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Adhersives & Bonding
Adhersives & Bonding
Adhersives & Bonding
skin protection
storage
fire
toxicity
describes the principles of testing for shear strength and peel strength of
adhesives
states that special epoxy resins are made to meet particular service
conditions
liquid or paste
In the course of time and during their development, adhesives have gained a stable position in an
increasing number of production processes. There is hardly any product in our surroundings that
does not contain at least one adhesive be it the label on a beverage bottle, protective coatings
Adhesives are typically organized by the method of adhesion. These are then organized into
reactive and non-reactive adhesives, which refers to if the adhesive chemically reacts to harden.
Alternatively they can be organized by whether the raw stock is of natural, or synthetic origin, or
by their starting physical phase.
Non-reactive adhesives
Drying adhesives
There are two types of adhesives that harden by drying: solvent based adhesives and polymer
dispersion adhesives, also known as emulsion adhesives. Solvent based adhesives are a mixture
of ingredients (typically polymers) dissolved in a solvent. White glue, contact adhesives and
rubber cements are members of the drying adhesive family. As the solvent evaporates, the
adhesive hardens. Depending on the chemical composition of the adhesive, they will adhere to
different materials to greater or lesser degrees.
Polymer dispersion adhesives are milky-white dispersions often based on polyvinyl acetate
(PVAc). They are used extensively in the woodworking and packaging industries. ; also used
with fabrics and fabric-based components, and in engineered products such as loudspeaker
cones.
Pressure sensitive adhesives
The following text needs to be harmonized with text in Pressure sensitive
adhesive.
Main article: Pressure sensitive adhesive
Pressure sensitive adhesives (PSA) form a bond by the application of light pressure to marry the
adhesive with the adherend. They are designed with a balance between flow and resistance to
flow. The bond forms because the adhesive is soft enough to flow (i.e. "wet") to the adherend.
The bond has strength because the adhesive is hard enough to resist flow when stress is applied
to the bond. Once the adhesive and the adherend are in close proximity, molecular interactions,
such as van der Waals forces, become involved in the bond, contributing significantly to its
ultimate strength.
PSAs are designed for either permanent or removable applications. Examples of permanent
applications include safety labels for power equipment. foil tape for HVAC duct work,
automotive interior trim assembly, and sound/vibration damping films. Some high performance
permanent PSAs exhibit high adhesion values and can support kilograms of weight per square
centimeter of contact area, even at elevated temperature. Permanent PSAs may be initially
removable (for example to recover mislabeled goods) and build adhesion to a permanent bond
after several hours or days.
Removable adhesives are designed to form a temporary bond, and ideally can be removed after
months or years without leaving residue on the adherend. Removable adhesives are used in
applications such as surface protection films, masking tapes, bookmark and note papers, price
marking labels, promotional graphics materials, and for skin contact (wound care dressings,
EKG electrodes, athletic tape, analgesic and transdermal drug patches, etc.). Some removable
adhesives are designed to repeatedly stick and unstick. They have low adhesion and generally
can not support much weight.
Pressure sensitive adhesives are manufactured with either a liquid carrier or in 100% solid form.
Articles are made from liquid PSAs by coating the adhesive and drying off the solvent or water
carrier. They may be further heated to initiate a cross-linking reaction and increase molecular
weight. 100% solid PSAs may be low viscosity polymers that are coated and then reacted with
radiation to increase molecular weight and form the adhesive; or they may be high viscosity
materials that are heated to reduce viscosity enough to allow coating, and then cooled to their
final form. Major raw material for PSA's are acrylate based polymers.
Contact adhesives
Contact adhesives are used in strong bonds with high shear-resistance like laminates, such as
bonding Formica to a wooden counter, and in footwear, as in attaching outsoles to uppers.
Natural rubber and polychloroprene (Neoprene) are commonly used contact adhesives. Both of
these elastomers undergo strain crystallization. In the construction industry a specialised
proprietary adhesive known as Liquid Nails (or liquid nails as the generic), is used.[22] This also
copes with tasks such as sealing artificial turf.[23]
Contact adhesives must be applied to both surfaces and allowed some time to dry before the two
surfaces are pushed together. Some contact adhesives require as long as 24 hours to dry before
the surfaces are to be held together.[24] Once the surfaces are pushed together, the bond forms
very quickly.[25] It is usually not necessary to apply pressure for a long time, so there is less need
for clamps.
