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Bonding of Composite

materials

Compiled
By
pak de jongko

duraposita chem.
Table of content

Part I General understanding and rules

Part 2The various chemical types of Adhesives for


composites, epoxy adhesives

Part 3 Various types of adhesives for composites: Acrylics,


urethanes-acrylates and Polyesters

Part 4 Various types of Adhesives for Composites:


Polyurethanes, Heat stable adhesives, Syntactics, etc…
Part I
General understanding and rules

Definition of composites and scope of these chapters

In this chapter, we will study the assembly and the adhesive bonding of 2 kinds
of composites:

• primary composite materials are those made of polymer matrixes


reinforced with fibers such as glass, carbon or aramid fibers,
• secondary composites are those made by assembly of the primary
composite materials, such as sandwich panels composed of composite
skins bonded to various core materials such as honeycombs, or complete
composite parts including a composite material + metal fixtures /
attachments.

Different methods of assembly of the composite materials

The primary composite materials are made by different techniques: lay out,
impregnation, molding, infusion, filament winding, pultrusion… All these methods
consist in impregnating fibers with a polymer resin ( epoxy, polyester, etc…), the
manufacturer may start with prepregs where the fibers are already impregnated
with resin, shaping the parts in various ways and then curing the polymer by heat
and pressure.

Co-curing

In most composites, the impregnation resin is by itself an adhesive resin,


because it has to bind strongly the fibers together. For instance, epoxy matrixes
are also excellent adhesives. Therefore it may be used to bond 2 composite
parts together at the same time as the cure of the composite matrix occurs. This
is called co-curing. No other adhesive is needed, although sometimes a special
film of adhesive is laid between the 2 parts. Refer to figure 1.
Figure 1: Monolithic primary composite parts, made by single operation: curing
or co-curing for all these simple parts, there are no assembly operations

This technique is widely used in aircraft construction to make, in one single


operation, a solid part which can be molded in a press or an aut°Clave. We will
not discuss this technique because it belongs to the composites manufacture (
except when an adhesive film is added ).

Adhesive bonding

EWhen the part is hollow, co-curing cannot be used, the 2 halves of the part
must be manufactured separately and then they have to be assembled, either by
mechanical fixtures or by using inserts, or by adhesive bonding. This chapter will
be devoted only to the adhesive bonding of composite materials and parts. Refer
to figure 2
Figure 2: Examples of composite bonded parts

Wet tabbing

We will also mention a technique which is frequently used in naval construction: this is
the "wet tabbing " (figure 3 ): in this technique, the cured composite parts are aligned
closely and then a prepreg ( reinforcing fibers impregnated with the raw, non cured resin
) is tabbed or laid onto the mating parts and then cured usually at room temperature.

Figure 3: Schematic diagram of tabbed stringers in naval construction


Several piles of impregnated fibers are applied on the corner between
hull and stiffeners.
This method has been used for years for shipbuilding, to join fiberglass
reinforced polyester parts by using also fiberglass mats impregnated with
polyester resins. However it is now often replaced by resin injection or by true
adhesive systems, as we will see later, in next sections.

To summarize, figure 4 shows the various techniques of assembly of GRP in


shipbuilding for instance.

Figure 4: Different techniques used in ship building for


the assemblies of composite parts
(Source: Scott Bader)

Inserts

A last technique is the use of inserts ( figure 5 ) : here metal inserts such as
studs, plates… are placed into the premix in the mold before curing, and the cure
of the matrix will bl°Ck the insert into the hardened resin. Here we use the
adhesive properties of the polymer resin, and also the possibility of bolting,
screwing the parts together, and mechanical engineers, who are accustomed to
use mechanical fasteners, like and rely with confidence on this technique.
However we will not study this technique here because it is a mechanical
assembly.
Figure 5: The 3 steps of the use of metal inserts in the
final assembly on large GRP part
(Source: BIGHEAD bonding fasteners Ltd., UK)

In any case, the composite parts must be assembled onto a frame, and this
frame is very ofter made of metal. This is true for automotives, aircrafts or
construction panels. Therefore it is mandatory to have some kind of metal
fasteners, attached to the composite part, which is then attached to the frame.

Figure 6 shows how the speed breakes of the F15 aircraft fighter are molded,
including bonding of titanium ribs and actuators. Here both techniques are mixed:
co-curing of the graphite-epoxy skins over honeycomb core, bonding of titanium
ribs and then final positioning and curing of the graphite-epoxy skins.

Figure 6: F-15 composite speedbrake


OML: outer moldline;
IML: inner moldline;
HC: honeycomb care
(Source: SAMPE 8th Conference)
Adhesives, as we know are able to assemble different materials, for instance
composites to metal, metals to metals, plastics to metals, … Epoxy adhesives,
which are very frequently used for the composite matrixes, are also an evident
choice to bond composites based on epoxy matrix. Compatibility between resin
and adhesive is evident. In the same fashion, polyester adhesives and putties
are an evident choice to bond glass fiber reinforced plastics.

Advantages and drawbacks of adhesive bonding for composites

Compared to mechanical fasteners, adhesive bonding provides many


advantages:

• mechanical fasteners require drilling holes in the parts, and this weakens
the composites because it cuts through the reinforcing fibers and also
creates weak points. Figure 7 shows the many failure modes that may
occur in a bolted joint. Bonding improves tensile resistance ( figure 7 ).
• Bonded joints exhibit lower stresses concentrations than mechanical joints
when holes are needed, and thus provides increased static strength,
• Risks of cracks propagation are reduced,
• Bonded joints provide always 10 to 25 % weight savings in primary and
secondary structures,
• Bonded joints enable the design of smooth external structures,
• For large surfaces bonding costs less than mechanical assembly, because
it needs less manpower ( although there are now huge riveting machines
which may place automatically thousands of rivets on the fuselage of large
aircrafts in a short time, but these machines have of course a very high
cost ),
• Adhesive may join together all kinds of materials: metals, composites,
plastics, wood etc…
• Adhesives can join very thin materials which could not be riveted or
bolted,
• Adhesives can join dissimilar materials without the risk of galvanic
corrosion,
• Adhesives may be flexible or rigid according to their formulation,
• Adhesives have an excellent resistance to fatigue.

However, adhesives bonding has also some drawbacks:

• elevated temperature creep resistance is fair or even poor for some


structural adhesives. In the Aircraft construction, there are for instance
several classes for the heat resistance of the structural adhesives:
resistance to 80 °C, 120 °C… and only some very sophisticated and
expensive adhesives can resist to a service temperature of 200-250 °C
which is required for some parts or military fighters. This means that
adhesives cannot be used in or near to the motors of aircrafts or
automotive.
• We will see that adhesives do not resist to peel stresses, and this is a
drawback compared to welding for instance,
• Bonded parts cannot be dismantled easily,
• Bonding requires specific design so that the parts will be stressed only in
shear mode ( refer to figure 7),
• Bonding requires an excellent and specific surface preparation of the
materials immediately before bonding,
• Bonded joints are difficult to inspect in a non destructive manner, although
there are several NDT such as X rays, ultrasonic inspection,
shearography, and others,
• Structural bonding requires an accurate mating of the parts because
adhesives do not give high performances in thick joints, ( will be discussed
in the section: Design and calculation of bonded joints)
• Water resistance of adhesives are often only fair,
• Durability of bonded joints must be assessed by difficult laboratory
accelerated aging tests.

