The newly engineered ERASPEC mid FTIR and NIR Analyzer (Figure 1) brings precise, automated, quick and comprehensive chemical analysis directly to your laboratory.

[Figure 1] ERASPEC mid FTIR and NIR.

Introducing the ERASPEC Mid-FTIR Analyzer, a cutting-edge chemical analysis device designed for rapid and precise measurement of various chemical properties. It features three cell sizes (20, 100, and 500 μm) to enhance result accuracy. This revolutionary analyzer, further enhanced with the NIR Upgrade Module, seamlessly integrates mid-FTIR and NIR spectroscopy, setting a new standard in the characterization and quality control of chemicals such as gasoline, diesel, and jet fuel formulations

Mid-FTIR and NIR: A Powerful Combination

The integration of mid-FTIR and NIR spectroscopy in the ERASPEC analyzer combines the
strengths of both techniques:

• Mid-FTIR: Offers in-depth analysis of the molecular structure and composition of chemicals. It is particularly effective for identifying and quantifying specific chemical bonds and functional groups.
• NIR: Provides rapid analysis, ideal for quantifying components and properties such as octane number, cetane number, and various physical parameters. Additionally, NIR can detect responses from compounds, such as alkanes, that are typically not as prominent in Mid-IR spectroscopy, thereby offering a broader scope of chemical analysis.

The ERASPEC analyzer with the NIR upgrade is a game-changer for chemical analysis, delivering multiple benefits:

• Comprehensive Analysis: Capable of analyzing gasoline, diesel, and jet fuels, ensuring broad applicability in fuel quality control and research.
• Accuracy and Speed: Combines the precise molecular analysis of mid-FTIR with the rapid assessment capabilities of NIR, offering unmatched accuracy and efficiency.
• Ease of Use: Designed for user-friendly operation, with minimal training required for accurate and repeatable results.
• Regulatory Compliance: Adheres to various ASTM standards, ensuring compliance with industry regulations and standards.

PLS MIR+NIR Fuel Prediction Model

The development and application of the Partial Least Squares (PLS), mid-FTIR (MIR) + near-Infrared (NIR) model for fuel prediction represent a significant advancement in fuel analysis technology. This report summarizes the key findings and implications of using the PLS MIR+NIR model. This model offers enhanced predictive capabilities compared to traditional Fourier-Transform Infrared (FTIR) and Multiple Linear Regression (MLR) models, particularly in addressing the variability in fuel composition due to changes in crude oil sources and distribution systems.

The ERASPEC analyzer has become a market leader due to its fast, easy-to-build libraries and reliable results. Traditional FTIR models, which were effective for localized fuel analysis, have struggled with the increasing complexity and number of variables in fuel compositions. This is due to the process of diverse crude oils and the widespread distribution of gasoline in refineries, which caused significant challenges in maintaining accurate and stable fuel models.

Model Performance

The PLS MIR+NIR model was developed using a comprehensive dataset of 715 samples collected across four regions of China, 15 European samples with ethanol. The model was further validated with 100 additional samples from China and 17 samples from Florida, USA.

[Figure 2] Models of Pentane and Decane.

Key Findings

1. Self-Prediction of the Model:
The PLS MIR+NIR model demonstrated superior accuracy compared to the MLR MIR model. The Standard Error of Calibration (SEC) was significantly lower for the PLS MIR+NIR model (0.37) compared to the MLR MIR model (0.78).

[Figure 3] Results of PLS and MLR models. It shows a superior accuracy of the PLS model.

2. Validation with Unknown Samples:
When tested on unknown samples similar to the model, both the PLS MIR+NIR and MLR MIR models performed well, but the PLS MIR+NIR model was approximately twice as accurate. The SEC for the PLS MIR+NIR model was 0.40, while it was 0.87 for the MLR MIR model.

[Figure 4] Results for the unknown samples for PLS and MLR models have the same trend.

The PLS MIR+NIR model’s ability to integrate new information from the NIR spectrum, particularly combination reports that provide additional information on CH2/CH3 distributions, has contributed to its enhanced stability and accuracy. This extended spectral range allows for better predictions for unknown fuels, and the model’s capacity to update directly on the instrument without external devices ensures its adaptability to new fuel compositions.

Real-World Impact

The ERASPEC analyzer’s dual spectroscopy approach significantly enhances the throughput and reliability of chemical testing in laboratories and industrial settings. It enables precise monitoring of fuel quality, helping to prevent engine and machinery damage, optimize performance, and ensure regulatory compliance. The integration of mid-FTIR and NIR spectroscopy in the ERASPEC analyzer opens up a wide range of applications across various industries, showcasing its versatility and advanced capabilities.

Refinery and Petrochemical Operations

It ensures precise fuel blending to meet specific quality standards and regulatory requirements.

Aviation Industry

It performs jet fuel analysis to ensure fuel quality meets the standards for safety and performance.

Environmental Monitoring

It analyzes fuel compositions to assess their environmental impact, and it helps industries to comply with environmental regulations by providing accurate data on fuel properties and emissions.

Renewable Fuels

It ensures the quality of biofuels such as ethanol and biodiesel.

Research and Development

It provides detailed analysis of experimental fuels under various conditions to evaluate their performance and potential applications.

Oil and Gas

It analyzes oil samples from exploration wells for reservoir characterization, and monitors production fluid to ensure the quality of produced oil meets required standards.

In summary, the ERASPEC mid FTIR Fuel Analyzer with the NIR Upgrade Module sets a new standard in fuel analysis, providing unmatched accuracy, efficiency, and versatility across a multitude of industries. The PLS MIR+NIR model is a significant improvement over traditional fuel prediction models, particularly in its ability to handle variability in fuel composition. Its enhanced accuracy, demonstrated by lower SEC values and better validation performance with unknown samples, makes it a valuable analysis tool for the modern fuel industry. Its advanced features and wide-ranging applications make it an essential tool for ensuring chemical quality, optimizing performance, and supporting regulatory compliance, thereby revolutionizing the field of chemical analysis.

Measuring the elemental content serves several critical purposes that are vital for ensuring the performance, reliability, and longevity of both the lubricants and fuels. Regularly checking the elemental content ensures that the lubricant maintains its specified composition, ensuring consistent performance. This is particularly important during manufacturing and before the lubricant is applied in critical machinery. Further reasons for conducting such measurements are the following:

• Detection of Wear Metals:
  As equipment components wear down during operation, metallic particles are generated and circulated throughout the lubrication system. Analyzing the elemental content helps in detecting wear metals that are released into the lubricant from machinery components. This can indicate the wear rate of parts, allowing for predictive maintenance and preventing catastrophic failures. In case of machinery failure, analyzing the elemental content of the lubricant can help identify the root cause.
• Contaminant Identification:
  The presence of certain elements can signify contamination from sources like dirt, coolant leaks, or sea water. Identifying these contaminants helps to understand error modes and narrow down the possible causes.
• Additive Depletion:
  Lubricants contain various additives that enhance performance by providing properties like anti-wear, anti-oxidation, and corrosion resistance. Measuring these elements helps in assessing the condition and remaining useful life of the lubricant. Professionals in the industry typically monitor potential changes in concentration over time, starting from the initial concentration of the fresh lubricant.

Table 1 summarizes the most important elements linked to their main origin.

Methods to perform elemental analysis

The history of elemental analysis goes back to the 1940s and 1950s when it was used in the railroad industry to determine the presence of wear metals in diesel engine oils.

In its present form, elemental analysis is used to determine the concentrations of more than 30 different elements.