Hot adhesives
Hot adhesives, also known as hot melt adhesives, are thermoplastics applied in molten form (in
the 65-180 C range) which solidify on cooling to form strong bonds between a wide range of
materials. Ethylene-vinyl acetate based hot-melts are particularly popular for crafts because of
their ease of use and the wide range of common materials they can join. A glue gun (shown at
right) is one method of applying hot adhesives. The glue gun melts the solid adhesive then allows
the liquid to pass through its barrel onto the material, where it solidifies.
Thermoplastic glue may have been invented around 1940 by Procter & Gamble as a solution to
water-based adhesives commonly used in packaging at that time failing in humid climates,
causing packages to open.
Reactive adhesives
Multi-part adhesives
Multi-component adhesives harden by mixing two or more components which chemically react.
This reaction causes polymers to cross-link into acrylics, urethanes, and epoxies.[citation needed]
There are several commercial combinations of multi-component adhesives in use in industry.
Some of these combinations are:
The individual components of a multi-component adhesive are not adhesive by nature. The
individual components react with each other after being mixed and show full adhesion only on
curing. The multi-component resins can be either solvent-based or solvent-less. The solvents
present in the adhesives are a medium for the polyester or the polyurethane resin. The solvent is
dried during the curing process.
One-part adhesives
One-part adhesives harden via a chemical reaction with an external energy source, such as
radiation, heat, and moisture.
Ultraviolet (UV) light curing adhesives, also known as light curing materials (LCM), have
become popular within the manufacturing sector due to their rapid curing time and strong bond
strength. Light curing adhesives can cure in as little as a second and many formulations can bond
dissimilar substrates (materials) and withstand harsh temperatures. These qualities make UV
curing adhesives essential to the manufacturing of items in many industrial markets such as
electronics, telecommunications, medical, aerospace, glass, and optical. Unlike traditional
adhesives, UV light curing adhesives not only bond materials together but they can also be used
to seal and coat products. They are generally acrylic based.
Heat curing adhesives consist of a pre-made mixture of two or more components. When heat is
applied the components react and cross-link. This type of adhesive includes epoxies, urethanes,
and polyimides.
Moisture curing adhesives cure when they react with moisture present on the substrate surface or
in the air. This type of adhesive includes cyanoacrylates and urethanes.
Natural adhesives
Natural adhesives are made from organic sources such as vegetable matter, starch (dextrin),
natural resins or from animals e.g. casein or animal glue. They are often referred to as
bioadhesives. One example is a simple paste made by cooking flour in water. Animal glues are
traditionally used in bookbinding, wood joining, and many other areas but now are largely
replaced by synthetic glues. Casein is mainly used to adhere glass bottle labels. Starch based
adhesives are used in corrugated board production and paper sack production, paper tube
winding, and wallpaper adhesives. Masonite, a wood hardboard, was bonded using natural
lignin, (although most modern MDF particle boards use synthetic thermosetting resins). Another
form of natural adhesive is blood albumen (made from protein component of blood), which is
/used in the plywood industry. Animal glue remains the preferred glue of the luthier. Casein
based glues are made by precipitating casein from milk protein using the acetic acid from
vinegar. This forms curds, which are neutralized with a base, such as sodium bicarbonate (baking
soda), to cause them to unclump and become a thicker plastic-like substance.[26]
Synthetic adhesives
Applicators of different adhesives are designed according to the adhesive being used and the size
of the area to which the adhesive will be applied. The adhesive is applied to either one or both of
the materials being bonded. The pieces are aligned and pressure is added to aid in adhesion and
rid the bond of air bubbles.
Common ways of applying an adhesive include brushes, rollers, using films or pellets, spray
guns and applicator guns (e.g., caulk gun). All of these can be done manually or can be
automated into a machine.
