REDUCTION OF SURFACE & SUB SURFACE OXIDE OF COPPER ROD

Oxidation kinetics of Copper:-

The oxidation kinetics of copper describes the rate at which copper reacts with oxygen
in the presence of various factors, such as temperature, pressure, humidity, and the presence
of impurities or catalysts. Copper oxidation can occur through various mechanisms, including
surface diffusion, oxide nucleation and growth, and oxidation-induced deformation.
At room temperature, the oxidation of copper is relatively slow and occurs through a
passive oxidation mechanism, in which a thin layer of copper oxide (CuO) forms on the surface
of the metal, protecting it from further oxidation. The growth of the oxide layer is influenced by
factors such as the oxygen concentration, relative humidity, and the presence of contaminants.
The formation of CuO is an exothermic reaction, and the rate of oxidation increases with
temperature, following an Arrhenius-like relationship.
At elevated temperatures, the oxidation of copper can occur through a more active
mechanism, in which oxygen diffuses into the bulk metal and forms subsurface oxide layers,
leading to a reduction in the mechanical properties of the metal. The oxidation kinetics of
copper at high temperatures can be influenced by factors such as the oxygen concentration,
temperature, and the presence of impurities, which can act as catalysts for the oxidation
reaction.
The kinetics of copper oxidation can be characterized using various experimental
techniques, including thermogravimetry, mass spectrometry, X-ray photoelectron
spectroscopy, and scanning electron microscopy. The study of the oxidation kinetics of copper
is essential in understanding the behavior and durability of copper-based materials used in
various applications, including electronics, corrosion-resistant coatings, and energy storage
devices.

Oxidation Laws of copper

There are different laws that describe the kinetics and rate of oxidation of materials, including
copper. Here are some of the most common ones:

The Law of Mass Action: The rate of a chemical reaction is proportional to the product
of the concentrations of the reactants raised to the power of their stoichiometric
coefficients. In the case of copper oxidation, this law can be expressed as:

Rate = k[Cu]^a[O2]^b

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where k is the rate constant, a and b are the orders of the reaction with respect to
copper and oxygen, respectively, and [Cu] and [O2] are the concentrations of copper
and oxygen, respectively.

Arrhenius Law: The rate of a chemical reaction increases with increasing temperature,
following the Arrhenius equation:
k = A exp(-Ea/RT)
where k is the rate constant, A is the pre-exponential factor, Ea is the activation energy,
R is the gas constant, and T is the temperature in Kelvin.
Parabolic Law: The rate of oxidation of a material decreases as the thickness of the
oxide layer increases, following the parabolic law:

dX/dt = k / (t + t0)^n

where dX/dt is the rate of oxide growth, k is the parabolic rate constant, t is time, t0 is
the incubation time, and n is a constant related to the oxide growth mechanism.

Wagner's Theory: This theory describes the oxidation kinetics of metals based on the
diffusion of ions through the oxide layer. According to this theory, the rate of oxidation
is proportional to the square of the thickness of the oxide layer, following the Wagner -
Schottky equation:

dX/dt = kD(O2) / X^2

where dX/dt is the rate of oxide growth, k is the rate constant, D(O2) is the diffusion
coefficient of oxygen in the oxide layer, and X is the thickness of the oxide layer.
The oxidation of copper follows the parabolic law, which states that the rate of
oxidation is proportional to the square root of the exposure time. This means that the
thickness of the oxide layer formed on copper increases with the square root of the
exposure time.

The parabolic law is a common oxidation law that describes the oxidation behavior of
many metals and alloys. It is derived from the assumption that the oxidation reaction is
controlled by the diffusion of oxygen through the oxide layer, and that the oxide layer
thickness increases parabolically with time due to the accumulation of diffusion-
generated vacancies at the oxide-metal interface.

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 In the case of copper, the parabolic law is a good approximation for the oxidation
behavior under many conditions, including ambient conditions. However, under certain
conditions, such as high-temperature oxidation, the oxidation of copper may follow a
different kinetic law, such as the linear or logarithmic law.
Understanding the laws of oxidation kinetics and rate of oxidation is essential in
predicting the behavior and durability of materials under different environmenta l
conditions and optimizing their performance in various applications.

