Algorithm Used for the Development Vappro VBCI

Products Using a Combination Equations of

Mathematical Physics Derived from Gas Law and
Coefficient of Diffusion.
Nelson Cheng1 PhD (Honoris Causa), Patrick Moe1 BSc, Grad Dip, MSc.
1Magna International Pte Ltd

Singapore

Dr Benjamin Valdez Salas2, Dr Michael Schorr2 Dr Nicola Nedev2

2Autonomous University of Baja California

Article Info Abstract

Article History This article relates to the use of combination equations of
Date of Publication:
mathematical physics derived from gas law, coefficient of
3rd August 2018
diffusion (Correlation of Fuller-Schettler-Giddings (FSG)
Available online:
7th August 2018 Fuller et al., 1966), and principle of adsorption for the
Keywords development of Vappro VBCI (vapour bio corrosion
Algorithm inhibitor) products. Understanding and applying the gas
Gas Law, Diffusion, law and coefficient of diffusion principle are essentials
Adsorption and foundational in the development good VBCI
VBCI, VCI.
Products. Controlling vapour pressure of VBCI Products is
the state-of-the-art of VCI manufacturers as different VCI
carriers are used to meet each unique application due to
the wide applications of VCI products.

Introduction

The VBCI compound present in the enclosed area or on the surface of the emitters
such as P.E Packaging film, Tyvek pouches, Polyurethane Foam, Kraft Papers, Mineral
Stone Paper, Oils, Solvents, Water, Powders, Tablets, etc reaches the metal surface via
a series of steps namely Vapour pressure, (evaporation for liquid or sublimation for
solids), Diffusion and Adsorption on metal surfaces.

Ascertaining the Vapour Corrosion Inhibition Ability of VBCI product is of paramount

importance to Manga International and all VCI manufacturers. The German test

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method TL 8135-002 is used to evaluate the vapour inhibition ability of all Vappro
VBCI products. [1][2][3][4]

In view of the above, an algorithm needs to be established using a combination of

equations of mathematical physics derived from Gas Law, Coefficient of Diffusion
(Correlation of Fuller-Schettler-Giddings (FSG) Fuller et al., 1966), and understanding
principle of adsorption of VBCI ions on metals is of paramount importance for the
development of all Vappro VBCI Products.

This journal only describes the equations of mathematical physics used in the
development of Vappro VBCI Products revolving around gas law and coefficient of
diffusion.

Transport theory using concentration gradient can be described by boundary value

problems for differential equations. A very wide class of models is reducible to such
boundary value problems.

A complete description of the evolution of physical processes requires, first, the

specification of the state of the process at some fixed moment of time (the initial
conditions) and, secondly, the specification of the state on the boundary of the
medium in which the process considered occurs (the boundary conditions). The initial
and boundary conditions form the boundary value conditions, and the differential
equations together with corresponding boundary value conditions define a boundary
value problem of mathematical physics.

The Algorithm used for the development Vappro VBCI Products using a combination
of equations of mathematical physics derived from gas law and coefficient of
diffusion (Correlation of Fuller-Schettler-Giddings (FSG) Fuller et al., 1966), is herein
described.

Vapour Pressure

Vapor pressure or equilibrium vapor pressure is defined as the pressure exerted by a

vapor in thermodynamic equilibrium with its condensed phases (solid or liquid) at a
given temperature in a closed system.

Vapour pressure is in important parameter to determine the effectiveness of Vappro

VBCI Vapour pressure is an important parameter for controlling effective Vappro
VBCI transportation.

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A vapour pressure that is too low leads to the slow establishment of corrosion
protection, which may result in it being insufficient. On the other hand, if the vapour
pressure is too high, the effectiveness of VBCIs will be limited to a short period of
action due to high consumption rates. [5]

Therefore, the VBCIs must have enough vapour pressure in order to ensure rapid
protection of metals because too high a volatility may lead to premature loss of
inhibitor.

In some instances, it may be desirable to combine VBCIs with different volatilities to

achieve a combination of rapid and long-term protection.
the vapour pressure of the VCI should be in the range of 0.002 – 1 Pa at 20℃.
(1.500123 x 10-005 – 0.0075mmHg). [5]

The vapour pressure determines the equilibrium concentration of a volatile bio

corrosion inhibitor (VBCI) in the surrounding atmosphere.

