"The Impact of Varnish on Ester Oil: A Catalyst for Control Valve Failures and

Elevated Maintenance Expenditure"

-Mr.Ashutosh V Jain, Minimac Systems Private Ltd.

Ester fluids, commonly used in different engineering and hydraulic systems, can start to break down
when they come into contact with moisture. This breakdown, called hydrolysis, is made worse by
temperature changes and sometimes by oxidation. During hydrolysis, the parts connected to the main
phosphate molecule, known as phenyl groups, are gradually set free. These released phenyl groups
contribute to the creation of acidic substances that are quite similar to phosphoric acid. The level of
acidity of these substances changes depending on how many phenyl groups are lost. If all three phenyl
groups are lost, it results in the creation of a strong corrosive phosphoric acid.

The EH molecule, despite its overall stability, exhibits a hygroscopic nature, indicating a strong affinity
for absorbing moisture from the surrounding environment. This characteristic renders it susceptible to
degradation if not adequately monitored.

Fig.1 Structure of Neutral Phosphate Ester

Fig 2. Effect of moisture on EH Oil molecule.

Simplifying this, when the oil molecule encounters water molecules, as depicted in Figure 2, it
undergoes a series of reactions. Initially, upon contact with EH oil molecules, it forms a mono-hydrogen
molecule while releasing an OH molecule. With continued exposure to moisture, it eventually breaks
down further into dihydrogen, which behaves as a weak acid. However, as this process continues and
the molecule progressively interacts with moisture, it eventually decomposes to create phosphoric acid,
a highly potent and robust acid. As we know high acid strong acids are also chemically reactive and can
form metal soaps or salts, for example with components of the fuller’s earth or activated alumina
adsorption media and these are subsequently dissolved or dispersed in the fluid. As the soaps eventually
precipitate (e.g. in servo-valves) causing sticking and also promote foaming and air retention.

Varnish formation is a critical issue that can significantly impact the operational efficiency and longevity
of various mechanical systems, including pipelines, tanks, and servo valves. In the context of the specific
situation you described, varnish formation is accelerated due to the presence of the strong acid,
phosphoric acid, which results from the degradation of the hygroscopic oil molecule in the presence of
moisture. This phosphoric acid, being a strong acid, has a tendency to react with various components
within the system, leading to the formation of metal soaps or salts.

These compounds, when they precipitate, can cause sticking, leading to operational discrepancies such
as hindered movement of servo valves. Moreover, they can promote foaming and air retention, further
aggravate the issues. The consequences of varnish formation are not limited to operational
discrepancies; they extend to accelerated wear and tear of components, potentially leading to turbine
or valve failures. This, in turn, significantly impacts the overall maintenance time and costs, as well as
the power generation capacity of a thermal power plant.

To mitigate the adverse effects of varnish formation, it is crucial to implement effective measures to
control moisture levels and prevent the formation of strong acids. Employing appropriate filtration
techniques and utilizing additives that can neutralize or inhibit the formation of these acids can be
effective strategies.

To monitor the deterioration of the ester fluid, a common method involves measuring the changes in
acidity through a process called titration. This method, often performed using ASTM 947 guidelines,
helps determine the total acid number (TAN) of the fluid. It has been observed that when the acid
number rises above 0.2 mgKOH/g, the risk of encountering problems, particularly in EHC systems,
significantly increases.

Upon reviewing BALCO oil samples and conducting various tests, it became evident that the high
moisture content had prompted the oil to undergo hydrolysis, leading to a significant increase in acidity
well beyond the recommended limit of 0.2 mgKOH/gm. This spike in acidity has consequently
heightened the potential for varnish formation, a parameter that should ideally be maintained ΔE: <=15
at all times.
Additionally, the interaction of the heightened acidic nature with metal ions, originating from the wear
and tear of equipment, has been identified as the fundamental process driving varnish production.
Neglecting the management of varnish over an extended period allows it to accumulate and adhere to
the surfaces of tubes, tanks, and valves. This leads to blockages, disrupts the regular flow of oil, and
ultimately contributes to various valve failures, issues with valve actuation, and uneven oil heating.

To counteract these issues, it is imperative to develop a robust action plan. Initially, the focus should be
on reducing the overall moisture levels of the unit to less than 500 PPM. Subsequently, the oils need to
be treated with specific resins to lower their acidity to less than 0.2mg KOH/gm, alongside
comprehensive filtration to remove solid contaminants and varnish using specialized depth filters.

The action plan will unfold in the following manner: First, reducing the overall presence of moisture in
all its forms—free, dissolved, and emulsified—within the unit. Following this, the oil will undergo
filtration to eliminate solid contaminants using super fine filters thus making oil cleaner.
Simultaneously, the oil will be processed through de-varnishing depth filters which are a type of
polishing filter making the oil super fine with additionally passing the oil through extensively
researched and tested resins to lower the overall acidity. After completing these four critical steps—
Moisture Removal, TAN Reduction, NAS improvement, and Varnish Removal—the oil and the overall
control system will operate with greater efficacy and reliability.