Page 1 of 13

Adhesive bonding - a guide to best practice

Surface pre-treatment: overview & specific methods

Overview:

Introduction
Purpose of pre-treatment
Main types of pre-treatment
Overview of mechanical, chemical & energetic pre-treatment

Introduction

Synthetic adhesives have been used successfully for many years in diverse sectors of industry
including aerospace, automotive, biomedical/dental, construction, electronic, marine, sport & leisure.

Although in a few applications no surface pre-treatment is necessary (the automotive industry has been
using specially designed adhesives for bonding oily metal adherends since the 1950s), it is accepted
that to obtain the optimum performance from an adhesive joint a pre-treatment is required. The type of
pre-treatment is often a compromise between the best surface preparation, economics of component
manufacture and health and safety issues.

If the economic and engineering advantages of adhesives are to be realised, the adherends must be
given a suitable surface pre-treatment. The benefits of using appropriate surface pre-treatments are:

enhanced mechanical performance of joint

improved joint durability in aggressive environments
increased service-life of component
ability to bond difficult adherends, e.g. polyolefins and polytetrafluoroethylene

Purpose of pre-treatment

Pre-treatment is carried out to achieve one or more of the following:

To remove completely, or to prevent formation of, what are often referred to as weak
boundary layers. A useful analogy to describe this concept is applying a pressure
sensitive tape (e.g. Sellotape) to an adherend coated with a powder (e.g. talc). The
Sellotape will simply adhere to and pull off the talc from the adherend. No bond will form
between the tape and adherend. Examples of weak boundary layers include weak oxide
scale on metallic substrates, plasticisers which have migrated to the surface of polymers,
mould release agents from processing of composites. Other surface contaminants are
dust, dirt, grease, oils and even finger marks!

It is well established that to form an effective bond, intimate molecular contact between
adhesive and adherend is required. The correct surface pre-treatment will optimise this
degree of contact, which may be brought about by chemical modification of the adherend
surface.

To protect the adherend surfaces before bonding. This is often necessary, particularly
with metals which after surface pre-treatment have a surface that is highly reactive not
only towards adhesives but also to atmospheric contaminants. To preserve the integrity
of the adherend surface it is usually necessary to bond the surface within a few hours of

04-01-2017
 Page 2 of 13
treatment, or to coat it with a primer which is compatible with the adhesive to be applied
later. A primed surface can protect the adherends for up to several months.

To produce a specific adherend surface topography, thereby altering the surface profile,
and possibly increasing the bondable surface area, that is, to roughen the surface.

Main t pes of pre-treatment

There is a wide range of surface treatments available. Many adhesives or adherend suppliers give
advice. est practice is collected in Standards ISO 5 (for metals) and ISO 1 95 (for plastics) are
currently under revision. Techniques can be classified into five groups, according to the nature of
treatment:

eaning egreasing: emoval of loose solids can be accomplished with a clean brush or blast of
clean, dry air. Organic solvent or alkaline aqueous solution removes organic materials such as grease,
oil and wax from adherend surfaces. This can be accomplished by wiping, dipping or spraying.

Surface oughening: Techniques where abrasive materials are employed to remove unwanted layers
and generate a roughened surface texture.

hemica reatments: Immersion of the adherend in an active solution which has the power to etch or
dissolve a part of the adherend surface or change it in such a way that the treated surface becomes
chemically active. An electrochemical reaction can also be included where current is transferred
through an electrolyte between an auxiliary electrode and the adherend surface, e.g. anodising, and
this introduces several additional factors to be controlled.

Ph sica reatments: Techniques where the adherend surface is cleaned and chemically modified by
exposure to excited charges or species. Techniques such as corona discharge, plasma, flame or
exposure to ultraviolet/o one are examples in this group.

Primers: Alternative surface treatments, often simpler than chemical or physical methods, applied by
dipping, brush or spray. They can chemically alter the surface (e.g. silane coupling agents, chromate
conversion coatings), or protect the preferred surface already generated by another method (e.g.
aerospace primers after anodising).