Nearly all oil analysis labs utilise one of two types of atomic emission spectrometers: either an inductively coupled plasma (ICP) instrument or a rotating disc electrode (RDE) instrument. The primary difference between these two lies in the method of sample vaporisation and atom excitation by the high-energy source. In an ICP instrument, the oil is injected into a high-temperature argon plasma, where the atoms are vaporised, excited, and subsequently emit light. In an RDE spectrometer, also known as an “Arc-Spark” instrument, the oil is vaporised and excited using a high-voltage discharge between an electrode and a rotating carbon disc.

Besides the different vaporisation and excitation methods, the rest of the instrument functions similarly in both ICP and RDE spectrometers. The emitted light from the excited atoms is collected and focused onto the spectrometer’s slit. Inside the spectrometer, a diffraction grating, which functions like a prism, splits the light into discrete wavelengths based on their angle of diffraction.

The light intensity at each angle, typically referred to as a channel, is measured using a light-sensitive photodiode. The resulting voltage signal is then converted into a concentration in parts per million (ppm) through a calibration procedure. Although ICP and RDE measure the elemental composition of a sample using a common principle, the practical implementation of the two techniques is radically different.

An ICP requires sample preparation, typically including acid pre-treatment and microwave digestion, and a supply of carrier gas. As the measurement procedure is quite involved, ICPs are typically found in well-equipped labs with skilled operators. The RDE method, on the other hand, does not require any sample preparation and the sample is measured as received. The instrumentation requires stable temperature conditions, but otherwise no additional materials. This means that the RDE method can be used not only in an industrial environment, but also in the field or at remote locations.

The ICP method offers the advantage of sub-ppm detection limits as well as the ability to detect sulphur in routine analysis. The RDE instruments typically do not detect sulphur due to the lack of a vacuum system but offer ppm detection limits for up to 32 elements, including the relevant elements found as wear in oil additive packages. For used oil analysis, RDE offers the advantage that it can detect particles up to 10 μm, whereas ICP typically only detects particles below 5 μm.

Data comparison

To investigate the relation between the elemental composition determined by ICP and RDE, 35 samples of gear oil, hydraulic oils and motor oils were collected from a steel plant. Both fresh and in-service oils were used for the study. The samples were measured using a 2500 ICP-OES spectrometer from Agilent according to ASTM D5185 and an ERAOIL RDE-OES spectrometer according to ASTM 6595. For the ICP measurements, the samples were treated with nitric acid and hydrogen peroxide and then microwave digested at 190°C. The RDE samples were measured without sample preparation.

Elements that were detected by ICP in at least 20% of the samples were used for the comparison.

In general, the ICP and RDE results match well for both the detected wear metals as well as elements that can be assigned to additives. Figure 1 shows the correlation between iron (Fe) and zinc (Zn) levels in the samples. Table 2 summarizes the obtained correlations for all investigated elements.

All investigated elements showed a high degree of correlation between the two methods with R2 factors above 0.95 and correlation factors close to unity. The deviation of the correlation factor from 1 is probably not related to a difference in calibration, as both techniques are calibrated with similar certified reference materials. It is possible that the difference is related to the sample preparation used for ICP and the different ways the two methods excite the atoms in the sample. In this way, the difference only appears for actual samples and not for the artificial metallo-organic complexes used to calibrate the instruments.

For a sub-set of the collected samples, a clear difference in the results from the ICP and the RDE could be shown for one element. The collected motor oils (diesel engine oils) had been overbased to boost the TBN value of the oil and consequently had elevated levels of calcium. The results for calcium on these overbased oils are shown in Figure 2.

[Figure 2] Calcium in overbased oils as determined with ICP and RDE.

For the high-concentration samples, the RDE method significantly underestimates the actual concentration (correlation factor 2.5) but still shows a high degree of correlation (R2=0.99).

Figure 3 shows the repeatability of the tests and the ERAOIL results shows very high repeatability for majority of parameters.

[Figure 3] High repeatability of ERAOIL results on the majority of parameters.

For the overbased oils, the results of RDE without sample preparation will underestimate the calcium concentration. As the different oils all had different additive packages, it is likely that this effect is general and applies to all types of calcium detergents used to overbase oils. However, the correlation between RDE without sample preparation and ICP is still excellent (R2=0.99), which shows that the difference in absolute values can be accounted for in the calibration procedure for overbased oils. The more cumbersome alternative is to employ the same sample preparation procedure for both methods.

Conclusion

Measuring the elemental content in all types of lubricants is essential to ensure their performance, reliability and longevity, as well as that of the machines in which they are used. Regular analysis detects wear metals, providing information on the wear rate of parts, contributing to predictive maintenance and preventing breakdowns. It also identifies contaminants and detects additive depletion that affects lubricant performance. Typically, oil analysis is performed for this purpose using either an inductively coupled plasma (ICP) or rotating disk electrode (RDE) device. ICP provides accurate results with prior sample preparation, while RDE is much easier to use and provides comparable results. A comparative study has shown that the measurement results between ICP and RDE generally correlate very well.

To compare ERAOIL from Eralytics, Inductively Coupled Plasma (ICP) analysis, it’s important to consider various factors such as technology, application, precision, advantages, and limitations. Here’s a detailed comparison:

Technology

• ERAOIL (Eralytics):
  • Technology: Uses patented QES (Quantum Electronics Source) technology.
  • Principle: Based on optical emission spectrometry (OES).
• ICP (Inductively Coupled Plasma):
  • Technology: Uses an argon plasma to excite atoms and ions.
  • Principle: Measures the emitted light from excited atoms/ions to quantify element concentrations.

Applications

• ERAOIL:
  • Applications: Used for wear metal analysis, contaminants, and additive elements in lubricants and oil.
  • Typical Use Cases: Condition monitoring of engines and industrial machinery.
• ICP:
  • Applications: Broad range, including environmental analysis, metallurgy, pharmaceuticals, food safety, and lubricants.
  • Typical Use Cases: Detection and quantification of trace elements in various matrices.

Precision and Accuracy

• ERAOIL:
  • Precision: High precision with consistent results.
  • Accuracy: Accurate for routine oil analysis and monitoring.
• ICP:
  • Precision: Very high precision, capable of detecting parts per billion (ppb) levels.
  • Accuracy: Extremely accurate and reliable for trace element analysis.

Advantages

• ERAOIL:
  • Advantages: Quick analysis, low operating cost, minimal sample preparation.
  • Portable: Some models are designed to be portable and user-friendly.
• ICP:
  • Advantages: Extremely sensitive and accurate, can handle complex matrices, multi-element analysis.
  • Versatile: Suitable for a wide range of applications beyond just oil analysis.

Limitations

• ERAOIL:
  • Limitations: Primarily focused on oil and lubricants, not suitable for broader applications. It can’t analyze particles with more than 10 microns.
  • Element Range: Limited to specific elements relevant to oil analysis.
• ICP:
  • Limitations: Requires significant sample preparation, higher cost of operation, and more extensive training for operators. It can’t analyze particles with more than 4 microns.
  • Equipment: Generally more complex and less portable.

Cost and Maintenance

• ERAOIL:
  • Cost: Moderate initial investment, low operational cost.
  • Maintenance: Minimal maintenance required.
• ICP:
  • Cost: High initial investment, high operational cost.
  • Maintenance: Requires regular and extensive maintenance.

Summary

• ERAOIL is ideal for quick, on-site oil analysis with a focus on lubricants and wear metals.
• ICP offers high precision and versatility for trace element analysis across various applications but is more expensive and complex.