We will study a number of these factors and properties in the following sections
of this chapter.

Figure 7 (a): Basic failure modes in a


double- lap bolted joint, the holes
weaken the composite
Figure 7 (b): Various modes of breaking into an adhesive
bonded composite part submitted to shear stresses

Materials to be bonded

• thermosetting matrixes ( epoxy, polyester, phenolics…) reinforced with


glass, carbon, graphite, aramid fibers,
• thermoplastic matrixes ( polyolefins, PEEK, nylon, polycarbonate…)
reinforced with the same fibers es above,
• various types of honeycombs: aluminium, Nomex, plastics,
• metal parts ( steel, aluminum, titanium in the aircrafts, metal alloys ),
• various types of sandwich panels with composite skins.

Surface preparation before bonding

Composite materials are made with polymer matrixes and the surfaces to be
bonded are made of these polymers. Therefore the required surface preparation
is the same as it is used for the pure polymer or plastic.

Cleaning:

Prior to bonding, parts must be cleaned, the demolding release agents used
during curing must be completely eliminated by washing with detergents or
solvents. Washing must be followed by a perfect rinse and drying with clean air.

Abrasion:

In order to eliminate pollution, mold release agents and obtain a slightly rough
surface for a better wetting, the surface may be gently abraded, for instance with
abrasive pad, but the abrasion must be very light so that it never goes down to
the reinforcing fibers, because these fibers must always be protected by a layer
of the polymer and embedded in the polymer. After abrasion, dust and pollution
must be eliminated by cleaning and rinsing thoroughly.

Tear plies:

This is the best technique to get a clean surface on which the adhesive will bond
readily. Refer to figure 8. During the manufacture of the composite part, a special
textile ( such as Dacron or other ) is applied on the surface of the polymer before
curing. Immediately before bonding, this peel ply or tear ply is peeled away, and
it leaves underneath a perfectly clean resin surface.

Figure 8: Structural reinforced plastic laminate with tear


ply to obtain perfectly clean bonding surfaces.

Chemical surface preparation

There are several chemical surface preparations which are specifically adapted
to the various polymers. Table 1 lists these surface preparations.
Cleaning Chemical and Physical surface preparation
with Light Plasma
Polymers None detergent Toluene
abrasion Atmospheric Low Flame Other
or Silination Sulfochromic sulfonic
treatment treatments
solvent Pressure pressure acid
Acrylonitrile - butadiene -
styrene (ABS)
Peel
Epoxy resins
ply
Melamine and Urea- Peel
Formaldehyde resins ply
Peel
Phenolic resins
ply
Polyacetal
Polybutyleneterephthalate
(PBT)

Polycarbonate (PC)
(Alcohol)

Polyester (Thermosetting)
(Ketone)
Titanate
PET: Polyester
primer,
(Thermoplastic)
NaOH
Polyetherether Ketone
PEEK
Corona
Polyolefins: PE, PP
(Ketone) treatment

Polyimide NaOH
(Ketone)

Polyamide (PA) Resorcinol


(Ketone)
PPO= Polyphenylene
oxide (Alcohol)

Polysulfone (PS)
(Alcohol)
Polyurethane (PU)
thermosetting

Table 1: Chemicals and Physical surface preparation for plastics, polymers and composites
1. When bonding with epoxy adhesives, the part may be up to 80°C and the adhesive is then affected while parts are still hot.
2. Laser may be also used now on thermosetting reinforced plastics.

In the next sections, we will introduce the different chemical types of adhesives
used for structural bonding of composites and their technical characteristics.

And after that we will study the main end uses of adhesives bonding in many
industries such as Automotive, Aircraft industry, transportation, shipbuilding and
others
Part 2
The various chemical types of Adhesives for composites,
epoxy adhesives
Introduction

In this section, we will study the adhesives which are used for bonding the most
important composite materials:

• thermosetting composites based on epoxy matrixes, the main market


being those used for aircraft parts,
• thermosetting composites based on polyester matrixes, mainly used in
naval construction and transportation equipment,
• other thermosetting composites such as those based on PU matrixes,
used in automotive exterior parts,
• thermoplastic composites based on various chemical compounds:
polyolefins, PPS,polyamides, etc...
• high heat resistant composites such as those based on cyanate esters, bis
maleimides, epoxy-phenolics, etc...

As we will see, when choosing an adhesive for a given composite material, the
first idea that comes to our mind is to select a chemical type which is the same
as the resin used as the matrix. Epoxy adhesives are of course totally compatible
with epoxy matrixes, therefore they are frequently used because they are the
best choice for carbon-epoxy and Kevlar-epoxy composites.

Epoxy adhesives, general knowledge, technical characteristics

The base of epoxies adhesives formulation is explained on figure 1


Figure 1: The box of epoxy resins formulations

Epoxy adhesives have a unique combination of useful properties:

• excellent adhesion to many materials, not only on epoxy matrixes but


also on many other polymers including thermosetting polyesters,
thermoplatic polymers, metals, glass, wood, concrete, etc…so that
different materials can be bonded together, for instance a composite to a
metal.
• very large possibilities of formulation, with many different types of
hardeners : aliphatic or aromatic amines, polyamides, polyaminoamides,
amino adducts, acid anhydrides, substituted imidazoles and others, refer
to table 1
Recommended Curing Curing agent
Curing agents Parts/100 parts Temperature Supplies and
Liquid resin °C rade Names
Aliphatic amines
D.E.H. (Dow
diethylene
chemical
triamine (DETA,
8-10 R.T.-150 Company),
DETA epoxy
Pacific
adduct)
Anchor
Amicure
(Pacific
triethylene
Anchor
tetramine (TETA, 10-13 R.T.-150
Chemical
TETA adduct)
Co.), Dow
Chemicals
Epo-Tuf
Aminoethyle
20-23 R.T.-150 (Reichhold
piperazine (AEP)
Chemicals)
Other aliphatic amines depends of the formulation pacific
Anchor, Huntsman, BASF
Aromatic amines
methylene Curithane
15-55 175 (2 hr)
dianiline (Dow)
4, 4-
Eporal
diaminodiphenyl 30-34 175 (2 hr)
(Huntsman)
Sulfone
Amicure (Air
Products and
Chemicals,
Inc.)
MDA/MPDA
100 Ancamine
eutectics
(Pacific
Anchor) Epon
(Shell
Chemical)
Cycloalphatic amines
Amicure (Air
Products)
wide vareity of
Ancamine
modified products dependson
R.T.-150 (Pacific
from major curing formulation
Anchor) Epo-
agent suppliers
Tuf
(Reichhold)
Versamine
(Henkel)
Polyoxypropylene Jeffamine
amines (Texaes)
Specialty amines Hiils
LAROMINE
(BASF)
Polyamines
ARADUR
(Huntsman)
ARADUR
Polyamines (Huntsman
adducts advanced
materials)
Polyamides
Henkel
wide variety of (Versamide)
polyamides Unirez (Union
curing agent with R.T. to 2 hr Camp)
range of @ 100 Ancamide
molecular (Pacific
weights Anchor)
Huntsman
Ancamides
Polyamido
depends on (Pacific
amines,
the Anchor)
Polyamido
formulations Aradur
amines adducts
(HUNTSMAN)
Heated activated
curing agents
Air Product
and catalysts
2-4 150 (2 hrs) and
benzyl
Chemical, Inc.
dimethylamine
(BDMA)
Ancaflex
(Pacific
Baron trifluoride
2-4 150 (2 hrs) Anchor)
amine complexes
Allied
chemicals
Polyurethome 150-160°C (2 Aradur
2-5
amines hrs) (HUNTSMAN)
Polymercaptan, 150-160°C (2 Aradur 90
2-5
polysulfide hrs) (HUNTSMAN)
Table 1: Curing Agents for Epoxy Resins Adhesives
Also, mixed compositions of polymers are very interesting, such as flexibilised
epoxy-nylon , heat resistant epoxy-phenolic, toughened epoxies which are
flexibilised by addition of elastomers,etc... Epoxies can be cured and coreacted
with many different resins. Therefore there are many different epoxy
formulations, with quite different technical characteristics,Epoxy formulations are
studied elsewhere in Specialchem4adhesives site. We will mention here only the
products and informations which are useful for composites bonding.

