Tagged: degradation

How do I know if Oxidation is occurring?

What Evidence is needed to prove that oxidation has occurred / is occurring?

However, understanding the oxidation process is just one part of the puzzle. When performing an investigation, we also need to know what factors or characteristics should be present. Additionally, we need to prove that their presence confirms our hypothesis of whether or not oxidation is occurring. This is where the line of evidence-based questioning plays a significant role.

When oxidation occurs, it is usual to see the presence of aldehydes, ketones, hydroperoxides, and even carboxylic acids. These can be confirmed using the FTIR (Fourier Transform Infrared test).

Typically, one will also find some deposits in the system. These deposits can be further characterized and tested to determine their nature using FTIR. Their presence, however, may be confirmed using the MPC (Membrane Path Colorimetry, ASTMD7843) test.

Identifying the presence of the deposits and/or the compounds listed above can lead to the conclusion that oxidation has occurred.

Another critical characteristic of oxidation is the depletion of antioxidants. This can be easily identified by utilizing the RULER® (Remaining Useful Life Evaluation Routine) test. This test quantifies the remaining antioxidants in the oil and gives the value for the amines and phenols (which is very important, especially in synergistic mixtures).

As such, one can detect the trend in the depletion of antioxidants and implement measures to prevent this before they become depleted.

The main tests to assist in determining the presence of Oxidation include:

RULER (Remaining Useful Life Evaluation Routine) levels less than 25% compared to new oil. This value represents the level of antioxidants in the oil. Hence, low levels indicate that the antioxidants are decreasing, possibly due to oxidation. This test can accurately give information on whether oxidation is currently occurring in the oil before deposits are formed.

An increase in acid number indicates the presence of acids resulting from oxidation. However, it must be noted that this change in acid number only occurs after oxidation has taken place. Hence this test is not a good indicator to determine if oxidation is occurring; instead, it is more definitive in letting us know that oxidation has already occurred.

Rapid color changes – darkening of the oil due to the deposits being present. While color is not the best indicator, in some instances, the darkening of the oil can provide a bystander to ask whether something is occurring in the oil. It is not a definitive test for the presence of oxidation.

FTIR test (Fourier Transform Infrared) for the presence of insolubles formed during the oxidation reaction. This can accurately determine the presence of any compound to assist us in determining whether oxidation is occurring.

MPC (Membrane Patch Colorimetry) levels outside the normal range (above 20). This lets us know that insoluble deposits are present in the oil. One must note that there may be instances where the deposits might not appear in the MPC test. As such, this should not be a standalone test to determine the presence of deposits.

RPVOT (Rotating Pressure Vessel Oxidation Test) levels are less than 25% compared to new oil (this is the warning limit). This is the industry standard, but this test does not have a high repeatability value in that if the same test were performed on identical samples, the values would be different. Additionally, the value (reported in minutes) is not easily translated into the environment of the components.

These tests provide us with the evidence we need to determine the presence of oxidation when performing the root cause analysis on the component’s failure.

Want to read the entire article? Find it here in Precision Lubrication Magazine!

Lubricant Degradation

How Can Oxidation Occur in Lubricants?

Typically, when an oil undergoes degradation, the first culprit to be blamed is oxidation. We often hear that the oil has oxidized, producing varnish, leading to its degradation. While this simple statement may seem plausible, it is not the only way oil can degrade.

If an oil has undergone oxidation, the real question we should be asking is not how much varnish has been produced but what caused the oxidation in the first place?

In this article, we will explore the various ways in which an oil can degrade via oxidation. However, as you know from previous articles, other degradation methods exist.

How Can Oxidation Occur?

Before diving further into the root cause of oxidation, one must first fully understand how oxidation occurs. When truly investigating a root cause for a failure, we should start with the question “How could?” rather than “Why?”.

This line of questioning heavily influences the answers. The “How could?” responses stem from a more evidence-based approach.

On the contrary, if we question “Why?” this is more opinionated and can mislead the investigation towards a biased opinion rather than the facts.

This leads us to the main question, “How can oxidation occur?”.

According to Ameye, Wooton, and Livingstone, 2015, oxidation occurs when there is any reaction in which electrons are transferred from one molecule. Ideally, in oxidation, during the initiation phase, free radicals are formed, which in turn produce more free radicals.

A free radical is a molecular fragment with one or more unpaired electrons which are accessible and can easily react with other hydrocarbons, as explained by Ameye, Wooton, and Livingstone, 2015.

After the initiation phase, which has the free radicals, the propagation phase follows, in which the antioxidants react with these free radicals to make them more stable. This is part of the reaction in which there is usually a drastic depletion of antioxidants or where the oil becomes sacrificial.

The antioxidants act as a barrier to protect the base oil from oxidizing. However, they can no longer protect the base oil once they become depleted. This leads to the termination phase, where the remaining free radicals attack the base oil.