Conclusion

ERAOIL from Eralytics offers a different approach for oil analysis compared to ICP due to its quick and efficient analysis, cost-effectiveness, user-friendly operation, portability, and specific focus on oil analysis. While ICP provides extremely high precision, its complexity and cost make it less suitable for routine oil analysis. Problems associated with ICP usage are high initial and operational costs, significant sample preparation and a controlled laboratory environment requirement, extensive training requirement for operators, overkill precision for routine oil analysis needs, and inability to analyze particles with more than 4 microns. Therefore, for most oil analysis applications, particularly those focused on wear metals, contaminants, and additives in lubricants, ERAOIL is the optimal choice.

The newly engineered CuDDI (Copper Digital Detection Imaging) by VISAYA is an advanced copper corrosion detection system that sets a new standard in copper quality analysis for various industries. CuDDI is a state-of-the-art copper quality analysis device designed to deliver rapid and accurate measurements of corrosivity in oil or petroleum products. Utilizing a high-resolution camera with optical intelligence, CuDDI identifies exact levels of corrosivity through an automated vision algorithm and classification process. Results are digitally recorded using software to ensure that it is precise and the process is easily repeatable.

Key Features and Benefits

Higher Precision and Elimination of Bias: CuDDI’s design eliminates guesswork and operator bias by automating the detection process. The digital detection imaging is achieved through a vision algorithm that records, and shows an accurate corrosivity ratings in seconds as the outcome.

User-Friendly Operation:

• Easy-to-use interface and automated process
• High repeatability
• Data storage, USB and enhanced connectivity
• High resolution digital images, notes and graphs as results which can be shared easily
• Quick and reliable results
• Compact and robust design

Real-World Impact

CuDDI’s advanced optical detection technology significantly enhances the throughput and
reliability of corrosion testing in laboratories and industrial settings. By providing precise
monitoring of copper corrosion, CuDDI helps to prevent machinery damage, optimize
performance, and ensure regulatory compliance.

Industry Standards and Compliance

CuDDI adheres to multiple ASTM standards such as ASTM D130, ASTM D1838, and
ASTM D4048, making it a reliable tool for a wide range of petroleum products including
gasoline, diesel, and lubricants.

Applications Across Industries

CuDDI’s advanced technology is applicable across various industries, ensuring compliance
with industry standards and enhancing operational efficiency.

Refinery and Petrochemical Operations

• Provides accurate certification of finished products and fuel blending before distribution to meet specific quality standards and regulatory requirements.

Aviation Industry

• Performs jet fuel analysis to ensure fuel quality meets the standards for safety and performance.
• Test on fuels with contamination, to prevent potential maintenance and safety hazards.

Electrical and Power Generation Industries

• Monitors the condition of copper used in electrical systems to prevent corrosion-related failures.
• Ensures the integrity of copper components in transformers, and other electrical equipment.
• Helps in the quality assurance of high-voltage power lines and electrical substations by assessing the quality of copper conductors.

Oil and Gas Industry

• Assesses the corrosion rate of copper used in downhole and surface equipment to prevent failures and leaks.

Environmental Monitoring

• Analyzes the rate of copper degradation to assess their environmental impact.
• Helps industries comply with environmental regulations by providing accurate data on fuel properties and their impacts.

Research and Development

• Assists in the development and testing of new fuel formulations such as ethanol and biodiesel based fuels and their effects on copper products and to meet strict environmental regulations.

Automotive Industry

• Tests automotive fuel blends for corrosivity to ensure long-term engine performance and reliability.

Lubricant and Hydraulic Fluids Industry

• Ensures the quality of lubricants and hydraulic fluids used in various industrial applications by assessing their corrosive properties.
• Monitors the corrosivity of synthetic and mineral oils used in steam and gas turbines.

Are traditional viscometers and density meters limiting your lab’s efficiency and accuracy? The ERAVISC X brings a cutting-edge solution that integrates density and kinematic viscosity measurements into one compact, reliable unit. With faster results, improved usability, and versatile testing capabilities, this device is built to elevate your laboratory’s performance.

The ERAVISC X is designed to address common challenges in viscosity and density testing. Traditional methods can be time-consuming, inaccurate, inconsistent, and labor-intensive, requiring frequent cleaning, recalibration, and multiple devices to handle different sample types. This means increased costs and reduced efficiency.

The ERAVISC X changes the game with features like:

• Dual measurement capabilities: Simultaneously measure density and kinematic viscosity with high precision.
• Durability: With a viscosity chamber made of Hastelloy, the unit offers robust resistance to corrosion, making it ideal for testing any liquid sample.
• Efficiency: Obtain results in less than a minute with a throughput of up to 40 tests per hour.
• Ease of cleaning: Cleaning is simple, automated and efficient with recommended solvents (IPA, acetone, or toluene) for different sample types within about 2 minutes.
• Wide operating range: Measure viscosity from 1 to 1,000 mm²/s with an impressive accuracy of 0.8% and repeatability of 0.25%. The temperature range spans 7.5 to 100 ºC, with accuracy as precise as 0.02 ºC.

Why Choose ERAVISC X?

Compared to other viscometers, the ERAVISC X stands out for its speed, lightweight design, and affordability. It simplifies calibration, accommodates testing at two different temperatures, and provides faster, easier cleaning, making it ideal for labs looking to maximize efficiency without compromising on quality.

Key Benefits:

• Speed: Perform up to 40 tests per hour.
• Cost-effectiveness: Minimize operational time and costs.
• Flexibility: Conduct API viscosity measurements at various temperatures and handle a wide range of sample types and temperature with ease.
• Design: Compact and portable design optimizes lab space and workflow.

The ERAVISC X is the smart choice for modern labs seeking a versatile, high-performance alternative to conventional equipment. Whether you’re handling oil-based or water-based samples, testing corrosive substances, or aiming to reduce testing turnaround times, this unit delivers unmatched reliability and simplicity.

Transform your laboratory efficiency today!

Discover the benefits of ERAVISC X and achieve unparalleled precision, productivity, and cost savings.

Introduction

An in-service lubricant encounters a myriad of factors that can cause or catalyze chemical changes in the oil. This alteration of the oil’s chemical makeup subsequently affects the lubricant’s ability to do its job.

Oxidation is an inevitable yet undesirable series of chemical reactions that causes an oil’s quality and value to degrade over time. Lubricants lack immortality primarily due to the oxidative process which leads to the reduction of the oil’s ability to properly protect against friction. The oxidation process plays a major role in the alteration of the lubricant’s chemistry and ultimately results in impaired physical and chemical properties of the base oil.

This process causes the viscosity to increase and thicken largely due to sludge formation, buildup of acids that catalyze corrosion and decrease demulsibility, and formation of deposits that can block filters or stick to valves, all of which lead to the lubricant becoming unusable.

Oxidation Chemistry

On its surface, oxidation can be defined chemically as the addition of an electronegative atom, commonly oxygen, to a compound. Oxidation is paired with a reduction process of an inverse definition: the loss of oxygen. These two half reactions occur simultaneously and that is where RedOx chemistry originates.

Oxidizing agents transfer an electronegative atom to another species in a chemical reaction. The transferred atom is most commonly oxygen because it is abundant in nature and has a high electronegativity. Electronegativity describes the chemical capability of an atom to attract electrons to fill out their valence electron shell. It is mostly affected by the amount of- and distance from- the nuclei its valence electrons exist. The oxidation number assigned to an atom is the amount of electrons that are lost or gained by that atom. This representative state is related to electronegativity and describes an atom’s oxidizing power. The sum of oxidation numbers in a neutral compound is zero. Oxygen with the second highest electronegativity on the periodic table has an oxidation number of negative two, indicating its strong oxidizing power.

