Adhesion Promoters: Adhesion Basics & Material Selection Tips for Adhesives

Adhesion promoters are a group of specialty bifunctional compounds that can react chemically and form a "chemical bridge" either between the adhesive and
adhesive matrix and internal fillers.

They are generally chosen by matching the organic functionality to the base polymer to optimize bonding. However, the choice of the correct adhesion promo
within a given family is often not a straight-forward task. Sometimes mixtures of adhesion promoters are used to provide enhanced hydrophobicity, thermal st
at the bonding site.

Learn how to optimize adhesion performance of your adhesives formulation by understanding:

   » Basics of adhesion
   » Methods to promote adhesion
   » Different types of chemical classes (organosilanes, organometallics…) of adhesion promoters used

…and get tips to select the best suitable adhesion promoter for your application.

Adhesion Basics & Material How to Improve Adhesion to a Substrate?

Selection Tips
TAGS:  Adhesion Promoters    Organofunctional Silanes 

The addition of adhesion promoter to

an adhesive or sealant is one of several
methods of improving adhesion to a
substrate. It is a specialty compound
that can react chemically with both the
substrate and/or the adhesive. It forms
covalent bonds across the interface
that are both strong and durable.

How to use adhesion promoter?

Adhesion promoter can be applied
either as:
An internal additive to a formulation
or
A substrate surface treatment (i.e., as a primer prior to applying the
adhesive / sealant)

Adhesion promoters/coupling agents are generally integrally blended into the

formulation either by the adhesive supplier or by the end-user immediately
before application. When mixed with the adhesive, the coupling agent can
migrate to the interface and reacting with the substrate surface as the
adhesive cures.

The adhesion promoter, therefore, acts as a chemical bridge

between the adhesive and the substrate

It also provides an interphase region that is more resistant to chemical attack from the
environment. Adhesion promoter usually consists of molecules with short organic chains with
the capability to form primary bonds to either or both the adherend and the bulk adhesive.

Adhesion promoter must be considered with regards to:

Compatibility with the base polymer in the formulation 
The chemical nature of the substrate to be bonded 
The end-properties that the formulator is trying to achieve

» View all Adhesion Promoters commercial grades and suppliers in SpecialChem Adhesives

Database

This adhesives database is available to all, free of charge. You can filter down your options by supplier,
suitable polymer. adhesive system (water-based, solvent-based...), final applications and many more
dimensions.

Before discussing the criteria of selecting an adhesion promoter for you specific
adhesive/sealant formulation or according to your end-use requirement, let’s first understand the
basics of adhesion…

Adhesion Theory - Basics of Adhesion

The mechanism of adhesion has been investigated for years; several theories have been
proposed in an attempt to provide an explanation for adhesion phenomena. However, no single
theory explains adhesion in a general, comprehensive way.

The bonding of an adhesive to an object or a surface is the sum of a number of mechanical,

physical, and chemical forces that overlap and influence one another

#1 Mechanical interlocking - The mechanical interlocking theory of adhesion states that good
adhesion occurs only when an adhesive penetrates into the pores, holes and crevices and
other irregularities of the adhered surface of a substrate, and locks mechanically to the
substrate.

The adhesive must not only wet the substrate, but also have the right rheological properties to
penetrate pores and openings in a reasonable time.

This theory explains a few examples adhesion such as rubber bonding to textiles and paper.
Since good adhesion can occur between smooth adherend surfaces as well, it is clear that
while interlocking helps promote adhesion, it is not really a generally applicable adhesion
mechanism.

#2 Electrostatic forces - The basis of the electrostatic theory of adhesion is the difference in
electonegativities of adhesing materials. Adhesive force is attributed to the transfer of
electrons across the interface creating positive and negative charges that attract one another.
For example, when an organic polymer is brought into contact with metal, electrons are
transferred from metal into the polymer, creating an attracting electrical double layer (EDL).

The electrostatic theory tell us that these electrostatic forces at the interface ( i.e. in the EDL),
account for resistance to separation of the adhesive and the substrate.

#3 Chemical bonding forces - This chemical adhesion mechanism is explained in the case of
the intermolecular forces by the adsorption theory, and in the case of chemical interactions by
the chemisorption theory. The processes that play a role in the bonding of similar types of
thermoplastic high-polymer materials, e.g. homogeneous systems, can be determined with the
diffusion theory.
a. Adsorption - The adsorption theory states that adhesion results from intimate
intermolecular contact between two materials, and involves surface forces that develop
between the atoms in the two surfaces.

This theory is the most important mechanism in achieving adhesion. The most common
surface forces that form at the adhesive-adherend interface are van der Waals forces.