In general, the above types of surface pre-treatment can be divided into three major categories:
mechanical chemical energetic. Each of these can be further subdivided into a given technique or
method of surface preparation, as illustrated in Table 1.

Overview of mechanica chemica & energetic pre-treatment

ab e Surface pre-treatments for adherends

Mechanica hemica nergetic

Alumina gritblast Solvent cleaning Plasma

ryoblast etergent wash orona discharge

Sodablast Acid etch lame
Peel ply Anodising Excimer laser

Silicon carbide abrasion Primer

Selection of a pre-treatment should be based on issues such as cost, production, durability and health
and safety. Pre-treatment facilities can include equipment, chemicals and consumables. ey surface
features which should be kept in mind are wettability, roughness, soundness, stability, contamination,
uniformity and adhesive compatibility.

Surface pretreatment must always be appropriate to performance requirements, and be compatible

with manufacturing procedures and costs. se of aluminium in four industries illustrates this:

Aerospace (wing skin to honeycomb)

- complex and high cost etch, anodise and prime sequence before lay-up with epoxy
adhesive

Automotive (bodyshell)
- metal supplier provides material with conversion coating and press lubricant applied,

04-01-2017
 Page 3 of 13
before application of epoxy paste adhesive by manufacturer

ail (carriage panels to frame)

- solvent clean, then primer or coupling agent applied to localised areas in factory, before
application of polyurethane adhesive

Automotive (engine-block flanges)

- alkali cleaning before application of anaerobic acrylic, or silicone sealant in factory

Mechanica pre-treatment

Mechanical abrasion is the most widely applicable surface preparation technique, being suitable for
most materials.

Mechanical abrasion will remove weak boundary layers. It will also change the surface topography of
the adherend, increasing the bondable surface area on a microscale. urthermore, mechanical
abrasion will enhance the adhesive s ability to wet (when the adhesive readily and completely covers)
the surface of the adherend.

The simplest form of abrasion uses silicon carbide paper to abrade/polish surfaces. This method may
be carried out dry or in conjunction with a suitable solvent. The quality of the adherend surface
obtained with silicon carbide depends upon the grit si e and whether the operation is performed
manually or mechanically. It is necessary to monitor carefully the abrasion since, if the process is
carried out for too long, surface debris initially removed can be re-deposited. or composites, it is
important to note that mechanical abrasion may cause fibre damage and impair performance of the
joint.

lasting is another form of mechanical abrasion and includes alumina grit blasting, shot blasting,
cryoblast and sodablast. Shot blasting is only appropriate for treating ferrous surfaces. or other
metals, grit such as alumina should be used. ryoblast and sodablast are used for preparing composite
adherends. yroblasting is less aggressive than alumina grit and consists of solid carbon dioxide
pellets.

Sodablasting was initially used in the aerospace industry as a preparative method for painting aircraft. It
uses a suspension of sodium bicarbonate in water. A disadvantage of sodablast is that it increases the
water content of composite and hence brings a need to dry the component before bonding. The
variables associated with blasting are the chosen particle, the particle si e, pressure of blast, exposure
time, angle of blast and distance between blast no le and adherend.

In the peel ply surface preparation method used for composites before curing, a fabric material is used
to cover the external surface of the composite. uring the cure cycle, part of the matrix will flow and
penetrate the fabric and eventually, after curing, becomes part of the laminate. hen the laminate is
required for bonding, the fabric is peeled off, fracturing the resin between the fabric and the first layer of
reinforcement, producing a clean, roughened surface to which the adhesive can be applied. The
surface morphology obtained is dependent on the nature of fabric and type of weave used.

hemica pre-treatment

There are several different chemical methods by which adherends can be cleaned and prepared for
bonding including: solvent cleaning, detergent wash, acid etch, anodising and primers.

Adherends are frequently contaminated with oils or grease. An effective method of cleaning ceramics,
glass and metal adherends is by an organic solvent vapour degrease. Solvent is boiled in a chamber
whereupon it condenses on the cooler adherend, and dissolves the oil and grease before it drips back
into the heating tank. ery clean surfaces can be obtained in this way. onsideration must be given to
local or national environmental regulations on the use of organic solvents.