Oxidation of oil usually occurs due to the presence of oxygen found in the air. The air reacts with the hydrocarbons found in the base oil of the lubricant to ultimately produce undesirable products like acids and polymers. The hydrocarbon-based lubricant is oxidized to form the acids and polymers. Carboxylic acids are an example of a byproduct that, if allowed to congregate, will disrupt machinery and cause severe corrosion of the systems. The formation of heavy molecular weight polymers is another example of an oil-oxidized product that leads to insoluble sludge, which can clog filters and valve systems.

Steps of Oxidation

Destructive oxidation is a cyclical, free-radical-driven process. If the cycle is left uninhibited, it will continually oxidize until the oil is utterly unusable.

This cycle consists of three major stages: initiation, propagation, and termination.

Initiation

The initiation phase revolves around the production of free radicals. These are highly reactive molecules due to their unpaired electrons which induce chemical instability. They aggressively seek out another molecule to react with in order to stabilize their own valence electron shell.

Free radicals by definition are reactive molecular species that contain at least one unpaired electron in their atomic nucleus shells and are able to exist independently. This first stage entails the mechanisms by which these free radicals are formed.

The lubricant composed of a base oil and additives undergoes some sort of reaction that initializes the oxidation process. The weaker areas in hydrocarbons react with some kind of oxidizer that forms these free radicals. The majority of refined hydrocarbon oils are mostly saturated, but persisting carbon-carbon double bonds become the targets for oxidizers. This is because strong oxidizers can more easily access the electrons in unsaturated sections making these double bonds more susceptible to attack from electrophilic molecules.

Examples of these reactants and catalysts include:

1. Elemental Oxygen
   
   Oxygen is the most notable reactant because it is the titular oxidizing agent. Atomic oxygen is critical in radical reactions at every stage so the oxygen found in the air as diatomic oxygen or ozone, or even the oxygen within water or other molecules can catalyze the oxidation sequence.
2. Nitro-oxides
   
   Nitrous-, nitric-, and nitrogen-dioxide are also notable prooxidants similar to oxygen. These oxidizing agents share similar oxidizing power but have lower electronegativities than elemental forms like diatomic oxygen and ozone.
   
3. High Temperatures
   
   The temperature also plays a critical role in catalysis. Like most reactions, elevated temperature promotes catalytic activity. Temperature also exponentially increases oxidation rates and studies have shown that the rate of oxidation can double for every 10°C increase in operation temperature above 82°C depending on which type of oil is used. Paired with other catalysts, the effects can be multiplied.
   
4. Shear Stress
   
   Pressure is also a common factor in catalyzing chemical reactions. This happens because of the kinetic conversion from mechanical energy into thermal energy. This is a direct result of friction; the very thing the lubricant is working to diminish.
5. UV Light
   
   High energy radiation from sources like sunlight initiates the formation of free radicals because it induces the formation of more unstable molecules via the excitement of electrons. This instability allows the chemical bonds to break more easily because of the pre-excited state the electrons are already in.
   
6. Wear Metals
   
   Ions found in transition metals like iron, chromium, copper, and cobalt can also accelerate oxidation because they too can act as oxidizing agents and interact in other ways with oil chemistry. Oxidation not only can create wear debris, but these worn metals can cycle back and promote further initiation.

A chain initiation step induced by or incorporating these reactants and catalysts involves dehydrogenating an alkane molecule and breaking a carbon-to-carbon bond forming alkyl radicals (•R). The stability of the radicals themselves is directly determined by the strength of the carbon-to-hydrogen bond in which it was derived. Tertiary hydrogens and alpha hydrogens in aromatic hydrocarbons are the most vulnerable to oxidation. This means the arrangement of radical stability is benzylic, which is more stable than allylic, then tertiary, secondary, and primary, with phenylic radicals being the least stable form.

Even whilst the free radicals progress to the second stage, further initiations of the oxidation sequence may continue.

Propagation

Due to the unstable and reactive nature of free radicals as a result of the unpaired electrons, once they form, they immediately react again and again. This propagation phase further establishes the presence of free radicals. The original free radicals propagate the process by reacting with more hydrocarbons and free or dissolved oxygen to form more free radicals and oxygenated compounds.

Oxygenated products like aldehydes, alcohols, ketones, and water form as a byproduct of several chain reactions of radicals and hydrocarbons. Alkoxyl and hydroxyl radicals are a species of free radicals in which they are highly reactive structural frameworks with localized radicals on the oxygen atom. The oxygen radical is bound to an alkyl group or hydrogen respectively and these radicals are nonselective, electrophilic, and oxygen-centered. Alkoxyl and hydroxyl radicals have a high bond dissociation free energy and alkoxyl radicals have weaker aliphatic C–H bonds which makes them highly oxidizing. Peroxyl radicals are more stable and occur when molecular oxygen reacts with carbon-centered radicals. Both are radical reactive oxygen species (ROS) and play major roles in oil oxidation.

Free Radical Mechanisms

Alkoxyl, hydroxyl, and peroxyl radicals are nonselective oxidizers and some of the most notable reactive oxygen species (ROS). These radicals can be formed by a direct reaction of oxygen with alkyl radicals (•R), the decomposition of alkyl peroxides (ROOH) into peroxyl (•OOR), alkoxyl (•OR), and/or hydroxyl (•OH) radicals, and even irradiation by UV light or the presence of transition metal ions can cause hemolysis of peroxides to produce these radicals.

Once formed, the alkyl radicals react quickly with a prooxidant and form peroxyl radicals. Once the peroxyl radical is formed, it abstracts a hydrogen atom from a hydrocarbon molecule and propagates the branching mechanism by generating another alkyl radical and hydroperoxide (HOOR). Peroxides are common examples of non-radical reactive oxygen species (ROS). This hydroperoxide, under suitable catalytic conditions as mentioned above, especially elevated temperatures, generates hydroxyl and alkoxyl radicals. These oxygen-containing radicals are then able to react with another hydrocarbon molecule to generate another alkyl radical and water (H₂O) or alcohols (ROH).

These radicals can be produced via a variety of specific mechanisms:

• Hydrogen Abstraction
  The hydrogen atom transfer (HAT) reaction is straightforward and occurs when a hydrogen atom is abstracted from a substrate like a hydrocarbon chain. The abstractor is often a free radical itself like peroxyl and produces alkoxyl radicals and this reaction is a critical component of oxidative propagation.
• Homolytic Scission
  Alkoxyl radicals are also the primary homolytic scission products of organic peroxides, nitrates, nitrites, hyponitrites, and hypohalites. Homolytic scission, also known as homolytic fission, hemolysis, or radical fission, occurs when a molecular bond is split and each half retains one of the original bonded electrons producing two free radicals. An example of this is when peroxides are split into alkoxyl radicals.
• Peroxyl Dimerization
  The dimerization of two peroxyl radicals produces alkoxyl radicals and peroxides (ROOR). With four oxygen atoms, only two can stabilize into a peroxide with the other two still unstable as radicals.
  These peroxyl radicals also participate in the peroxyl radical addition (PRA) reaction. The PRA reaction occurs when a peroxyl radical adds to a carbon-to-carbon double bond and subsequently can form more free radicals via peroxide bond scission (releases an alkoxyl radical) and simply reacts again with molecular oxygen (forms another peroxyl radical).
• One-Electron Reduction (OER)
  
  A process that involves the transfer of one or two electrons from a donor to an organic substrate. An electron transfer in OER can occur from a variety of donors like neutral organic substrates and electron-rich olefins, but to form alkoxyl radicals, a transition metal commonly acts as the donor. An OER of O₂ produces a superoxide anion radical (O₂•^–) which can undergo another OER paired with protons (H⁺) or two HAT reactions to form hydrogen peroxide, and another OER with a proton/HAT reaction can form a hydroxyl radical.
• Fenton Reaction
  
  This is a metal-catalyzed one electron reduction reaction in which a ferrous ion (Fe²⁺) is oxidized by hydrogen peroxide (H₂O₂) to form a ferric ion (Fe³⁺), hydroxide ion (OH^–), and hydroxyl free radical.
  In the presence of another hydrogen peroxide molecule (H₂O₂), the ferrous ion (Fe²⁺) is regenerated alongside a hydroperoxyl free radical (•OOH) and a proton, and the free radical production cycle is propagated.

