CHAPTER 1

INTRODUCTION

Acid rain occurs when sulphur dioxide (S02) and nitrogen oxide (N02) react with oxygen in the air in the
presence of water to form carbonic acid (H2C03) and nitrous oxide (HN02-). These fall on the surface of
roofing materials and have devastating effects. The pH of these acids are generally lower than 5. The acid
rain has in addition to the nitrous and the sulphurous oxides contains heavy metals, carbon monoxide,
and photochemical oxidants. A synergistic damaging effects is produced by the reactions between these
materials. Recall that an electrolyte is required for corrosion to occur, roofing sheets therefore, corrode
under acidic water and or condensation that can’t run off or become trapped. The greenhouse gases
(methane, C0, C02,S03, S02, and N02) are the main pollutants with respect (Ovri and Iroh, 2013) to
corrosion. The reaction between the pollutants and roofing sheets is complex and involved variables such
as the pollutants’s concentration and the climatic conditions and the exposed surface of the roofing sheet.
Once the pollutant gets to the surface of the roofing sheet, the interaction will depend on the amount,
duration of exposure, reactivity of the various materials (gases, moistures etc). Acid rain is a major
environmental problem in the Niger Delta of Nigeria. This is more serious during the raining session when
the humidity is high and with the presence of the greenhouse gases, there is an increase in the corrosion
of roof sheets. The effects of acid rain on corrugated iron sheet has been documented by (Barton, 1997,
Graedel and Schwartz, 1997 and Haynic,1982). The effect of gas flaming on roofing sheets in a gaseous
and non-gaseous flaring areas has been documented by ( Ovri and Iroh, 2013). This investigation is aimed
at providing a data base for roofing sheets commonly used in the Niger Delta areas of Nigeria. These areas
are often plagued with acid rain. The roofing sheets investigated were, (i) galvanized steel, (ii) Aluminum
roofing sheet (Alumaco) and Aluminum / zinc alloy roofing sheet ( Cameroon roofing sheet). The relative
corrosion resistance of these roofing sheets in the various environments were evaluated and
recommendations made on the most suitable sheets for these environments. The results of this
investigation will be invaluable to engineers, designers, Architects and builders.

Table 1.1: Chemical Composition of the Roofing Sheets

1
Weight Loss of Corrosion Coupons The weight loss of the corrosion coupons as a function of exposure
time in the various environments are given in Table 1.2 and displayed in Figure 1.1

Table 1.2: Weight Loss as Function of Exposure Time for the Roofing Sheets in the Various Environments.

2
 CHAPTER 2
LITERATURE REVIEW

2.1 Sheet:
Sheet is metal formed by an industrial process into thin, flat pieces. It is one of the fundamental forms
used in metalworking and it can be cut and bent into a variety of shapes. Countless everyday objects are
fabricated from sheet metal. Thicknesses can vary significantly; extremely thin sheets are
considered foil or leaf, and pieces thicker than 6 mm (0.25 in) are considered plate.

Sheet metal is available in flat pieces or coiled strips. The coils are formed by running a continuous sheet
of metal through a roll slitter.

There are many different metals that can be made into sheet metal, such
as aluminium, brass, copper, steel, tin, nickel and titanium. For decorative uses, important sheet metals
include silver, gold, and platinum.

Sheet metal is used in automobile and truck bodies, airplane fuselages and wings, medical tables, roofs
for buildings and many other applications. Sheet metal of iron and other materials with high
magnetic permeability, also known as laminated steel cores, has applications in transformers and electric
machines. Historically, an important use of sheet metal was in plate armor worn by cavalry, and sheet
metal continues to have many decorative uses, including in horse tack.[1]

2.2 Importance of Sheet:

Carbon steel sheet is a popular domestic choice for metal roofing, primarily for economic
reasons. In the field of home appliances, steel is used abundantly for exteriors, chasses,
panels, and motor parts, etc. For example, looking at the material composit ions of various
home appliances recycled in 2009, the weight percentage of steel is 47% for flat -panel TVs,
56% for refrigerators, 53% for washing machines and 32% for air conditioners. Thus, steel
accounts for large proportions of the materials used in ho me appliances, although its use
has somewhat decreased since recycling began in earnest. Steel, which is an abundantly
available low-cost material has long been employed for home appliances because of its
strength and formability. Since the 1970s, the use of surface-treated steel sheet having

3
better corrosion resistance and aesthetic appeal has been increasing. Surface -treated steel
sheet has been subjected to plating, conversion coating or painting to impart good
corrosion resistance to the steel sheet . [ 2]

2.3 Classification of Sheet:

Any Rigid Classification is Impossible but Sheets are arbitrarily divided into four groups which has different
properties and characteristics satisfied by the metalworking community.

These four classes are:

1. Galvanized Iron Sheet.

2. Electro Galvanized Steel Sheet.
3. Hot Dip Galvanized Steel Sheet.
4. Galvalume.

2.3.1 Galvanized iron sheets

Galvanization is the process of applying a protective zinc coating to steel or iron in order to prevent it from
rusting. The term is derived from the name of Italian scientist Luigi Galvani. Galvanized iron (GI) sheets
are steel sheets which are basically coated with zinc and include a range of hot dip galvanized and electro-
galvanized steel sheets. Zinc weathers at a very slow rate, so the coating generally has a long life. Zinc has
a greater electro-negativity than iron and hence provides cathodic (or sacrificial) protection to the steel.
This results in the zinc corroding in preference to the steel if the coating is chipped or damaged to expose
the base metal. Besides acting as galvanic protector,The other functions of the zinc layer are as follow:
• To retain the steel intact with its full initial strength.
• To provide the surface a more pleasing appearance.
• To increase the life of any suitable organic finishing system applied over it.
• To protect the steel from corrosive attack in most atmospheres, acting as a continuous and lasting
shield between steel and the atmosphere.

2.3.1.1 GI sheets specification:

The galvanized iron (GI) sheets are produced as plain coils / sheets (GP) and corrugated sheets
(GC). Corrugated sheets are also known as corrugated galvanized iron (CGI) sheets. These are
value added steel products which are tough, sturdy, light weight, bright, corrosion resistant and

4
easy to transport. These are usually produced in the thickness range of 0.15 mm to 2.0 mm and
width range of 800 mm to 1560 mm. The weight of zinc coating varies from 100 grams square
meter (gsm) to 750 grams square meter.

2.3.1.2 Application of GI sheets:

GI sheets are sheets are used extensively in various applications. Some of common uses are given below.
• Agriculture – Grain silos, sprayers, pans and feeding troughs etc.
• Automobile sector – Car, bus and truck bodies, undercarriage work, air and oil filters, fuel and oil tanks,
exhaust pipes etc.
• Construction – Roofing, side walls, partitions, panels, valley gutters, louvers, false ceilings, partition
walls and ducks, rolling shutters, highway bumpers, slotted angles and paint coated products etc.
• House hold things – Trunks, ice boxes, tubs, buckets, storage bins, water tanks, washing machines,
house hold machines, pipes, pipe fittings and bath room doors etc.
• Electrical appliances – Air conditioners, refrigerators, freezers, electrical panels, decorative lamps etc.
• Furniture and fixtures – Desk, lockers, almirahs, racks, light weight chairs etc.
• Other general uses – Ducting, drums/barrels, containers, thermal cladding, railway coaches, sign
boards, hoardings and road signs etc.

2.3.1.3 Advantages with use of GI sheets:

The use of GI sheets gives the following advantages.
• Low cost – Galvanizing is lower in first cost than many other commonly specified protective coatings
for steel.
• Less maintenance cost – GI sheets are virtually maintenance free and last longer.
• Long life -The life expectancy of GI sheets is quite high in rural, urban and coastal environments.
• Reliability. Galvanizing is usually carried out as per standards and minimum coating thicknesses are
applied. Coating life and performance are reliable and predictable.
• Toughest coating – A galvanized coating has a unique metallurgical structure which gives outstanding
resistance to mechanical damage in transport, erection and service.

5
• Automatic protection for damaged areas – Galvanized coatings corrode preferentially to steel,
providing cathodic or sacrificial protection to small areas of steel exposed through damage. Unlike
organic coatings, small damaged areas need no touch up.
• Complete protection – Every part of a galvanized iron sheet is protected.
• Ease of inspection – Galvanized coating is assessed readily by eye, and simple non-destructive
thickness testing methods can be used.
• Galvanizing process is not dependent on weather conditions.

• The surface of GI sheet is aesthetically pleasing. [3]

2.3.2 Hot dip galvanized steel sheet products and

Characteristics:
The coating quality and corrosion resistance of steel sheets hot-dip galvanized by the conventional
method in a semiautomatic plant were studied. The effect of various treatment processes such as surface
pretreatment, dipping techniques and post-treatment processes on the coating quality, type and extent
of defects was investigated. It was found that the coating quality was markedly influenced by the mode
and the amount of zinc bath additives, in particular aluminium or antimony. The required amounts of such
additives should be added at intervals in the form of binary zinc master alloys with a maximum aluminium
or antimony content of 10%. The correlation of the bath temperature and the withdrawal speed with the
sheet thickness is an important factor for quality improvement. Hot-dip galvanized coatings are used on
a multitude of materials in myriad construction sectors from electric utility to artistic sculptures. Ranging
in size from small parts such as nuts, bolts, and nails to very large structural shapes, galvanizing is integral
to the North American infrastructure. Most commonly batch hot-dip galvanizing is used in atmospherically
exposed steel; however, it is also used in fresh and salt water applications, buried in the soil, embedded
in concrete, and much more. Galvanized steel sheets have found a wide range of applications during
recent years where quality and corrosion resistance are of particular importance. The protection
properties of zinc coatings compared with those of other metal coatings such as aluminium, cadmium,
lead or tin are very good in sea water. Zinc-coated steel is therefore used in the shipbuilding industry and
for protecting structural steel work on docks. The quality of sheet galvanized by the hot-dip process is an
important factor in determining the economics and serviceability of the products. The surface
pretreatment, dipping techniques and post-treatment processes are important factors, each of which has

6
a bearing on the quality of the coating. In addition, the dipping techniques greatly affect the structure and
coating thickness as discussed elsewhere . Many defects arise from the lack of correlation between the
temperature of the zinc bath and the withdrawal speed. Horstmann and Burns and Bradley described the
various defects that occur in hot-dip-galvanized sheets and their possible causes. To achieve an
improvement in the appearance and lustre of galvanized steel, aluminium and aluminium in combination
with other metals such as antimony are the most common additives. Antimony is added to effect the
formation of an attractive crystalline spangled coating . The presence of metal impurities in the zinc melt
as well as metals added during galvanizing may change the corrosion properties of the coatings. Some
investigators found that aluminium addition reduces the corrosion resistance of the coatings in industrial
atmospheres as well as in sea water.