Mechanisms of adhesion
Main article: Adhesion
Adhesion, the attachment between adhesive and substrate may occur either by mechanical
means, in which the adhesive works its way into small pores of the substrate, or by one of several
chemical mechanisms. The strength of adhesion depends on many factors, including the means
by which it occurs.
In some cases, an actual chemical bond occurs between adhesive and substrate. In others,
electrostatic forces, as in static electricity, hold the substances together. A third mechanism
involves the van der Waals forces that develop between molecules. A fourth means involves the
moisture-aided diffusion of the glue into the substrate, followed by hardening.
Failure of the adhesive joint
There are several factors that could contribute to the failure of two adhered surfaces. Sunlight
and heat may weaken the adhesive. Solvents can deteriorate or dissolve adhesive. Physical
stresses may also cause the separation of surfaces. When subjected to loading, debonding may
occur at different locations in the adhesive joint. The major fracture types are the following:
Cohesive fracture
Cohesive fracture is obtained if a crack propagates in the bulk polymer which constitutes the
adhesive. In this case the surfaces of both adherents after debonding will be covered by fractured
adhesive. The crack may propagate in the center of the layer or near an interface. For this last
case, the cohesive fracture can be said to be cohesive near the interface.
Interfacial fracture
The fracture is adhesive or interfacial when debonding occurs between the adhesive and the
adherent. In most cases, the occurrence of interfacial fracture for a given adhesive goes along
with a smaller fracture toughness. The interfacial character of a fracture surface is usually to
identify the precise location of the crack path in the interface.
Other types of fracture
The mixed type, which occurs if the crack propagates at some spots in a
cohesive and in others in an interfacial manner. Mixed fracture surfaces can
be characterised by a certain percentage of adhesive and cohesive areas.
The alternating crack path type which occurs if the cracks jump from one
interface to the other. This type of fracture appears in the presence of tensile
pre-stresses in the adhesive layer.
Fracture can also occur in the adherent if the adhesive is tougher than the
adherent. In this case, the adhesive remains intact and is still bonded to one
substrate and remnants of the other. For example, when one removes a price
label, the adhesive usually remains on the label and the surface. This is
cohesive failure. If, however, a layer of paper remains stuck to the surface,
the adhesive has not failed. Another example is when someone tries to pull
apart Oreo cookies and all the filling remains on one side; this is an adhesive
failure, rather than a cohesive failure.
Modes of failure
As a general design rule, the material properties of the object need to be greater than the forces
anticipated during its use. (i.e. geometry, loads, etc.). The engineering work will consist of
having a good model to evaluate the function. For most adhesive joints, this can be achieved
using fracture mechanics. Concepts such as the stress concentration factor and the strain energy
release rate can be used to predict failure. In such models, the behavior of the adhesive layer
itself is neglected and only the adherents are considered.
Failure will also very much depend on the opening mode of the joint.
Mode I is an opening or tensile mode where the loadings are normal to the
crack.
Mode II is a sliding or in-plane shear mode where the crack surfaces slide
over one another in direction perpendicular to the leading edge of the crack.
This is typically the mode for which the adhesive exhibits the highest
resistance to fracture.
As the loads are usually fixed, an acceptable design will result from combination of a material
selection procedure and geometry modifications, if possible. In adhesively bonded structures, the
global geometry and loads are fixed by structural considerations and the design procedure
focuses on the material properties of the adhesive and on local changes on the geometry.
Increasing the joint resistance is usually obtained by designing its geometry so that:
Shelf life
Some glues and adhesives have a limited storage life, and will stop working in a reliable manner
if their safe shelf life is exceeded.