• good to excellent heat resistance according to the formulation: ranging


from 70°C for simple 2 components formulations, up to 150°C service
temperatures and more for heat curing formulations used in aircraft
construction, refer to Table 2
• very high cohesion, high modulus, and sometimes they are brittle and
this causes low peel strength, so that it has been necessary to give them
some flexibility by adding elastomers to the formulations, this is called:
Toughened epoxies. We study it hereunder. Refer to Table 2 for modulus
and elongation.
• Very high tensile shear resistance, as it is indicated on table 2, ranging
from 25 to 35 MPa ar ambient temperature. Table 2 also provides the
tensile lap shear resistances at other temperature such as 93°C and -
55°C this latter temperature being the low temperature reached on exterior
parts when the aircraft reaches the cruise altitude.
• intrinsic water resistance is good, but the sides of the bonded parts
should be protected against water ingress to the bond line, because this
water could penetrate between the epoxy adhesive and the substrates
and damage the bond.

Click here for Table 2

We will now review the different types of epoxy adhesives which may be used for
composite bonding

One component, heat curing epoxies

Here the hardeners is usually dicyandiamide because this product is a solid


which becomes miscible with epoxy resin only when the temperature reaches
140°C. The curing takes place at temperatures ranging from 140 to 180°C,
during times from 20 to 60 minutes. Other one components epoxy adhesives are
the epoxy-phenolic and epoxy-nylon.

Co curing:

In the aircraft construction, these adhesives can be cured at the same time that
the composite part itself (prepregs ) . This is called cocure. In this technique, the
parts prepregs are stacked together with the film epoxy adhesive, between the
mold and a vacuum bag for instance ( refer to figure 3 ), the whole system is
loaded into an autoclave where the prepregs and the adhesive are cured
simultaneously. This means that the curing conditions ( temperature, time and
pressure ) must be the same.One component, heat curing adhesives may have
different forms:

Figure 2: Manufacturing and cocuring honeycomb sandwich


parts, with prepregs and film adhesives

• film adhesives, supported by a carrier, that must be stored at low


temperatures -10 to -20°C to prevent the curing reaction to start, can be
stored only for a few months. table 3 presents the properties of HEXCEL
REDUX film adhesives, many of them are epoxy based, these film
adhesives are mostly used in Aircraft construction, very often by cocuring
technique. These film adhesives are usually expensive, because they are
high performance adhesives designed for aircraft construction. But it
should be possible to formulate cheaper formulations for other
applications such as Transportation equipment and Automotives. Figure 4
shows the manufacture of sandwich parts with carbon-epoxy facings and
epoxy film adhesives.
• or paste adhesives. ( refer to suppliers catalogs: HUNTSMAN, HEXCEL,
HENKEL Aerospace...)
Applications Product Performance
Honeycomb Key
Maximum Typical Flatwise Features
Product Composite Metal to Lap shear climbing
Honeycomb service cure tensile at Tg Dry and
Metal at R.T. drum peel
Bonding Bonding temperature temperature *1 *1 R.T.*1 (°F/°C)*2 Applications
Bonding (MPa/psi) at R.T.
(°F/°C) (°F/°C) (MPa/psi)
(N/76mm)
Epoxy Film Adhesive
Flame
retarded .
Co-cures
with 120°C
prepregs.
Redux®
185/85 250/120 30/4300 240/27 7/1000 230/110 Panel
610
bounding for
rail interiors,
marine,
building
applications.
Outstanding
peel
Redux®
195/90 250/120 40/5800 750/84 8/1200 175/80 performance,
335
ideal for
motorsport.
Short cure
cycle:30
Redux® minutes at
210/100 250/120 40/5800 650/73 9/1300 220/105
312 120°C for a
wide range of
applications.
Ideal for
composite to
255, composite
Redux®
- 275/135 350/175 40/6000 N/A 6.9/900 365/125, bonding and
330
195 lightning
strike
applications.
High peel
performance
for wide
range of
applications,
275, particularly
Redux®
300/150 350/175 36/5200 600/68 9/1300 390/135, automotive
319
200 and
aerospace
(engine
nacelles,
flaps, aileron
bonding).
250, High
Redux®
300/150 350/175 40/6000 620/70 12.5/1800 385/120, performance
641
195 adhesive for
industrial
markets.
Exceptional
honeycomb
bonding.
Very high
temperature
performance.
For military,
engine
nacelles,
Redux® missile
350/175 350/175 20/3000 240/27 8/1200 390/200
322 bonding,
aerospace,
motorspace
and high
temperature
industrial
applications.
Low weight
295, film
Redux®
350/175 350/175 42/6100 550/62 N/A 390/145, adhesives for
340SP
200 space
applications.
BMI Film Adhesive
Very high
temperature
375+post
performance.
Redux® cure/
445/230 26/3800 200/23 5/700 430/220 Good co-
HP655 190+post
cure with
cure
BMI
prepregs.
Cyanate Ester Film Adhesive
Low out-
Redux® glassing and
- - 320/160 350/175 23/3300 N/A 4/600 310/155
A54 moisture
absorption
Table 3: Redux® Film Adhesives
Source: HEXCEL
*1 Room Temperature= 77°C/25°F
*2Tg are for standard cure cycle by DMTA , log E

Two components, RT or elevated temperature cure

Table 2 lists a number of 2 components paste adhesives designed for


composites bonding in aircrafts, and provides their technical characteristics.
These adhesives cure at RT in a few hours or days, or at moderate temperatures
such as 80°C, in one hour, they usually have good peel strength, for instance 2
components epoxy-polyamide have excellent peel strength, and also good
tensile lap shear strength. Prices are quite lower than the epoxy film adhesives.
They have usually lower heat resistance than the one component heat curing
epoxies.Table 4 provides the technical characteristics of 2 components epoxy
adhesives from HUNTSMAN

Let us mention that recently 2 components epoxy paste adhesive have been
developed for cold curing in aircraft construction: this is for instance the
EPIBOND 1590 A/B of Vantico now HUNTSMAN.