However, many investigators found that aluminium or antimony increases the corrosion resistance of the
coatings in industrial environments and moist air. The tendency towards wet storage stain formation is
not substantially affected by these additions. The aim of this work was to study the effect of the various
factors which affect the quality of galvanized sheets processed in a conventional semiautomatic plant.
The quality of the products was estimated with regard to the extent of defects, type of defect, appearance
and uniformity of the coating. It was also of interest to establish whether aluminium or antimony, when
added in small amounts to the zinc bath, increases the corrosion resistance of galvanized steel [4]

2.3.3 Galvalume :

GALVALUME® Steel Sheet is carbon steel sheet coated with aluminum-zinc alloy by a continuous hot-dip
process. The nominal coating composition is 55% aluminum and 45% zinc. A small but important addition
of silicon is included in the coating alloy. It is added not to enhance the corrosion performance, but to
provide good coating adhesion to the steel substrate when the product is roll-formed, drawn, or bent
during fabrication.

GALVALUME® steel sheet combines the excellent barrier corrosion protection of aluminum with the
galvanic protection of zinc. The result is a coating that lasts a long time, a coating that provides cut-edge
protection along sheared edges, and therefore, a coating that offers excellent protection to steel sheet.

7
Although there are a few exceptions, for most applications in most types of environment, GALVALUME®
steel sheet is the preferred product when long-term resistance to atmospheric corrosion is desired. It
outlasts a galvanized coating of comparable thickness, and offers cut-edge protection that is not available
with aluminum-coated sheet. This cut-edge protection means there is less rust-staining along sheared
edges, at scratches, and other imperfections in the coating. Also, since the coating is so resistant to
corrosion, it retains a very bright surface appearance when exposed to most atmospheres. These
attributes make GALVALUME® steel sheet the preferred material for roofing.

The superior corrosion resistance of GALVALUME® steel sheet is achieved by the presence of microscopic
zinc-rich and aluminum-rich areas within the coating. The aluminum-rich areas, which corrode very slowly,
provide the long-term durability while the zinc-rich areas, which corrode preferentially, provide galvanic
protection.[5]

2.3.3.1 Chemical Composition of Galvanized Sheet and Galvalume:

For general applications, the galvanized sheets have 19 µm of zinc thickness per side. This corresponds to
a two-side coating mass of 275 g/m2 . Heavier coatings are used in applications which require higher
corrosion resistance, such as highway drainage culverts. In the automobile industry, where formability
and weldability are key considerations, lighter coatings such as 90 g/m2 are more typical (Townsend,
1993). The galling, a form of adhesive wear, affects the cost of forming steel in automotive stamping since
it increases die maintenance costs and scrap rates (Kim et al., 2008). Most of the coating is nearly pure
zinc. There is an intermetallic layer containing about 6 % Fe, between the substrate and the zinc coating.
Aluminium, typically in the range of 0.1 % to 0.2 %, is added to the zinc bath in order to prevent the
formation of a thick, continuous zinc-iron intermetallic layer that could lead to poor coating adhesion
during forming. Aluminium reacts preferentially with the steel to form a thin iron-aluminium intermetallic
layer which acts as a barrier and delays the growth of the zinc-iron intermetallic layer. There is generally
a direct correlation between the amount of zinc application and the steel’s atmospheric corrosion
resistance. The more the zinc, the more the corrosion resistance. The amount of zinc (referred to as
coating weight) is usually represented in ounces per square foot (or sometimes grams per square meter)
total both sides. For example, its designation may be A40, constituting .40 oz/ft2. As such, the material
would have approximately one-third less protection than A60 (.60 oz/ft2 ). Generally, Galvannealed has

8
become the preferred product of automobile, appliance and many other OEMs and fabricators, given the
product’s excellent paintability, and lower cost compared to Electrogalvanized. Since the 1980s, it has
almost completely supplanted Bonderized (phosphatized). Galvannealed (like hot-dipped Galvanized
sheet) is typically produced in accordance with ASTM A653 standards and tolerances.

Micrograph (x200) of a typical hot dip galvanized coating on “silicon killed” carbon steel within the silicon
range of 0.15% to 0.25% Coating thicknesses range between 100µm to 150µm

Galvalume® is the trade name of steel sheets coated with 55%Al-Zn alloy. It is applied by a continuous hot
dip process similar to that of galvanized coatings. This coating combines the durability of aluminium and
the galvanic protection of the zinc, resulting in a product which shows excellent corrosion resistance in
marine and industrial environments, high temperature oxidation resistance, heat reflectivity of the
aluminium coatings and a pleasant and distinctive appearance. The 55%Al-Zn coating shows long-term
atmospheric corrosion resistance due to the combination of the durability of aluminium which acts as a
mechanical barrier and the galvanic protection given by zinc (Gronostajski, 1995). Exposition tests of the
zinc coated steel sheet (coating G90) and Galvalume® (coating AZM 150) were done by Bethlehem Steel.
The test panels were exposed at rural, industrial, moderate marine and severe marine environments. The
results showed that the corrosion resistance of the 55%Al-Zn is generally at least two to four times higher
than that of an equal thickness of galvanized coating (BHP Steel, 1994a). Recent work found that the zinc
coating experiences a degree of corrosion between 1.7 times (marine-industrial atmosphere) and 4.5
times (rural atmosphere) greater than that of the 55%Al-Zn coating, considering the results obtained after
five years of atmospheric exposure (Palma et al., 1998).
The steel sheet coated with 55%Al-Zn alloy can be used at higher temperature conditions compared to
the zinc coated steel sheet. In terms of appearance at higher temperatures, Galvalume® maintains its
superficial brightness up to 320 ºC, while the galvanized sheet maintains its brightness up to 230 ºC

9
 Density of AlMZnMSi Alloy is 3.75 gms/cm3, and the density of galvanized metal is 7.14 gms/cm3. Due to
this density difference, AlMZnMSi Alloy coating mass gives higher coating in microns as compared to the
same coating mass in Galvanized product. AlMZnMSi Alloy coating gives 52.5% more coating thickness
than galvanized coating.[6]

2.3.3.2 The Estimated Soluble Carbon in Steel Substrate of Galvanized

and Galvalume® Sheets :
Because of the higher molten metal temperature and the higher cooling rate at the up-leg cooling during
a 55%Al-Zn coated steel production (BHP Steel, 1994c), higher levels of carbon in solid solution of the
substrate of 55%Al-Zn coated sheets compared to the substrate of galvanized sheets are expected (Lake
and Browne, 1978). In pure iron, the solubility of carbon in the body-centered cubic cell was measured as
a function of temperature (Lake and Browne, 1978). Table 1 shows some of the values of the carbon
solubility.

Table 1. The solubility of carbon in the iron body-centered cubic cell in equilibrium with
Fe3C as a function of temperature.

Temperature Carbon level

(ºC) (ppm)
700 168
600 68
450 13.5
350 2.8

The values shown in Table 1 are equilibrium values and they are not necessarily achieved in the practical line
situation. At 600 ºC the equilibrium solubility are approached within few seconds, but at 450 ºC several minutes
may be required to achieve the equilibrium depending on the previous metallurgical history of the steel (Lake

10
and Browne, 1978). Based on the statement as the 55%Al-Zn coated steel is rapidly cooled from 600 ºC, it is
expected that soluble carbon levels will be of the order of 60 ppm. The zinc coated steel is held at about 465 ºC
before the immersion and then cooled at a lower rate (compared to 55%Al-Zn coated steel). The carbon level
will be somewhat greater than 13 ppm, because there will not be enough time for the carbon to precipitate to
its equilibrium value at 450 ºC. The measurements of the actual carbon content in a solid solution for 55%Al-Zn
and for zinc coated steel exhibit values of 45-60 ppm and 20-30 ppm, respectively, so that there is a significant
difference between the levels for the two products (Lake and Browne, 1978; Marder, 2000). Those differences
in carbon content in solid solution can represent significant differences for the mechanical properties between
55%Al-Zn and zinc coated steel sheets (Safaeirad et al., 2008). The higher levels of soluble carbon of the 55%Al-
Zn coated steel may possibly increase the yield and tensile strength, and decrease the ductility (measured by
the total elongation). [7]
]

2.3.3.3 The microstructure of 55 w/o Al—Zn—Si (Galvalume)

hot dip coatings:

Light metallography, x-ray diffraction, scanning electron microscope (SEM), (EMPA), and scanning
transmission electron microscope (STEM) were used to study the microstructural characteristics of 55
w/o Al—Zn-Si (Galvalume) hot-dip coatings on steel. Processing variables of coating thickness and dip
time were studied and a thin foil sample preparation technique involving ion beam thinning for the
STEM evaluation of coating cross sections was developed. The spangled coating surface was comprised
of a fine dendritic network, and correlations between dendrite arm spacing and spangle size with
coating thickness have been made. The overlay, or solidified bath, consists of grains of A1-rich dendrites
along with Zn-rich interdendritic zones. EMPA in conjunction with TEM imaging showed that these Zn-
rich interdendritic regions had a heavy concentration of precipitates. Selective etching of the overlay
revealed a forest of Si particles which grew out from the alloy layer. The alloy layer was studied using
the EMPA and STEM and it was found that up to five intermetallic phases were present after long dip
times.

11
 Microstructure evolution of a 55 wt.% Al–Zn coating on press hardening steel during rapid heating

The commercial coating consists of nominally 55 A1, 43.4 Zn, and 1.6 Si [all in (w/o)]. Silicon is added to
the bath to prevent a very strong and rapid exothermic reaction between the A1-Zn bath and the steel
sheet. During the coating process a diffusion layer forms between the bath and the steel. This region is
called the alloy layer, and consists of Fe-A1 and Fe-A1-Si compounds. Another feature of the Galvalume
coating is that Si particles are formed in the overlay and result from the supersaturation of the AI-Zn
AlMZnMSi Alloy coating has unique microMstructure consisting of 2 layers i.e.an AlMZn overlay coating
and a Fe containing intermetallic /alloy layer. Alloy layer forms at the interface between the coating and
steel substrate. Due to this, AlMZnMSi Alloy combines the Galvanic corrosion protection of Zn with the
barrier protection of Aluminum as compared to only Galvanic protection in galvanized metal. bath upon
cooling. The studies of Cleary and Zoccola et al.concentrated on the corrosion behavior of the coating,
while Hart and Friel .completed some of the more recent work on determining the composition of the
alloy layer. Cleary found that as the secondary dendrite arm spacing (DAS) and the A1 dendrite size
decreased and the density of the Si particles increased, the corrosion resistance increased. Zoccola et al.
investigated the atmospheric corrosion behavior of a wide range of A1-Zn alloys, which led to an A1/Zn
ratio in Galvalume of 1.2. Hart studied the constitution of the alloy layer in a rapidly cooled commercial
panel using Auger electron microscopy, and found that the approximate composition was 55.8% A1,
33.7% Fe, 6.7% Si, 3.8% Zn. Friel found two alloy layers in a commercial panel using EMPA, where the
compositions were 53.1% A1, 25% Fe, 8.9% Si, 13% Zn and 56.6% A1, 36.7% Fe, 3% Si, 3.7% Zn.[8]

12
2.3.3.4 Study of the Mechanical Properties of the Hot Dip
Galvanized Steel and Galvalume® :

Corrosion protection methods employed to protect steel include: altering the metal by alloying, changing
the environment by lowering its humidity or by using inhibitors, controlling electrochemical potential by
applying cathodic or anodic currents and applying organic and metallic coatings (Parisot et al., 2004).
Application of metallic coatings by a continuous hot dip process is one of the most widely used means of
protecting steel. In this process, the metallic strip is fed through a bath of molten coating metal in a
continuous process.