Alternatively, if small enough, the adherend can be immersed in an ultrasonic bath containing a solvent.
Agitation of the adherend increases the speed of treatment.

Solvent cleaning in its simplest form can be performed by using a suitable cloth to apply the solvent to
the adherend. The cloth should be applied so that the surface is wiped in one direction only, to prevent
any surface debris from being re-deposited. The cloth should also be replaced regularly.

Solvent cleaning is often applied to polymeric materials, but the correct solvent must be chosen with
care since solvents are organic based and may attack, be absorbed by, or plasticise the adherend.
Plastics material suppliers can usually advise.

04-01-2017
 Page 4 of 13
etergents dissolved in water, alkaline or acidic solutions and used at temperatures of about 50- 0
may also be used to supplement or replace the organic solvent cleaning process.

Metal adherend surfaces are rarely of pure metal, but are a combination of oxides, sulphides, chlorides
and other atmospheric contaminants. This results in a surface which is mechanically weak and is prone
to crack and flake off.

Acid etching is a well established method of removing weak metallic scale, in favour of forming an
oxide layer which is mechanically and chemically compatible with the adhesive. ence, different acid
treatments are applied to different metal adherends, for example, chromic acid for aluminium, sulphuric
acid for stainless steel and nitric acid for copper. Some metals require an alkaline, rather than an acid,
pretreatment, such as alkaline peroxide used for titanium.

Acid pre-treatment can also be applied to certain plastics. hromic acid is used to surface treat
polyolefins. Even PT E, known as a non-stick material, can be bonded when treated with a solution of
sodium naphthalenide in tetrahydrofuran.

Anodising has been exploited extensively by the aerospace industry as a surface pre-treatment for
aluminium and titanium alloys. Anodising is performed only after the adherend has been etched. The
purpose of anodising is to deposit on the adherend a porous and stable oxide layer on top of the oxide
layer formed after etching. The porous oxide layer enables adhesive (or primer) to penetrate the pores
readily to form a strong bond and is resistant to environment attack by O.

Anodising is a type of electrolysis where the adherend is the anode, and a typical electrolyte is
phosphoric acid. An inert electrode is used for the cathode. The differences in the structures of
aluminium oxide layers before and after anodising are illustrated in ig. 1. A disadvantage of anodising
is that it is a time-consuming operation. In addition, there are a number of variables which must be
carefully controlled: applied voltage, time of anodising, temperature and concentration of electrolyte.

ig O ide a er on a uminium:

a efore anodising b After anodising

Application of a primer to an adherend is another form of surface pre-treatment mainly used for
materials such as metals and ceramics. enerally, the primer is the final stage of a multistage pre-
treatment process. The primer acts as a medium which can bond readily to the adherend and adhesive.

Some adhesives have high viscosities and thus do not flow readily over the adherend, or the
adherends have difficult to bond surfaces (e.g. copper). The primer, which is formulated so that it
represents a solvented version of the adhesive, readily wets the adherend. The primer is then cured on
the adherend as desired. The adhesive, when applied to the primed surface, being chemically
compatible, will establish a strong joint on curing.

Primers often contain ingredients which enhance the environmental resistance and thermal stability of
the joint, as well as protecting the adherend from hydration and corrosion. The cured primer can protect
the adherend for several months before bonding.

nergetic pre-treatment

Energetic surface pre-treatments which have been reported in the literature include flame, corona
discharge and plasma ( P) and excimer laser. All of these procedures cause a change in the
surface texture of the adherend, brought about by the interaction of highly energetic species with the
adherend surface. These pre-treatment methods have been applied to metals and in particular
composites and plastics.

A plasma is an excited gas consisting of atoms, molecules, electrons, ions and free radicals. A plasma
is generated by applying a high frequency and high voltage between, for example, parallel plate
electrodes in a low pressure chamber. The advantage of this method is that it allows treatment of
adherends by different plasmas of argon, ammonia, oxygen or nitrogen.