Click here for Table 4

Toughened epoxies

There are several ways to flexibilise epoxy adhesives systems. One way is to
use HYCAR carboxyl terminated reactive liquid polymers at 10 to 25 parts of this
rubber for 100 parts of epoxy resin. This increases impact strength, peel strength
and fracture surface energy with little loss of modulus and heat resistance.
HYCAR polymers are acrylonitrile-butadiene copolymers ( CTBN ) bearing free
carboxyl groups at the polymer end of the chain or distributed along the chain.
Their structure is shown on figure 5. They react with epoxy rings as indicated on
figure 6 and this gives flexible links.

Figure 5: Structure of HYCAR CTBN

Figure 6: Chemical reaction between epoxies and


carboxyl groups of the HYCAR CTBN
The interesting effects of toughening is indicated on figures 7 and 8. Toughened
epoxies are very often used when the bonded parts are subjected to peel or
clivage efforts and fatigue, for instance for aircraft and automotive parts.

Figure 7: Demonstates that for all test temperature,


tensile energy increases as concentration of Hycar®
CT - RLP is increased to 20 phr

Table 2 provides technical characteristics of some toughened epoxies used in


aircrafts construction.

Figure 8: Show that tensile strength is significantly


improved by increasing concentration of Hycar® CT-
RLP at all strain rates tested
Epoxy-polymers alloys

These alloys are formulated with epoxy resins modified by the addition and co-
reaction of other polymers:

• epoxy-phenolics provide high heat resistance up to 250°C,


• epoxy-nylon give excellent flexibility and peel strength,
• epoxy-polysulphide are more flexible than standard epoxies.

All are one component heat curing adhesives that require high temperature for
the cure.

In the next section we will study the other types of adhesives for composites,
namely the structural acrylics, polyurethanes, polyesters, heat stable adhesives
and related products such as Syntactics.

In following sections later we will describe all the main applications / end uses of
adhesives in the various industries that use large amounts of composites, such
as Aerospace, Automotive and Transportation equipment, windmills and naval
construction.
Part 3
Various types of adhesives for composites: Acrylics,
urethanes-acrylates and Polyesters.

Introduction

In this section, we will study several types of structural adhesives which are used
for the assembly of composites: Acrylics, Polyesters, and others.

Acrylics and methacrylates:

These are also called "engineering acrylics" or "structural acrylics", in order to


differentiate it from the non structural acrylics which are used for Pressure
sensitive adhesives or Construction and decoration applications.

There are several types but all are based on the same chemistry:

The formulations include methacrylate monomers plus a dissolved rubber


polymer added as a toughener, cure accelerator and a free radical generator,
sometimes also crosslinking agents. It may be one part adhesive with an
activator applied on one of the substrates or 2 part adhesives. These adhesives
cure at room temperature by a redox reaction of the accelerator with a free
radical source - a peroxide -. This gives free radicals that open the double bonds.

Accelerators may be N-phenyl 2-propyl 3,5 diethyl 2 dihydropyridine, or aromatic


amine such as NN dimethyl para toluidine. Tougheners may be ABS polymers,
acrylonitrile rubbers and other soluble and miscible rubbers. These toughening
agents provide flexibility, impact and crack propagation resistance.

Standard 2 components RT curing methacrylates:

This is the main family of structural acrylics. They display very interesting
properties for the assembly of composites:

• excellent adhesion to a variety of substrates: GRP, other reinforced


plastics, several plastics, metals, wood... Table 1 indicates the tensile
strength that may be obtained on steel ( grit blasted ) tested according to
ASTM D 1002. It is common to obtain from 15 to 30 MPa , according to
the substrates, in tensile shear strength on these materials.
• These adhesives are much more flexible than epoxies and offer excellent
peel strength: 150 N for a 25 cm width. They give also a good resistance
to impact ( 25 J in the ASTM D 3163 test ). Therefore they are often used
for the construction of transportation equipment in cars, buses for
instance.
• Very high resistance to fatigue, as indicated on figure 1: this is very
important for naval construction where the boats have to withstand
hundreds of thousands repeated shocks on the waves during life time.

Figure 1: Fatigue data for Adhesively bonded Lap Shear


(ASTM D 1002) joints
Source: ITW- PLEXUS

• Their flexibility provides a better distribution of loads and also reduces


noise and vibrations, and allows to bond dissimilar materials for instance
metals to GRP.
• They have also an excellent resistance to humidity, so that they are used
in naval construction,
• Heat resistance may reach 100 to 120 oC for continuous service
temperature, depending on the formulation,
• Mixing ratios vary from 1 to 1 to 10 to 1, according to the type of
formulation. In some cases it is not necessary to premix the resin and the
hardener but the resin may be applied on one substrate and the hardener
on the other. Application is easy with different types of applicators such as
twin pump mixing equipment equipped with static mixers, when the mixing
ratio is close to 1/1 .
• They cure at room temperature: full cure takes 1 to 6 hours, but we can
define a "fixture time": it is the length of time between the combining of
adhesive and activator or hardener and the development of sufficient
strength to permit handling of the bonded parts without deformation or
rupture of the bond. Fixture times vary from 15 minutes for the faster
grades to 4 hours for the slower.
• An important feature is the fact that they can fill the gaps between the
parts to be bonded, with some formulation it may fill gaps up to 10 mm or
even 20 mm thickness. This is very useful in naval construction where the
hulls and decks may have wide dimensional tolerances resulting from
demoulding of the GRP large parts.
• Also important is that they usually require little or no surface preparation.

Table 1 provides the technical characteristics of the ITW PLEXUS range of


structural acrylics, as an example.