Table 1. Process Parameters of the Continuous Galvanizing Line.

Parameter Zn coated steel 55%Al-Zn
coated steel
Direct Fire Furnace (ºC) 590 590
Heating Section (ºC) 720 720
Soaking Section (ºC) 720 720
Annealing
Slow Cooling Section 650 630
Furnace
(ºC)
Jet Cooling Section – 470 - 520 560 - 580
Snout (ºC)
Bath Temperature (ºC) 465 600
Al - 53.0 to 57.0
Zn - 41.0 to 44.0
Al - 0.16 to 0.20
Si - 1.4 to
Bath Chemical Composition (%) Sb - 0.04 to 0.06
1.6
Zn - balance
Fe - 0.4 to
0.6

Table 2.Characteristics of the zinc and 55%Al-Zn coating.

Coating Standard Designation Weight Thickness

(g/m2) (µm)
Zinc ASTM A 653M G90 275 38,51
(2004)
55%Al- ASTM A 792M AZM 150 150 40,54
Zn (2003)

13
The tensile testing was conducted using a Shimadzu Universal Testing Machine with an extensometer.
The cross head speed was 3.0 mm/min up to 1.5 % elongation, when the speed was increased to 10.0
mm/min until the end of the test. The gauge length was 80.0 mm. The tensile strength, the yield strength
(0.2 % offset) and the total elongation were obtained from stress strain curves. The strain hardening
exponent was determined directly from the tensile machine software (EMIC).

The values of the specific yield strength and the specific tensile strength, both for galvanized and
Galvalume® sheets, showed a good correlation with the sheet thickness as can be observed in Fig. 1. These
properties can be represented as a function of the sheet thickness through the 1st grade equations as
shown in Fig. 1.

Figure 1. Mechanical properties as a function of the sheet thickness both for galvanized and Galvalume®
sheets considering the mean value among the three directions: (a) specific yield strength and (b) specific
tensile strength.

14
Again, as expected, the galvanized sheet showed higher total elongation than that of the steel sheet
coated with 55%Al-Zn alloy for all of the range of thicknesses and for the three directions. The total
elongation showed some correlation with the sheet thickness, Fig. 2.

38
Galvanized
36 Galvalume
y = 12,34x + 26,765
34
R 2 = 0,6433

32

30

28

26

24 y = 24,914x + 13,201
R 2 = 0,7874
22
0,38 0,43 0,48 0,53 0,58 0,63

Total Sheet Thickness (mm)

Figure 2. Total elongation of the galvanized and Galvalume® sheets – mean value among the three
directions.
(1)
= 12.34 t + 26.765

εGL = 24.914 t + 13.201 (2)

Equation (3) represents the difference between Eqs. (1) and (2) and shows the difference of the total
elongation between the galvanized and Galvalume® sheets as a function of the thickness.

∆ε = -12,574 t + 13,564 (3)

Through the above equation, it can be verified that, for 0.50 mm of total thickness, the galvanized sheet
should present total elongation of 7.27 % higher than the Galvalume®sheet.

The galvanized sheet showed higher hardening coefficient than that of the steel sheet coated with
55%Al-Zn alloy for all of the range of thicknesses and for the three directions. The hardening coefficient
also shows some correlation with the total thickness in the three directions, as can be observed in Fig. 3.

15
 0,22

0,21 Galvanized
Galvalume
0,20 y = 0,0207x + 0,1986
R2 = 0,7922
0,19

0,18

0,17
y = 0,0876x + 0,1219
0,16
R2 = 0,6281

0,15
0,38 0,43 0,48 0,53 0,58 0,63

Total Sheet Thickness (mm)

Figure 3. Hardening coefficient of the galvanized and Galvalume® sheets considering the mean value
among the three directions.

2.4 Comparison between Galvanized and Galvalume® Sheets –

Stripped State :

By comparison of the galvanized and Galvalume® sheets, both at the stripped state, it can be verified that
the Galvalume® sheet showed yield and tensile strengths slightly higher than that of the galvanized sheet.
This observation is an indicative of the action of the higher molten metal temperature of the 55%Al-Zn
bath compared to the zinc bath, and the higher cooling rate of the coating during Galvalume® processing
on the base steel properties. Figure 4 shows the specific yield and tensile strengths for galvanized and
Galvalume® sheets, both at the stripped state and in the diagonal direction.

The influence of the thermal cycle of the galvanized and Galvalume® sheets on the total elongation of the
base steel is shown in Fig. 5. The higher molten metal temperature of the 55%Al-Zn bath and the higher
cooling rate of the coating required during Galvalume® production lead to a lower total elongation of the
stripped samples for Galvalume® sheet compared to the galvanized sheet. A correlation between the total
elongation and the strip thickness was not found.

Significant differences of the hardening coefficient of the galvanized and the Galvalume® sheets, both at
the stripped state, were not observed.

16
s
Figure 4. Mechanical properties as a function of the base steel thickness for galvanized sheet and
Galvalume®, both at the stripped state for diagonal direction: (a) specific yield strength and (b) specific
tensile strength.

Galvanized
36
Galvalume

33

30

27

24
0, 30 0, 35 0, 40 0, 45 0,50 0,55 0,60 0,65

Thickness (mm)

Figure 5,Graphic representation of the total elongation for the galvanized and the Galvalume® sheets,
both at stripped state, in the transverse direction.

17
The steel sheets coated with 55%Al-Zn alloy showed higher specific yield and tensile strengths and lower
total elongation and hardening coefficient compared to the galvanized sheets for all ranges of thicknesses
(between 0.35 mm and 0.65 mm) and for the three studied directions. Due to the good correlation found
between the specific yield strength, the specific tensile strength, the total elongation and the hardening
coefficient with the total thicknesses, these properties may be represented as a function of the total
thickness through 1st grade equations.

Figure 6. Specific yield strength calculated based on base steel and total thicknesses (mean value
among the three directions): (a) galvanized sheets and (b) Galvalume® sheets. [9]

18
2.5 EFFECT OF CHEMICAL COMPOSITION OF STEEL ON THE
STRUCTURE OF HOT – DIP GALVANIZED COATING:

Effect of Silicon:
Oxygen is introduced to the steel during its production to specifically reduce carbon content, but also
other impurities. Excess amounts of free oxygen are removed via steel deoxidation, i.e. the addition of
elements with a higher overall affinity for oxygen than carbon. For this purpose Si, Al, and Mn are often
used, with silicon being the deoxidizer of choice. Such steels are then referred to as silicon-killed steels.
However, silicon in the steel significantly increases the solubility of iron in the zinc melt. Consequently,
coatings may be formed not only of great thickness, but with insufficient adhesion to the substrate,
therefore easily descaling. The silicon contained in the steel may also influence the composition of the
coating.In terms of the influence of the silicon content in the steel on the creation of the zinc coating, the
amount of silicon can be divided into four types. Steel with a low silicon content (killed steel) of < 0,03 wt.
% Si, steel with a silicon content in the “Sandelin range” (according to RW Sandelin), i.e. (0,03 to 0,12 wt.
%), steel in the “Sebisty range” (according to JJ Sebisty), i.e. (~0,15 to 0,25 wt. %) and, lastly, steels with
high silicon content (> 0,25 wt. %).Low-silicon steel (non-silicon-rimmed) (< 0,03 wt.% Si) is clearly the best
for creating quality coatings in the hot - dip galvanizing process. The coatings on these steels are
characterized by good mechanical properties, cohesive alloy layers and excellent adhesion of the coating
to the steel substrate. When galvanizing steel with this content of silicon, a substantial portion of delta
phase (δ1k + δ1p) is formed, which in this case consists of extremely closely spaced hexagonal columnar
crystals. This phase effectively prevents the diffusion of iron atoms; therefore, the rising phase zeta (ζ)
has a limited thickness. When galvanizing this kind of steel, the zeta (ζ) phase is very fine, and its upper
part is often imbued with an adherent layer of pure zinc (eta (η) phase). When the steel is left longer in
the galvanizing bath, only the delta phase (δ1k + δ1p) grows. If the amount of silicon in the steel is
increased (> 0,03 wt. % Si), i.e. silicon steel is “rimmed”, then there is a fundamental change in the
structure of the coating and also its overall thickness. The coating of steel with a silicon content in the
“Sandelin range” (0,03 to 0,12 wt. %) is 600 microns thick, but only after the normal time period (8-10
min) in the zinc bath. When the total time for the steel in the bath is longer, the coating thickness can
reach over 1500 micrometers. The resulting coatings are formed of non-oriented monoclinic crystals of
the zeta (ζ) phase (FeZn13). Due to the dominance of this phase, the coatings are very fragile and
susceptible to mechanical damage.When dipping steel parts with a silicon content in the “Sandelin range”

19
a thin layer of group phase delta (δ1k + δ1p) is formed on the surface which is covered with a layer of
phase zeta (ζ). Continued immersion time in the galvanizing bath results in a discontinuous layer of group
phase delta (δ1k + δ1p) on the steel’s surface. This layer is unable to limit the diffusion of iron towards
the phase zeta (ζ), because the external phase (bordering with molten zinc L (Zn) grow uncontrollably in
thickness. Virtually unlimited access to zinc atoms and a high rate of formation of intermetallic FeZn13 is
the explanation for the formation of very disordered crystals of monoclinic phase zeta (ζ). The slurry of
fine crystals encloses the pure, unreacted zinc atoms. The surface of such coatings further often contains
defects caused by intense diffusion of iron from galvanized steel (e.g. Shrinkage porosity, etc.). For steels
with this silicon content, an outer layer formed of substitutional solid solution of iron in zinc (i.e. η phase)
does not form. A suitable compromise for achieving zinc coating on silicon killed substrate is to use steel
with a silicon content in the “Sebisty range” (~ 0,15 to 0,25 wt. %). These coatings are typically thicker and
more brittle than those arising from silicon - killed steels, but thinner and with better pronounced
structure than those formed on steels with silicon content in the “Sandelin range” (0,03 to 0,12 wt. %).
However, the thinner coating consists of a compact group of delta phase (δ1k + δ1p) and often the
grouping phase gamma1 (Γ1 ) and gamma (Γ). The mechanical resistance of the coatings formed on these
steels is sufficient . Conversely, steels with silicon content above 0,28 wt. % are not recommended for hot
dip galvanizing. The coating again consists of disordered crystal phase group zeta (ζ) which block
unreacted zinc atoms . Figure 7 summarizes the effect of silicon content in the galvanized steel on the
coating thickness formed on a profile with a wall thickness of approximately 5 mm.