In addition, acid-base interactions and hydrogen bonds, generally considered a type of

acid-base interaction, may also contribute to intrinsic adhesion forces.

The mechanism of adhesion in many adhesive joints only involves interfacial

secondary forces. The calculated attractive forces between two surfaces are
considerably higher than the experimentally measured strength of adhesive joints; this
discrepancy between theoretical and experimental strength values has been attributed to
voids, defects or other geometric irregularities which may cause stress concentrations
during loading.

To obtain good adsorption, intimate contact must be reached such that van der Waals
interaction or the acid-base interaction or both take place; hence good wetting is
essential. According to Young's equation, the surface tensions (liquid/vapor: γLV,
solid/liquid: γSL and solid/vapor: γSV) at the three phase contacts are related to the
equilibrium contact angle σ through:

γSV = γSL + γLV . cos σ

The one important factor that influences the adhesive joint strength is the ability of the
adhesive to spread spontaneously on the substrate when the joint is initially formed. For
spontaneous wetting to occur:

γSV ≥ γSL + γLV

We can say that for good wetting: γSV < γLV

Angle of contact of a drop of liquid with the surface of a solid object

Generally speaking, the liquid surface tension of the adhesive should be less than the
critical wetting tension of the solid surface of the substrate

b. Chemisorption - The chemical bonding mechanism suggests that primary chemical

bonds may form across the interface. Chemical bonds are strong and make a significant
contribution to the intrinsic adhesion in some cases.

c. Diffusion - The diffusion theory attributes the adhesion of polymeric materials to the
inter-penetration of chains at the interface. The major driving force for polymer
autohesion and heterohesion is due to mutual diffusion of polymer molecules across the
 interface. This theory requires that both the adhesive and adherend are polymers, which
are capable of movement and are mutually compatible and miscible.

Parameters affecting the diffusion process are: contact time, temperature, molecular
weight of polymers and physical form (liquid, solid). Polarity generally increases
adhesion.

Having learnt about the different theories of adhesion, let’s now discuss about the different
strategies to promote adhesion...

Methods to Promote Adhesion

There are a number of ways to promote adhesion for adhesives and sealants to adhere well to
other materials. The main mechanisms of promoting adhesion are:

1. Blending or Compatibilizing
2. Surface Modification
3. Adhesion Promoting Agents

Blending or Compatibilizing

Blending is a common way to enhance the adhesion of one polymer to a substrate. It

sometimes is used to directly bond (without adhesive) one plastic to another or to an inorganic
substrate.

Blending improves adhesion by making the initial polymer better wetting and more compatible
(chemically and physically) with the secondary substrate. Physical mixing of a polymer
enriched with another compatible polymer is a simple technique for improving adhesion.
Copolymerization is more difficult although used in numerous plastics such as:
ABS, SAN, ASA versus polystyrene
EVA, versus polyethylene or vinyl acetate

Non-reactive adhesion promoters draw their functionality mainly from their polarity introduced
by a co-monomer. An intermediate polarity is then achieved, and adhesion is assured by Van
der Waals forces.

Non-reactive adhesion promoters include ethylene copolymer of ethylene and acrylates (EMA,

EEA, and EBA). These are often used as adhesion promoters in formulating tie layers for multi-
layer laminates.

Surface Modification

Surface modification is broadly used to improve adhesion of a substrate because of its

versatility. The process is applied to the substrate and generally there is no need to alter the
adhesive formulation.

Surface treatment processes are continually evolving. They improve adhesion by either
creating active chemical sites on the substrate surface or physically altering the surface
topology to allow for mechanical adhesion.

Discover why low surface energy substrates are

difficult to bond and find the best technologies like
surface treatment, miscibility of adhesive and the
adherend etc. overcoming these problems... Click
here »

Primers are also, at times, considered to be adhesive promoters. These work by producing a
more easily wettable surface and by diffusing somewhat into the substrate via a solvent carrier
or low viscosity compatible monomer. Although there are many types of adhesion promoting
primers, the most common are:
1. Chlorinated polyolefins that are used mainly as adhesion promoter on thermoplastic olefins
such as those used in the auto industry and 
2. Primers for cyanoacrylate adhesives
Adhesion promoters

Adhesion promoters increase adhesion by incorporating functional additives into the adhesive

formulation that can chemically bond to the adhesive and / or the substrate.

Ideally, this interfacial bridge will improve the initial joint strength and prevent delamination of
the adhesive from the substrate, even when water, oxygen, and salts migrate to the joint
interface. Several theories have been suggested to explain the mechanisms by which
adhesion promoters improve strength and resistance to moisture:
Strong chemical bonds are formed at the adhesive and substrate interfaces
Deformable layer allows stresses which are relieved by the new interface
Improved surface wetting
Interfacial layer provides an intermediate modulus that transfers stresses efficiently
between the substrate and the adhesive
Oxide reinforcement of metal substrates provides for the strengthening of the boundary
layer

Let’s discuss about several types of adhesion promoters available today and tips to select the
best suitable adhesion promoter for your application...