How to Reduce Surface & Subsurface oxides ?

To reduce subsurface oxides and surface oxides of copper rod in the Contirod process, several
methods can be employed, including:

• Control of Oxygen Levels: One of the most effective ways to reduce subsurface and
surface oxides is to control the oxygen levels during the manufacturing process.The use
of an inert gas atmosphere such as nitrogen or argon can also help to reduce oxidation.
• Surface Treatment: Surface treatment techniques such as pickling, electro-polishing,
and chemical passivation can be used to remove surface oxides and improve the surface
quality of the copper rod. These treatments can also help to reduce the potential for
subsurface oxidation by removing contaminants that can act as catalysts for the
oxidation reaction.
• Optimization of Process Parameters: The Contirod process parameters such as casting
speed, cooling rate, and temperature can be optimized to minimize subsurface and
surface oxidation. For example, reducing the casting speed can improve the cooling rate
and reduce the potential for oxidation.
• Use of Protective Coatings: The use of protective coatings such as anti-oxidation
coatings or passivation layers can help to prevent oxidation and reduce the potential for
subsurface and surface oxides.
By implementing these methods, it is possible to reduce subsurface and surface oxides of
copper rod in the Contirod process and improve the quality and durability of the final product.

Are there any agents can be added to water which will reduce rate of oxidation
of a metal during cooling process?
Yes, there are agents that can be added to water to reduce the rate of oxidation of a
metal during the cooling process. One such agent is an antioxidant, which is a substance that
inhibits or prevents oxidation reactions.

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Examples of antioxidants that can be added to water to reduce the rate of oxidation of a metal
include:
At temperatures of 800 to 600 degrees Celsius, copper undergoes rapid oxidation and
can form a thick oxide layer on its surface. To reduce the rate of oxidation and the formation of
the oxide layer during cooling, antioxidants can be added to the cooling water or solution.
However, it is important to note that the use of antioxidants in cooling water or solution may
require specialized equipment and safety precautions due to the high temperatures involved.
Some examples of antioxidants for copper at these temperatures that can be added to cooling
water or solution include:

• Sodium benzoate: Sodium benzoate is a common antioxidant that can be added to

cooling water or solution to reduce the rate of oxidation of copper at high
temperatures.
• Sodium nitrate: Sodium nitrate can also be added to cooling water or solution to reduce
the rate of oxidation of copper at high temperatures.
• Sodium metabisulfite: Sodium metabisulfite can act as an antioxidant in cooling water
or solution by reducing the dissolved oxygen content, which can slow down the
oxidation of copper.
• Sodium hydroxide: Sodium hydroxide can also be added to cooling water or solution to
reduce the rate of oxidation of copper by increasing the pH and reducing the dissolved
oxygen content.
• EDTA: Ethylenediaminetetraacetic acid (EDTA) can act as a chelating agent in cooling
water or solution, which can help to reduce the rate of oxidation of copper by binding
with metal ions that can promote oxidation.
Again, it is important to note that the effectiveness of these antioxidants may vary depending
on the specific temperature and conditions of the cooling water or solution, as well as the
specific type and form of copper being used.

How increase in Ph will results in reducing the rate of oxidation of copper?

An increase in pH can result in reducing the rate of oxidation of copper by decreasing
the dissolved oxygen content in the environment. Copper oxidation is an electrochemical
process that involves the reaction of copper with oxygen in the presence of water. The rate of
oxidation is dependent on the availability of oxygen and the rate of electron transfer at the
surface of the copper.
When the pH is increased, the concentration of hydroxide ions (OH-) in the solution also
increases. This can result in the formation of a protective layer of copper hydroxide (Cu(OH)2)
on the surface of the copper. This layer can act as a barrier, preventing further oxidation by
limiting the availability of oxygen and water to the copper surface. Additionally, the hydroxide

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ions can react with dissolved oxygen to form water and decrease the amount of oxygen
available for the oxidation reaction.
In summary, increasing the pH can result in reducing the rate of oxidation of copper by
promoting the formation of a protective layer on the surface of the copper and decreasing the
availability of oxygen and water for the oxidation reaction. However, it is important to note that
the effectiveness of this method may depend on the specific conditions of the environment and
the specific type and form of copper being used.

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