Adhesive bonding (also referred to as gluing or glue bonding) describes a wafer bonding
technique with applying an intermediate layer to connect substrates of different materials. These
produced connections can be soluble or insoluble.[1] The commercially available adhesive can be
organic or inorganic and is deposited on one or both substrate surfaces. Adhesives especially the
wide established SU-8 and Benzocyclobuten (BCB) are specialized for MEMS or electronic
component production.[2]
The procedure enables bonding temperatures from 1000 C down to room temperature.[1] The
most important process parameters for achieving a high bonding strength are:[3]
adhesive material
coating thickness
bonding temperature
processing time
chamber pressure
tool pressure
Adhesive bonding has the advantage of relatively low bonding temperature as well as the
absence of electric voltage and current. Based on the fact that the wafers are not in direct contact,
this procedure enables the use of different substrates, e.g. silicon, glass, metals and other
semiconductor materials. A drawback is that small structures become wider during patterning
which hampers the production of an accurate intermediate layer with tight dimension control.[3]
Further, the possibility of corrosion due to out-gassed products, thermal instability and
penetration of moisture limits the reliability of the bonding process.[4] Another disadvantage is
the missing possibility of hermetically sealed encapsulation due to higher permeability of gas
and water molecules while using organic adhesives.[5]
The adhesive bonding with organic materials, i.e. BCB or SU-8, has simple process properties
and the ability to form high aspect ratio micro structures. The bonding procedure is based on
polymerization reaction of organic molecules to form long polymer chains during annealing.
This cross-link reaction forms BCB and SU-8 to a solid polymer layer.[3]
The intermediate layer is applied by spin-on, spray-on, screen-printing, embossing, dispensing or
block printing on one or two substrate surfaces. The adhesive layer thickness depends on the
viscosity, rotational speed and the applied tool pressure. The procedural steps of adhesive
bonding are divided into the following:[1]
1. Cleaning and pre-treatment of substrates surfaces
2. Application of adhesive, solvent or other intermediate layers
3. Contacting substrates
4. Hardening intermediate layer
The most established adhesives are polymers that enable connections of different materials at
temperatures 200 C.[5] Due to these low process temperature metal electrodes, electronics and
various micro-structures can be integrated on the wafer. The structuring of polymers as well as
the realization of cavities over movable elements are possible using photo-lithography or dry
etching.[5]
The hardening conditions depend on the used materials. Hardening of the adhesives are possible:
[1]
at room temperature
using UV light
by applying pressure
SU-8
Overview
SU-8 is a 3 component UV-sensitive negative photo-resist based on epoxy resin, gamma
butyrolactone and triaryl sulfonium salt. The SU-8 polymerizes at approximately 100 C and is
temperature-stable up to 150 C. This polymer adhesive is CMOS and bio-compatible and has
excellent electrical, mechanical and fluidic properties. It also has a high cross-linking density,
high chemical resistance and high thermal stability. The viscosity depends on the mixture with
the solvent for different layer thicknesses (1.5 to 500 m). Using multilayer coating a layer
thickness up to 1 mm is reachable. The lithographic structuring is based on a photoinitiator
triaylium-sulfonium that releases lewis acid during UV radiation. This acid works as catalyst for
the polymerization. The connection of the molecules is activated over different annealing steps,
so called post exposure bake (peb).[5] Using SU-8 can achieve a high bonding yield. In addition,
the substrate flatness, clean room conditions and the wettability of the surface are important
factors to achieve good bond results.[6]
Procedural steps
The standard process (compare to figure "Schematic bonding process") consists of applying SU8 on the top wafer by spin-on or spray-on of thin layers (3 to 100 m).
Subsequently, the structuring of the photo-resist using direct UV light exposure is applied but can
also be achieved through deep reactive-ion-etching (DRIE). During coating and structuring of
the SU-8 the tempering steps before and after exposure have to be considered. Based on thermal
layer stress the risk of crack formation exists. While coating the photoresist the formation of
voids due to the layer thickness inhomogeneity has to be avoided. The adhesive layer thickness
should be larger than the flatness imperfection of the wafer to establish good contact.[3] The
procedural steps based on a typical example are:
Thermal oxidation
Dehydration
Softbake
o 120 s at 65 C
o 300 s to 95 C
o Cooling down
Post-exposure-bake
o 2 to 120 min at 50 to 120 C
o to room temperature
relaxation time
development
Examples
Adhesive bonding using SU-8 is applicable to zero-level packaging technology for low cost
MEMS packaging. Metallic feed-throughs can be used for electrically connections to packed
elements through the adhesive layer.[7] Also biomedical and micro fluidic devices are fabricated
based on SU-8 adhesive layer as well as micro fluidic channels, movable micro-mechanical
components, optical waveguides and UV-LIGA components.[8]
Benzocyclobutene (BCB)
Overview
Schematic process flow of dry etch and photosensitive BCB wafer bonding technique.[9]
Benzocyclobutene (BCB) is a hydrocarbon that is widely used in electronics.[10] BCB exists in a
dry etch and a photosensitive version, each requiring different procedural steps for structuring
(compare BCB process flow).[11]
It does release only small amounts of by-products during curing which enables a void-free bond.