Adhesion Promoters Classes & Key Characteristics

It is well established that judicious use of the correct adhesion promoter increases adhesive
strength and resistance of the cured joint to moisture. Over the last 20 years the adhesion
promoter marketplace has evolved to include a plethora of materials. The main classes of
adhesion promoters include:

Organosilane adhesion promoter

Organotitanate adhesion promoter
Zirconate adhesion promoter
Zircoaluminate adhesion promoter
Alkyl phosphate ester
And more (Chrome Complexes, Amines...)

Among these classes organo silane adhesion promoters have secured a prominent position in
the market. Titanate and zirconate adhesion promoters are less well-recognized compounds
that also perform as coupling agents and / or adhesion promoters.

Each adhesion promoter type has a specific set of characteristics:

Inorganic Organic Molecular Moisture Solubility in

Type
Groups Groups Stability Sensitivity Solvents
Organosilane -OR Varied Excellent Poor Excellent
Organotitanate -OR Varied Fair/good Poor Excellent
Zirconate -OR Varied Fair/good Poor Excellent
Zircoaluminate -OH, -Cl Varied Excellent Excellent Fair
Alkyl phosphate ester -OH Alkyl/aryl Good Fair Good
Metal organics -OH Varied Excellent Excellent Good

Characteristics of Various Classes of Adhesion Promoters 

Overall, all adhesion promoters share several common characteristics such as:

Although the best results can be obtained in using adhesion promoters as substrate primers,
they can also be added to the adhesive with some effect.

Let’s discuss each class in detail...

Silane Coupling Agents

Coupling agents usually consist of molecules with short organic chains having different
chemical composition on either end of the chain.
On one end is an organofunctional group that is particularly compatible with the given
adhesive material 
At the other end of the chain is an inorganic functionality that is especially compatible with
a given substrate

The most well-known of these compounds is the organosilanes. These have been used
extensively as internal additives and primers for adhesives and sealants to improve:
Adhesion, 
Compounding properties, and 
As a crosslinking agent 

Organosilane adhesion promoter is commonly used to enhance adhesion between polymeric

and inorganic materials.

Continue reading or click to go on specific section of the page:

Function of an Organosilane
Silane Effectiveness
Silanes Compatibility with Base polymer
Formulating with Organosilanes - Adhesion Promoter Primer or as Additive?

Function of an Organosilane

The main function of an organosilane is to form a strong, impermeable "chemical bridge"

between the adhesive / sealant and the substrate. In order to support the "ends" of the bridge,
organosilanes are made of bifunctional compounds that can react chemically with both the
substrate and the adhesive.

They usually have the form:

(RO)3-Si - R' - X

Silicone (Si) is the center of the silane molecule, which contains the organofunctional group
(RO) and a second functional group (X).
RO is a hydrolyzable group, typically methoxy, ethoxy, or acetoxy, which reacts with water to
form silanol (Si - OH) and ultimately forms an oxane bond with the inorganic substrate (Si- O
- Metal).
X is an organofunctional group, such as amino, epoxy, or methacrylate, which attaches to
the organic resin. The compatibility of this group with various base polymers can be seen in
the table below.
R' is typically a small alkylene linkage.

Hence, the resulting interface provides:

A strong chemical bridge between the substrate and organic polymer
A barrier to prevent moisture penetration to the interface
Transfer of stress from the resin to the substrate, thereby improving joint strength

It should be noted that the bond to the organic polymer molecule is more complex than the
bond to the inorganic substrate. It is important that the chemistry of the organosilane and
polymer be well matched for optimum properties. For example, an epoxy silane or amino
silane will bond to an epoxy resin, an amino silane will bond to a phenolic resin, and a
methacryl silane will bond to an unsaturated polyester resin.
For thermosetting polymers, the reactivity of the polymer should be matched to the reactivity
of the organosilane. With a thermoplastic molecule (such as in thermoplastic hot melt
adhesives or composites) bonding occurs by diffusion of the organosilane network in the
interphase region of the joint.