In many of these cases, the product of one radical-forming reaction is a substrate of another reaction thus propagating the radical formation process in oxidation.

Termination

Oxidation can proceed either unfavorably or favorably. Oxidation proceeds unfavorably when the oxygenated compounds continue to react with the hydrocarbons and oxygen. Oxidation may also terminate favorably when the free radicals are stabilized. This termination usually occurs via chain-breaking antioxidants which effectively halt propagation by reacting with and stabilizing the radicals produced previously into inert byproducts.

Polycondensation and Polymerization

The unfavorable procession of oil oxidation occurs when oxygenated compounds like ketones continue reacting to form organic acids and heavy polymer products. High temperatures drastically increase this procession. This unfavorable termination occurs largely through polymerization and polycondensation processes.

Aldehydes and other oxygenated compounds are oxidized further to form things like esters and carboxylic acids. Polymerization occurs when monomeric units link in addition reactions to form larger and larger products without the release of a smaller molecule. Polycondensation also results in a heavy polymer chain but reaches this product via the reaction of monomeric units’ functional groups in condensation reactions.

This increase in the molecular weight of compounds leads directly to the production of insoluble sludge and varnish deposits. Besides the formation of insoluble products, oxidized oil products also produce organic acids, and these alongside water corrosively attack the surfaces of the oil container.

The ultimate result of oxidation can be summarized to lead to the production of deposits, varnish, and sludge as well as increased oil viscosity on top of system corrosion by acids and water. These processes completely alter the original integrity of the oil producing a product entirely deficient in the characteristics that the lubricant was originally intended for.

Antioxidants

However, lubricants are designed with oxidation in mind and manufacturers incorporate antioxidants as a strategic first line of defense. Antioxidants (AOs) are additives that prolong the life of base oils by increasing their resistance to oxidation and improving thermal stability. Mechanical stress, heat, and gasses catalyze hydrocarbon molecules found in the lubricants to break down and form radicals that react with oxygen. Still, antioxidants help eliminate these radicals and prevent this breakdown.

Antioxidants work as a sacrificial unit that will readily oxidize before the components of the base oil and it is the only substantial protection warding off premature failure of the lubricant. They are organic compounds typically containing nitrogen, sulfur, phosphorus, and even metals. The inert byproducts produced by antioxidants to terminate oxidation favorably can take the form of things like water and alcohols.

Some common antioxidants include sterically hindered phenols, semicarbazide and thiosemicarbazide, and phenolic or aromatic amines.

Two major types of antioxidants exist: primary and secondary AOs.

1. Primary AOs
   Primary AOs act as scavengers seeking out free radicals. They react quickly and stabilize radicals formed in the first two phases of oxidation; this drastically slows the degradation of the oil. These types of AOs break the chain of oxidation by donating hydrogen to free radicals which generate a resonance-stabilized compound. The donation of a labile hydrogen produces a stable hydroperoxide and these AOs form byproducts like water and alcohols.

   Sterically hindered phenols and some arylamines are typical types of primary AOs.

2. SecondaryAOs
   Secondary AOs act as hydroperoxide decomposers produced by the primary AOs. These AOs react with peroxides to inhibit the cycle and branching effects of propagation. They react with and convert peroxides into nonreactive, stable nonradicals.

   Phosphites and sulfur-containing compounds like thioesters and thioethers are examples of secondary AOs.

   Metal deactivators are also important in deactivating metal ions mechanized by oxidation. They operate by binding to metal ions that propagate the oxidation reactions, thus preventing these metal ion-catalyzed oxidation reactions.

Limitations of AOs

Although antioxidants are necessary for lubricant formulation, it is important to note that they do not stop oxidation, but rather delay it. They also have limitations that determine the extent in which they can effectively delay oil oxidation.

Primary AOs function best at temperatures below 93°C, but lose efficacy at higher temperatures. At lower temperatures, metal deactivators cannot work efficiently, but function better at higher temperatures when metal catalysis becomes more prominent. Phenols are also known to deplete early in the lubricant’s lifetime. Amines are known to be slow to start preventative maintenance, but last longer than phenolic AOs.

Antioxidants can also interact with other additives like anti-wear additives in the lubricant formulation. They particularly interact negatively with additives containing heavy metals. For example, zinc dialkyldithiophosphate (ZDDP) is one such additive that is affected by AOs. The AOs interact with the phosphate moieties which lessens the adherence ability of ZDDP and ultimately decreases its anti-wear effectiveness. These types of inverse interactions become more important at elevated temperatures and pressures where anti-wear capabilities are even more important.

The actual lifetime of a lubricant is entirely dependent on the lifetime of effective antioxidants. Once AOs are depleted past a point of effectiveness, the lubricant drastically loses its lubricity. The timeline for AO depletion and thus lubricant lifetime varies largely due to the factors that can speed up or slow down the usefulness of AOs like temperature, pressure, and contaminants.

Considering the limitations of certain antioxidants under specific conditions, finding the right balance of additives is incredibly important in lubricant formulation. Formulations are developed with these limitations and interactions in mind, masking each additive type’s weaknesses and maximizing their effectiveness.

Lubricant Composition Monitoring

A lubricant’s expected versus actual service life drastically differs, largely due to the catalysts and frequency in which the oil operates. Properly and regularly analyzing the chemical and physical makeup of the oil is essential to accurately determining the state of the lubricant.

There are a plethora of base oil formulations with an even wider range of additives that can be combined to make the lubricant. Understanding the composition of the lubricant when choosing which formulation to use is essential before, during, and even after use. Ensuring the lubricant is designed for the operations-specific variables in which it will be used is critical. Using a lubricant not designed for the job at hand will usually result in expedited oxidation amongst a variety of other issues, like increased acidity which leads to corrosion and decreased overall lubricity.

A variety of tests are used to qualify and quantify the decomposition of lubricant.

Color

The easiest, but least reliable analysis technique is to simply look at the oil’s color. Oils will darken as they are in use due to heat, contaminants, and oxidation. This is due to the generation of chromophores and auxochromes.

Chromophores are molecules or moieties within the chemical structure that absorb particular wavelengths of visible light (400-700 nm) in the electromagnetic spectrum. For color to exist (to humans) an object has to reflect wavelengths of light within the visible light spectrum. This is only possible when a molecule absorbs visible light, has at least one chromophore, and has a conjugated system. A conjugated system is a chemical structure of alternating single and double bonds that allow for the delocalization of electrons – necessary for light absorption through the allotment of charged lattice distortions. Due to the structure of oils typically being long chains of hydrocarbons with double bonds strewn within the structure, most oils have active chromophores, giving them the yellowish hue in which they are often associated.

An auxochrome is a functional group that attaches to a chromophore which enhances the chromophore’s ability to absorb light at certain wavelengths. This supplement intensifies the color production often by extending the conjugated system via electron donation. Examples of common auxochromes include hydroxyl, amino, and carboxyl groups. As mentioned above, hydroxyl and carboxyl groups are ubiquitous oxidation products, and as more of these auxochromes are generated, the light yellowish tint intensifies into caramels and inevitably into dark browns. For example, when mechanics check the oil on a car’s dipstick, the color gives them insight into the health of the lubricant.