Mix
Working Fixture Tensile1 Tensile Shear2
Description/ Ratio
Adhesive Viscosity (cps) Time Time Strength Elongation Strength
Substrates (By
(min) (min) (psi) (%) (psi)
Volume)
A:
High strength, all- 40,000~60,000
MA300 1:1 4~6 12~15 3000~3500 15~25 3000~3500
purpose adhesive B:
40,000~60,000
A:
High strength
40,000~60,000
MA310 adhesive for difficult- 1:1 15~18 30~35 4000~4500 5~15 3000~3500
B:
to-bond plastics
40,000~60,000
A:
Gray version of
40,000~60,000
MA330 MA310 for difficult- 1:1 15~18 30~35 4000~4500 5~15 3000~3500
B:
to-bond plastics
40,000~60,000
A:
Excellent to low-
135,000~175,000
MA320 temp and toughness 10:1 8~12 25~30 2000~2500 100~140 1500~2000
B:
properties
40,000~70,000
A:
All-purpose
100,000~125,000
AO420 adhesive; Fast 10:1 4~6 15~18 2700~3000 100~125 1750~2250
B:
curing
50,000~70,000
A:
All-purpose
100,000~125,000
MA422 adhesive; Medium 10:1 17~24 35~40 2000~2500 75~100 1500~1800
B:
open time
40,000~60,000
A:
All-purpose
100,000~125,000
MA425 adhesive; Long open 10:1 30~35 80~90 2000~2500 120~140 1500~1800
B:
time
40,000~60,000
A:
Excellent marine 130,000~160,000
MA550 10:1 40~45 70~75 1750~2000 30~45 1300~1800
adhesive; UV Stable B:
40,000~60,000
For boat-building; A:
Low exotherm 190,000~220,000
MA556 10:1 40~45 110~120 2500~3000 140~160 1250~1500
adhesive for bond B:
line to 1" thick 40,000~60,000
A:
Low exotherm
180,000~220,000
MA557 adhesive for bond 10:1 80~90 180~220 2000~2500 120~160 1250~1550
B:
line to 1.5" thick
40,000~60,000
A:
Primerless adhesive
80,000~110,000
MA820 for metal bonding; 10:1 4~6 15~18 3300~3700 75~100 2000~2400
B:
Fast cure
50,000~70,000
A:
Low-odor; all-
100,000~125,000
MA920 purpose adhesive; 10:1 4~6 15~18 2700~3000 80~100 1500~2000
B:
Fast cure
50,000~70,000
A:
Low-odor; all-
100,000~125,000
MA922 purpose adhesive; 10:1 17~24 35~40 1800~2200 75~100 1400~1700
B:
Medium open time
40,000~60,000
A:
Low-odor; all-
100,000~125,000
MA925 purpose adhesive; 10:1 30~35 80~90 1700~2200 100~120 1400~1700
B:
Long open time
40,000~60,000
A:
Low-shrink/odor;
100,000~125,000
MA1020 Fast cure, Multi 10:1 4~6 15~20 1750~2000 90~110 1250~1600
B:
purpose
50,000~70,000
Low- A:
shrink/odor/exotherm 180,000~220,000
MA1025 10:1 20~25 40~45 1750~2000 90~110 850~1200
for bond lines to 1" B:
thick 40,000~60,000
Table 1: Typical characteristics of structural, 2 component engineering acrylic adhesives
Source: (ITW- PLEXUS USA)
1: Tensile strength of coat adhesive
2: shera strengthon git blasted sheet

Applications:

• Naval construction, for all bonding jobs of deck to hull, partitions to hull,
stiffeners to hulls.

For these applications, structural methacrylates tend to replace polyester


adhesives and wet tabbing operations,

• Automotives and transportation equipment:

Figure 2 shows the many composites parts which may be bonded in a modern
bus. Here all the excellent properties of the structural acrylics mentioned above
are very interesting, mostly the adhesion to these composites, the high fatigue
and shocks resistances, the gap filling properties, the ease of application in the
plants where there are no large manufacturing series for buses, and the room
temperature cure.
Figure 2: Schematic of a bus showing composite parts that may
be bonded with adhesives

These structural acrylics may also be used in automotive body jobs, for instance
to bond composite parts such as fenders, stiffeners to door panels, doors, sliding
roofs. Note that their cure could be accelerated by mild heating at 60°C for
instance in order to adapt to the production line speed. There will be no
deformation of the composite parts at these low temperatures.

One interesting application is for bonding plastic bumpers in USA: these bumpers
are made of XENOY alloy based on polycarbonate and polyester. These acrylic
adhesives are used to bond the face bar or fascia to the back bar or
reinforcement.

12 - 2 components structural methacrylates resisting to low temperatures ( - 25°C


) These adhesives also display a good adhesion to metal oily surfaces and are
used in automotive body work.

13 - There are also hybrid epoxy-acrylates that provide high heat resistance up to
150°C service temperatures, and urethane-acrylates.

Main suppliers of engineering / structural acrylics and methacrylates are:


HENKEL- LOCTITE, ITW PLEXUS USA , LORD Corporation USA ,
PERMABOND ( USA and Europe ), and others.
PLEXUS
MA 320 MA 425 MA 550 MA 555
Adhesive
Helm and
Stringer; Stringer;
Helm and console;
Liner; Deck Liner; Deck
console; Radar arch;
Typical Use and hull and hull
General-purpose General-
bonding bonding
bonding purpose
(12' to 24') (16' to 80')
bonding
Working Time
8~12 30~35 40~45 40~45
(mins)
Fixture Time
25~30 80~90 70~75 110~120
(mins)
Mix Ratio 10:1 10:1 10:1 10:1
Mixed
Viscosity (cps 135~175 100~125 130~160 115~130
x 1000)
Lap Shear
1500~2000 1500~1800 1300~1800 1250~1500
Strength (psi)
% Elongation 100~140 120~140 35~45 140~160
Gap Filling yes yes
Methacrylates
• Polyesters • ABS • PVC
Adhesive are • FRP
• Vinyl ester • Nylon • SMC
recommended
for bonding:
Table 2: Properties of structural, 2 component methacrylates adhesives
recommended for Naval constructor
Source: ITW- PLEXUS, USA

Urethane-acrylates:

Here a urethane component is fully reacted into the molecular backbone, it


provides the excellent adhesion properties of polyurethanes without the hazards
associated with isocyanates, and the molecules include acrylic sections which
can be crosslinked by addition of styrene, in order to obtain a crosslinked
thermoset adhesive.

These adhesives have many excellent features:

• excellent adhesion to composites, Glass reinforced plastics, cured


laminates, glass and carbon fibers,
• toughness, resilience,
• flexibility and superior fatigue resistance compared with polyesters,
• high mechanical strength even in thick sections, they fill gaps up to 25 mm
thickness, to bond decks to hulls for instance, or very large parts such as
windmills blades,
• a range of curing conditions to fit the various industries and jobs,

Curing conditions:

These adhesives need the addition of accelerator and catalyst, for instance
Cobalt/MEKP or amine/BPO curing systems that will initiate the cross linking
reaction between styrene monomers and the acrylates sections, in a way rather
similar to the cure of polyesters.

Table 3 provides an overview of the CRESTOMER range of products from


SCOTT BADER, UK, and table 4 gives the bond strength of several of these
CRESTOMER adhesives.
Crystic *Gel Tensile1 Tensile1 Elongation
Performance
Crestomer Description Approvals Time Strength Modulus at Break
Characteristics
Product (mins) (MPa) (MPa) (%)
High Structural
Lloyds
Performance adhesive for
1152PA Acceptance *50 26 500 100
Structural demanding
DNV
Adhesive applications
Multi
High strength
Purpose
Lloyds gap filling
Structural
1181A Acceptance **120 14 800 6 adhesive with
Adhesive
DNV extended gel
Amine
time
Accelerated
Multi
Lloyds High strength
Purpose
1186PA Acceptance *35 14 800 6 gap filling
Structural
DNV adhesive
Adhesive
Low density
adhesive
Structural
Lloyds specifically
Core
1196PA Acceptance *50 18 1300 4 developed for
Bonding
DNV demanding core
Adhesive
bonding
applications
High
Performance
Structural Structural
Lloyds
Advantage Adhesive adhesive for
Acceptance 25 26 500 100
Adhesive Amine demanding
DNV
Accelerated applications
For Bulk
Application
High High
Performance performance
Lloyds
Advantage Structural structural
Acceptance 30 32 500 120
30 Adhesive adhesive for
DNV
pre-packed convenience
in cartridges and flexibility
Table 3: Product range of urethane-acrylic adhesive
Source: CRESTOMER OF SCOTT BADER UK
* 2% Butanox® M-50 at 25°C
** 2% Perkadox® BT-50 at 25 °C

It shows that these adhesives can be used everywhere in marine and


transportation industries, for bonding FRP, GRP, metals, wood ( teck for decks ),
when high adhesion ,gap filling properties, toughness, flexibility and fatigue
resistance are needed together.
Marine Stainless
FRP Aluminium Teak
Ply Steel
FRP 10 4 10 10 5
Crystic
Marine Ply 4 4 4 4
Crestomer
1152PA Aluminium 10 10 5
Stainless
12 5
Steel
Teak 5

Marine Stainless
FRP Aluminium Teak
Ply Steel
FRP 10 4 10 10 5
Crystic
Marine Ply 4 4 4 4
Crestomer
1186PA Aluminium 10 10 5
Stainless
12 5
Steel
Teak 5

Crystic uPVC Foam uPVC Foam uPVC Foam


Balsa
Crestomer Low Density Med Density Hi Density
1196PA FRP 6 3 7 12
Table 4: Bond strength of urethane-acrylic adhesives with different
substrates.