However, the rate at which the VBCI can be delivered across the air gap to a metal
surface is determined by the gas permeability. [5]

Gas Permeability [6]

In some practical systems, the surface concentrations C1, C2 may not be known but
only the gas or vapour pressures p1, p2 on the two sides of the membrane. The rate
of transfer in the steady state is then sometimes written

F = P(p1 - p2)/l Eq1

and the constant P is referred to as the permeability constant.

Here P is expressed, for example, as cm3 gas at some standard temperature and
pressure passing per second through 1 cm2 of the surface of a membrane 1 cm thick
when the pressure difference across the membrane is 1 cm of mercury.

The permeability constant is a much less fundamental constant than the diffusion
coefficient which is expressed in units such as cm2 s-1 particularly as different
investigators use different units and even different definitions of P.

If the diffusion coefficient is constant, and if the sorption isotherm is linear, i.e. if
there is a linear relationship between the external vapour pressure and the

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corresponding equilibrium concentration within the membrane, then eqns (1) and (2)
are equivalent, but not otherwise.

F = -D dC/dx = D(C1-C2)/l Eq2

The linear isotherm may be written

C=Sp Eq3

where C is the concentration within the material of the membrane in equilibrium with
an external vapour pressure p, and S is the permeability. Since C1, p1 and C2, p2 in (1)
and (2) are connected by (3) it follows that, with due regard to units,

P = DS
Gas permeability is the product of the vapour pressure and the diffusion coefficient:

SA = PADAB
S = permeability, Pa m2/s
P = vapour pressure, Pa
D = diffusion coefficient, m2/s
A = sample compound A (corrosion inhibitor)
B = gas

The VCI vapour is transferred to the metal surface to be protected by a diffusion

process. [5]
The air that surrounds the metal part to be protected acts as a secondary reservoir
for VCI molecules. In fact, if ideal gas behaviour can be assumed, the equilibrium
concentration is given by Ideal gas law. [5]

The Ideal Gas Law

The volume (V) occupied by n moles of any gas has a pressure (P) at temperature (T)
in Kelvin. The relationship for these variables,
PV=nRT
n/V = P/RT

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n/V = C

CA = PA/RT

C = concentration, mol/m3’

The concentration of A assumes a constant value at the sample surface that equals
the equilibrium concentration at the prevailing temperature and pressure as defined
by Eq. (1). [7]

Diffusion (transport of matter down a concentration gradient)

Transport properties of gases use kinetic theory to calculate several transport
properties of gases.

Flux is the rate at which matter, energy, charge, or some other property is
transported, passing through a unit area per unit time. [7]

Transport of some property generally occurs in response to a gradient in a related

property, and the flux is generally proportional to the gradient.

Note that both the flux and the gradient are vector properties. For example, if there
is a concentration gradient in some direction z, there will be a component of mass
flux in the same direction.

Jz ∝

This proportionality of matter flux (more commonly known as diffusion) to the

concentration gradient is often referred to as Fick’s first law of diffusion. The constant
of proportionality is called the diffusion coefficient, and is usually given the symbol
D. [7]

For diffusion in only the z direction, the Fick’s rate equation is: [8]

dc
J , = −D
dz
where:
𝐉z: is the molar flux in the z direction relative to the molar average velocity,
𝐝c/𝐝𝐳: is the concentration gradient in the z direction and
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𝑫𝑨𝑩: the proportionality factor, is the mass diffusivity or diffusion coefficient for
component A diffusing through component B.

D a negative sign because matter diffuses down a concentration gradient from

higher to lower concentration. i.e. if dc/dz is negative (concentration decreasing in
the positive z direction) then Jz will be positive (flow of matter in the positive z
direction) [7].

Fick’s first law of diffusion (that the flux of diffusing molecules is proportional to the
concentration gradient), and also to determine value for the diffusion coefficient, D.
[7]

The diffusion coefficient

Definition of 𝑫𝑨𝑩: the mass or molar flux per unit concentration gradient
Factors affecting diffusion coefficient:
The diffusion coefficient depends on:
a) temperature
b) pressure
c) composition of the system

Gas phase diffusivity [9]

The theory describing diffusion in binary gas mixtures at low to moderate pressure
can be derived by solving the Boltzmann equation, and the diffusion coefficient can
be expressed as (Reid et al., 1987)

.
0.00266T
D(A, B, P) =
P M(A. B) σ ΩD

where D(A, B, P) is the diffusion coefficient (cm2 s−1) of gas A in gas B at a pressure
of P (bar), T is the temperature(K), M(A, B) is equal to twice of the reduced mass of
molecule A and molecule B, 𝜎 is the characteristic length(10−1 nm) , and ΩD is the
dimensionless diffusion collision integral (Lennard-Jones Constant). To derive
Equation, it is also assumed that the gases investigated obey the ideal-gas law and
gas A is only present in trace amount compared to B.

