincate/stannate-process. The TALAT 5105 9
  • 10. electrolytic plating processes often require this pretreatment to improve the adhesion and to avoid the aluminium from getting dissolved in the plating bath, because aluminium is amphoteric (dissolves in both alkaline and acid solution). When used as pretreatment to plating correct process parameters are of great importance to the adhesion and corrosion resistance of the plated coating. The standard ASTM B253-83 specifies the correct pretreatment process routines for aluminium (zincating etc). Ion-Exchange Plating Principle : Al 3+ Al 3e - Men+ alu Ion-Exchange Plating 5105.02.07 Training in Aluminium Application Technologies 5105.03 Electrolytic Methods • Electropolishing • Electroplating • Platable metals on aluminium • Anodizing Group III can be subdivided into electropolishing, electroplating and anodising. Electropolishing Electropolishing is a controlled electrochemical dissolution of the basis metal by which a semi- to mirror-bright surface can be produced. Electropolishing is a method by which surface metal is removed by applying an external power supply and letting the sample be the anode in the process. Actually, it is a kind of "reverse plating" where aluminium is dissolved into the electrolyte instead of metal being plated from an electrolyte. Its applications are much like those of the chemical polishing, but by electropolishing corners and burrs are attacked more than the flat surfaces. The process can be substituted by chemical polishing. Since the polished surface is vulnerable to scratches TALAT 5105 10
  • 11. and corrosion, it is usually combined with anodising or transparent organic finishing. The process is used for producing reflectors and decorative components. The best result is obtained by using pure aluminium (Al > 99,9%) (Figure 5105.03.01). Electropolishing Principle : Surface metal removed electrochemically Properties : Similar to chemical polishing, except that corners and burrs are attacked more than surfaces Elimination of scratches and burrs Smoothing and brightening High reflectivity Use : Reflectors Decorative components Often before anodizing or lacquering alu Electropolishing 5105.03.01 Training in Aluminium Application Technologies Electroplating There are a number of difficulties to be considered when electroplating on aluminium: 1. Aluminium is amphoteric, i.e. it is dissolved in both alkali and acid. 2. The difference in potential, between the aluminium matrix and second phase constituents can affect the deposition reaction. 3. The position of aluminium in the electrochemical series can lead to formation of immersion deposits in the plating solution. 4. The coefficient of thermal expansion of aluminium and its alloys differs from most of the metals commonly deposited on it. This can lead to decohesion between coating and substrate when the plated aluminium part is subjected to high temperature elevations or to temperature shocks. 5. The difference in atomic diameter and crystal lattice structure between the aluminium substrate and the metal deposited on it. One of the major problems when plating on aluminium is the readiness by which aluminium reacts with the air to form oxide. It is also a problem that aluminium is amphoteric, i.e. aluminium is dissolved in both acidic and alkaline plating baths. These problems can be overcome by removal of the oxide and electrodeposition of the metal in the same process, or, alternatively, by using an intermediate pretreatment layer deposited by ion-exchange plating (zincate or stannate processes as described earlier). When the oxide is removed in the same bath as the electrodeposition takes place the TALAT 5105 11
  • 12. process is called a direct plating process. It is possible to electrodeposit copper, nickel, silver, brass and chromium by using the direct plating method. This technique has only limited use in the industry. The most frequent technique used is to plate an intermediate pretreatment layer, deposited by the ion-exchange technique as described earlier. Though plating on aluminium is a relatively expensive technique, it is increasingly important because of the possibility of combining the low density of aluminium with the functional properties of the deposit. Good results can be obtained with a suitable combination of metal and process (Figure 5105.03.02). Electroplating Methods : Direct plating Anodic preparation Zinc immersion Tin immersion Hard chromium Properties added by electroplating ( examples ) : Wear resistance, corrosion resistance, electrical properties, weldability, solderability, etc. Use : Portable computers, telephones etc. Computer harddisk General engineering applications like machine elements etc. alu Electroplating 5105.03.02 Training in Aluminium Application Technologies Platable Metals