Cohesive Failure
Substrate Failure

Polyester adhesives:

Most GRP parts for naval construction or Buildings have been made traditionally
with glass fiber reinforced polyester resins. Therefore the paste adhesives that
were traditionally used for bonding or wet tabbing of these parts were also
polyester based, and are supplied by the same companies as the suppliers of
polyester resins: REICHHOLD, SCOTT BADER, ASHLAND, ...

Polyester adhesives cure by the addition of styrene plus accelerator and or


catalyst, at room temperature, the gel times vary from 10 minutes to 2 hours, the
complete hardening from 3 to 10 hours, the gap filling properties are good
enough from .3 to 10 mm maximum.
The shear strength may reach 6 to 15 MPa for FRP to FRP bonds, flexural
modulus are in the range 2 to 3 Gpa. These adhesives are always very rigid, not
at all flexible, the elongation at break is only 2 to 3 %, and for this reason tend to
be replaced by methacrylates or urethane-acrylates.

However they are still used in naval construction in large quantities, for deck to
hull bonding, wet tabbing or bonding of stiffeners to the hull etc...and they are
cheaper than the other naval adhesives, because polyesters are manufactured in
very large quantities for GRP.

Table 5 provides the technical characteristics of the bonding pastes ENGUARD


from ASHLAND which are based on polyesters.

Viscosity* Typical
Description & Tanks Gel Linear
Building/ 2=Low MEKP- Hardening bond/gap
Product Main Marine & Transpose Time shrinkage
Sanitary 3,4=High 50 % Time (hrs) thickness
Characteristics Silos (mins) (%)
& thrixol (mm)
Thixotropic - Low
density - Flexible -
Bonding/ TH 06 Easy to sand - Low 3 18 2 5 0,3 - 3 <1
Joining/ shrinkage
Fixing All - around
TH 72 bonding paste - 3 10 2 3 0,3 - 3 2 - 2,5
short gel time
Same as TH 72
TH 72
with catalyst 3 10 2 3 0,3 - 3 2 - 2,5
AR
indicator
High thixotropic -
containing glass
TH 75 fibres and catalyst 4 10 2 3 3-5 2 - 2,5
indicator - Short gel
time
Fire resistance -
Catalyst indicator
TH 80 3 23 2 4 3-5 < 0,5
with low
shrinkage/exotherm
High thixotropic -
Catalyst indicator -
TH 89 4 18 1 4 3-5 < 0,5
Low shrinkage -
Low exotherm
High thixotropic -
TH 95 Catalyst indicator - 4 45 2 6 3-5 < 0,5
Low shrinkage
Low thixotropic with
long gel time -
TH 725 Shrinkage 3 35 2 5 0,3 - 3 1,5 - 2
controlled - Good
flexibility
Same as TH 725
with low viscosity -
TH 730 2 35 2 5 0,3 - 3 1,5 - 2
High mechanical
values
High thixotropic
containing glass
TH 751 fibres and catalyst 4 35 2 5 3-5 2 - 2,5
indicator - Long gel
time
Thixotropic with
TH
long gel time - Low 3 60 1,5 6 0,3 - 3 < 0,5
1725
Shrinkage
TH ixotropic - Very
TH
long gel time and 3 90 1 6 3-5 < 0,5
2000
low shrinkage
VER based resin -
Using Standard
TH
MEKP - Low 2 45 2 6 0,3 - 10 1,5 - 2
6000
thixotropic with long
gel time
All - around
TH 72 bonding paste - 3 10 2 3 0,3 - 3 2 - 2,5
short gel time
High thixotropic
containing glass
TH 75 fibres and catalyst 4 10 2 3 3-5 2 - 2,5
indicator - Short gel
time
Thixotropic - Low
density - Easy to
TH 86 3 13 2 3 0,3 - 3 1,5 - 2
sand - Short gel
time
Very flexible -
TH 90 3 18 2 4 0,3 - 3 < 0,5
Thixotropic
High thixotropic -
TH 97 4 60 1,5 6 0,3 - 3 1,5 - 2
Low density
Sandwich TH 724 Low thixotropic with
2 10 2 3 0,3 - 3 2 - 2,5
core catalyst indicator
bonding Low thixotropic with
long gel time -
TH 725 Shrinkage 3 35 2 5 0,3 - 3 1,5 - 2
controlled - Good
flexibility
Low thixotropic -
TH 727 2 17 1 4 0,3 - 3 < 0,5
Low shrinkage
High thixotropic
containing glass
TH 751 fibres and catalyst 4 35 2 5 3-5 2 - 2,5
indicator - Long gel
time
Low viscosity - Low
TH 761 density - Low gel 2 35 1,5 5 0,3 - 3 1,5 - 2
time - Easy to sand
Thixotropic with
TH
long gel time - Low 3 60 1,5 6 0,3 - 3 < 0,5
1725
shrinkage
Table 5: Technical characteristics of polyester bonding parts ENGUARD® (registered symbol) from
ASHLAND
In the next section, we will study the other adhesives that may be used for
composites bonding, namely Polyurethanes, heat stable adhesives and also
syntactics
Part 4
Various types of Adhesives for Composites: Polyurethanes,
Heat stable adhesives, Syntactics, etc…

Introduction

In previous chapters we have studied several types of adhesives for composites:


epoxies, polyesters, structural acrylics... We are now studying other types
available.

Polyurethanes:

Polyurethane chemistry is a very wide subject, PU enjoy a very versatile


chemistry: there are one and 2 components PU, chemically curing, humidity
curing, PU reactive hot melts, they may be flexible or rigid adhesives,
thermoplastic or thermosetting adhesives, adhesives and/or sealants, semi-
structural or non structural adhesives. These different products depend on the
formulation, by using various polyols, prepolymers, isocyanate terminated
polymers, various isocyanates...

Therefore we must define here the types of PU adhesives which are used for
composite bonding: these adhesives are usually 2 components, semi-structural,
high performances adhesives. They may cure at room temperature or provide
accelerated curing by mild temperature heat curing, at temperature ranging from
60 to 100°C.

Figure 1 shows the typical curing mechanism of 2 components PU adhesives,


explained in a short and simple way, because many chemical reactions occur
during the cure of polyurethanes.
Figure 1: Curing mechanism of 2C-PUR
adhesives. R and R' are polymer chains.

Isocyanate terminated prepolymers can react with water, alcohols, amines and
other reactive chemicals. For more details we advice our readers to refer to
comprehensive handbooks on PU chemistry, which is very complex, and cannot
be explained here in details.