There are a number of silane adhesion promoters available, and

they differ from each other in the nature of their reactivity to the resin or adhesive

Some common organosilanes are:

3-Chloropropyltrimethoxysilane
Vinyltriethoxysilane (VES)
γ-Methylacryloxypropyltrimethoxy-silane
γ-Glycidoxypropyltrimethoxy-silane (GPMS)
γ-Mercaptopropyltrimethoxy-silane
γ-Aminopropyltriethoxysilane
N-b-Aminoethyl-aminopropyl-trimethoxysilane (AAMS)

Silane Functionality Application (Suitable Polymers)

 Free radical cure systems: crosslinked
 Vinyl, methacryl  polyethylene, peroxide cured elastomer,
 polyester, polyolefins, EPDM, urethane, alkyd
 Epoxy, phenol, epichlorohydrin, PVC, polyester,
 Epoxy
 urethane, polysulfide
 Methacryl  Unsaturated polyester, acrylic
 Epoxy, phenolic, melamine, furan, urea, PVC,
 Amino  urethane, polysulfide, polyvinyl  butyral,
 polyimide, polychloroprene, nitrile rubber, etc.
 All elastomers, epoxy, sulfur cure rubber,
 Mercapto
 urethane, polysulfide, PVC
 Ureido  Phenolic, urethane, melamine, epoxy
 Chloro  Epoxy, polyurethane, thermoplastics

Recommended Silane Functionality for Various Base Resins

The small amount of water required for hydrolysis is commonly supplied by trace moisture on
the surface of the substrate or from the moisture inside the adhesive formulation. The
hydrolysis and competition between the substrate and possible fillers are points of concern
in formulating practical systems.

Reaction of organosilanes to the inorganic substrate involves four steps.

Initially, hydrolysis of the alkoxy groups occurs. 

After the first and second alkoxy groups are hydrolyzed, condensation to oligomers follows. 
The third methoxy group upon hydrolysis is oriented toward the hydroxyl sites and hydrogen
bonds with these sites on the substrate. This produces a polysiloxane network that is
covalently bonded to the surface (a slower reaction than the initial hydrolysis). 
Finally, during drying or curing, a covalent bond is formed with the substrate, and water is
liberated. 

At the interface there is usually only one bond from each silicon of the organosilane to the
substrate surface. This mechanism results in a continuous chain of covalent bonds from the
substrate to the adhesive.

Organosilane adhesion promoter reacts with water to form silanols (hydrolyzed silanes), which react with
the surface of the inorganic substrate

Organosilanes will bond well to hydroxyl groups on most inorganic substrates. Because of the
importance of the hydrolysis reactions, water is necessary at the interface for the organosilane
bonds to form. With the application of organosilanes as a primer, a water solution is
commonly employed. However, if applied from a non-aqueous solvent, it is frequently
recommended that the primer coating be rinsed with water and again dried before application
of the adhesive.
The hydrolysis reaction also may require an acid or base catalyst. This is generally supplied by
the addition of traces of acidic acid or by the basic nature of the metal. Aminofunctional
organosilanes do not require a catalyst because the amine will catalyze auto-condensation in
the presence of water.

Silane Effectiveness

Silanes form strongly adsorbed polysiloxane films on ceramic and metal surfaces. The
chemical and mechanical integrity of these films are highly dependent on the organic
polymers in the adhesive formulation as well as the chemical nature of the substrate. The
image below shows the relative influence of the type of substrate on the effectiveness of the
silane coupling agent in improving adhesion.

It should be noted that:

Smooth, high energy substrates are excellent substrates for silane attachment; and 
Rough, discontinuous substrates show little benefit

Effect of substrate type on silane adhesion promotion

The interphase provided by the adhesion promoter may be hard or soft depending on the type
of silane employed, and this could affect mechanical properties.

A soft interphase, for example, can significantly improve fatigue and other properties and it
will reduce stress concentrations 
A rigid interphase improves stress transfer of resin to the adherend and improves interfacial
shear strength. 

Adhesion promoters generally increase adhesion between the resin matrix and substrate,
thus raising the fracture energy required to initiate a crack

Organosilane adhesion promoters are not generally applicable for bonding polymer surfaces
that are devoid of active hydroxyl functionality. Nor do they apply to bonding graphite or noble
metals such as gold, silver, or platinum to polymer matrices. These substrates have no hydroxy
"handles".

However, organosilanes will bond to polymeric substrates when:

Inorganic fillers or reinforcement are exposed on the surface (generally through machining
or abrasion), 
The plastic itself provides hydroxy functionality through its molecular chain, and 
The plastic is subjected to a surface treatment to provide hydroxyl functionality (e.g.,
corona and plasma treatment)

Silanes Compatibility with Base polymer

The silane adhesion promoters vary by their:

 Inorganic and organic reactive groups 
Molecular stability 
Moisture sensitivity 
Solvent solubility, and 
Cost

Some specific examples of organosilane coupling agents are given in the table below.