As a result, this gives rise to the condensation phase, where we begin to physically notice the changes in the oil’s viscosity and the presence of insoluble by-products. These are the deposits that are known are lube oil varnish to some but can further be defined by their chemical composition.

Understanding how oxidation occurs can assist us in determining the root cause when an oil degrades. It allows us to identify the different stages to further help us determine if it is indeed oxidation that is occurring or not.

Want to read the entire article? Find it here in Precision Lubrication Magazine!

Lubricant Degradation

The Influence of Lubricant Selection on Degradation

Guidelines should always be followed when selecting a lubricant for a particular application. OEMs will have specific criteria ranges for specialty applications that must be satisfied. Some general guidelines which should be considered can be summarized in the table below based on the listed mechanisms above.

Based on the three listed mechanisms above, one can identify that choosing a lubricant can impact the type of degradation which occurs during its lifetime. As such, when selecting lubricants, it is critical to note their applications and the conditions they will endure.

Having a history of lubricant failures for particular equipment can also assist in this regard by informing users of past failure trends. Therefore, when selecting a lubricant, operators can be more mindful of the properties which should not be compromised during the selection process.

The process of troubleshooting degradation in lubricants has been covered in detail in the book, “Lubrication Degradation – Getting Into the Root Causes” by Bob Latino and myself, published by CRC Press, Taylor and Francis.

Want to read the entire article? Find it here in Precision Lubrication Magazine!

Lubricant Degradation

Which Degradation Mechanism Is Affected?

My previous article published in Precision Lubrication covered six degradation mechanisms: oxidation, thermal degradation, microdieseling, electrostatic spark discharge, additive depletion, and contamination.

Upon further investigation, there are only three mechanisms where selecting the correct lubricant will impact the degradation mode. These are; oxidation, microdieseling, and electrostatic spark discharge. The properties of the lubricant can easily influence each of these degradation mechanisms.

When selecting a lubricant, especially for rotating equipment, one of the critical areas of importance is the performance of the antioxidants. When formulated, oils must be balanced to protect the components in various aspects.

Thus, some oils that boast a high level of antioxidants may suffer from low levels of antiwear, or these increased levels can react with other components to reduce the performance of the oil. During oxidation, antioxidants are depleted at an accelerated rate which can lead to lube oil varnish. Hence, the choice of lubricant can influence this degradation mechanism.

A good trending test, in this case, would be the RULER test to accurately quantify and trend the remaining useful antioxidants for the oil. This test can easily distinguish and quantify the type of antioxidant rather than providing an estimate of the oxidation, as with the RPVOT test.

It has been noted that oils with an RPVOT of more than 1000 mins have a low reproducibility value which can mislead users during trending of lubricant degradation. Corrosion inhibitors, not just antioxidants, have also influenced the RPVOT values. Thus, there are better tests for monitoring the presence of antioxidants and helping operators to detect the onset of possible lube oil varnish.

On the other hand, during microdieseling, entrained air can lead to pitting the equipment’s internals and eventually the production of sludge or tars depending on whether the entrained air experiences a high or low implosion pressure.

If bubbles become entrained in the lubricant and do not rise to the surface, this can directly result from the lubricant’s antifoaming property. The antifoaming property is essential when selecting an oil, especially for gearboxes. Typically, OEMs will have recommendations for their components that should be followed.

Another degradation mechanism that can be influenced by lubricant selection is electrostatic spark discharge. This mechanism occurs when the lubricant accumulates static electricity after passing through tight clearances. These then discharge at the filters or other components inside the equipment, providing sharp points or ideal areas to allow static discharge.

This is frequently seen in hydraulic oils due to the very tight clearances within the equipment. If fluid conductivity is above 100 pS/m, the risk of static being produced is reduced. Some OEMs also provide particular values the lubricant should meet for this property.

Want to read the entire article? Find it here in Precision Lubrication Magazine!

Lubricant Degradation

The Six Forms of Lubricant Degradation

Oxidation

The most common form of degradation is oxidation. While this is the most recurrent form of degradation, the term is often misused to describe all forms of degradation. During Oxidation, a free radical is formed, which is highly reactive. Its primary purpose is to create other free radicals which can attack the base oil.

However, lubricants have been formulated with antioxidants. These knights in shining armor react with the free radicals to neutralize them and protect the base oil. As such, during the oxidation process, one will notice a decline in the concentration of antioxidants typically evaluated using the RULER® (Remaining Useful Life Evaluation Routine) test.

Eventually, the antioxidants become depleted, and the free radicals begin attacking the base oil. During this stage, polymerization can occur, which leads to the formation of deposits within the lubricant. Not every deposit is chemically similar.

The deposit will gain its characteristics from its environment and the products present during the chemical reaction. When these deposits occur, they can get lodged in the smaller clearances (particularly servo valves), which leads to possible malfunctioning of the equipment. Due to the nature of lube oil varnish, it can act as an insulating layer that increases the temperature throughout the equipment.