04-01-2017
 Page of 13
Plasmas created from inert gases are generally used to clean the surfaces of adherends. The excited
species generated can have one or more of the following effects on the adherend:

surface clean
- the excited species may have sufficient energy to displace some surface contaminants

degradation and ablation

- the plasma can cause degradation of the surface of polymeric materials and lead to
removal of debris from the surface

crosslinking
- the surface of the adherend may become crosslinked and prevent the formation of weak
boundary layers

oxidation
- the plasma can lead to introduction of oxygen-containing groups, for example carbonyl,
brought about by oxidation of the polymer surface this can lead to the adherend being
readily wetted by the adhesive

If instead, a plasma is created in air at atmospheric pressure, the air when ionised appears as a
blue/purple glow with faint sparking, and is termed a corona. The effects which the corona discharge
can have on the adherend surface are similar to those described above. orona treatments are usually
applied for preparing thin polymer films and composite laminates.

The effect of a flame treatment is to oxidise the adherend, which produces polar groups such as
- OO , - O, -O , -NO , -NO and -N . This creates a surface better suited to wetting by the
adhesive. This method of surface pre-treatment has been applied successfully to carbon/PEE and
glass/polypropylene composites.

The variables of flame treatment include type of gas, gas/air (oxygen) ratio, the rate of flow of mixture,
exposure, time and distance between flame and adherend.

ig ffects of surface pretreatment

on the durabi it of a uminium
a o toughened epo oints
sub ected to acce erated ageing in
water at

igure illustrates the effect that some of the surface

pre-treatments described have on lap shear strengths of
aluminium/epoxy joints. learly, the best performance is
obtained from bonded joints having been prepared by an
etchant and post-anodised. In contrast, a simple solvent
degrease or gritblast in this type of environment is
inadequate.

Specific methods for pre-treatment

Introduction
Standard method for simple surface preparation
Surface preparation method - SPM
Preparation of:
- metals
- plastics, composites & rubber
- ceramics, paints & fabrics
Etching solutions

Introduction

Substrate surface pre-treatment is necessary in order to:

remove chemically incompatible layers

overcome any low surface energy effects which inhibit bonding
achieve a surface topography which is receptive to the adhesive
ensure good durability of the bonded joint

Standard method for simp e surface preparation

04-01-2017
 Page of 13
Simple surface preparation techniques such as cleaning and degreasing are required for most
adhesives. ertain adhesives, for example cyanoacrylates, may be used alone on plastics materials as
they can penetrate or dissolve away surface debris.

Cleaning and degreasing

use non-ionic detergents, alkaline cleaners or isopropyl alcohol (IPA)

do not wipe with fibrous cloths or tissues
allow to dry

Surface preparation method - SPM

The following method is suitable for most materials. A silane coupling agent may be used to indicate
surface wettability and increase the bonded joint s long-term durability.

emove oil or grease contamination

Abrade or shot blast using medium grit (1 0 - 00 mesh suitable). rit should preferably
be alumina (bauxite). o not use steel or iron shot of any description on aluminium alloys
emove coarse debris (if present) with water jet
emove fine debris with solvent impregnated wipes
Ensure surface is completely dry
ond or prime immediately

Preparation of metals

Aluminium and its alloys

Method A
Etching ( E STAN 0 - / : Method 0)

1. se simple SPM and degrease in alkaline cleaner

. Immerse in etchant A for 0 minutes at 0- 5
. emove and rinse thoroughly in cold distilled or de-ionised water
. ry with hot air ( 5 ) for 10 minutes
5. ond immediately

Method
Anodising ( oeing PAA 5555)

1. Etch as in Method A
. Immerse in phosphoric acid bath at room temperature (1 - 0 )
. aise voltage to 10 . eep current low ( A) for 0- 5 minutes. O NOT O E - N
. isconnect power
5. emove and rinse thoroughly in running water
. ry in oven at 0- 0
. Prime or bond within 1 hours

Aluminium honeycomb

1. egrease in vapour bath of trichloroethane

. Stand for hours at room temperature, or for 15 minutes at 9 ( 00 )

Note: Alternatively, do nothing. Aluminium honeycomb core has low thermal mass and vapour
degreasing may be ineffective.