Figure 7: Effect of silicon in the steel on the total thickness of the resulting zinc coating.

20
Effect of Phosphorus :

In unalloyed steels, a small amount of phosphorus appear as a ballast material from the steel production
process itself.

In the case of batch galvanizing, it is generally accepted that phosphorus, like silicon, increases the
dissolution rate of iron in the zinc melt and thereby promotes formation of a thicker coating with phase
zeta (ζ) dominating the structure. This problem was observed primarily in rolled sheets destined for the
automotive industry, where the coating was created by continuous hot-dip galvanizing with the addition
of aluminium in the working bath. It has, however, been accepted that the negative effect on the zinc
coating of the silicon content of the steel outweighs the negative effect of the phosphorus
ballast.Therefore, empirical relationships were established summarizing the negative influence on coating
formation of both elements within continuous hot dip galvanizing. Equation {1} presents the relationship
limiting the maximum levels of both ballast elements for cold rolled steel to achieve high-quality coating.
Equation {2} presents the same for hot-rolled sheets (unit representation of individual elements in the
steels is given in wt. %) . Si < 0,03 and Si + 2,5 P < 0,04 {1} Si < 0,02 and Si + 2,5 P < 0,09 {2} The effect of
phosphorus content in the steel on the development and thickness of the zinc coating resulting from
batch, low - temperature hot-dip galvanizing is discussed only marginally. The findings summarized above
are based on practical experience rather than substantiated research work. The reason is probably that
for steels intended for batch zinc galvanizing, the composition and the coating thickness is primarily
affected by the silicon content of the steel and possibly other parameters (thickness of galvanized parts).
The effect of phosphorus on development, composition and total thickness of the coating is then
distorted.The influence of the phosphorus content on the composition and the thickness of the zinc
coating is closely discussed in professional circles with regard to continuous galvanizing (t ~ 450 ° C) of
plates. Sheets are made of ferritic steel and, therefore, contain a low carbon content for improved
malleability. The steel is further alloyed with low contents of

and/or Nb (interstitial - free steels) to further improve the malleability and simultaneously prevent the
segregation of carbon in the form of Fe3 C and phosphorus in the form of Fe3 P at the grain boundaries
during annealing. In this case, we discuss the influence of these elements on the phase Fe3 P segregation
at grain boundaries, since their presence leads to phase segregation of Ti - P and/or Nb - P within the
grains. Their influence thus maintains high reactivity of the grain boundaries of ferritic steel. The influence
of these factors on the formation, composition and thickness of the zinc coating must be addressed with
a further coating in a zinc bath with additional aluminium (usually 0,2 wt. %). Furthermore, the effect of

21
subsequent annealing on the coating process should be considered. Annealing results in diffusion
processes forming a continuous layer of intermetallic phases, which ensures the appropriate combination
of mechanical and corrosion properties. This grouping ensures high quality coating with a suitable
combination of mechanical and corrosion properties and good adhesion to the steel substrate and
between phases. Use of a bath containing aluminium may result in the formation of an undesirable
outburst structure, which is an unevenly developed layer of zinc on the steel. This structure is a typical
feature of the delta phase (δ1k + δ1p) with strongly scattered grains on the follow-up phase zeta (ζ). The
gamma (Γ + Γ1 ) phase only occurs marginally in this structure. The formation of this structure is
synergistically associated with the aluminium content of the zinc melt and the reactivity of the grain
boundaries of steel, while inhibiting the formation of an uneven coating of Fe2 Al5 . In this regard, we
discuss the influence of the phosphorus content on the Fe3 P phase segregation at grain boundaries,
which results in reduced activity for the formation of a coating at these locations. In the case of baths
without aluminium content, the phosphorus content does not affect the creation kinetics and structure
of the zinc coating. If the aluminium content of the bath is within the usual amounts (0,2 wt. %), then the
kinetics of the formation of the local inhibitory layer of Fe2 Al5 is not affected by the phosphorus content
of the steel. The studied delayed creation of individual intermetallic Fe - Zn is therefore not affected by
the content of phosphorus in the steel, but rather by the overall reactivity of the grain boundaries. Jordan
and Marder describe the effect of the content of Ti (Ti + Nb + P) on the kinetics of formation and
composition of the zinc in the bath with and without the usual aluminium content at 450° C. In the case
of aluminium-free baths, it is obvious that the increased amount of Ti in the steel has no effect on the
kinetics of the coating composition; however, an increased amount of phosphorus in steels containing Ti
and Nb is likely to slow the growth of phase gamma (Γ + Γ1 ). Baths containing aluminium are used to limit
the growth phase zeta (ζ). At the same time an increased amount of Ti in the steel accelerates the kinetics
of formation of intermetallic phases Fe - Zn. Even in this case, it was verified that an increased amount of
phosphorus slows the growth of phase gamma (Γ + Γ1 ). Gamma phase grouping (Γ + Γ1 ) growth slowdown
due to the phosphorus content of the steel is also documented in. According to recently conducted
research [8], it has been verified that the addition of phosphorus to steel refines the steel grain, although
the Fe3 P phase is segregated at the grain boundaries of the steel. This phase slows the growth of phase
gamma (Γ + Γ1 ) or even prevents its occurrence. Conversely, with increasing phosphorus content growth
phase zeta (ζ) is promoted. It can be summarized that phosphorus has a generally negative effect on hot-
dip galvanizing (i.e. even in batch galvanizing processes), probably increases the solubility of iron in the
melt, and promotes a negative “Sandelin effect”. Additional undesirable effects include constraints on

22
phase gamma (Γ + Γ1 ) growth and, simultaneously, increasing the layer thickness of the zeta phase (ζ),
which generally impairs the overall mechanical properties of the coating and its adhesion to the substrate.

Effect of Carbon:

Most often batch galvanized-steel with a carbon content up to 0,2 wt. % is intended for welded
construction. For these steels, it has not been shown that carbon content had a significant effect on the
formation, composition and thickness of the zinc layer. Likewise, the different structures due to the
resulting steel carbon content are irrelevant, and thus comparable to coatings formed on ferritic and
ferritic – pearlitic steels. However, increased carbon content (> 0,3 wt. %) can increase the reaction rate
of dissolution of iron in the melt and, therefore, disproportionately increase the overall coating thickness
of phase zeta (ζ) growth. Such a coating is then very fragile and easily descales from the steel.Conversely,
in professional circles, it has been shown that for steels with a low carbon content the undesirable
outburst structure can occur. With increasing carbon content in the tested steels, this phenomenon
disappear. However, as shown above, this may be related more to the total area of the grain boundaries,
than to the carbon content. Effect of Aluminium Because of the risk of formation of unfavorable coatings
on silicon-killed steels (“Sandelin effect”) structural steel intended for hot dip galvanizing is often
deoxidized by aluminium. Due to its high affinity for nitrogen, is has the added advantage of providing
increased resistance to aging. Compared to silicon, aluminium has a higher affinity for iron, and therefore
forms intermetalic phases, usually Fe2 Al5 , FeAl2 , FeAl3 . However, the free aluminium may, diffuse to the
surface of the steel and create a discontinuous Fe2 Al5 inhibition layer during hot galvanizing. In parallel,
as in baths containing aluminium, the formation of this layer may result in the formation of an undesirable
outburst structure. Although there are no specialized studies summarizing the effects of aluminium
content on the kinetics of formation, composition and thickness of the zinc coating, it is believed that a
comparable aluminium content in the steel, compared to silicon content, does not cause the undesirable
“Sandelin effect”. Effect of Manganese Because of its position in the periodic table and comparable size
with iron atoms, manganese is commonly contained in construction steel as a ballast material. Unlike
other elements, its effect on the kinetics of formation, the thickness and composition of the zinc layer is
entirely negligible. Conversely, it was shown that an increased amount of manganese (> 1,25 wt. %) in
silicon-killed steel positively influences the mechanical properties of the coating. This is most likely due to
the closer arrangement of the resulting zeta (ζ) phase. Effect of Sulfur The increased sulfur content in steel

23
due to deliberate alloying, e.g. cutting steel (manufacture of fasteners), ensures its easy machinability. In
operation, galvanizing showed that sulfur contents greater than 0,15 wt.% again increase the solubility of
iron in molten zinc, and lead to the formation of thick coatings with insufficient mechanical properties.

2.6 Effect of welding current on mechanical properties of

galvanized chromided steel sheets in electrical resistance spot
welding:

In this study, the effect of welding current on the quality of weld joint and obviously on tensile-shear and
tensile-peel strengths of galvanized chromate steel sheets having 1.2 mm thickness in electrical resistance
spot welding was investigated. A timer and current controlled electrical resistance spot welding machine
having 120 kVA capacity and pneumatic application mechanism with a single lever was used to prepare
the specimens. Welding periods were chosen as 5, 10, 12 and 15 cycles and also welding currents were
increased from 4 kA up to 12 kA by rise of 1 kA. The electrode force was kept constant at 6 The prepared
welding specimens were exposed to tensile-shear and tensile-peel tests. Motor-car manufacturers must
be answerable to the desires of customers to cope with worldwide competition. These are corrosion
resistance of chassis, the high strength values of used sheet, the stiffness of weld joint when exposed to
an external force and the ability to absorb impacts, low cost and comfort. Some investigations were done
in order to maintain the requirements mentioned above by automotive engineers. One of them was
micro-alloyed sheets usage having high welding ability, strength and good resistance to corrosion. There
are a number of methods to make sheets resistant to corrosion without changing the composition of steel
such as coating the surface to prevent from corrosion damage called galvanization, or chromate. Some
methods contain the alloying element addition which is enduring the corrosion failure to the steel during
production of automotive sheets. In the spot welding process, two or three overlapped or stacked
stamped components are welded together as a result of the heat created by electrical resistance. This is
provided by the work pieces as they are held together under pressure between two electrodes (Fig 8) .
Spot welding may be performed manually, robotically or by a dedicated spot welding machine. The similar
spot welds having the same property can be obtained in high production speeds by controlling welding
current, electrode force and weld time automatically. The required low voltage and high current intensity
for welding process is obtained from transformators and the pressure is obtained from hydraulic,
mechanic and pneumatic devices (Fig. 9).The heat required for these resistance welding processes is

24
produced by the resistance of the workpieces to an electric current passing through the material. Because
of the short electric current path in the work and limited weld time, relatively high welding currents are
required to develop the necessary welding heat. The amount of heat generated depends upon three
factors; the amperage, resistance of the conductor and the duration of current. These three factors affect
the heat generated as expressed in the formula

where Q is the heat generated (J), I is the current (A), R is the resistance of the work (X) and t is the
duration of current (s). The secondary circuit of a resistance welding machine and the work being welded
constitute a series of resistances. The total resistance of the current path affects the current magnitude.
There are, in effect, at least seven resistances connected in series in a weld that account for the
temperature distribution and the sum of them is expressed as R as shown in (Fig 8).

