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File:AdhesivesForHouseUse004.jpg

Nitrocellulose adhesive outside a tube

An adhesive, or glue, is a mixture in a liquid or semi-liquid state that adheres or bonds items together. Adhesives may come from either natural or synthetic sources. The types of materials that can be bonded are vast but they are especially useful for bonding thin materials. Adhesives cure (harden) by evaporating a solvent (these are most adhesives that cure at room temperature) or by exposing them to an elevated temperature.[1][2]

The earliest date for a simple glue is 200,000 BC[3] and for a compound glue 70,000 BC.[4]

History[]

The oldest known adhesive, dated to approximately 200,000 BC, is from spear stone flakes glued to a wood with birch-bark-tar, which was found in central Italy.[3] The use of compound glues to haft stone spears into wood dates back to round 70,000 BC. Evidence for this has been found in Sibudu Cave, South Africa and the compound glues used were made from plant gum and red ochre.[4] The Tyrolean Iceman had weapons fixed together with the aid of glue.[5]

6000-year-old ceramics show evidence of adhesives based upon animal glues made by rendering animal products such as horse teeth. During the times of Babylonia, tar-like glue was used for gluing statues. The Egyptians made much use of animal glues to adhere furniture, ivory, and papyrus. The Mongols also used adhesives to make their short bows, and the Native Americans of the eastern United States used a mixture of spruce gum and fat as adhesives to fashion waterproof seams in their birchbark canoes.

In medieval Europe, egg whites were used as glue to decorate parchments with gold leaf. The first actual glue factory was founded in Holland in the early 1700s. In the 1750s, the English introduced fish glue. As the modern world evolved, several other patented materials, such as bones, starch, fish, and casein, were introduced as alternative materials for glue manufacture. Modern glues have improved flexibility, toughness, curing rate, and chemical resistance.

In the late 1800s in Switzerland, casein was first used as a wood glue. Today, it is seen to be used to glue grocery bags.[6]

Types[]

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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, electrical conductivity, or synthetic origin or by their staring physical phase.

Non-reactive adhesives[]

Pressure sensitive adhesives[]

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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") 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 sheer-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.

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.[7] Once the surfaces are pushed together, the bond forms very quickly.[8] It is usually not necessary to apply pressure for a long time, so there is less need for clamps.

Hot adhesives[]

File:MVC-013F.jpg

A glue gun, an example of a hot adhesive

Hot adhesives, also known as hot melt adhesives, are simply 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. These adhesives are 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 water-based adhesives commonly used in packaging at that time failing in humid climates, causing packages to open and become damaged.

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 (PVA). Used extensively in the woodworking and packaging industries. Also used with fabrics and fabric-based components, and in engineered products such as loudspeaker cones.

Reactive adhesives[]

Multi-part adhesives[]

Multi-part 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]

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 are mainly used in glass bottle labelling. Starch based adhesives are used in corrugated board production and paper sack production, paper tube winding, wall paper adhesives. 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.[6]

Synthetic adhesives[]

Synthetic adhesives are based on elastomers, thermoplastics, emulsions, and thermosets. Examples of thermosetting adhesives are: polyvinyl acetate, epoxy, polyurethane, cyanoacrylate and acrylic polymers.

Mechanisms of 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[]

File:Adhesive2.svg

Failure of the adhesive joint can occur in different locations

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 centre of the layer or near an interface. For this last case, the cohesive fracture can be said to be “cohesive near the interface”. Most quality control standards consider a good adhesive bond to be cohesive.

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 interphase.

Other types of fracture[]

Other types of fracture include:

  • 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 jumps 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, 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.

Design of adhesive joints[]

File:Fracture modes v2.svg

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.
  • Mode III is a tearing or antiplane shear mode.

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:

  • The bonded zone is large
  • It is mainly loaded in mode II
  • Stable crack propagation will follow the appearance of a local failure.

Testing the resistance of the adhesive[]

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Testing devices

A wide range of testing devices have been devised to evaluate the fracture resistance of bonded structures in pure mode I, pure mode II or in mixed mode. Most of these devices are beam type specimens. We will very shortly review the most popular:

  • Double cantilever beam tests (DCB) measure the mode I fracture resistance of adhesives in a fracture mechanics framework. These tests consist in opening an assembly of two beams by applying a force at the ends of the two beams. The test is unstable (i.e. the crack propagates along the entire specimen once a critical load is attained) and a modified version of this test characterised by a non constant inertia was proposed called the tapered double cantilever beam (TDCB) specimen.
  • Peel tests measure the fracture resistance of a thin layer bonded on a thick substrate or of two layers bonded together. They consist in measuring the force needed for tearing an adherent layer from a substrate or for tearing two adherent layers one from another. Whereas the structure is not symmetrical, various mode mixities can be introduced in these tests. This is one of the more common methods of evaluating paper strength in library and archival preservation.
  • Wedge tests measure the mode I dominated fracture resistance of adhesives used to bond thin plates. These tests consist in inserting a wedge in between two bonded plates. A critical energy release rate can be derived from the crack length during testing. This test is a mode I test but some mode II component can be introduced by bonding plates of different thicknesses.
  • Mixed-mode delaminating beam tests (MMDB) consist in a bonded bilayer with two starting cracks loaded on four points. The test presents roughly the same amount of mode I and mode II with a slight dependence on the ratio of the two layer thicknesses.
  • End notch flexure tests consist in two bonded beams built-in on one side and loaded by a force on the other. As no normal opening is allowed, this device allows testing in essentially mode II condition.
  • Crack lap shear tests (CLS) are application-oriented fracture resistance tests. They consist in two plates bonded on a limited length and loaded in tension on both ends. The test can be either symmetrical or dis-symmetrical. In the first case two cracks can be initiated and in the second only one crack can propagate.

See also[]

  • Adhesive surface forces
  • Glue stick
  • Sealant

References[]

  1. Todd, Allen & Alting 1994, p. 400
  2. Lau et al. 2002, p. 1.12
  3. 3.0 3.1 Mazza, P (2006). "A new Palaeolithic discovery: tar-hafted stone tools in a European Mid-Pleistocene bone-bearing bed". Journal of Archaeological Science 33: 1310. doi:10.1016/j.jas.2006.01.006. 
  4. 4.0 4.1 Wadley, L; Hodgskiss, T; Grant, M (2009). "From the Cover: Implications for complex cognition from the hafting of tools with compound adhesives in the Middle Stone Age, South Africa.". Proceedings of the National Academy of Sciences of the United States of America 106 (24): 9590–4. doi:10.1073/pnas.0900957106. ISSN 0027-8424. PMID 19433786. 
  5. Sauter F, Jordis U, Graf A, Werther W, Varmuzahttp K. (2000). Studies in organic archaeometry I: identification of the prehistoric adhesive used by the “Tyrolean Iceman” tofix his weapons. ARKIVOC, 1:[5] 735-747
  6. 6.0 6.1 CCMR - Ask A Scientist!
  7. Information about contact adhesive
  8. Definition of contact adhesive on About.com

Bibliography[]

External links[]

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