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Corrosion, Degradation and Oxidation
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Rusted Riveted Stream EngineCorrosion, oxidation and degradation commonly spoil the aesthetics, leads to component weakening, the requirement for remedial actions and, in the worse case, failure of materials in products. Often this is directly due to the aggressive environment that a product is exposed to over its operational life. In the case of plastics or paint coatings it can be embrittlement or discolouration, paint delamination or solvent swelling. Metals can be attacked by aqueous based corrosion or oxidised at elevated temperature.

Aqueous Corrosion

In order for aqueous corrosion to occur the following have to be present:-

  • Anodic area where components degredation occurs
  • Cathodic area
  • Electrolyte to transport corrosive species and various ions
  • Electron conduction path connecting anode and cathode

Pipes corroding in open airThe corrosion rate is dependent on many factors, some of which are listed below:-

  • Relative areas of the anode and cathode
  • Electrolyte conductivity and whether the metal is immersed in water, underground or just corroding as a result of surface moisture related to the humidity
  • Availability of fresh reactants; corrosive species such as oxygen and chloride ions
  • Removal of corrosion products and the tendency of the oxide to spall away which allows attack to continue virtually unhindered
  • Resistance in the metallic circuit
  • Electrical Resistance and durability of any protective coatings or surface treatments
  • Temperature

Mechanisms to minimise the impact of the environmental attack are often in place, but have failed to be effective for a range of possible reasons:

  • Unusual or unexpected exposure conditions (chemical, humidity, pH, turbulence from flowing water etc, differential aeration etc.)
  • Mistaken use or wrong choice of material or metal alloy for the environment
  • Galvanic cell set up with another nearby metal component electrically in contact with the corroding part, with the circuit completed by an electrolyte, which can be as little as surface adsorbed water
  • Failed protection system
  • Ineffective or insufficient biocides or inhibitors in a closed system like a heating system as microbiological attack can be very aggressive

Corroding and flaking paint on a building supportThe protection system designed to slow down or prevent corrosion can be

  • Passivation having or deliberately growing a protective oxide. Stainless steel has a protective surface oxide and aluminium and titanium are often anodised to grow thicker oxides
  • Choice of material / alloy to insure the material is passive or immune in the environmental conditions the component is likely to see over life
  • Avoid two phase alloys which can provide the anode and cathode locally close together and give phenomena such as dezincification of brasses where one phase can be preferentially eaten away
  • Cathodic protection by use of a sacrificial anode or impressed current to make a key component cathodic and so not corrode
  • Anodic protection using impressed current to make a material passive
  • Painting, spraying or dip coating to provide a diffusion barrier to slow down or stop the ingress of corrosive species such as oxygen or chloride ions
  • Use of conversion coatings
  • Avoid rough surfaces as points protruding into the electrolyte will preferentially corrode
  • Cracks or small pits should be avoided as, from the catchment area principle, the anode at the crack tip (because of a lower availability of oxygen) is small with respect to the cathode and attack can be relatively fast giving pits. Aluminium and stainless steels are susceptible to pitting corrosion for example.

Depending on the materials involved SEM/EDX and optical microscopy together with a combination of various surface analysis techniques, Anion Chromatography and FTIR generally are used to analyse and identify the failure mechanism and then the source of the aqueous corrosion. This can lead to the laboratory making recommendations on how to best avoid or solve the problem in the future.

 

Stress Corrosion Cracking and Fatigue

Corrosion, with the exception of pitting, is generally a slow process. However, it can combine with mechanical loading to produce a particularly aggressive form. In stress corrosion cracking (SCC) a tensile stress or residual stress from component manufacture forces the crack tip open to allow the attacking elements in and concentrated chemical attack. The corrosion component of SCC allows areas crack growth to continue even when the stress is lowered.

Combining fatigue with corrosion is probably the most catastrophic form of attack affecting aluminium alloys in aircraft for example. SCC is distinct in SEM/EDX and AES (Auger).

 

High Temperature Oxidation

Oxide thickness effecting colour of copper surfaceHigh temperature oxidation of metals occurs when the temperature is sufficient to allow interdiffusion of metal and oxygen. It can be deliberate:

  • Furnace produced coloured metal for controlled heat transfer characteristics (emissivity)
  • Growing a certain layer thicknesses of silicon oxide insulation or silicon oxynitride as a dielectric on semiconductor wafers
  • Furnace oxidation method of cleaning contaminants off metals prior to thermal reduction

In other cases oxidation is to be avoided or only permitted until a protective oxide is produced. Areas of interest may be:-

  • Inside a jet engine
  • Automotive engine components
  • Air leaks in a reducing or other gas furnace process such as hardening or annealing
  • Welding under a protective inert gas shield

Surface oxidation can be evaluated by a combination of surface analysis techniques and SEM/EDX. The laboratory also has facilities to mimic thermal processes under a range of reducing and oxidizing gas environments.

 

Degradation of Polymers and Coatings

Plastics (polymers) or paint coatings are generally considered to be pretty robust to the everyday environment. However, they are still attacked by the often harsher environment to which they are exposed, particularly if the materials formulation and mixing is not optimised. Examples of degradation are:-

  • Embrittlement due to further cross-linking induced by ultra-violet light (UV): The extent can be investigated by FTIR
  • Discolouration induced by ultra-violet light (UV). XPS can measure the surface changes that result including oxidation
  • Swelling of the polymer caused by solvent ingress is best investigated by FTIR to determine if the, often complex, formulation is correct. In composite materials the size that bonds the fibres to the matrix is crucial for maintaining barrier properties along the interface
  • Exposure to a high temperature can degrade a polymer material and even graphitize it. These effects can be seen by FTIR and XPS if it is a surface effect
  • Paint bubbling or lifting can be a result of corrosion of the substrate and this is often a result of poor interfacial adhesion to the substrate or it acting as a poor diffusion barrier related to a poor formulation

Application Notes
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