PU polymers and adhesives have a very interesting balance of strength, flexibility


and excellent adhesion to many different substrates, plastics, composites,
metals, wood. On the opposite, epoxy adhesives have very high strength but
they are very rigid and brittle.

It is interesting to compare 3 types of adhesives which are used for composites,


namely PUs, epoxies and toughened acrylics. When bonded samples are pulled,
the stress / strain curves look like those in figure 2, according to ASHLAND's
PLIOGRIP technical catalog.
Figure 2: Comparison of stress - strain
curves of polyurethane, epoxy and
structural adhesives acrylics
Source: According to ASHLAND's
PLIOGRIP technical catalog

PU adhesives withstand much higher elongation ( refer to table 1 )


Pot life, Maximam Cure Lap Shear
Mix Handling e Coefficient Maximam
Viscosity, Mixed Min @ b Time, Strength Suggest
Ratio, Strength, Tg, Elongation, of Thermal Service
t Components, Viscosity, 77°F+ Hrs e Applicat
By Wt./ Hrs @ Min @ Min @ psi @ psi @ °F/°C % at break Expansion Temp.,
cP cP (80 g @ Commen
ByVol. 77°F+ 140°F+ 212°F+ 77°F+ 180°F+(d) in/in./°F °F/°C
sample) 77°F+
Very flex
adhesive
offer exce
e® 100:108/ 48,000 115/
50,000 20 10 48 120 30 1,700 380 250 8.50x10-5 120/50 adhesion
100:100 50,000 46
polycarbo
nylon and
plastics.
Flexible
adhesive
bonding a
e® 80:100/ 50,000
50,000 15 4 16 120 10 2,800 600 122/50 250 7.50x10-5 140/60 variety of
100:100 20,000
plastics.R
minimal s
preparati
Fast-sett
flexible a
for bondi
e® 80:100/ 50,000 wide vari
50,000 3 1 6 60 10 2,800 600 122/50 250 7.50x10-5 140/60
100:100 20,000 substrate
Requires
minimal s
preparati
Low visco
adhesive
bonding a

veriety of
0 100:50/ 200
5,000 8-10 4 24 3 30 2,000 600 122/50 30 6.40x10-5 140/60 substrate
er 100:40 20,000
Excellent
0
term
environm
performa
Fast-sett
flexible a

with good
0 80:100/ 50,000
50,000 8 2 12 90 10 2,800 600 122/50 250 7.50x10-5 140/60 resistanc
er 100:100 20,000
bonding
5
thermopla
and meta
Table 1: Two-Component of Polyurethane Adhesives
Source: VANTICO/HUNTAMAN

TEST METHOD
Viscosity: ASTM D-2393
Specific Gravity: ASTM D-792
Pot Life: ASTM D-2471
Lap Shear Strength: ASTM D-1002 (Tested on aluminum)
Tg per DMA
Elongation ASTM D-638
Ultimate Tensile Strength: ASTM D-638
Coefficient of Thermal Expansion: ASTM E-831
' Below Tg
" Above Tg
+77°F = 25°C
104°F = 40°C
140°F = 60°C
180°F = 82°C
212°F = 100°C
248°F = 120°C
302°F = 151°C
356°F= 180°C
a = Tested on SMC
b = Time to achieve 150 psi lap shear strength
c = Time to achieve 1500 psi lap shear strength, in most products
d = After room-temperature cure
e = Temperature at which bond maintains 1,000 psi lap shear strength, in most
products
VISCOSITY IN CENTIPOISE CONSISTENCY SIMILAR TO
1 Water
500 #10 Motor Oil
2,500 Pancake Syrup
10,000 Honey
25,000 Chocolate Syrup
50,000 Catsup
This means that the work required to break the bond, which is proportioned to the
area under these curves, is higher for the PU adhesives, although the tensile
strength of the PU is lower. This fact has been used in the last 15 years by PU
adhesives manufacturers to promote these PU adhesives even in structural
applications, mostly for automotive and transportation equipment.

Let us consider for instance the bonds of composite parts to metal parts in
automotives. Here there are sometimes large deformations of the parts and the
bond, because of the relative movements of the car body. PU adhesives and
sealants will withstand very well these movements thanks to their flexibility, while
rigid epoxies will not. Epoxies are perfect for metal to metal bonding and rigid
bonding with very low deformations, but when it comes to bonding of reinforced
plastics to metals, semi-structural PU may be a better choice.

PU adhesives have also a high adhesion to many substrates, especially to


plastics and composites, as indicated in Table 1. This table also provides the
characteristics of utilisation of some PU semi-structural and structural PU
adhesives, such as: viscosities, curing conditions, handling strength, and also
their performances.

ASHLAND Chemicals offers the PLIOGRIP PU systems, based on polymeric


MDI ( methylene diisocyanate ) based prepolymers + hardening resins, which are
often used as structural adhesives in the manufacture of trucks and cars body
panels. These adhesives provide many advantages:

• gap filling properties,


• excellent impact strength,
• excellent adhesion to thermoplastic and thermosetting reinforced plastics,
especially to PU body panels: fenders, hoods and trunk lids, roof top and
spoilers,...
• allow bonding of reinforced plastic parts to metal frames, because these
PU adhesives withstand differential movements of these materials.

Table 2 provides some technical characteristics of a typical PLIOGRIP PU


structural adhesive used for cars and trucks assembly.
Bulk Adhesive
Assembly
Single Components System Properties
Criteria @ 23C
@ 23C:
Resin Tensile Opening-
Prepolymer 17 5-20
(Polyol) Modulus, MPa time, min
Handling
Young's
Color Tan Green 388 Strength.
Modulus, MPa
min
12.000 Poisson's 15-
Viscosity 28.000 cps 0.4 @ 23C
cps Ratio 60
Density 1.6 kg/l 1.1 kg/l Elongation, % 55 @ 125C 2-8
Hardness, Volume
60 0.005
Shore A Cost, S/cc
Table 2: Technical characteristics of a typical PLIOGRIP Polyurethane,
2 components
Source: ASHLAND Chemicals

Figure 3 shows the lap shear values of a PLIOGRIP 2 components PU adhesive


on SMC reinforced plastic. It is important also to note that the curing may be
accelerated by heat, in order to met the requirements of the fast production lines
in automotive industry: figure 4 shows the effects of heat for a 2 parts PU
adhesive.