Organosilane
N-[2(vinylbenzylamino]-ethyl- 3-
Polymer  N-(2 aminoethyl)-3- 3-methacryloxy
3- glycidoxypropyl-
aminopropyltrimethoxysilane propyltrimethoxysilane
aminopropyltrimethoxysilane  trimethoxysilane
 Thermoset Polymers:
Diallyl
 
phthalate
Epoxy  
Furan    
Polyimide    
Melamine    
Paralene      
Phenolic  
Polyester    
Polyurethane    
 Thermoplastic Polymers:
Acrylic  
ABS      
Alkyd  
Cellulosics      
Nylon      
Nitrile rubber      
PEEK      
Polyamide
Polycarbonate      
Polyethylene      
Polyphenylene
     
oxide
Polyphenylene
   
sulfide
Polypropylene      
Polystyrene  
Polysulfone      
Polyvinyl
     
butyral
Polyvinyl
   
chloride

They are generally chosen by matching the organic functionality to the base polymer to
optimize bonding. However, the choice of the correct adhesion promoter family or a type within
a given family is often not a straight-forward task. Sometimes mixtures of silanes are used as
adhesion promoters to provide enhanced hydrophobicity, thermal stability, or crosslinking at
the bonding site.

Formulating with Organosilanes - Primer or Integral Adhesion Promoter?

In general, adhesion promoters may be used as substrate pretreatments or as additives.

Organosilanes as Primer

In the former case the promoter is used generally as a solution in a suitable solvent (e.g.,
methanol, ethanol, and isopropanol) or solvent mixture. After the primer is applied and allowed
to dry, excess material can be gently wiped-off or rinsed-off with alcohol. The silane layer is
then cured for 5-10 min at 110°C or for 24 hrs at ambient conditions.

The silane primer can also be applied from a low VOC aqueous solution (0.5-2.0% of silane
with pH adjusted to 4.5-5.5 pH with acetic acid). Stability of the aqueous silane solutions
varies from hours for the alkyl silanes to weeks for the amido silanes.
Organosilanes as Additives

In the integral method, organosilanes are incorporated into the adhesive or sealant as an
additive to the formulation. Adhesives and sealants can be prepared by the addition of silanes
to blends of liquid polymer prior to compounding. When applied in this manner, silanes are
generally effective in concentrations ranging from 0.05 to 1.00%.

The silane additive must be able to diffuse or migrate to the inorganic substrate and react at
the interface. Effective coupling action with silanes as additives depends on several criteria:
a. Good mechanical dispersion of the silane into the formulation will assure uniform coupling
and best efficiency.
b. The solubility parameters and reactivities of the polymer and the silane must be
compatible. No reaction should occur in storage. Matched solubility is necessary for silane
interpenetration into the polymer. Proper pH ranges must be maintained to avoid silane
condensation.
c. Some excess silane should be used if inorganic fillers are present in the formulation.
Silanes will be adsorbed onto the fillers and concentrations need to be adjusted so that
sufficient silane can migrate to the substrate surface. 
d. Hydrolysis must occur to render the silane active for coupling. Proper moisture conditioning
of filler or addition of extra water will help assure that the silane hydroxyls and couples.

Advantages & Disadvantages - Primer & Additive Approach

There are advantages and disadvantages inherent in both the primer and additive approach.

Several critical parameters need to be recognized by the formulator with the additive approach.
These include potential polymer reactions, depletion of the promoter by water, and shelf life.

In studies regarding the use of organosilanes as primers and additives, there is no conclusive
evidence to indicate that one method of application is significantly better than the other. It
appears that the effectiveness of the silane as an additive greatly depends on the mutual
solubility, viscosity, and curing rate of the base polymer that is used in the adhesive
formulation.

   » Select the Right Organofunctional Silane for your Application

Titanate and Zirconate Coupling Agents

Organotitanates and organozirconates are adhesion promoter chemistries, other than silanes,
have been extensively promoted for many years.

They are promising adhesion promoters but have not achieved the broad success of silane
coupling agents. In metals, the highly metallic nature of zircoaluminates makes them uniquely
reactive with metal surfaces. Similarly, organotitanates via their nature as excellent wetting
agents and the ability to design molecules with dual, organic and inorganic, functionality can
function as adhesion promoters.

Although there are many references to the improvement in adhesion obtained by the use of
organometallic titanates and zirconates, quantitative data are sparse with regard to adhesive
systems. In addition to providing improved adhesion, organometallic coupling agents have
been claimed to:
Improve dispersion and rheology 
Improve impact strength, as well as 
Perform several other functions

Organometallic adhesion promoters / coupling agents typically can provide a dual function of

improving processing and improving adhesion

Titanates have been used predominantly to modify the viscosity of filled thermoset and
thermoplastic systems.