Chrome plate

1. se simple SPM
. Immerse in etchant for 1-5 minutes at 9
. emove and rinse thoroughly in cold distilled or de-ionised water
. ry in hot air stream ( 55 ) for 10 minutes
5. ond immediately

Copper and its alloys -brass, bron e ( E STAN 0 - / )

1. se simple SPM
. Immerse in etchant , or E for specified time
. emove and rinse thoroughly in cold distilled or de-ionised water
. ry in clean, cold pressurised air (hot air will discolour surface)
5. ond immediately

04-01-2017
 Page 7 of 13
ead and pe ter

se SPM . ust must be carefully controlled.

Magnesium and its alloys ( E STAN 0 - / )

1. egrease. o not abrade

. Immerse item in sodium hydroxide solution for 10 minutes at 0 5
. ash thoroughly in cold tap water
. Immerse item in etchant for 10 minutes at room temperature
5. ash thoroughly with cold tap water
. ash again with distilled or de-ionised water
. ry in hot air ( 5 )
. ond immediately

Note: I E A A - never place magnesium components in a vapour bath

Nic el and its alloys

1. se SPM
. Immerse for 5 seconds at room temperature in concentrated nitric acid (specific gravity
1. )
. emove and rinse thoroughly in cold distilled or de-ionised water
. ry in hot air stream ( 5 ) for 10 minutes
5. ond immediately

Steel - mild and iron ( E STAN 0 - / A- )

1. se SPM
. Immerse for 10 minutes in etchant at 0
. rush off black deposit with a stiff nylon brush under clean, cold running water
. low dry with clean air
5. ipe with isopropyl alcohol (IPA)
. Allow to dry
. eat for 1 hour at 1 0
. ond immediately

Note: or exterior use and demanding environments, use a silane coupling agent (Permabond SIP or
Accomet )

Steel - stainless

1. se SPM - alumina (1 0/ 0) shot blasting is preferable

. ash in detergent solution for 10 minutes at 5 5
. inse in cold water
. inse in distilled or de-ionised water
5. Immerse in etchant for 5-10 minutes at 0
. inse in cold water
. inse in cold distilled or deionised water
. ry in hot air stream, oven or with infrared lamps for 10 minutes ( 95 )
9. ond immediately

in

se SPM

itanium and its alloys

Method A

1. apour degrease
. se SPM
. ash in detergent solution for 10 minutes at 5 5
. inse in cold distilled or de-ionised water
5. ry in hot air stream, oven or with infrared lamps ( 95 ).
. Immerse in etchant I for 5-10 minutes at room temperature
. ash in cold distilled or de-ionised water
. Oven dry at 5 5 for 10-15 minutes
9. ond immediately

Method
04-01-2017
 Page of 13
1. apour degrease
. se SPM
. apour degrease again
. se sodium hydroxide anodiation (S A) process at 10 and 5M NaO at room
temperature
5. ash and oven dry at 5 5 for 10-15 minutes
. ond immediately

inc and its alloys, including hot dipped galvanised steel, electrogalvanised steel and iron- inc alloy
coated steel ( E STAN 0 - / )

1. egrease surface
. Immerse for 5 minutes in onderite 1 (an alkaline cleaner)
. ash thoroughly in distilled or de-ionised water
. Treat in 5 volume solution of Accomet , to yield a dry oxide coating of 0.5g/m
5. Oven dry or in hot air stream at 115 5
. ond immediately

Note: If a dark yellow or green layer appears, the passivate is too thick and therefore weak and friable.

inc - passivated

1. se SPM
. Then use the standard method for inc and its alloys

Preparation of plastics composites and rubber

se SPM or P (flame, corona discharge or plasma) techniques.

A S acrylonitrile butadiene styrene

yanoacrylate, toughened acrylic and solvent-based adhesives will bond without surface preparation.
se minimum quantity of initiator for two-part acrylics and ensure no surface residue after bonding.