There are also analytical techniques that are much more accurate and comprehensive than simple qualification by eyesight. Because oxidation is generally a slow reaction accelerated primarily by heat and produces undesirable byproducts, a common approach is to measure the byproducts to analyze the stage of health of the lubricant. A classic way oxidation of an oil can be tracked is by measuring the amount of weak acids present in the oil over time. Both free radicals and the long-chain polymers produced as end-products are acidic so this test is reliable as long as a baseline value is available. This is known as the Total Acid Number (TAN) and the TAN will increase as oxidation progresses. There are a few ways to determine TAN.

Titration

Titration operates by mechanizing the pH scale (0-14). The low end of the scale indicates a sample is highly acidic whereas the upper limit indicates greater alkalinity, and a value of 7 describes neutrality. As acidic byproducts accumulate due to the oxidation cycle, the pH will slowly become more acidic. Tracking this descent of the pH value over time provides information on the extent to which a lubricant has been oxidized. However, it is important to note, that acids can form from other pathways and may also preexist depending on the oil formulation.

To perform a titration, a weighted amount of oil is mixed with a titration solution and is then titrated with alcoholic potassium hydroxide (KOH) to determine the acid number. This value is determined by adding a known concentration of KOH, which is a strong base to the oil until the acid is neutralized. The amount of base used to neutralize the acid is then used to calculate the TAN value.

A similar approach using a strong acid like hydrochloric acid (HCL) titrated into an oil sample can help determine the Total Base Number (TBN) which can be useful for determining the concentration of components able to neutralize acidic byproducts thus extending the lubricant’s life.

Spectroscopy is another analytical tool to measure TAN and oxidative progression. It is the study of how matter interacts with radiated energy and spectroscopic analyses are used in a wide variety of industries. Infrared (IR) spectroscopy passes infrared light (780 nm – 1 mm) through a sample to determine the chemical composition. The IR light provides enough energy to vibrate the bonds within a sample and use it to determine the chemical structure. IR light is used because it has a lower energy level than visible light, allowing it to excite molecular vibrations without causing an electron to transition from one energy level to another. This makes it ideal for determining functional groups by analyzing their unique vibrational frequencies. For example, the resulting spectrum of a molecule with several different types of bonds like alkanes (C_nH_2n+2) and carbonyls (C=O), will depict at least two different absorption bands. The quantifiable absorption denoting the intensity of the peak is described by the Beer-Lambert law which states the IR absorbed is proportional to the concentration of the absorption species and the distance the IR light has to travel. Thus these vibrational frequencies appear as distinct peaks with measurable intensity on an IR spectrum which allows for the identification and quantification of these molecules. There are two main spectroscopic techniques used to analyze oil oxidation of lubricants.

Dispersive Spectroscopy

Dispersive IR spectroscopy is the more traditional method used to measure samples. In this type of analysis, an IR light is shone onto a diffraction grating, which separates the light by its respective wavelength. The angle of the light is directly related to the wavelength of the light as it exits the grating. Once the IR beam is separated by wavelength, a slit is used to isolate a singular wavelength of IR light. The monochromatic beam is then directed to the sample and the absorbance is measured. The diffraction grating angle is then altered to isolate a different wavelength and the absorbance of that wavelength is measured. This process is repeated for every wavelength. The resulting data is then plotted to produce an IR spectrum.

Interferometric Spectroscopy

A newer and faster method, called Fourier-Transform IR spectroscopy (FT-IR) uses a different approach to produce an IR spectrum. In this method, an interferometer is used to induce IR interference with itself. Light of any wavelength travels in sinusoidal waves with peaks and troughs. The location of these peaks and troughs describes the phase of the wave. Waves with different phases have what is called a phase difference. This phase difference dictates how the two waves will interact and this is known as the interference.

An interferometer measures these interferences. The IR light is directed to a beam splitter which dissects the beam into two, which each go to two mirrors (one stationary and one adjustable), and subsequently bounce back to recombine and interact with the sample for detection. The phase difference is adjusted by moving one of the mirrors which results in a different interference pattern. This difference in interference pattern generates different wavelengths in each recombined beam. The resulting data is plotted in an interferogram.

An interferogram shows how strongly the sample absorbs IR light as a function of the position of the adjustable mirror. This is known as the wavenumber (cm^-1): the number of full waves of a particular wavelength per centimeter of length. To produce a spectrum from the interferogram, this data needs to be converted to show how strongly the sample absorbs each frequency of light. This is possible because wavenumbers are directly related to energy levels. A mathematical model called the Fourier-Transform converts this data. It does this by taking the data from wave interference with different frequencies and extracts the frequencies of the original waves. This produces the familiar IR spectrum showing frequency absorption.These IR spectra indicate oxidation by showing peaks in the 1800-1670 cm^-1 carbonyl (C=O) region which is typically inactive in new lubricants. This is indicative of oxidation because oils are primarily made up of carbon and hydrogen. Hence, the presence of molecular oxygen means chemical processes have occurred to introduce oxygen to the lubricant. These peaks can thus be inferred to be the result of oxidation, and evidence can be given describing the extent of oxidation more extensively than just TAN.

An IR spectrum is also advantageous over titration because it can provide even more information. For example, 600-2000 cm-1 peaks can indicate additives still present in the oil. The presence of nitration products (NO, NO₂, and N₂O₄) is also useful in analyzing degradation progress because nitro-oxides are also prooxidants. These nitro-oxides have a characteristic absorbance just below that of carbonyl products (1650-1600 cm^-1). Sulfation products can also indicate degradation and these products are the culprits of the foul smell associated with bad oil. Sulfur is not typically found in lubricant formulations, but it is found in crude oils and may be introduced as additives in fuel or lubricants themselves. Therefore it is not uncommon for sulfur compounds to contaminate or preexist in lubricating oils, and these molecules will also catalyze degradation to produce sulfur di- and tri-oxide (SO₂ and SO₃). These compounds can also interact with water generated from other byproducts like peroxides to form strong acids like sulfuric acid (H₂SO₄). These degradation products generate peaks between 1180-1120 cm^-1. Both nitration and sulfation products in oil are codegradants to oxidation and give insight into the level of degradation of the oil.

Oil and lubricant systems can be monitored by a variety of other techniques as well. These four analytical techniques are some of the most commonly used monitoring systems.

New Research

Lubricants exist extensively across nearly every industry in some fashion. With the considerable need for lubricating oils, research into extending lubricant lifetimes is a hot topic being investigated worldwide. Some of these research groups are searching for alternatives to petroleum-based lubricants, some are developing new additives for antioxidation and anti-wear amongst other properties, and others are seeking ways to limit the need to replace or even use lubricants in certain systems.

A group based in China (Song, et al. 2024) recently published their ester-based oil anti-aging research on alkylated diphenylamine antioxidant molecular modeling simulations. The group aims to provide a molecular theoretical basis for lubricant oxidation. They combined molecular simulation with experimental methods to determine the anti-aging molecular basis of 4,4′-dimethyldiphenylamine (DMDPA), 4,4′-dioctyldiphenylamine (ODA), and 4,4′-dinonyldiphenylamine (T558) antioxidant activity. They investigated these diphenylamines’ mobility, activity, and diatomic oxygen migration. The molecular simulation results determined that the T558 antioxidant displays better physical resistance to oxidative stress. The experimental results corroborated these simulation results and showed that T558 exhibited better antioxidant properties due to its larger relative molecular mass and longer amine para-alkyl chain. Molecular modeling paired with supportive experimental analyses may be able to determine formulation parameters of lubricants in the future more effectively.