Fig 8: The occurrence of resistances in electrical resistance spot Welding .

where these resistances can be divided into two groups as material resistances (R2, R4, R6, R7) and
contact resistances between electrode and workpiece (R1 and R5). Material resistances are generated

25
depending on the physical properties of workpieces (i.e., R2 and R4), and electrodes (i.e., R6 and R7).
These cannot be changed, while contact resistances are variable generated depending on the conditions
of electrode toes. The required resistance for spot weld formation is R3. The higher the value of it, the
higher the weldability is obtained easily. The magnitude of this resistance depends upon the surface
condition of the base metal and the electrode force; F in welding current, I at welding time, t. This is a
point of high heat generation, but the surface of the base metal does not reach the fusion temperature
during the current passage, due to the high thermal conductivity of the other electrodes and the fact that
they are usually water cooled. The resistance R in the heat formula is influenced by welding pressure
through its effect on contact resistances, R1, R3 and R5, at the interface between the workpieces. The
heating in R1 and R5 contact zones must be compensated and these electrodes temperatures must be
low. This is achieved by means of good conducting materials and electrode surfaces. In order to perform
accurate heat conduction, the surfaces must have been cleaned from dirty substances like oil, rust or paint
which act as a barrier to the heat passage. The contact resistances affect the strength of weld joint. The
effect of welding current on heat generation According to Joule law, mentioned above, the most
important parameter affecting the amount of heat obtained is welding current, I. The welding current
decreases with increasing resistance and induction in constant secondary voltage. The magnitude of
induction may be varied due to lever spacing in secondary circuit and magnetical materials inside here.
The constant welding current affecting the weld joint is only maintained by constant resistance and
induction. Inadequate heat energy cannot be achieved by bonding. However, excess welding current
causes void and crack formations, partially spurt out of molten metal and so the tensile-shear strength of
joint decreases.[11]

Fig 9: The schematic illustration of electrical resistance spot welding.

26
2.7 EXPANSION OF LONG LENGTH SHEETS:
Any piece of metal, free to move, will increase in size with an increase in temperature, and will decrease
in size with a decrease in temperature. The magnitude of this thermal expansion and contraction varies
between different types of metal, but for each metal, the change in length is proportional to the change
in temperature and the sheet length. The change in sheet length can be calculated as:

∆L = 12(∆T)(L)(E) where:
∆L = change in sheet length,inches
∆T = change in temperature,degrees F
L = total sheet length,feet
E = coefficient of linear expansion,
= 0.0000065 for Galvanized or Galvalume Steel
When designing a structure, the expansion of the sheeting must be considered, especially when aluminum
panels (which expand twice as much as galvanized steel) are used. Standing seam roof systems like
Sentrigard Metal Roofing Systems' 1 1/2" SSR are designed to allow for thermal movement of the sheets.
Careful attention must be paid to the ridge and gable details and any roof penetrations. All of these
transitions must allow for expansion and contraction. If they do not, fastener holes will elongate and leaks
will occur. Sentrigard Metal Roofing Systems' Standing Seam installation manuals provide recommended
details. In exposed fastener systems, the expansion/contraction of long length sheets may cause fastener
hole elongations and eventually leaks. Therefore, the overall sheet lengths must be limited. Sentrigard
Metal Roofing Systems recommends limiting exposed fastened aluminum panels to 16’ long and steel
panels to 40’ or 45’ maximum length. For run lengths longer that these, end laps with butyl sealant should
be used.[12]

27
 Table 3: Change in panel Length for Galvanized and Galvalume Steel Panels.

2.8 Zn Coating Characteristics and Performance:

The batch hot-dip galvanized coating consists of a series of zinc-iron alloy layers with a surface layer of
pure zinc (Figure 4). The unique intermetallic layers are tightly bonded (3,600 psi) to and harder than the
base steel, offering excellent abrasion resistance. The zinc-iron alloy layers are metallurgically bonded to
the steel; and thus, become an integral part of the steel rather than just a surface coating. Furthermore,
as mentioned previously, zinc is anodic to steel; therefore, even if the durable intermetallic layers of the
hot-dip galvanized coating are damaged (up to ¼” in diameter) adjacent zinc will sacrificially protect the
exposed steel until all of the surrounding zinc is consumed. Another unique characteristic of the batch
hot-dip galvanized coating is its uniform, complete coverage. During the diffusion reaction in the kettle,
the zinc-iron alloy layers grow perpendicular to all surfaces, ensuring edges, corners, and threads have
coating equal to or greater than flat surfaces. Additionally, because hot-dip galvanizing is a total
immersion process, all interior surfaces of hollow structures and difficult to access recesses of complex
pieces are coated. This complete, uniform coverage means critical points where corrosion commonly

28
occurs are afforded the same protection as accessible flat, exterior surfaces. Batch hot-dip galvanizing
produces a coating thicker and/or denser than other zinc coating processes. The governing specifications
for hot-dip galvanizing; ASTM A123, A153, and A767 as well as CSA specification G 164, and ISO 1461
contain minimum coating thickness requirements based on steel type and thickness.

Because both are hot-dip processes, continuous sheet and batch hot-dip galvanizing are often confused.
One major difference in the two coatings is the thickness. The continuous sheet galvanizing process has
greater control and preciseness when it comes to zinc thickness as the air knife used after galvanizing
ensures a uniform thickness across the steel sheet. The coating is mostly unalloyed zinc, though minimal
alloy layers are present, and is ductile and able to withstand deep drawing or bending without damage.
This is important as the coating is applied prior to final fabrication such as punching, bending, and cutting.
Because of the precise control of coating thickness, continuous sheet is stocked in a variety of coating
weights. One of the most common zinc coatings is Class G90, which has 0.9 oz/ft2 of zinc (total both sides)
or about 0.80 mils (20 µm) per side. Because the continuous sheet coating is applied pre-fabrication, final
forming and placement often includes punching holes, bending, cutting, etc., which creates uncoated
areas. Like batch hot-dip galvanizing, the surrounding zinc of continuous sheet coatings will provide
cathodic protection to these uncoated areas; however, as there is much less zinc present, best practice is
to touch up any exposed areas after fabrication to extend service life.[13]

2.9 The Spangle on Hot-Dip Galvanized Steel Sheet:

For years, galvanized articles made by hot-dip coating techniques were identified by the characteristic
spangled appearance. In many cases, this is still true today. However, because of some changes in the
manufacturing processes associated with zinc production and the galvanizing process, not all hot-dip
galvanized steel sheet made today has a visible spangle.

29
2.9.1 What is a Spangle?
The dictionary defines “spangle” as a glittering object. When spangle is used to define the surface
appearance of galvanized steel sheet, it includes the typical snowflake-like or six-fold star pattern that is
visible to the unaided eye. The following photograph shows the details of this pattern. This photograph
shows the typical spangle pattern of a galvanized coating. The surface is magnified about 10X.

Note the 6-fold

symmetry of this
spangle.

Red arrow defines

the direction of
growth of the
“primary” dendrite
arm within the
solidifying grain of Zn
.

“Secondary” dendrite
arms growing laterally
away from the primary
arm.

Fig 10: The spangled structure of a hot-dip galvanized coating.

2.9.1.1 The Solidification Process:

First, one needs to understand that the development of spangles occurs when the molten zinc adhering
to the steel sheet is cooled below the melting point of zinc. The freezing point is approximately 419°C
(787°F). At this temperature, the randomly-arranged atoms in the liquid zinc begin to position themselves
into a very orderly arrangement. This occurs at many random locations within the molten zinc layer. This
transformation from a disordered arrangement of the atoms into an orderly arrangement defines the
“solidification” or “crystallization” process. The small solidifying areas within the molten zinc are defined

30
as “grains”1. As the individual atoms of molten zinc attach themselves to a solidifying grain (causing grain
growth), they form into a distinct array, or crystal. In the case of zinc, the crystals form with hexagonal
(six-fold) symmetry. It is this fundamental way in which the individual atoms of zinc arrange themselves
as the solid zinc grains grow larger that leads to the often-visible hexagonal symmetry of the final spangle.
When the coating is finally completely solidified, the individual spangles define specific individual grains
of zinc.

“Nucleation” is the term used to define the process of transformation of randomly arranged atoms of
molten metal into a small, organized array of atoms in the “seed” crystals at the initial stage of
solidification. A high rate of nucleation during the freezing process would tend to cause the formation of
numerous small grains in the final solidified structure, while a low rate of nucleation would tend to favor
the growth of large grains.

2.9.1.2 Dendritic Growth:

There is another aspect of the solidification process that leads to the snowflake pattern in galvanized
coatings, viz., “dendritic” (meaning tree-shaped) growth. Dendritic growth causes the individual growing
(solidifying) grains to grow into the melt (the molten zinc coating) with a distinct leading rounded edge.
A “primary” dendrite arm is identified in the photograph above. There are secondary dendrite arms that
grow laterally away from the “primary” dendrite arms.

Dendritic growth of grains during the solidifying of metals is very common. The reason that the dendrites
are readily visible in a galvanized coating is that we are basically seeing a two-dimensional version of an
as-cast, dendritic, solidified grain structure. Remember, the coating is less than 0.001 in (25 µm) thick,
considerably less than the diameter of a spangle. In other metals (for instance in the steel substrate), the
original as-cast, three dimensional, dendritic structure of the grains is subsequently broken up into many
smaller, more equiaxed grains. This is related to the effects of hot rolling (for example, rolling a 9-inch

31
thick slab of steel into a 0.050-inch thick steel sheet), cold rolling and recrystallization during the sheet-
annealing process.

The rate of growth of the dendrite arms during the solidification of a galvanized coating competes with
the rate of nucleation of new grains within the molten zinc. This process determines the final size of the
completely solidified structure. In the case of the above photograph, which is a galvanized coating with
a well-defined large spangle pattern, the rate of dendrite growth dominated the solidification process
leading to a small number of large spangles. One characteristic of such spangles is that they are thickest
at their centers and thinnest at their edges, or grain boundaries. The grain boundaries can be said to be
“depressed” and are difficult to smooth by subsequent temper passing.