Note: Take care to avoid stress cracking

1. egrease surface
. Immerse in etchant for 15 minutes at room temperature
. emove and rinse thoroughly in cold water
. inse again in hot water
5. ry in a hot air stream ( 0 )
. ond immediately

Acetal (also known as polyoxymethylene or POM)

1. Stress relieve material

. ollow method for A S
. Alternatively, use corona discharge

Acrylics

1. se SPM
. Take care to avoid stress cracking

Al yds (polyalkyds)

se SPM or P

Note: If using cyanoacrylate adhesive, use only alcohol for pretreatment

Cellulose - acetate/butyrate/nitrate

1. egrease using solvent

. If using with epoxides, heat plastic parts for one hour at 9
. Apply adhesive while still warm

Note: Elevated temperature will increase cure rate

Al yl phthalate (polyalkyl phthalate)

se P

04-01-2017
 Page of 13
po y (and composites)

se SPM or P

Note: heck for presence of mould release agent. Take care to avoid stress cracking

Polyamide (Nylon)

Method A

1. se SPM
. ry the material (polyamides are hygroscopic)
. ond immediately

Method

1. egrease
. Immerse in etchant for seconds seconds at room temperature
. ry in well-ventilated atmosphere at for 0 minutes or less
. Allow to dry
5. ond immediately

Polycarbonate (P )

se SPM or P

Polyester - thermoset, including composites

se SPM or P

Note: heck for presence of mould release agent within structure

Polyester - thermoplastic

se P

Polyetherether etone P

se P

Polyethylene

1. se P
. Alternatively, use a sodium naphthalene etch solution for halogenated polyethylenes

Polyimide

se P

Polymethylmethacrylate (PMMA or perspex )

See acrylics

Phenolic

se SPM or P

Phenolic foam

oes not require surface pre-treatment

Polyphenylene o ide

se SPM or P

Polypropylene

See polyethylene

Polystyrene

See acrylics

04-01-2017
 Page 10 of 13
Polystyrene foam

oes not require surface pre-treatment

Polysulphone

se SPM or P

Polytetrafluroethylene P

se TetraEtch (an Albright & ilson product)

Note: See polyethylene

Poly inylchloride P C

See acrylics

P C foam

oes not require surface pre-treatment

Polyurethane foam P

oes not require surface pre-treatment

ubber

se SPM

Note: If using a cyanoacrylate, use alcohol only to degrease

Silicone rubber

se SPM

Note: se silicone-based adhesives

Preparation of ceramics paints and fabrics

Cellulose (i.e. wood)

1. Plane surface
. Sand to provide evenly abraded surface
. emove debris using a brush or air-blast
. ond immediately

Note: ood with 0 moisture must be dried prior to bonding - ideal moisture content is - 10 by
weight. ellulose has a slightly acidic surface if bonding with cyanoacrylate adhesive, use activator to
neutralise surface.

Cementitious (including concrete, mortar)

1. egrease using non-ionic detergent

. ash thoroughly with water
. Sand-blast to remove 1- mm of bonding surface
. emove debris
5. ry surfaces
. ond immediately

Note: If limestone, dolomite or carbonate aggregates present, acid etch surface after sand-blasting.
ash thoroughly. Alternatively, use dilute sulphuric acid.

ituminous concrete

1. Scrub surface with detergent solution

. inse with high pressure water jet.
. ry
. ond immediately

Ceramics (including ferrites, masonry and pottery)

04-01-2017
 Page 11 of 13

Note:

Fabrics

Note:

Friction materials

Glass

Note:

Leather

Paint

Paint

Etching solutions

Etchant A

or

Note:
Phosphoric acid bath

Note:

Etchant B

Note:
Etchant C

04-01-2017
 Page 12 of 13

Note:
Etchant D

Note:
Etchant E

Note:
Etchant F

Note:

Note:
Etchant G

Note:
Etchant H

Note:

Etchant I

Note:

04-01-2017
 Page 13 of 13
Note 1:

Note 2:
Etchant J

Note:
Etchant K

Note 1:
Note 2:
Etchant L

Note:

Disclaimer

04-01-2017