It has been shown that a small percentage of titanate in a heavily filled resin system can
reduce the viscosity significantly. Thus, titanate adhesion promoters allow higher filling of
particulate matter to either improve properties or lower the cost of the systems without having
a negative effect on the viscosity. Improved bond strength even to halocarbon surfaces and
improved hydrolytic stability are also claimed.

Organic titanates and zirconates provide several other important functions as additives for
organic adhesives and sealants. At least eight primary functions have been proposed.

Organic titanates and zirconates can be used as:

1. Catalysts for manufacture of adhesive and sealant prepolymers 
2. Adhesion promoters 
3. Wetting agents 
4. Surface protection 
5. Water scavengers 
. Crosslinkers 
7. Catalyst for crosslinking 
. Thixotropic agents

 Type Coupling Agent Application / Advantages

 Titanate

 Stearic acid functionality; aids in  dispersion

 Monoalkoxy titanate
of  mineral fillers in polyolefins

 Chelate titanate  Greater stability in wet environments

 Water soluble, aids adhesion of water

 Quat titanate
 soluble  coatings and adhesives
 Eliminates pretreatment associated with
 Neoalkoxy titanate  fillers,  can be used as a concentrated  solid
 additive
 Ultra-high thermal properties for  specialty
 Cycloheteroatom titanate
 applications

 Zirconate

 Phosphite functionality; reduces epoxy

 Coordinate zirconate
 viscosity without accelerating cure
 Accelerates peroxide and air based cures
 Neoalkoxy zirconate  (e.g.,  polyester SMC / BMC); adhesion
 promoter and  primer for organic  substrates
 Adhesion promoter for printing inks on
 Zirconium propionate
 treated  polyolefin films

 Zircoaluminates  Comparable to organosilanes at lower  cost

Zirconium acetylacetonate  Adhesion promoters and primers for

zirconium methacrylate  treated  polyolefins

Common Titanate and Zirconate Coupling Agents and Their Applications

The organic titanate or zirconate can be incorporated as an additive into an adhesive, sealant
or coating at a concentration of about 0.5-3%. It can also be applied as a primer via a 0.5-5%
solution in solvent such as isopropanol.

Synergistic effects can also be achieved when the organic titanates or zirconates are blended
with organosilanes
 Organic titanates and zirconates, as additives or primers, have been noticed to improve the
adhesion adhesives or sealants to polyethylene terephthalate film, polyoflefins, polyimides,
nylon, polyurethanes, epoxies, phenolics and silicones.
Organmetallic compounds have also been used as primers to promote the adhesion of
silicone rubber adhesives to metal, plastic, glass, ceramics, concrete, wood, and fabrics.

Let’s read about Organotitanates and Organozirconates in detail…

Organotitanates

The titanate structure may be tailored to provide desired properties through the six
functionalities on the basic structure shown below.

(RO)m-Ti-(O-X-R2-Y)n

The (RO)m is the hydrolysable proton that attaches to the inorganic substrate. It also
controls dispersion, adhesion, viscosity and hydrophobicity.
The X group enhances corrosion protection and acid resistance and may provide
antioxidant effects, depending on chemistry.
The R2 provides entanglements with long hydrocarbon chains and bonding via van der
Waals forces. 
The Y group provides thermoset reactivity chemically bonding the filler to the polymer. It
can be one of any number of chemical functions reactive with a number of different
matrices.

Titanate condensation on a hydroxyl containing surface

Like the silanes, the organic titanates react with surface hydroxyl groups. But there is no
condensation polymerization to produce a polymer network at the interface. Titanate coupling
agents are unique in their reaction with free protons on the substrate surface. It results in a
monomolecular layer on the surface whether it is a filler or substrate. The properties of this
film depend on the type and amount of organometallic coupling agent used, the chemistry of
the organometallic, and the processing properties used to apply the coating.

These coatings modify the surface of the filler or substrate to provide the following unique
properties.
They promote adhesion of adhesives and coatings to glass, metal, and plastics. 
The organometallic interface improves dispersability of pigments and fillers in aqueous and
non-aqueous systems and reduces viscosity. 
It can provide scratch-resistant and reflective properties to glass. 
It can modify frictional characteristics of the substrate

The best performance is obtained when the substrate contains functional groups with active
hydrogens. However, the substrate can be reactive or unreactive inorganic materials or even
organic polymers that have been activated by corona, plasma, or flame pretreatment.

The one problem associated with using organic titanates is over concentration. Since excess
titanate (amount greater than necessary to form a monolayer) does not result in a polymer
network at the interface, it is suspected that it can form a weak boundary layer resulting in
degraded properties. Thus, the amount of titanate that is used is an important parameter.