This polymer ensures very strong bonds and excellent chemical resistance to numerous acids,
alkalines and solvents. The BCB is over 90% transparent to visible light that enables the use for
optical MEMS applications.[10]
Compared to other polymers the BCB has a low dielectric constant and dielectric loss.[12] The
polymerization of BCB is taking place at a temperature around 250 to 300 C and it is stable up
to 350 C. Using BCB does not ensure a sufficient hermeticity of sealed cavities for MEMS.[13]
Procedural steps
The procedural steps for dry etch BCB are:
1. Cleaning
2. Supplying the adhesion promoter
3. Drying of the primer
4. BCB deposition
5. Photosensitive BCB
1. Exposure and development
6. Dry etch BCB
1. Pre-bake/soft-cure
2. Patterning of the BCB layer by lithography and dry-etching
7. Bonding at specific temperature, ambient pressure for specific amount of time
8. Post-bake/hard-cure to form solid BCB monomer layer
The wafers can be cleaned using H2O2 + H2SO4 or oxygen plasma. The cleaned wafers are rinsed
with DI water and dried at elevated temperature, e.g. 100 to 200 C for 120 min.[11]
The adhesion promoter with a specific thickness is deposited, i.e. spin-coated or contact printed
on the wafer to improve the bonding strength. Spray coating is preferable when the adhesive is
deposited on free standing structures.[13]
Cross-sectional view of bonded wafer pair with an intermediate layer width of 100 m.[3]
Subsequently the BCB layer is spin or spray coated, usually 1 to 50 m thick, to the same wafer.
To prevent that the patterned layer has a lower bond strength than the unpatterned layer, due to
the cross-linking of the polymer, a soft-curing step is applied before bonding.[14] The pre-curing
of the BCB takes place for several minutes on the hot plate at a specific temperature 300 C.
The soft cure prevents bubble formation and unbonded areas[15] as well as the distortion of the
adhesive layer during compression to improve the alignment accuracy.[16] The degree of
polymerization should not be over 50%, so it is robust enough to be patterned and still
sufficiently adhesive to be bonded.[14]
If the BCB is hard-baked (far over 50%), it loses its adhesives properties and results in an
increased amount of void formation. But also if the soft-curing is above 210 C the adhesive
cures too much, so that the material is not soft and sticky enough to achieve a high bonding
strength.[9]
The substrates with the intermediate layer are pressed together with subsequent curing results in
a bond.[4] The post-bake process is applied at 180 to 320 C for 30 to 240 min usually in a
specific atmosphere or vacuum in the bond chamber. This is necessary to hard-cure the BCB.
The vacuum prevents air trapped in the bond interface and pumps out the gases of the outgassing residual solvents during annealing. The temperature and the curing time are variable, so
with a higher temperature curing time can be reduced based on a quicker cross-linking.[10] The
final bonding layer thickness depends on the thickness of the cured BCB, the spinning speed and
the shrink rate.[9]
Examples
Adhesive bonding using a BCB intermediate layer is a possible method for packaging and
sealing of MEMS devices, also structured Si wafers. Its use is specified for applications that does
not require hermetic sealing, i.e. MOEMS mirror arrays, RF MEMS switches and tunable
capacitors. BCB bonding is used in the fabrication of channels for fluidic devices, for transfer
protruding surface structures as well as for CMOS controller wafers and integrated SMA
microactuators.
Technical Specifications
Substrate:
Si
SiO2
Glass
Materials
Intermediate layer:
Adhesive
high transparency
penetration of moisture
Temperature
Advantages
Drawbacks
Researches