Adhesive Failure Analysis / Adhesion Testing

One of our areas of specialized expertise has long been the analysis of adhesive bonding. Adhesive failures are commonly said to be either cohesive failures or adhesive failures.  A cohesive failure is a failure in the bulk layer of the adhesive and is usually the desired mode of failure.  An adhesive failure occurs at the interface between the adhesive and the adherend, or the material to be bonded.  Such disbonds at the interface with all of the adhesive on one side of the separated materials is desired in some cases, such as in use with temporary notes or a backing on a roll of tape.

Areas of adhesive and cohesive failure are shown for an adhesive bonded to a frit on glass.

Adhesive failures often require sophisticated analysis to understand.  The location of the failure may be in a very thin layer at an interface.  The interface may have become contaminated during any of the processes used to prepare the metal surface or afterwards.  Fatal contamination layers are often less than 3 nm thick!  One classic example is a silicone or dimethyl siloxane release agent or lubricant, which is what caused the failures at the frit interface in the above image.  This thin layer of dimethyl siloxane was not detected by two prior laboratory investigations.

In other cases, a metal surface may be treated to promote adhesion with a high surface area, then treated to retard corrosion with a very thin layer of solid particles, and then treated with a silane adhesion promoter which may be thinner than 10 nm thick.  Many things may go wrong in these processes.  The adhesive itself may have numerous component ingredients and some may be at very low concentrations in the bulk of the adhesive, but are supposed to migrate to the interface to promote adhesion.  Sometimes this migration process does not work right.  Sometimes an impurity migrates to the interface instead.  Exposure of a metal surface to humidity may also cause interfacial or adhesive bond failures in the metal surface.

Bonding to plastic, glass, ceramics, inorganic particles, or composite materials may suffer failures at or near interfaces for many reasons.  Inorganic particle filler materials are often given treatments to promote polymer resin wetting, whether in composite materials, paints, or sealants.  When that fails in a composite material, the material is greatly weakened.  In a paint or sealant, they may agglomerate, which may allow degradation due to UV exposure or it may cause the paint or sealant to peel off the adherend.  Or, such inorganic particles may lose bonding due to excessive hydration.  Glass surface bonds may fail if the glass surface was too alkaline when bonded, as Dr. Anderson demonstrated was the cause of Space Shuttle External Fuel Tank failures in the early 1990s.  Metal surfaces, especially those with +2 valence states are inclined to suffer from excessively alkaline chemistries at surfaces also.  Plastic bonding may fail due to migration of plasticizers to the surface or residues of mold release agents.

Determine surface and interface chemistries using XPS surface analysis:

  • Surface analysis of adherend or substrate material as prepared for bonding
  • Surface analysis of both sides of peeled or failed interfaces to find locus of failure, identify chemistry, and identify any contaminants
  • Correlate surface chemistry of samples tested to failure with measured strength
  • Examine aging and degradation effects on the chemistry at the interface as a function of time and exposure environment
  • Determine differences of bondline adhesive chemistry from the bulk adhesive chemistry, since distinct and often radically different interfacial adhesive interphase layers are common
  • Identify interfacial contaminants due to hydrolysis, silicones or siloxanes, plasticizers, surfactants, hand lotions, cutting oils, hard water deposits, solder fluxes, insufficient rinse of pretreatment acids or bases, mold release agents, and photoresists

Prepare very clean adherend surfaces for reference to mechanically tested bond strengths of manufactured or prototype bonded materials.

Microscopy – SEM and Optical – Failure Analysis:

  • Locates failure plane
  • Indicates type of failure
  • Reveals gas bubbling effects due to contaminants or improper 2-part adhesive mixtures

Failed lap shear tested coupon for analysis to determine the cause of adhesive failure.

Honeycomb skin with poor adhesive bond in some areas for analysis to determine the cause of failure.

Thermal Analysis:

  • TMA to determine differences of thermal expansion of adherends and adhesive
  • TMA to indicate whether thermoplastics have too much crystallinity, which may produce a large thermal expansion spike at the crystalline melting temperature
  • TMA and DSC to determine maximum temperatures appropriate for curing adhesive bondlines or to prevent phase changes and degradation processes in use
  • DSC to determine good adhesive curing conditions or problems due to improper mixtures of 2-part adhesives

Electrochemistry – Electrochemical Impedance Spectroscopy (EIS):

  • Measures water and ionic concentration buildup in organic coatings and adhesives
  • Measures effect of adhesive or coating pores, holidays, and fisheyes upon water reaching interface to cause hydrolysis attack of bondline

FTIR Spectroscopy Analysis:

  • Identify differences at bondline relative to in the bulk of the adhesive
  • Contrast chemistry of 1 μm depth to that of the 8 nm measured by XPS
  • Identify plastic, rubber, resin, and laminate materials being bonded
  • Identify the adhesive and/or the primer to which adhesive is applied, as it is in aerospace adhesive bonds to aluminum surfaces

Optical Microscopy:

  • Very useful in determining which areas to further analyze with the above techniques and for documenting the microscopic appearance associated with the subsequent results.