Typically, titanate treated inorganic fillers or reinforcements are hydrophobic, organophilic, and
organofunctional and, therefore, exhibit enhanced dispersability and bonding with the polymer
matrix. When used in filled polymer systems, titanates claim to improve impact strength,
exhibit melt viscosity lower than that of the base polymer at loadings above 50%, and enhance
the maintenance of mechanical properties during aging.

Check out typical titanate coupling agents used here. There are many types and chemistries
available. They can be made available as liquids (solutions and water soluble salts), powder
and pellet concentrates.
Organozirconates

Zirconate coupling agents have very similar structure to the titanates. They also perform
similar functions. Zirconium compounds exist in both water and organic solvent soluble forms.
Like the titanates, zirconate coupling agents are useful in improving the dispersion
characteristics of fillers in polymer systems. Examples of zirconate coupling agents and their
applications are given in the table above.

The aqueous chemistry of zirconium is complex and dominated by hydrolysis. One aspect is
that polymerization takes place when salt solutions are diluted. The polymeric species can be
cationic, anionic, or neutral. Polymers that are formed include ammonium zirconium
carbonate, zirconium acetate, and zirconium oxychloride.

Zirconium propionate is used as an adhesion promoter for printing inks on polyolefins that
have been treated by corona discharge. It is believed that hydrogen bonds are formed with the
nitrocellulose in the inks. The mode of attachment to treated polyolefin is by functional groups
on the surface displacing ligands on the zirconium polymer. Surface COOH groups seem to be
most likely to do this, and the reaction is shown below.

Zirconium compounds provide improved adhesion by attachment to functional groups

Solvent soluble zirconium compounds include:

Zirconium acetylacetonate 
Zirconium methacrylate, and 
The family of neoalkoxy zirconates

The synthesis of certain soluble zirconium compounds has demonstrated improved adhesion
on glass and aluminum substrates for polymethyl methacrylate, polyethylene, and
polypropylene when used as hot melt compounds.

Major suppliers of titanate and zirconate coupling agents include DuPont (Tyzor) and Kenrich
Petrochemicals (Ken-React). They can be made available as liquids (solutions and water
soluble salts), powder and pellet concentrates. Typical titanate and zirconate coupling agents
are shown in the table above. There are many types and chemistries available. They have
similar structures and perform similar functions.

Zircoaluminates

Zircoaluminates claim performance at least comparable to that of silanes at substantial cost

savings. Several functionalities are available. They are stable and soluble in an aqueous
environment and do not require the presence of water to function. The surface reaction is
irreversible. Among the fillers treated successfully are silica, clay, calcium carbonate, alumina
trihydrate and titanium dioxide.

Other Adhesion Promoters

In addition to the adhesion promoters described above, a large number of functional inorganic,

organometallic, and organic compounds have been investigated, usually in specific adhesives
and coatings or on selected substrates. A comprehensive account of coupling agents is
provided by Cassidy and Yager and by Walker.

Some adhesion promoters apart from Silanes, Titanates, and Zirconates are:

Chlorinated Polyolefins
Chrome Complexes
Phosphorous Containing Compound
Amines
Other Reactive Polymers
Chlorinated Polyolefins

In automotive coatings, the term adhesion promoter refers to the primer, which achieves
adhesion of the subsequent paint layer to thermoplastic polyolefin (TPO) substrate. This
adhesion promoter is usually comprised of chlorinated polyolefin (CPO) as the active
adhesion-promoting component, other resins, and pigment.

Although used primarily as a primer, CPOs can also be used as an additive. Both solvent and
waterborne systems are available. The CPO bonds well to the substrate due to its chemical
similarity. Additionally, being relatively hydrophobic, they tend to migrate to the adhesive
interface and orient themselves with their pendant maleic anhydride and / or halogen groups
toward the adhesives layer.

Chrome Complexes

Chrome complexes have been formed as adhesion promoters by the reaction of chromium

chloride with methacrylic acid. The chromium oxide portion of the adhesion promoter reacts
with a substrate while the methacrylic portion reacts with a free radically curing outer layer.

Chromium containing adhesion promoters fall into two main classes: inorganic and organic.

Examples of the inorganic type are the chromate conversion coatings that were previously
used extensively in aerospace industries for prebond surface treatment of aluminum. These
act as both corrosion inhibitor and adhesion promoter. Today, these chromate conversion
coatings have fallen from favor due to toxicity issues. 
Examples of the organic type include coordination complexes of trivalent chromium
chloride and carboxylic acids. The most notable is Volan, manufactured by DuPont as a
fiberglass finish. 