Thermal Degradation

Another form of degradation is called thermal degradation. As its name suggests, heat is one of the environmental conditions required for this degradation mechanism. During thermal degradation, the oil can experience temperatures over 200°C.

The Arrhenius equation is one of the industry’s rules of thumb whereby for every 10°C rise over 60°C, the life of the oil is essentially halved. At 200°C, the oil is cooked and produces carbon-based deposits, which is this mechanism’s characteristic type of deposit. The FTIR (Fourier Transform Infrared) test is instrumental in identifying the presence of these deposits.

Microdieseling

One can argue that microdieseling is a form of thermal degradation and should be classed as such. However, during microdieseling, air becomes entrained in the oil and moves from a low-pressure zone to a high-pressure zone.

If the oil does not have good air release properties, then the entrained air will not make its way to be dissipated at the surface. This entrained bubble in the oil can cause temperatures to rise to 1,000°C.

The bubble interface usually experiences some carbon accumulation and then implodes. This can be through a high implosion pressure which results in soot, tars, or sludge, or through a low implosion pressure which can form carbon insolubles such as coke, tars, or resins.

Electrostatic Spark Discharge

Electrostatic spark discharge may be classified under thermal degradation as it involves temperatures over 10,000°C. During this mechanism, oil builds up static electricity at a molecular level when the dry oil passes through tight clearances in the equipment.

Eventually, the static will build to a point where it produces a spark, and free radicals are formed. This can lead to uncontrolled polymerization producing varnish, sludge, or other insoluble materials. One of the tell-tale signs of this mechanism is the presence of burnt patches of membranes on the filters.

Additive Depletion

Additive depletion is often a form of degradation which gets left behind. As stated earlier, additives are sacrificial and will be depleted over time. Their purpose is to protect the lubricant and the machine, but they can be significantly depleted in some instances, leaving them vulnerable.

This type of degradation can produce two types of deposits, organic or inorganic. During degradation, rust and oxidation additives can become reacted with other components. These types of reacted additives can form organic deposits.

Alternatively, inorganic deposits such as ZDDP (Zinc dithiophosphate) can deplete and form a tenacious layer. The Depletion of ZDDP will impact the wear rate as this is the antiwear additive.

Contamination

Often, the most unrecognized form of degradation is contamination. Some may argue that this is not a form of degradation. On the contrary, this degradation mode can be the initiator for other mechanisms such as oxidation, thermal degradation, or even microdieseling.

Essentially, contamination occurs when foreign material is present in the lubricant. Often, this foreign material can become a catalyst for one of the other forms of degradation. Therefore, it must be acknowledged separately, as only the degradation mode can be eliminated by removing the contaminant.

Want to read the entire article? Find it here on Precision Lubrication Magazine!

Lubricant Degradation / Storage & Handling of Lubricants

Conditions that affect lubricants

What conditions affect lubricants?

How are your lubricants currently stored?

Are you storing lubricants under the correct conditions?

These questions have come up a dozen times during audits and countless warehouse meetings!

To answer these questions, there are five main conditions that can affect lubricants. We have detailed them along with the effects of these conditions on the lubricant.

Temperature – if incorrect can lead to oxidation. For every 10C rise in temperature above 40C the life of the lubricant is halved.
Light – too much can lead to oxidation especially for light sensitive lubricants such as transformer oils. Hence the reason that most packaging is opaque.
Water – this usually works with additives to cause their depletion or contamination of the product. Water in any lubricant is bad (especially for transformer oils as they are involved in the conduction of electricity.
Particulate contamination – contamination can occur by air borne particles if packaging is left open or if dirty containers/vessels are used to transfer the lubricant from its packaging to the component.
Atmospheric contamination – this affects viscosity and promotes oxidation and can occur if packaging is left open. For instance, if a drum is not properly resealed or capped after usage or the most common practice of leaving the drum open with the drum pump on the inside.

Different types of lubricant degradation

Why is it important to know the types of lubricant degradation?

It’s important since it helps us to figure out why or in some instance how, the lubricant degraded! Usually degradation is the change that occurs when the lubricant can no longer execute its five main functions:

the reduction of friction
minimization of wear
distribution of heat
removal of contaminants and
improvement of efficiency.

Types of lubricant Degradation Mechanisms

There are 6 main types of Lubricant Degradation as detailed below. Each type produces various by products which can enable us to understand the reason for the degradation and eliminate that / those reasons.

Here are the 6 main types of Lubricant Degradation:

1. Oxidation
2. Thermal Breakdown
3. Microdieseling
4. Additive Depletion
5. Electrostatic Spark Discharge
6. Contamination

As discussed, each mechanism produces distinct results which help us in their identification! Check out our article on why lubricants fail for more info!