To estimate diffusion coefficients for the above equation, the values of 𝜎 and ΩD
need to be calculated/ estimated.

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Ghosal (1993) used the Lennard-Jones method to estimate the diffusion coefficients
of a variety of atmospheric trace gases, and Ivanovet al. (2007) found that the
diffusion coefficients of OH, H2O, and O3 estimated by the Lennard-Jones method
agree well with their experimentally measured values. However, to calculate 𝜎 and
ΩD, the Lennard-Jones method requires molecular parameters 𝜎 and ΩD, which are
not readily available.

In the absence of experimental data, semi-empirical expressions have been

developed which give approximations, sometimes as valid as experimental values
due to the difficulties encountered in their measurement.

Several empirical/semi-empirical methods are available to directly estimate diffusion

coefficient, e.g. the method proposed by Fuller et al. (1966, 1969). [9]

Reid et al. (1987) compared the estimated diffusion coefficients of a large range of
molecules using different methods, including the Lennard-Jones method and Fuller’s
method, with measured values, and found that Fuller’s method in general yields the
smallest errors. Therefore, in this work Fuller’s method is used. [9]

The diffusivities estimated using Fuller’s method are typically found to be in good
agreement with the measured values within ±30 %, and therefore Fuller’s method
can be used to estimate the diffusivities of trace gases for which experimental data
are not available. [9]

The empirical correlation for estimating the diffusion coefficient recommended by

Fuller-Schettler-Giddings (FSG) (Fuller et al., 1966) is: [8]

/
. 1 1
10 T +
M M
D =
/ /
P (∑ 𝛎) + (∑ 𝛎)

𝐷 = Binary gas phase diffusivity of A in B in cm2/s

T = Absolute temperature in Kelvin
P = Absolute pressure in atmospheres
MA, MB = Molecular weights of A and B respectively
(∑ 𝝂) , (∑ 𝝂) = molecular volumes in cm3/ g-mol

The diffusion volume 𝝂 is obtained from below table [8]

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Atomic diffusion volumes for use in estimating DAB by method of Fuller, Schettler,
and Giddings. [8]

Atomic and structure diffusion-volume increments, 𝝂

C 16.5 Cl 19.5
H 1.98 S 17.0
O 5.48 Aromatic ring -20.2
N 5.69 Heterocyclic ring -20.2
Diffusion volume for simple molecules, 𝝂
H2 7.07 Ar 16.1 H 2O 12.7
D2 6.70 Kr 22.8 CCIF2 114.8
He 2.88 CO 18.9 SF6 69.7
N2 17.9 CO2 26.9 CL2 37.3
O2 16.6 N2O 35.9 Br2 67.2
Air 20.1 NH3 14.9 SO2 41.1

Based on the Vapour pressure of the VBCI and estimated value of the diffusion
coefficient determine the effectiveness of the Vappro VBCI chemical.

Mechanism of VBCI as adsorption corrosion inhibitors

VBCI adsorption corrosion inhibitor inhibits or reduces corrosion via polarization of

ions on the metal surfaces by forming extremely thin layer of their molecules
adsorbed on the metal.

Vappro VBCI adsorption inhibitors are substances mainly organic materials capable
to form chemisorbed bonds with surface metal atoms

Polarization is a deviation of the electrochemical process from equilibrium due to an

electric current passing through the galvanic cell. Polarization may occur either at the
cathode (cathodic polarization) or at the anode (anodic polarization). Cathodic
polarization is common.

There are three types of polarization: Activation polarization, Concentration

polarization and Resistance Polarization will be discussed in our next journal.

Reference:

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[1] Cheng, Nelson & Moe, Patrick & Valdez Salas, Benjamin & Wiener, Michael.
(2018), Establishing the Vapour Inhibition Ability Vappro VBCI 849 Using German Test
Method TL 8135-002 Methodology for Ascertaining Contact Pressure of a Timken
Load Machine.

