Tagged: oxidation

Determining the Root Causes of Oxidation in Lubricants

Finally, we’ve arrived at the point where we can effectively determine the root cause. It is critical that the analyst understands oxidation and has knowledge of the evidence needed before embarking on the root cause journey. As noted in the first part of this article, the question we should ask is, “How could?”.

We hypothesize that oxidation is occurring. In a complete root cause analysis, we should hypothesize the occurrence of all the degradation mechanisms and eliminate them with evidence-based data.

There are two main ways in which oxidation can occur either through the presence of oxygen and temperature over the normal operating temperature of the system or if there is a less-than-adequate presence of antioxidants.

If we follow our line of questioning with the presence of oxygen and temperature and again ask, “How could?” we can get two primary responses. Either there was an air leak in the system, or the system was being pushed beyond its operating limits.

If we further investigate the air leak into the system, we ask, “How could it?” again. There are two main ways: either there are damaged components, or a less-than-adequate system design allows air to enter the system.

If we follow the pathway of investigating “how could” the system be pushed beyond its operating limits, then we can come up with two hypotheses. Either an increase in production was required, or there was a malfunction of the components, which caused strain on the other components.

Both of these hypotheses are physical and can be investigated further, but we will focus on the lubricant aspect of this article. Hence, we will follow the questioning surrounding the less-than-adequate presence of antioxidants.

We begin with the question, “How could we have a less-than-adequate presence of antioxidants?”. From the information gathered in this article, we know this can result from free radicals or less than adequate lubricant specifications.

We will investigate the “Presence of free radicals” first.

“How could we have the presence of free radicals?” Free radicals can emerge as a result of chemical reactions.

“How could these chemical reactions produce free radicals?” There are two main ways in which this can occur. Either the lubricant got contaminated, which introduced catalysts for these chemical reactions, or adverse operating conditions gave rise to these chemical reactions.

Then, we must ask again, “How could we have contamination?” Contamination can occur if leaks are getting into a closed lubrication system or if there is ingress of foreign material from the environment.

Our line of questioning continues when we ask, “How could we have leaks in a closed lubrication system?”. These can result from damaged components or seals allowing leaks into the system or if the system is less than adequately designed.

These are physical attributes of the system, so we will go back to investigating the lubricant aspect.

This is where we get to ask our famous question, “How could we have ingress of foreign material from the environment?”. Ideally, this can be classified in three ways;

There are openings which are allowing materials to enter the system or
Wrong lubricant was placed in the system or
Contaminated lubricant was placed in the system

Let’s investigate all three aspects, starting with the openings allowing foreign material to enter the system. There are two main ways in which this can occur. Either the openings were not closed after use, or the safety latches malfunctioned.

Suppose the openings were not closed after use. In that case, there is a possibility that there were less than adequate inspections to verify that these were closed after use or a less than adequate procedure for the task being completed which required the opening of the hatch.

On the other hand, if the safety latches malfunctioned, this could result from less than adequate checks to verify the functioning of the safety latches.

In these cases, the root causes are not the physical elements but rather the systemic reasons for these procedures not being adequately performed.

Now we investigate the second central hypothesis, “How could the wrong lubricant be placed in the system?” While there are many ways in which this can occur, we have narrowed it down to two main areas.

Either there were less than adequate checks to verify that the technician received the correct lubricant, or there were less than adequate procedures to dispatch the correct lubricant from the warehouse. We will not go further into these two as they are now systemic causes that must be addressed.

Onto the third hypothesis of “How could a contaminated lubricant be placed in the system?”. There are two main avenues for this to occur. Either there were improper storage and handling procedures, or there needed to be more adequate procedures to verify the cleanliness of the lubricant before entering the system.

The other hypothesis stemming from the “less than the adequate presence of antioxidants” is having “less than adequate lubricant specifications.” Let’s investigate this one a bit further.

“How could we have a less than adequate lubricant specification?” Typically, this can result from the lubricant not being blended properly or less than adequate antioxidant levels, which were inappropriate to protect the lubricant.

Now, the line of questioning changes to “Why?” as we have gone past the physical element and some decision-making was involved in this hypothesis. We must ask, “Why wasn’t the lubricant blended properly?”

This can result from less than adequate procedures to ensure the quality of the lubricant by the supplier or less than sufficient checks for the proper blending mix being processed.

These are factors one should consider when receiving any lubricant from their supplier.

On the other hand, if we follow the line of questioning of “How could there be a less than adequate antioxidant level to protect the lubricant?” we can come up with the following.

Either the operating environment caused the antioxidants to be depleted at a higher rate. This would be as a result of a harsh but normal operating environment. In this case, we may be unable to make those environmental changes (without the OEM’s consent).

Or the antioxidants used were not suited to the operating conditions. This is where the line of questioning again shifts to “Why were they not suited?”. This could result from inadequate information in choosing the right lubricant suited for the system.

What Is the Real Root Cause of Oxidation?

From the logic tree that we have created, we can see that there is no sole root cause for oxidation. It can stem from various causes, including physical, human, and even systemic roots. The main takeaway from this exercise is to acknowledge that root causes are not limited to physical causes, such as leaks in the system.