Dendritic growth is not the only way in which grains can grow during the solidification process. It requires
one or more special conditions to be present. One of these conditions is the presence of other elements
in the molten metal. These can be either intentionally added alloying elements or impurities. In the case
of galvanized coatings on steel sheet, the most common reason for the well-defined dendritic growth
pattern is the presence of lead in the coating. It has long been thought that the reason lead results in
large spangles is that it has the effect of reducing the number of nucleation sites. In recent work, it is
proposed that that the presence of lead decreases the solid/liquid interfacial energy in the solidifying
coating. This leads to an increase in dendrite growth velocity, resulting in large spangles. Lead
precipitates at the coating surface and the varying distribution of lead particles across the surface define
the optical appearance (dull vs. shiny spangles).

Lead is a common impurity in zinc. In years gone by, the most common form of zinc metal production
involved smelting, distillation and condensation. Lead is a common metal found in zinc-containing ores,
and this refining process carried it through as an impurity in the zinc. Therefore, in the early days of
galvanizing, lead was almost always present in the zinc, and it was common to see the spangle pattern.
Galvanized coatings on steel became identified by the characteristic spangle. Essentially, all hot-dip
galvanized coatings had a spangled appearance. If the spangle wasn’t visible, the users “knew” that the
steel had not been galvanized.

The first galvanized coatings contained as much as 1% lead. During the past 25 years, the presence of
such high lead levels has not been common in the galvanized coatings on steel sheet, at least not in North
America, Europe, and Japan. Typical concentrations of lead in most galvanized sheet made during the

32
past 25 years are less than 0.15%, often as low as 0.03 to 0.05%. However, this amount of lead is still
sufficient to develop dendritic growth behavior during the solidification process. Today, a typical level of
lead in the coating bath on lines where the primary product has a well-developed spangle pattern is in
the range of 0.05 to 0.15% lead.

2.10 Non-Spangled Coatings:

In recent times, the production of zinc from zinc-containing ores has been changed to an electrolytic
recovery method. In this method of zinc production, the refined zinc is very pure, with the lead being
excluded. This change occurred at a time when many users of galvanized sheet, especially those desiring
a high quality finish after painting, such as the automotive and appliance industries, needed a non-
spangled coating. Removing the lead gave them the product they desired. The amount of lead in the
coating for lead-free coatings is less than 0.01%.

Lead-free coatings still have a grain pattern that is visible to the unaided eye. Typically, the spangles are
about 0.5 mm in diameter and are clearly visible when seen at 5 to 10X. However, the grains no longer
grow by a dendritic mode but by a cellular mode of growth. Essentially, the grains of zinc nucleate on the
steel surface, and grow outward toward the free surface. The absence of lead takes away the strong
driving force for growth in the plane of the sheet, preventing the formation of large spangles. Rapid
spangle growth cannot occur and the absence of lead results in the coating appearing uniformly shiny.

This non-spangled coating, when combined with temper rolling by the galvanized-sheet producer, can be
made very smooth. The large grain boundary depressions and surface relief of a spangled coating are not
present. The coating can be painted to give a very smooth, reflective finish.

An added advantage of producing a lead-free galvanized coating is that is not susceptible to a problem
known as intergranular corrosion. This is a coating failure mechanism in damp environments caused by
the lead concentrating at the spangle boundaries.

2.11 Why is Lead Still Used on Many Galvanizing Lines?

The manufacture of non-spangled coatings, or lead-free coatings, is not easily done. The reason relates
to the influence of even a small amount of impurities, such as lead, on the viscosity of the molten zinc. It

33
is difficult to avoid small sags and ripples in the coating when the lead is totally removed. The thicker the
coating, the greater the tendency to form sags and ripples. Fortunately, the automotive and appliance
industries need only relatively thin coatings (typically 60 to 80 g/m2/side) of zinc to obtain the level of
corrosion resistance their customers demand. Also, the products used by these industries are made on
relatively new high-speed lines, or older lines that have been refurbished to allow production at high
speeds. The combination of high processing speeds and low coating weights allows the producer to use
lead-free coating baths, avoid the development of spangles, and still attain a smooth coating.

If the end user requires a heavier coating mass (100 g/m2/side and higher), there is a distinct tendency
for the coating, when applied from a lead-free bath, to develop very visible sags and ripples. The result is
that the surface is not smooth and the coating locally is composed of thick and thin regions. This tendency
for sags is exacerbated a low line speeds (<75 meters/minute). Thus, older, low speed coating lines, lines
designed to process heavy-gauge sheet, and those that are used to make heavy coating weight products
(275 g/m2 meter or G90 and heavier) typically still have some amount of lead in the coating bath to
improve the final coating uniformity. Often, the concentration of lead in the coating bath is between 0.05
and 0.15%.

The net result is that the final product from many lines still has a visible spangle pattern. This meets with
the marketplace needs in that a number of industries, especially those that use bare (unpainted)
galvanized sheet, still want the large, bright, reflective spangle pattern. Some galvanized-sheet
manufacturers have established practices on their older or low-speed lines where they use essentially
lead-free zinc, but add a small amount of antimony to the zinc coating bath. The antimony addition
accomplishes the same influence on viscosity and spangle formation as lead. The final result is a smooth,
[14]
visible spangle coating. Typically, the amount of antimony in the coating bath is about 0.03 to 0.10%.

2.12 Corrosion:
Corrosion is degradation of materials’ properties due to interactions with their environments, and
corrosion of most metals (and many materials for that matter) is inevitable. While primarily associated
with metallic materials, all material types are susceptible to degradation. Degradation of polymeric
insulating coatings on wiring has been a concern in aging aircraft. Even ceramics can undergo degradation
by selective dissolution. The fundamental cause or driving force for all corrosion is the lowering of a
system’s Gibbs energy. As a result of this uphill thermodynamic struggle, the metal has a strong driving

34
force to return to its native, low energy oxide state. This return to the native oxide state is what we call
corrosion and even though it is inevitable, substantial barriers (corrosion control methods) can be used
to slow its progress toward the equilibrium state. Thus it is the rate of the approach to equilibrium that
is often of interest. This rate is controlled not only by the nature of the metal surface, but also by the
nature of the environment as well as the evolution of both.[15]

2.12.1 The Electrochemistry of Corrosion:

The surfaces of all metals (except for gold) in air are covered with oxide films. When such a metal is
immersed in an aqueous solution, the oxide film tends to dissolve. If the solution is acidic, the oxide film
may dissolve completely leaving a bare metal surface, which is said to be in the active state. In near-
neutral solutions, the solubility of the oxide will be much lower than in acid solution and the extent of
dissolution will tend to be smaller. The underlying metal may then become exposed initially only at
localised points where owing to some discontinuity in the metal, e.g. the presence of an inclusion or a
grain boundary, the oxide film may be thinner or more prone to dissolution than elsewhere. If the near-
neutral solution contains inhibiting anions, this dissolution of the oxide film may be suppressed and the
oxide film stabilised to form a passivating oxide film which can effectively prevent the corrosion of the
metal, which is then in the passive state. When the oxide-free surface of a metal becomes exposed to the
solution, positively charged metal ions tend to pass from the metal into the solution, leaving electrons
behind on the metal, i.e.

The accumulation of negative charge on the metal due to the residual electrons leads to an increase in
the potential difference between the metal and the solution. This potential difference is called the
electrode potential or, simply, the potential of the metal, which thus becomes more negative. This change
in the potential tends to retard the dissolution of metal ions but to encourage the deposition of dissolved
metal ions from the solution onto the metal, i.e. the reverse of reaction (1). Continuation of the
dissolution and deposition of metal ions would result in the metal reaching a stable potential such that
the rate of dissolution becomes equal to the rate of deposition. This potential is termed the reversible

35
potential Er and its value depends on the concentration of dissolved metal ions and the standard
reversible potential Eo for unit activity of dissolved metal ions, aMn+, i.e.

where R is the gas constant, T the absolute temperature, F the Faraday and in the number of electrons
transferred per ion. Once the potential reaches the reversible potential, no further net dissolution of
metal occurs. The net amount of metal which dissolves during this process is generally very small. The
potential of a metal in a solution does not usually reach the reversible potential but remains more positive
because electrons can be removed from the metal by alternative reactions. In acid solutions, electrons
can react with hydrogen ions, adsorbed on the metal surface from the solution, to produce hydrogen gas.

The occurrence of reaction (4) permits the continued passage of an equivalent quantity of metal ions into
solution, leading to corrosion of the metal. Reaction (4) is also reversible and has a reversible potential
given by

where PH2 is the partial pressure (fugacity) of hydrogen gas. If the partial pressure of hydrogen is allowed
to build up, then the reversible potential of reaction (4) could be attained. No further net reaction of
hydrogen ions would occur and so the net dissolution of metal ions would effectively cease. Normally
hydrogen escapes from the system, so that the potential remains more negative than the reversible

36
potential and corrosion continues. In neutral solutions, the concentration of hydrogen ions is too low to
allow reaction (4) to proceed at a significant rate, but electrons in the metal can react with oxygen
molecules, adsorbed on the metal surface from air dissolved in the solution, to produce hydroxyl ions

Again, the potential of the metal remains more negative than the reversible potential for reaction (6)

Thus, corrosion can proceed by the coupling of reactions (1) and (6).

In electrochemical terminology, an electrode at which an oxidation reaction occurs is called an anode.

The process of oxidation involves a loss of electrons by the reacting species, as occurs in the metal
dissolution reaction (1). Thus an area of a corroding metal where metal dissolution occurs is an anode and
metal dissolution is the anodic reaction of corrosion. An electrode at which a reduction reaction occurs is
called a cathode. Reduction involves a gain in electrons, as occurs in reactions (4) and (6). The reduction
of hydrogen ions and oxygen are thus the cathodic reactions of corrosion and the area of a corroding
metal where these reactions occur is a cathode.[16]

2.12.2 Classifications of Corrosion:

Corrosion can be classified in different ways, such as Chemical and electrochemical High temperature and
low temperature Wet corrosion and dry corrosion. Dry corrosion occurs in the absence of aqueous
environment, usually in the presence of gases and vapours, mainly at high temperatures. Electrochemical
nature of corrosion can be understood by examining zinc dissolution in dilute hydrochloric acid. Zn + 2HCl
= ZnCl2 + H2 Anodic reaction is Zn = Zn++ + 2e with the reduction of 2H+ + 2e = H2 at cathodic areas on the
surface of zinc metal. There are two half reactions constituting the net cell reaction. Environmental effects

37
such as those of presence of oxygen and other oxidizers, changes in flow rates (velocity), temperature,
reactant concentrations and pH would influence rates of anodic and cathodic reactions. Each form of
corrosion has a specific arrangement of anodes and cathodes and specific patterns and locations
depending on the type can exist. The most important types are:

38
 Table 4: ASM Classifications of Corrosion Types:

Crevice corrosion is a localized attack on a metal adjacent to the crevice between two joining surfaces
(two metals or metal-nonmetal crevices). The corrosion is generally confined to one localized area to one

39
metal. This type of corrosion can be initiated by concentration gradients (due to ions or oxygen).
Accumulation of chlorides inside crevice will aggravate damage. Various factors influence crevice

corrosion, such as. Materials: alloy composition, metallographic structure. Environmental conditions such
as pH, oxygen concentration, halide concentrations, temperature. Geometrical features of crevices,
surface roughness. Metal to metal or metal to nonmetal type.