Another interesting recent publication on inerting lubricant systems could provide insight into alternative enclosed operational designs to limit or even eradicate oxidation. The idea to operate a system utilizing a lubricant in an inert atmosphere to limit oxidation was proposed in the 1960s, but without proper technology, this concept was revisited only recently. The results indicate that without the presence of oxygen, oxidative degradation can be severely diminished. Blanketing the operation system in nitrogen could extend the life of in-service lubricants. However, system engineering presents a feasibility problem and more research needs to be done in order to determine the applicability of this project to current systems.

Summary

Lubricants are constantly under attack by oxidizers, but the addition of protective antioxidants helps prolong the life of in-service oils. Molecular oxygen and nitro oxides, contaminants and wear metals, pressure and shear stress, high energy photons including UV light, and notably temperature work in conjunction to expedite the oxidative process of oil. After the process is initiated and free radicals form, the immediate products propagate the cycle, leading to the eventual termination of the cycle only delayed by additives that, once depleted, inevitably signify the end of a lubricant’s lifecycle. The lubricant loses the physical and chemical properties in which it was designed as the oxidative process moves along. The generation of acidic products leads to alterations in the viscosity and lubricity, and the production of heavy molecular weight polymers produces sludge and varnish that disrupt machinery, ultimately inducing clogs and corrosion in the operational system. Composition monitoring of the oil is increasingly important to determine its degree of degradation. It can be done in a variety of ways like visually by analyzing color, chemically by analyzing the acid number, or molecularly by using spectroscopic methods to analyze the overall molecular makeup. New research is constantly being conducted to develop new monitoring methods, manufacture higher-efficiency antioxidants and formulations, and even model new oxidation-inhibiting systems. Oxidative degradation is inevitable in oil systems exposed to the atmosphere, but efforts to understand and diminish its effect on lubricant systems will always be a relevant topic of discussion and research.

[Figure 1] Hydrogen Sulfide.
Figure 1 is displaying carbon dioxide and hydrogen sulfide in their molecular form.

Foamability also increases due to a variety of other contaminants such as suspended solid particles like iron sulfide and dust, and thermal and oxidative degradation of the amine.

[Figure 2] Contractor/Absorber example.
Figure 2 shows an example of a gas-sweetening contractor. Sour, hydrogen sulfide-contaminated natural gas enters the abstractor near the bottom; while lean amine enters near the top. As the liquid amine travels down the column and the sour gas travels up, the amine abstracts the hydrogen sulfide which produces sweet gas leaving the contactor at the top and rich amine now containing the hydrogen sulfide exits at the bottom.

Foam mitigation is a critical parameter when concocting a lean amine solution to act as the acid extractor in natural gas contactors. Alkanol amines are the most common solutions in these lean amine solutions and these solutions are often specifically designed for the operation parameters of the system. Numerous studies all over the world are currently aiming to identify other compounds that can counteract surfactant contamination.

Antifoam agents are often introduced to aid in foam breakage inside gas sweetening systems, but with it comes a distinctive paradox: while adding antifoam in small quantities decreases foam formation, at higher quantities it actually catalyzes more foam formation.

Foamability and stability testing gives operators a reliable idea of the foaming tendency and retention in the contactor for various amine solutions.

Visaya’s fully automated Foam Digital Detection Imaging™ (FoamDDI) system accurately and reliably automates foam testing to diagnose and differentiate high and low foam amine solutions without implementing them into the operation stream or undergoing manual analyses that have been proven to have extensive operator bias.

[Figure 3] Results screen of the FoamDDI
Figure 3 is showing the results screen displayed following an analysis.

The protocol is designed using the ASTM D892 method as a blueprint. After designating parameters for the test, the sample is heated accordingly, and once stable, controlled air is introduced via a diffuser and the foam generation is recorded through its collapse after airflow is stopped.

In the manual protocol, the operator is required to turn on and off the airflow, visually record the height, and then determine the time it takes for the foam to collapse. With such a dynamic characteristic as foamability, operator bias and the myriad of variables affecting data collection often lead to inconsistent and unreliable results.

The FoamDDI device eliminates user bias by mechanizing Visaya’s augmented vision system which operates with invaluable edge contrast precision to determine foam height and stability. The automation allows the operator to run up to four analyses asynchronously and unattended with the addition of up to four modules per logic box. The device provides photo and video records of the entire test to be analyzed manually following the procedure, and even has a manual override option denoted by an O on the results screen in the rare case the edge is not easily identified by the device.

With the FoamDDI’s newly added amine application calibration, gas-sweetening amine solution analysis has never been easier and more reliable.

Categories of Elements:

     Wear Metal: Metal elements originating from expected wear and tear of the system.

     Contaminant: Exogenous elements introduced into the formulation from external sources.

     Additive: Intentional elements added to formulations for protective or performance-enhancing properties.

Note: The categorical delineation of elements is relative to the specific formulation and application. Elements commonly belong to one category but may fall into another under certain conditions.

LUBRICANT

FUEL

COOLANT

Part 1 – General Information on the Field

The Bakken Formation is one of the most significant oil-producing regions in North America, located primarily in North Dakota, Montana, and extending into parts of Canada (Saskatchewan and Manitoba). It is a vast underground rock formation rich in shale oil and has played a major role in the U.S. energy market expansion. In this report, the size, importance, recent development, process stages and the related companies are discussed. The companies mentioned in this report are those that appeared on the search and there could be other companies involved in the development of this field and missed in this report.

Figure 1: Williston Basin overview showing the size of the layer; Bakken shale update 2024 (rextag.com)

Size and Production

• Area: The Bakken Formation spans about 200,000 square miles (520,000 km²).
• Reserves: The U.S. Geological Survey (USGS) estimates 4.3 to 11.4 billion barrels of recoverable oil using current technology.
• Production: At its peak, Bakken contributed over 1 million barrels per day (bpd), making North Dakota the second-largest oil-producing state in the U.S. after Texas.
• Depth & Thickness: Oil-bearing rock layers are about 10,000 feet (3,000 meters) deep and 35 to 50 feet thick.

Figure 2: Continental’s wells, showing the oil production activity in this region (rextag.com)

Top players

These are the big companies with the right to produce oil and gas within this region.

• Continental Resources
• Exxon Mobil and ConocoPhillips
• Hess (Chevron acquiring it)
• Energy Transfer
• Enbridge
• ONEOK

Importance

1. Major Contributor to US Energy Independence: The Bakken helped the U.S. reduce reliance on foreign oil imports and contributed significantly to the shale oil revolution.
2. Economic Impact: The boom in Bakken oil led to a population and job surge in North Dakota, creating a robust local economy with high wages and rapid infrastructure growth.
3. Technological Advancements: The field demonstrated the effectiveness of hydraulic fracturing (fracking) and horizontal drilling, which later expanded to other U.S. shale plays.
4. Geopolitical Influence: Increased U.S. oil production from fields like Bakken has impacted global oil markets, reducing OPEC’s control over oil prices.
5. Environmental Concerns: Fracking and oil transport (pipelines and rail) have raised environmental and safety concerns, including groundwater contamination, flaring, and methane emissions.

Previous forecast on increasing production:

2025 Update

There is an article (link published in 2025) discussing the discovery of a new reservoir segment in the Bakken shale that will increase the production. In another article (link) it is shown that the production increased in 2024 and the field still has the potential to be a key player in the market. The reason for this increment was some IOR and EOR techniques that improved the production. Now it produces around 10% of total oil in the US (others are 55% permian Texas and New Mexico, 5% Alaska, 5% Colorado, 5$ Oklahoma, …).