Phosphorous Containing Compound

Phosphate esters have been shown to bond chemically to metal surfaces to improve adhesion
and provide a barrier to moisture ingress. They can be used in air-dry and bake systems that
are either water or solvent borne. Both polymerizable and non-polymerizable phosphorous
derivatives are available. Polymerizable phosphous materials having ethylene unsaturation are
advantageous.

They are especially useful as an adhesive promoting additive in ultrahigh molecular weight
polyethylene composites 

Mono- and diphosphate esters have been used as adhesion promoters in bonding acrylic
adhesive on metals and as a primer for aluminum bonded with epoxy. 
Unsaturated acid phosphates have been used as primers on metals to be bonded with free
radical adhesives.

Amines

Amines have been used as adhesion promoters in a wide range of applications.

Hydroxylbenzamines, used as primers or additives, have been claimed to improve the
adhesion of a wide range of polymers to metallic substrates. Amines have also been
examined as adhesion promoters for aromatic isocyanate cured adhesives. Primary aliphatic
amines are claimed to improve the bondabilty of polyolefins.

Other Reactive Polymers

Reactive adhesion promoters will contain functional groups to react with the base polymer and
/ or the substrate. These can be carboxylic acid, epoxy, maleic anhydride or other chemical
groups.

Acrylic acid and maleic anhydride modified polypropylene have been used to improve the
adhesion of polypropylene to reinforcing materials. 
Copolymers of styrene and maleic anhydride have also been produced to provide improved
properties in thermoplastic composites. 
Di- and tri-isocyanates are used as adhesion promoters for fibers that have only a few
reactive groups, or that have only low reactivity such as polyester or aramid. Due to the high
reactivity of the isocyanate groups, these fabrics must be processed quickly after an
adhesion promoter is applied. 

The examples of above mentioned adhesion promoters, their suitable polymer and substrate
as well as applications are:

Adhesion Most Suitable Most Suitable Applications

 Promoter Polymer Substrate
Acrylic &
acrylic
copolymers  Used as primers or additives for
Alkyd improved adhesion to plastics
Polyolefins, other (mainly polyolefins) 
Chlorinated Chlorinated low surface
rubber Solvent and waterborne types
polyolefin energy
available
Polyester thermoplastics
Most used as primers in the auto
Epoxy
industry
Maleic resins
Polyurethane

Excellent flame retardant and

Acrylic & corrosion protection for metals 
acrylic Both water- and solvent borne
copolymers  Metals, formulations available
Phosphorous
Alkyd ceramics, other Phosphate-based acrylic
containing
inorganics adhesive promoters improve the
Amino
adhesion of acrylic structural
Polyester adhesives to metals including
metals coated with mill oils 

Silicone and Acrylic and

acrylic Generally used as an additive in
silicone Glass, ceramics, silicone RTV formulations 
modified copolymers  metals, some
polymers (not Polyamide plastics Promotes adhesion by improved
silanes) wetting of the base polymer
Silicone

Polyolefins  Acts as an adhesion promoter

Acrylic acid and dispersing agent
Metals, paper,
modified EVA
plastic film Often used in heat seal coatings
polyolefin EVOH for packaging applications

Maleic anhydride grafted

Polyolefins  polymer is used in tie layers for
Maleic flexible packaging 
Nylon
anhydride Metals, paper, Chlorine-free, water borne
EVA
modified plastic film promoter used as an alternative
polyolefin EVOH to chlorinated polyolefin
Nylon Also used in polyolefin
composites

Epoxy  Often used in bonding of rubber

Metallic to metals 
PVC Metals
diacrylate Used in UV cure acrylic
Elastomers adhesives

Epoxy 
Metals, Particularly useful as a promoter
Fatty ester PVC
polymers, glass for fibers in tire cords, belts, etc.
Elastomers

Epoxy 
Nylon Useful in tire cords 
Melamine Metals,
Polyesters Also provides flame resistance
cyanurate polymers, glass
Polyolefins and lubrication
Polyurethane

Note: The term "coupling agent" refers generally to additives that work on fillers and
reinforcements within a resin matrix to improve properties such as dispersion stability,
viscosity, etc. In this case, the primary substrate is the filler or reinforcement. The term
"adhesive promoter" generally refers to a material that can be incorporated into an adhesive
formulation or as a surface primer to enhance adhesion at the joint interface. Very often the
same materials can function as both "coupling agents" and "adhesion promoters".

Commercially Available Adhesion Promoters Grades

Dynasylan® SIVO 203
Evonik
Dynasylan® SIVO 203 by Evonik is a multifunctional aminosilane compound. Acts as an ad‐
hesion promoter. Provides improved product performance and quality. It is soluble in alco‐
hols, aliphatic and... view more

D l ® 1122

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