[2] Cheng, Nelson & Moe, Patrick & Valdez Salas, Benjamin & Wiener, Michael.
(2018), Ascertaining the Vapour Inhibition Ability of Vappro VBCI Corro-Pill

[3] Cheng, Nelson & Moe, Patrick & Valdez Salas, Benjamin & Wiener, Michael.,
Ascertaining the Vapour Inhibition Ability (VIA) of Vappro 5 VCI Foam Emitter Using
German Test Method TL 8135-002.

[4] Cheng, Nelson & Moe, Patrick & Valdez Salas, Benjamin & Wiener, Michael.,
Ascertaining the Vapour Corrosion Inhibition Properties of Vappro 10 VCI Foam
Emitter Using German Test Method TL 8135-002

[5] Niel Pieterse, Walter W. Focke, Eino Vuorinen, Ilona Ra´cz, Estimating the gas
permeability of commercial volatile corrosion inhibitors at elevated temperatures
with thermo-gravimetry

[6] J. CRANK, The Mathematics of Diffusion, second edition

[7] Dr Claire Vallance, Properties of Gases

[8] Dr Mohamad Helmy, Fundamentals of Mass Transfer

[9] M. J. Tang,2, R. A. Cox, and M. Kalberer, Compilation and evaluation of gas phase
diffusion coefficients of reactive trace gases in the atmosphere: volume 1. Inorganic
compounds

About the authors

Nelson Cheng

Nelson Cheng received a Dr. honoris causa from the Universidad Autonoma de Baja
California, Mexico. He is the Founder and Chairman of Magna Group, consisting of
Magna International, Magna F.E. Chemical Pte Ltd, Magna Chemical Canada Ltd,
Magna Australia Pvt. Ltd, and Lupromax International Pte Ltd. He graduated as a
marine engineer under the United Nations Development Program Scholarship.
He is recognized as Singapore’s leading inventor and the Singaporean with highest
number of patents from the Intellectual Property Office of Singapore. He is inventor
of several technologies for corrosion protection including, Vappro VBCI (Vapour Bio

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Corrosion Inhibitors). He is a member of American Chemical Society and European
Federation of Corrosion.

Patrick Moe

Patrick Moe is the senior technical manager of Magna International Pte. Ltd. He has a
BSc in Industrial Chemistry, Grad. Dip and MSc in Environmental Engineering.
His key responsibilities at Magna International as follows: assisting the CEO in
research and development of new products, finding out customers’ needs and
develop customized new products, helping in synthesizing new compounds by
making appropriate modifications of known methods, recommending and
implementing methods to increase the quality of products and service, management
of hazardous raw materials. He is a member of National Association Corrosion
Engineers (NACE) and World Corrosion Association (WCA).

Professor Benjamin Valdez Salas

Benjamin Valdez Salla was the director of the Institute of Engineering during 2006–
2013, Universidad Autonoma de Baja California. He has a BSc in chemical
engineering, an MSc and PhD in chemistry and is a member of the Mexican Academy
of Science and the National System of Researchers in Mexico. He was a guest editor
of Corrosion Reviews, in which he produced two special issues on corrosion control in
geothermal plants and the electronic industry, including VCI uses. He is a full
professor at the University of Baja California. His activities include corrosion research,
consultancy, and control in industrial plants and environments.

Dr Michael Schorr Weiner

Michael Schorr is a professor (Dr. honoris causa) at the Institute of Engineering,

Universidad Autonoma de Baja California. He has a BSc in chemistry and an MSc in
materials engineering from the Technion-Israel Institute of Technology. From 1986 to
2004, he was an editor of Corrosion Reviews. He is acquainted with the appreciation
of VCI in industrial environments. In addition, M. Schorr was a corrosion consultant
and professor in Israel, USA, Latin America, and Europe. He has published 410
scientific and technical articles on materials and corrosion

Professor Nicola Nedev

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Dr. Nicola Nedev received the Ph.D. degree in physics from the Institute of Solid State
Physics, Bulgarian Academy of Sciences, in 1990. He is a Professor of Semiconductor
Physics and head of the laboratory Semiconductors, Microelectronics and
Nanotechnology with the Institute of Engineering, Autonomous University of Baja
California, Mexico. His research interests include nanostructured materials,
semiconductors and semiconductor device technologies. He authored and co-
authored more than 90 refereed papers and collaborates with the semiconductor and
automobile industry in Mexico. Dr. Nedev is member of the Mexican Academy of
Sciences and Mexican National System of Researchers.

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