In January 2024, North Dakota’s Oil & Gas Division reported a total oil production of over 34 million barrels, with an average daily output reaching about 1.1 million barrels across 18,674 producing oil wells. The month also saw significant drilling activity, including the start of 76 new wells, the extension of 76 others, and the completion of 108 workovers, all supported by 38 operational drilling rigs.

In February 2024, Chord Energy announced it would acquire Enerplus Corp. for nearly $4 billion in a combination of stock and cash, aiming to become the largest producer in the Williston Basin. The merger will result in an $11 billion operation in the basin, marking the end of Enerplus’s nearly two-decade-long presence in the Bakken, which started with its early investments in Montana’s horizontal shale formations.

The merged entity will operate as a leading company in the Williston Basin, controlling 1.3 million net acres with a combined production capacity of 287,000 barrels of oil equivalent per day (boe/d). Of this total production, about 100,000 barrels are from what used to be Enerplus’ production and it is added to the daily output for the acquirer. Crude oil will constitute 56% of the new company’s total production output.

Part 2 – Stages

This part of the report is arranged to discuss different stages of the crude oil’s journey from extraction, transportation, testing, refining, to lubricant production and the companies involved. ​

1. Extraction: The companies (listed alphabetically) operated in the Bakken and some of them are still active in that field: Apache Corporation, Arsenal Energy Inc., ConocoPhillips, Continental Resources, Earthstone Energy, Enerplus, EOG, Resources, ExxonMobil, Forestar Group, Halcon Resources, Hess, Kodiak Oil & Gas Corp, Linn Energy, Marathon Oil, MDU Resources Group, Inc., Newfield, Norstra Energy, Northern Oil & Gas Inc., Oasis, Occidental Petroleum (Oxy), Penn Virginia Corporation, Petro-Hunt, Petro-quest, Prima Exploration, Questar, Resolute Energy, Samson Resources, Slawson Exploration, SM Energy (St. Mary Land & Exploration), Statoil (Brigham), Triangle Petroleum, US Energy, Whiting Petroleum, WPX Energy, XTO, Yuma.
2. Transportation: Once extracted, the crude oil requires transportation to refineries. This is achieved through pipelines and rail systems.
   • Dakota Access Pipeline (DAPL): A 1,172-mile underground pipeline transporting crude oil from North Dakota to Illinois. It is operated by Dakota Access, LLC, a subsidiary of Energy Transfer Partners, with minority interests from Phillips 66, Enbridge, and Marathon Petroleum. You can find more information about DAPL in this link.
   • Double H Pipeline: A 462-mile pipeline carrying crude oil from North Dakota to Wyoming, owned by Kinder Morgan Inc. For more info on this pipeline refer to this link.
   • Rail Transport: Companies like Canadian Pacific Railway facilitate the movement of Bakken crude oil to various markets, especially when pipeline capacity is limited.
3. Testing and Inspection: Ensuring the quality and safety of the crude oil during transportation and before refining is crucial. This is a lab so we can check with them on the unit requirements:​
   • Intertek: Provides testing, inspection, sampling, and certification services in the Bakken region, supporting shale oil, natural gas, refining, and transportation operations. This is the link to their website discussing their activities related to the North Dakota region.
4. Refining: The transported crude oil is processed into various petroleum products at refineries. ​
   • Marathon Petroleum: Engages in refining operations and holds a minority interest in the Dakota Access Pipeline, linking it to Bakken crude supplies.
   • PBF Energy: Owns and operates multiple refineries across the U.S., including facilities in Delaware, New Jersey, Ohio, Louisiana, California, and Illinois, where Bakken crude is processed into fuels and lubricants.
5. Lubricant Manufacturing: Post-refining, specific companies specialize in producing lubricants. ​
   • Calumet Specialty Products Partners, L.P.: Manufactures lubricating oils, solvents, waxes, and other specialty products. They operate facilities in various locations, including Illinois and Louisiana.

Implementing an Oil Condition Monitoring (OCM) program isn’t just about diagnostics, but about unlocking measurable, recurring savings. Consider a single injection molding unit used by a recent client, the Injection Machine PT 350 3500 Kn, which requires approximately 410 liters of hydraulic oil per tank. At a representative cost of $5 per liter, one full oil change costs $2,050.

In a facility with eight similar machines, an initial oil investment of $16,400 is required. Assuming biannual oil changes, the annual operating cost for hydraulic oil alone is $32,800, or roughly $2,733.33 monthly.

If oil quality was measured and found to still be within operational parameters for just two additional months, the oil change interval could be extended. This shifts the cost from a 6-month interval to an 8-month interval, reducing the monthly cost to $2,050 and saving the company $8,200 annually. And this is from just one oil type, on just one process line.

Material and Tangible Value of OCM

Let’s look at other common industrial and commercial systems, where the value of OCM becomes even more pronounced:

Even modest savings can translate into thousands of dollars per year when scaled across fleets or production lines. Consider, large fleets of semi-trucks, how many elevators are in an urban hotel, or a large warehouse facility with rows and rows of production lines. Even the low-end annual savings above, when considering how many units are under operation in a single facility, can have massive effects in the long run.

Benefits of OCM

OCM selling points:

• Extended oil change intervals through real data, not guesswork.
• Early fault detection, preventing catastrophic equipment failure.
• Improved asset uptime by scheduling oil changes and maintenance only when needed.
• Reduced waste and environmental footprint, aligning with sustainability goals.

For example, if a wind farm with 10 turbines extended oil changes from 12 months to 18 months, they could save $44,167 per year ($26,500 → $17,667 × 10 turbines). That’s one dataset, in one facility.

Even conservative models show that routine implementation of OCM can save tens of thousands annually per facility. When extended across different oil types, systems, and industries the return on investment for OCM hardware, software, and analysis becomes undeniably compelling.

Expanded and Ergonomic Value of OCM

That’s without any predictive failure reduction or extended uptime. Just smarter scheduling.

These numbers only consider the tangible cost of the lubricating oil itself. In real operations, taking into account labor and equipment, the value of OCM skyrockets.

Extending oil change intervals decreases the labor associated with the process of changing the oil itself; especially, if the oil changing process is outsourced like cars/trucks going to an auto shop. For example, BlueLine Taxis has over 1000 cars in its fleet. Using a cheap provider for the oil change costing ~$40 per change and a biannual interval, the outsourced cost is over $80,000. Extending the oil change just one month decreases the cost per year to $68,571—an $11,429 annual saving.

Outside of the labor costs, the major savings are a result of preventing downtime of equipment. One machine going down in a facility can cost the company thousands upon thousands of dollars. A critical machine going down could result in the work coming to a standstill for prolonged periods, and the cost of repairing/replacing the unit drastically increases the bill. If electricity or cooling generators go down in a warehouse, operations may have to stop until working conditions are reinstated, costing the company yet again. If machines like elevators go down in a hotel or ski lifts go out on a mountain, all of a sudden you have guests that are frustrated and could feasibly demand money back, whilst likely not returning, costing even more money. Inconvenience breeds antagonism in industries catering to guests.

In mining operations, the typical cost of downtime alone is $130,000 per hour plus around $180,000 for repairs and replacements plus shipping and labor associated with critical equipment. Unaddressed machines that have recurrent issues are estimated to cost up to 10 billion USD.

The value of OCM is unparalleled, especially in large-scale operations across all industries. Considering the material oil costs, labor costs, replacements and repairs costs, and operational costs, the savings that OCM can provide are well worth the investment. Rather than blindly following off-based intervals, you could be making knowledgeable decisions and confidently saving thousands or even millions of dollars in the long run.