Filiform corrosion is a special type of crevice corrosion. Pitting corrosion is a localized phenomenon
confined to smaller areas. Formation of micro-pits can be very damaging. Pitting factor (ratio of deepest
pit to average penetration) can be used to evaluate severity of pitting corrosion which is usually observed
in passive metals and alloys. Concentration cells involving oxygen gradients or ion gradients can initiate
pitting through generation of anodic and cathodic areas. Chloride ions are damaging to the passive films
and can make pit formation auto-catalytic. Pitting tendency can be predicted through measurement of
pitting potentials. Similarly critical pitting temperature is also a useful parameter. Uniform corrosion is a
very common form found in ferrous metals and alloys that are not protected by surface coating or
inhibitors. A uniform layer of “rust‟ on the surface is formed when exposed to corrosive environments
Atmospheric corrosion is a typical example of this type.

Galvanic corrosion often referred to as dissimilar metal corrosion occurs in galvanic couples where the
active one corrodes. EMF series (thermodynamic) and galvanic series (kinetic) could be used for prediction
of this type of corrosion. Galvanic corrosion can occur in multiphase alloys. Eg: - Copper containing
precipitates in aluminium alloys. Impurities such as iron and copper in metallic zinc. Differential aeration
(oxygen concentration cell) and ion concentration (salt concentration) cells create dissimilar polarities
(anodic and cathodic areas) Eg:-Pitting of metals. Rusting of iron.

40
 Fig 11: Differential oxygen cells in rusting of iron

Selective leaching (Dealloying) refers to selective dissolution of active metal phase from an alloy in a
corrosive environment. Examples:

a) Brass containing copper and zinc. Since zinc is anodic to copper, selective dezincification occurs in a
corrosive medium, enriching the cathodic copper in the matrix (colour of brass turns red from yellow).

b) Graphitization of grey cast iron-graphite being cathodic enhances dissolution of iron in the matrix,
leaving behind a graphite network. There are several other examples of dealloying besides the above. Tin
Bronzes in hot brine or steam-Destannification.

Precious metal alloys such as gold containing copper or silver – strong acids, sulfide environment -
preferential dissolution of copper or silver. Cupro-nickel alloys in condenser tubes-denickelisation.
Localised attack at or nearer to grain boundaries in a metal or alloy can be termed as intergranular
corrosion. Generally the following factors contribute to intergranular corrosion. Impurities and
precipitation at grain boundaries. Depletion of an alloying element (added to resist corrosion) in the
grainboundary area. A typical example is sensitized 18-8 stainless steels when chromium carbide is
precipitated along grain boundaries. Lowered chromium content in the area adjacent to grain boundaries,
leads to formation of anodic and cathodic areas. Such intergranular corrosion is common in stainless steel

41
welded structures and is referred to as weld decay. Intergranular attack can occur in other alloys as well.
For example, Duralumin-type alloys (Al – Cu) due to precipitation of CuAl2

Erosion corrosion is the deterioration of metals and alloys due to relative movement between surfaces
and corrosive fluids. Depending on the rate of this movement, abrasion takes place. This type of corrosion
is characterized by grooves and surface patterns having directionality. Typical examples are Stainless alloy
pump impeller, Condenser tube walls. All equipment types exposed to moving fluids are prone to erosion
corrosion. Many failures can be attributed to impingement (impingement attack). Erosion corrosion due
to high velocity impingement occurs in steam condenser tubes, slide valves in petroleum refinery at high
temperature, inlet pipes, cyclones and steam turbine blades. Cavitation damage can be classified as a
special form of erosion corrosion. This is usually caused by formation and collapse of vapour bubbles in
liquids closer to a metal surface. Typical examples include ship‟s propellers, pump impellers and hydraulic
turbines. Surface damage similar to that of pitting can occur and both corrosion and mechanical factors
are involved.

Corrosion occurring at contact regions between materials under load subjected to slip and vibration can
be termed Fretting. Such friction oxidation can occur in engine and automotive parts. Fretting is known
to occur at bolted tie plates on rails. Parameters promoting fretting include: Relative motion between
two surfaces. Interface under load. Both the above produce slip and deformation of surfaces. Wear-
oxidation and oxidation-wear theories are proposed to explain fretting corrosion.

Stress corrosion cracking (SCC) refers to failure under simultaneous presence of a corrosive medium
and tensile stress. Two classic examples of SCC are caustic embrittlement of steels occurring in riveted
boilers of steam-driven locomotives and season cracking of brasses observed in brass cartridge cases due
to ammonia in environment. Stress cracking of different alloys does occur depending on the type of
corrosive environment. Stainless steels crack in chloride atmosphere. Major variables influencing SCC
include solution composition, metal/alloy composition and structure, stress and temperature. Crack
morphology for SCC failures consists of brittle fracture and inter - or trans-granular cracking could be
observed. Higher stresses decrease time before crack initiation. Tensile stresses of sufficient threshold
levels are involved (applied, residual or thermal stresses). Hydrogen embrittlement although many a time
classified under stress corrosion, need be considered separately since the two types respond very
differently to environmental factors. Fracture of metals and alloys under repeated cyclic stresses is
termed fatigue and corrosion under such circumstances is corrosion fatigue (reduction of fatigue

42
resistance). Electrochemical factors come into play in many of the above corrosion forms. Both
thermodynamic and kinetic aspects of electrochemistry of corrosion are discussed in the following
lectures with respect to both corrosion mechanisms and corrosion protection. [17]

2.12.3 Corrosion Theory:

Corrosion is a chemical reaction. A metallic surface is consumed it react with the environment through
redox Reaction.

The first reaction is oxidation reaction and the second reaction is reduction reaction. Corrosion of
potential reduction reaction has higher potential than the corrosion potential of oxidation reaction.

[
IJASR International Journal of Academic and Scientific Research ISSN: 2272-6446 Volume 2, Issue 4

(November-December 2014), PP 01-07]

43
2.12.4 Corrosion Mechanism:

According electro chemistry the corrosion reaction can be considered as taking place by two simultaneous
reactions. The oxidation of a metal at an anode and the reduction of a substance at the cathode, in order
for the reaction to occurs the following conditions must exist .

1. A chemical potential difference must exist between adjacent sites on a metal surface (between alloys
of a different compositions).

2. An electrolyte must be present to provide solution conductivity and as a source of material to be

reduced at the cathode.

3. An electrical path through the metal or between metals must be Available to permit electron flow.
Electro chemical corrosion of iron in contact with water is an example of case that can be used to describe
the electro chemical reactions. In an early neutral or slightly acid environment, the water is dissociated
in to hydrogen ions (H+ ) and hydroxyl ions (OH- ) as

When metal is placed in contact with a liquid surface ionization occurs because of the electric charge
difference at the solid liquid interface. For example iron dissolves in water in the form of positively
charged ferrous ions (Fe2+) where

Electro chemically a chemical substance is oxidized when it loses electrons to a second substance. The
electrode at which oxidation takes place is called anode. A chemical substance is reduced when it acquires
electrons. The electrode at which reduction takes place is called cathode. Hence oxidation reactions
results in the formulation of positive charge ferrous iron at the anode. Ferrous ions moving away from
the metal surface are further oxidized to ferric ions (Fe3+) as follow.

44
The positively charged ferric ion are attracted to the negatively charged hydroxyl ions and from the
corrosion product Fe (OH) 3

The rust consists of iron hydroxide or iron oxide hydrates in various states depending on the degree of
oxidation and dehydration. The reduction reaction at the cathode must be take place concurrently in
order to continue the corrosion process. Several reactions are possible and the one that occurs is
determined by the environment. Without the presence of air or oxygen hydrogen ions can be reduced by
the excess of electrons at the cathode surface and evolves as molecular hydrogen by;

Hydrogen evolution or oxygen reduction within the formation of water is likely to occur in acid media on
the other hand oxygen reduction with formation of hydroxyl ion is more dominant in a neutral or alkaline
environment. In either case there is an increase in alkalinity of the solution at the cathode.

[18]

2.12.5 Causes of Corrosion:

Corrosion can be caused by reactivity of metals. The following are the common causes of corrosion.

1, water on the metal surface dissolves CO2 and O2

45
2, Fe in contact with dissolved CO and O2 under goes oxidation

3, Electrons lost by Fe are taken by H+

On multipoint the first equation by 4 and adding to the second

The dissolved o2 can take electrons directly also

4, Fe2+ reacts with dissolved O2 and water

This chemical formula of rest (Fe2 O3. nH2O) is caused in the presence of salt accelerates or speed up the
rate of Corrosion. Generally Corrosion can be caused by different types of factors those are reactivity of
metal, presence of impurities, presence of electrolyte, presence of air moisture gas like O2 and CO2.[18]

46
2.12.6 Corrosion Resistance:

When iron or steel is exposed to atmospheric oxygen in the presence of water, the wellknown rusting
process takes place. The metal is degraded to form ferric rust, a red-brown compound, which is a sure
sign of electrochemical oxidation of the underlying metal.