on Aluminium As an example of the plating techniques, gold is deposited on aluminium for an aerospace application. The process is: • Zincate / stannate • electrolytic copper deposit, 5µm • electrolytic nickel deposit, 10µm • electrolytic gold deposit, 5µm By using the above process sequence it is possible to eliminate the difficulties when plating aluminium that were listed earlier. The copper deposit has an excellent ability to absorb stress resulting from differences in the coefficient of thermal expansion. The nickel deposit eliminates the risk of galvanic corrosion by forming a dense and pit-free layer. The nickel layer is also necessary to prevent diffusion of copper into the gold. The gold is the desired top coating and by depositing 5µm a pit-free layer is obtained, i.e. no corrosion of the underlaying layers is possible. The gold layer is 100% resistant to corrosion and has the desired electrical and thermal characteristics. TALAT 5105 12
  • 13. The above described gold-plating is tested by the following test sequence: • 10 temperature-shocks (quick) from -55°C to +125°C. • 200 temperature cycles (slow) from -55°C to +125°C. • 240 hours at 95% relative humidity at 40°C. • High temperature storage at 125°C for 1000 hours. After this test cycle no visible or electrical changes can be allowed. Other more common applications of plated aluminium coatings are machine elements and many leight weight components. The metals that are platable on aluminium either directly or by use of an intermediate zincate or stannate layer are many. The most common ones are chromium, nickel, silver, gold tin, zinc and copper (Figure 5105.03.03). Chemical Conversion Coatings (Methods) Methods: ! With chromate chromate processes chromate-phosphate processes ! Non-chromate phosphate processes molybdate-phosphate process oxide processes alu Chemical Conversion Coatings (Methods) 5105.02.03 Training in Aluminium Application Technologies The obtainable properties by plating aluminium are changed wear resistance and friction. Thermal conductivity, solderability and electrical resistance are main properties in many electronics. The commercially most common reason for surface treatment are decorative or corrosion resistance related (Figure 5105.03.04). TALAT 5105 13
  • 14. Properties of Electrolytic Plated Metals on Aluminium Cr Ni Cu Ag Sn Pb Cd Zn Au Rh Wear " " " Friction " " " Thermal " " Electrical " " " " " Decorative " " " " " " Corrosion " " " " " " " Solderability " " " " " alu Summary of Properties and Use 5105.03.04 Training in Aluminium Applicat ion Technologies Anodising Anodising is a commonly used method for surface treatment of aluminium. This is due to a number of properties offered by this technique. Depending on the process condi- tions the following properties can be obtained: • Corrosion resistance • Decorative surfaces • Surfaces in almost any colour on the palette, except white • Hard and wear resistant surfaces • Electrical and thermal insulation • The surface can be used as a base for organic finishing and for plating The anodising technique is expected to have an increasing advantage over many other surface treatment processes, because the technique does not require toxic chemicals, heavy metals etc., and the anodised aluminium is easily recycled (Figure 5105.03.05). Anodizing Principle: Controlled oxidation of the aluminium metal surface, forming aluminium oxide ( alumina ) Properties : Increased wear resistance and hardness Corrosion protection Colourable to many colours High coefficient of heat emission and electrical isolating Improved adhesion for organic coatings Corner defects due to brittleness Use : Architectural (house facing, window frames etc. ) Cars and aerospace ( structural, decorative, engine parts ) Domestic, holloware, pots and pans alu Anodizing 5105.03.05 Train ing in Aluminium Application Technologies TALAT 5105 14
  • 15. 5105.04 Literature Wernick, S., Pinner, R. & Sheasby, P.G.: The Surface Treatment and Finishing of Aluminium and its alloys, 5th edition, Hübner, W. & Speiser, C.T.: Die Praxis der anodischen Oxidation des Aluminiums, 3rd edition, Montgomery, D.C.: Light Metals Finishing Process Manual, AESF 1990 5105.05 List of Figures Figure No. Figure Title (Overhead) 5105.00.01 Methods of Surface Treatment for Aluminium 5105.01.01 Mechanical Finishes 5105.01.02 Organic Finishes 5105.02.01 Pickling and Etching 5105.02.02 Chemical Polishing 5105.02.03 Chemical Conversion Coatings: Methods 5105.02.04 Chemical Conversion Coatings: Properties 5105.02.05 Electroless Plating: Properties 5105.02.06 Electroless Plating: Reactions 5105.02.07 Ion-Exchange Plating 5105.03.01 Electropolishing 5105.03.02 Electroplating 5105.03.03 Platable Metals on Aluminium 5105.03.04 Summary of Properties and Use 5105.03.05 Anodizing TALAT 5105 15