Instead, the actual root causes can be linked to systemic areas of concern where there may not have been enough information to guide the analyst in choosing the most ideally suited lubricant for the application. There are also root causes related to the lubricant not being appropriately blended.

It is critical to thoroughly investigate the real root causes when the lubricant becomes degraded to avoid being stuck in the loop of constantly experiencing degradation.

For more info on other methods, check out the book Bob Latino, and I authored called “Lubrication Degradation – Getting Into the Root Causes,” published by CRC Press.

References:

Ameye, Jo, Dave Wooton, and Greg Livingstone. 2015. Antioxidant Monitoring as Part of a Lubricant Diagnostics – A Luxury or Necessity. Rosenheim, Germany. February 2015.

Latino, Bob, Sanya Mathura. 2021. Lubrication Degradation – Getting into the Root Causes. CRC Press, Taylor & Francis.

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

Lubricant 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 / Used Oil Analysis

Additives and their properties

Properties of Additives in Lubricants

Each lubricant has a varying percentage of additives as not all lubricants are created equally. Lubricants are designed based on their application or use within the industry. For instance, an engine oil is typically composed of 30% additives, 70% base oil while turbine oils comprise 1% additives and 99% base oil.

Therefore, particular attention must be paid to getting the additive compositions to be just right for the application and ensuring that the additives can perform their functions.

Each additive has a particular function and is used as per the application of the lubricant. We have adapted the following from Analysts Inc – Basic Oil Analysis which describes the purpose of some of the most commonly used additives in lubricants.

Lubricant Degradation / Storage & Handling of Lubricants

Lubricant Deterioration Identifications

What the difference between Shelf Life and Service Life?

There’s a major difference between Shelf life and Service life especially when it concerns lubricants!

No one wants to put expired lubricants into their equipment! This can cause unexpected failures which can lead to unplanned downtime which can continue to spiral down the costly path of unproductivity!

Shelf Life

The Shelf life is usually what is stamped by the Manufacturer indicating the length of time the product can remain in its current packaging before being deemed unsuitable for use. These can typically be found on the packaging.

Service Life

The Service life however is determined by the application and conditions under which the lubricant is being used. Usually, estimated running hours / mileage are given by the equipment manufacturer in the maintenance section of the manual. (Condition monitoring can also be used to determine appropriate service intervals.)

However, how will someone know if the product has deteriorated while still in its original packaging? What should someone typically look for?

Above are some tips for identification of deterioration in lubricants. Take a note of these for the next time you are unsure of the integrity of your lubricants.

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!

Lubricant Degradation / Used Oil Analysis

Oxidation

What is Oxidation?

One of the major types of oil degradation is Oxidation. But what is it exactly, as applied to a lubricant?

Oxidation is the addition of oxygen to the base oil of the lubricant to form either of the following:

Aldehydes
Ketones
Hydroperoxides
Carboxylic Acids

Wow… too many chemical names right?! These help to pinpoint the conditions responsible and then we can address them accordingly. Each of these by products are produced by different types of reactions or in some cases different stages of the oxidation process. It is key to note the type of by product as it gives us a clue to the root of the issue through which oxidation occurs.

For instance, the presence of Carboxylic acids can result in the formation of Primary Amides which can lead to heavy deposits. Early detection of the Carboxylic acids can help us prevent this. Once we determine the source of oxidation to produce the carboxylic acids, we can in turn remove this from the system.

Oxidation Stages

Oxidation does not happen in an instant. Usually, it follows a series of events which eventually lead to oxidation. Like any process in life, there are different stages for Oxidation:

Initiation – Production of the free radical via the lubricant and catalyst.
Propagation – Production of more free radicals via additional reactions
Termination – Continuation of oxidation process after the antioxidants have been depleted or the antioxidant stops the oxidation process.

Results of Oxidation

Why is Oxidation bad for the lubricant? What can it ultimately result in?

Well, oxidation can result in the formation or lead up to the following:

Varnish
Loss of antifoaming properties
Additive depletion
Base oil breakdown
Increase in viscosity
Sludge

None of these are good for the lubricant!!!!!!!!! If you see any of these signs be sure to test for oxidation and identify the root cause for the introduction of oxygen in your system.

Oxidation Tests

Now that we know more about oxidation… what tests can be performed to prevent it?

There are 6 main tests that can be performed:

RPVOT (Rotating Pressure Vessel Oxidation Test)
RULER (Remaining Useful Life Evaluation Routine)
MPC (Membrane Patch Calorimetry)
FTIR (Fourier Transform Infrared)
Colour (ASTM D1500)
Acid Number (ASTM D974)

One must be careful in selecting which test to apply, this is heavily dependent on the type of lubricant and its application.

For instance, if we perform the RULER test and the antioxidant levels have depleted significantly, we can suspect that oxidation is occurring or has stopped. Charting the rate of antioxidant depletion, can determine the rate of oxidation. This can assist us to forecast the time remaining before antioxidants have been depleted and can no longer protect the base oil.