EX-1516 Toughened Cyanate Ester Film Adhesive (250°F to 350°F


Cure)
Meets NASA Outgassing Specifications
Excellent Microcrack Resistance Compared to Epoxy
Electrical Properties Superior to Epoxy Film Adhesives
Product Delivery Forms
Unsupported Films (0.006 - 0.030 Lbs/Sq Ft Weights)
Supported with Polyester, Fiberglass or Quartz (0.035, 0.045, 0.060
Lbs/Sq Ft Areal Weight)
EX-1516 Physical Properties
Moisture Absorption 0.6 - 0.7%
Dielectric Constant 2.6 - 2.7
Loss Tangent 0.005 - 0.006
Mechanical Poperties:
Fiberglass Non-Woven Suppoted (0.045 Lbs/Sq in)
4310 psi on 6061 T-6
Lap Shear
Aluminum
T Peel 23.6 Lbs/In Width
Unsupported (0.002" Thickness)
-67°F 77°F 180°F 250°F
Flat Wise Tensile 2500 psi 2800 psi 2400 psi 1700 psi
Table 3: Specialty Adhesive for Space and Electrical Use
Source: CYTEC, USA

Figure 3: Lap shear values of a PLIOGRIP PU


adhesive
Source: ASHLAND Chemicals

Figure 4: Heat Accelerated Cure Calculated Conversion


Rate for a PLIOGRIP 2-part PU Adhesive

Note: Some PU reactive Hot melts may be also used for composites bonding.
Utilisations of PU adhesives for composites bonding:

in Car manufacturing :
bonding of RRIM injected fenders made of glass fibers reinforced PU
resin, to metal frame, bonding of glass fiber reinforced stiffeners to door
panels, roof panels, reinforced PU spoilers, ( figure 5 ) hood and fenders
assemblies for trucks, some truck's cabs are made with a complete outer
shell made of SMC panels , including the front, sides, doors, rear and
underbody ,which are bonded to a steel frame with 2 components PU
adhesives. Bonding body parts for buses and recreational vehicles (
caravans walls and roof panels ) assembly of front grills and fascia made
of reinforced thermoplastics,...

Figure 5: Bonding of 2 parts of a rear door


of a car, made of SMC, with a 2
components of PU adhesive, mixed with
automatic metering system and applied by a
rolot
in shipbuilding:
in the past, deck to hull assembly was made with polyester putties, but
now it is done with PU adhesives
let us also mention the assembly of deck to hull in jet skis, Bulkheards are
also bonded to the GFRP hull with 2 components PU.

Heat stable adhesives:

These are adhesives that withstand fairly high temperatures, higher than the
standard epoxies ( which resist only to service temperatures up to 100-150°C )

Bismaleimides
( in short BMI ) may withstand service temperatures up to 230 - 250°C

Up to now, they are used only for aircrafts manufacturing because their price is
very high ( 200 euros / M2 for films ) They are used to cure with BMI prepregs.
Let us mention here the HYSOL EA 9673 film from HENKEL Aerospace that may
withstand a service temperature up to 290°C, and REDUX HP 655 from
HEXCEL, maximum service temperature 230°C. Figure 6 describes the
chemistry of these resins and adhesives.

Figure 6: Examples of bismaleimides (BMI) monomer


and maleimide-terminated resin prepared via Michael-
type addition of 4, 4'-methylenebisbenzeneamine (MBA)
to the carbon-carbon double bond of BMI. Thermal
polymerization of oligoimide generates the cross-linked
network

Cyanate esters:

These are based on cyanate ester resin, supplied by LONZA for instance, refer
to figure 7 showing their chemical base formulation. Cyanate ester resins and
adhesives requires high curing temperature up to 300°C. Service temperatures
may reach up to 400°C. Of course these products are still quite expensive, and
they are used only for special aircrafts and aerospace parts.
Figure 7: Chemical formulation of Cyanate esters

Table 3 provides, as an example, the technical characteristics of a cyanate ester


film adhesive.

Other heat stable adhesives:

These include Polyimides ( refer to figure 8 ), phenolic resins,


polybensimidazoles.

Figure 8: Thermosetting polyimide resins

Syntactic compounds and adhesives:

Syntactic compounds are resins filled with low density, high strength, glass
microspheres.
Syncore from HENKEL Aerospace is supplied as a controlled thickness film, it is
used with reinforced thermoset or thermoplastic prepreg face sheets, ( figure 9 );
after assembly the sandwich laminate is vacuum bagged and cured by using the
recommended cure cycle of the prepreg itself.

Figure 9: SynCore® Sandwich Construction


Source: HENKEL Aerospace

SYNCORE provides many advantages: it replaces plies of reinforcing fibers, (


figure 10 ) reduces density ( we will see hereunder that there are also expanding
syntactics ), it is very simple to use and reduces manufacturing costs since it is
co-curable with the prepregs faces, it may be used in thin core sections ( while
this is not possible with honeycomb ), it fits to curved and complex shapes, and
provides high adhesion to the face sheets.

Figure 10: Comparative Advantages of Syntactic Core vs.


Composite Structural Configuration
Source: HENKEL Aerospace, USA
Expanding syntactics are syntactics that expend 2 to 4 times during the heat
cure, also sometimes called foaming compounds, they have basically the same
uses and advantages as the former syntactics, but with lower specific gravity.

Syntactics are used for thin but strong sandwich construction in aircraft
construction, for inserts reinforcements and protection, they seal the sides of the
parts against moisture, they provide high stiffness to weight panels with
decreased deflection compared to a solid laminate design, close the honeycomb
edges and tapers, absorb acoustic vibrations.

Table 4 provides technical characteristics of some Syntactics from HUNTSMAN.


HENKEL Aerospace also supplies syntactics.

Pot
Mix Room Compressive
Product Specific life Accelerated Max service
ratio by temperature strength Features
Reference Gravity at heat cure temperature
weight cure MPa
23°C
• long work
life at room
EPOCAST 30
0.5 - - 120°C 1 hr 90°C 17 at 23°C temperature
1610 days
• ultra low
density
• 8 hour
work life
• good
strength up
120°C 90 117 at 23°C
EPOCAST to 180°C
0.75 - 8 hrs - mins 180°C 76 at 120°C
1614ATF • low
175°C 1 hr 62 at 175°C
COLD density
STORAGE 1 • extrudable
COMPONENT • self-
extinguishing
• very high
compressive
strength
• excellent
120°C 90 150 at 23°C
EPOCAST 24 temperature
1.2 - - mins 200°C 90 at 175°C
927 hrs performance
175°C 1 hr 69 at 200°C
up to 200°C
• extrudable
• self-
extinguishing
• soft paste,
non-sag
after
application
EPOCAST
• pale
ROOM 87005A/B- 0.5 100.50 2 hrs 2 days 50°C 5 hr 90°C 17 at 23°C
cream color
TEMPERATURE 80 suitable for
STORAGE 2 interior
COMPONENTS • ultra low
density
• ultra low
density
EPOCAST •
50 50°C 5 hrs
0.5 100.30 2 days 100°C 17 at 23°C extrudable,
1637A/B-1 mins 65°C 2 hrs
non-flow
after
application
• low out-
gassing
• self-
ARALDITE 60
0.65 100.40 3 days 70°C 2 hr 80°C 35 at 23°C extinguishing
252A/B mins
• good
surface
finish
• soft paste,
easy to
handle
60-
EPOCAST • high
0.7 100.20 90 7 days 50°C 5 hr 90°C 38 at 23°C
1617A/B strength,
mins
room
temperature
cure
• easy to
apply from
1:1 mix
cartridges
• good
EPOCAST 15
0.7 100.100 5 days 50°C 5 hr 70°C 31 at 23°C compression
1631A/B mins
strent
• self-
extinguishing
• cream
color
Table 4: Syntactics from HUNTSMAN
We have now finished the study of the different types of Adhesives for
Composites, and in the next sections we will study the numerous applications in
Aerospace, Aircrafts, Automotive and Transportation equipment, buses and
railway equipment, sports goods and other industries.