4Fe + 3O2 + 2H2O → 4FeO.OH (1)

Nearly all metals, with the exception of gold and platinum, will corrode in an oxidising environment
forming compounds such as oxides, hydroxides and sulphides. The degradation of metals by corrosion is
a universal reaction, caused by the simple fact that the oxide of a metal has a much lower energy than the
metal itself. Hence there is a strong driving force for the oxidation of metals. For example the familiar
metal aluminium, which is used in aircraft, window frames and cooking utensils, is attacked by oxygen to
form the oxide as follows:

4Al + 3O2 → 2Al2O3 (2)

This reaction is strongly exothermic, releasing -1680 kilojoules per mole of oxide. In fact the driving force
of the reaction is so great that powdered aluminium will burn to produce very high temperatures,
sufficient to melt steel. It is important to realise that corrosive attack on a metal can only occur at the
surface of the metal, hence any modification of the surface or its environment can change the rate of
reaction. Thus we have a basis for designing methods to protect metals from corrosion. A number of such
methods have been developed, and they are set out in Table 3. The table shows a variety of different
concepts by which the surface reaction rate can be reduced. Each of these has given rise to a number of
technologies, the majority of which are represented in New Zealand industry. In some cases these
industries are on a very large scale. For example paint manufacture is a major chemical industry which
consumes large quantities of solvents, resins and pigments. Most paint products in New Zealand are used
in corrosion protection. Other major industries involved in corrosion control include electroplating,
anodising, galvanising and the production of corrosion resistant alloys. In this article we will concentrate
on two important methods of corrosion control used in New Zealand industry, namely cathodic protection
and chemical inhibitors. Other types of corrosion control technology, such as electroplating and surface

47
coatings, are covered elsewhere. number of such methods have been developed, and they are set out in
Table 3. The table shows a variety of different concepts by which the surface reaction rate can be reduced.
Each of these has given rise to a number of technologies, the majority of which are represented in New
Zealand industry. In some cases these industries are on a very large scale. For example paint manufacture
is a major chemical industry which consumes large quantities of solvents, resins and pigments. Most paint
products in New Zealand are used in corrosion protection. Other major industries involved in corrosion
control include electroplating, anodizing, galvanizing and the production of corrosion resistant alloys. In
this article we will concentrate on two important methods of corrosion control used in New Zealand
industry, namely cathodic protection and chemical inhibitors. Other types of corrosion control technology,
such as electroplating and surface coatings, are covered elsewhere.

Table 5: Corrosion protection techniques

48
Sacrificial anode is frequently used for ships in seawater and for offshore oil and gas production
platforms such as the Maui gas platform operated by Shell BP Todd Oil Services Ltd. The principle here is
to use a more reactive metal in contact with the steel structure to drive the potential in the negative
direction until it reaches the immunity region. Figure 12 illustrates the principle. Zinc is often used as the
sacrificial anode. In the absence of zinc the corrosion potential ECORR is given by the intersection of the
anodic and cathodic curves. If a zinc electrode is now attached, it produces an anodic dissolution current
at a more negative potential. The intersection with the cathodic curve now occurs at a more negative
potential EPROT in the region in which the steel itself has a negligible corrosion rate. In practice a
reference electrode is used to check that the steel structure has indeed reached the immunity region. A
potential of around -900 mV with respect to the Ag/AgCl reference electrode in seawater is the criterion
for immunity of the steel. In the case of the Maui platform it was not feasible to apply surface coatings to
the steel structure before it was installed, hence the corrosion protection of the 6,000 tonnes of steel
forming the tower depends entirely on cathodic protection by sacrificial anodes made from the aluminium
alloy "Alanode". Some 580 tonnes of this alloy has been used to produce several hundred separate anodes
attached to the legs and braces of the tower under the sea so as to give complete and uniform protection
to all parts of the steel structure. Regular monitoring of the potential of the steel is carried out using
submerged reference electrodes of Ag/AgCl. Aluminium is a sufficiently reactive metal to provide the
required corrosion protection, but a small proportion of indium, about 0.1%, is included in the alloy to
provide efficient anodic action. Pure aluminium alone has such a resistant oxide film that its reactivity is
insufficient to properly protect the steel structure.[19]

49
 Figure 12 - Cathodic protection by a sacrificial anode

2.13 Mechanisms of Anodic Dissolution:

Anodic dissolution proceeds via the formation of chemical bonds between surface atoms and solution
species (solvent molecules and ions). The elucidation of the mechanisms of anodic dissolution consists in
identifying the intermediates species formed on the metal surface and their kinetic role in the irreversible
reaction leading to stable cationic species dissolved in the solution. The complex pH, anion and potential
dependence of the dissolution rate observed experimentally is assumed to reveal the competitive role of
the different mechanisms involving the metallic elements in various oxidation states and anion and
solvent species of the solution. Several mechanisms operating competitively are generally considered.
They take place after a common adsorption-hydrolysis step leading to MOHads intermediate species:

M + H2O → MOHads+H++e- (absorption step)

50
The metal atoms bonded to hydroxyl ligands can then dissolve according to the hydroxo-ligand
mechanism. In the dissolution step, the dissolving atom can maintain its bond with the solution species,
this is the so-called non-catalyzed or consecutive mechanism:

(non catalyzed dissolution step)

The dissolving atom can also translate its ligand to a first nearest neighbor (M'), this is the so-called
catalyzed or catalytic mechanism:

M´+MOHads→M´-MOHads

M´-MOHads+OH- →MOH+aqs+M´OHads+2e- (catalyzed dissolution step)

There is also a competitive branching to prepassive and passive states:

These mechanisms have been studied in detail for iron. The reaction paths found in acidic media are
illustrated in Figure 13. The K1-K2 path is the non-catalytic mechanism operating at low pH and low current
density (i.e., low potential). The K1-K3-K4 path is a catalytic route operating in the ascending part of the
anodic peak at higher current density and at higher pH. The K1-K5-K6 path is the main dissolution route
(catalytic type) of Fe(II) species operating at still higher pH and higher current densities (i.e., higher
potential). Fe(II) species are dissolved. The route leading to Fe(II) prepassivating and Fe(III) passivating
species branches from the Fe(II)ads intermediate species. These different paths illustrate the dependence
of the mechanisms of anodic dissolution on the pH and potential. The mechanisms of anodic dissolution
of other metals are not so well established. Cobalt seems to behave similarly to iron with formation of a
Co(I)OHads catalytic surface species. In contrast the mechanism of anodic dissolution of nickel is quite

51
controversial. As far as chromium is concerned, the non-dependence on pH of the active dissolution rate
is indicative of less complex dissolution routes than for iron. The dissolution route is similar to the K1-K2
path in Figure 13 with Cr(I)OH and Cr(II)OH+ adsorbed intermediates leading to the dissolution of Cr(II)
species and branching to Cr(II)ads pre passive states that may also dissolve. H2 evolution is thought to take
place simultaneously. The contribution of anions other than hydroxyls is commonly experienced through
the dependence of the dissolution on the electrolyte composition at a given pH.

Figure 13. Non-

catalytic and Catalytic Reaction Paths Leading to the Anodic Dissolution and Passivation of Iron in Aqueous
Solutions

The metal atoms can dissolved bonded to anion ligands (A) according to the aniono-ligand mechanism:

Dissolution in the active state can differ from the hydroxo-ligand mechanism in the presence of anions
able to strongly bond to metal atoms. Mixed adsorbed intermediate species, (M(OH)2)ads, (M(OHA))ads and
(M(A)2)ads, have been proposed to play a role in the case of iron in acetate solutions. The competitive
adsorption between halide ions and hydroxyls largely dominates the active dissolution of iron and other

52
metals in the presence of halide ions. A gradual increase of the Cl- content initially reduces the
contribution of the K1-K5-K6 catalytic path in favor of a catalytic step similar to K1-K3-K4, the intermediate
species being Fe(I)Clads instead of Fe(I)OHads [20]

2.14 Hot Dip Galvanizing:

Hot-dip galvanizing is one of the most economical, maintenance-free corrosion protection systems
available. Like any other manufacturing process, hot-dip galvanized steel requires an inspection of the
finished product to ensure compliance with applicable specifications. The inspection process requires a
clear understanding of specification requirements and compliance measurement techniques to make an
accurate assessment. A key feature of hot-dip galvanized (HDG) products is durability, which yields
decades of maintenance-free performance. For any environment, the time to first maintenance of HDG
steel is directly proportional to the thickness of the zinc coating. To plan for this extended service life, the
estimated time to first maintenance in atmospheric exposures can be seen in Figure 14.

FIGURE 14: TIME TO FIRST MAINTENANCE OF HOT-DIP GALVANIZED COATINGS

53
Coating thickness is an important requirement in the specification and effectiveness of hot-dip galvanizing
as a corrosion protection system. However, measuring coating thickness is only one of the many
specification requirements in the inspection process. Other key requirements include adherence,
appearance, and finish.

The requirements for hot-dip galvanized coatings are found in three ASTM specifications:

• A123/A123M Specification for Zinc (Hot-Dip Galvanized) Coatings on Iron and Steel Products.

• A153/A153M Specification for Zinc Coating (Hot-Dip) on Iron and Hardware.

• A767/A767M Specification for Zinc-Coated (Galvanized) Steel Bars for Concrete Reinforcement.

The difference between these specifications is the type of steel product covered by each. ASTM
A123/A123M covers structural steel, pipe and tubing, flat/round bar, wire, reinforcing steel and
assemblies of these steel products. ASTM A153/A153M includes small castings, nails, nuts, bolts, washers,
and small parts centrifuged after galvanizing to remove excess zinc. And ASTM A767/A767M covers only
reinforcing steel bars.[21]

2.15 INFLUENCE OF CHEMICAL COMPOSITION ON CORROSION

RESISTANCE OF GALVANIZED STEEL:

Long-term corrosion protection of galvanized material is ensured predominantly by the coating thickness,
but a significant improvement in corrosion properties of the coated steel material can be achieved by
adjusting the chemical composition of the zinc layer. Properly chosen alloys reduce zinc electrochemical
activity and thus inhibit the formation of corrosion products, which leads to increased corrosion resistance
of coated material. An important group of such hot-dip galvanized coatings consists of coatings enriched

54
by magnesium and aluminum. This paper describes the effect of magnesium and aluminum on the
corrosion resistance of steel sheets in various thicknesses, i.e. different coating weights compared to
conventional zinc coatings. Corrosion test of coatings was carried out in neutral salt spray according to EN
ISO 9227. Reviewed was the surface attack by red rust, i.e. perforation-corrosion of the coating. Keywords:
corrosion resistance, magnesium and aluminum, zinc coating, red rust, perforation-corrosion. Currently,
the zinc coatings are the most widely used method of steel corrosion protection. One of the most
important indicators of the lifetime of galvanized steel sheets is their corrosion resistance in particular
corrosive environment.

Zinc coatings protect in two ways:

• Barrier action (prevent action of oxygen and moisture on the steel surface)

• Cathodic protection at the place of defects (scratches, peeling, cutting edges)

Zinc (Zn) itself is un noble metal with a high susceptibility to corrosion. Nevertheless, its corrosion rate
(kinetics) is low in most environments. It's due to the fact that the zinc surface is rapidly covered by
corrosion products, which protect against further corrosion – the surface is naturally passivated.
Important opportunity in improving the corrosion resistance is alloying the zinc by different metals, which
reduce the electrochemical activity of zinc or its corrosion products and thus increase its corrosion
resistance. A very important group of coatings with increased corrosion resistance consists of zinc coatings
enriched by magnesium. In literature, the effect of magnesium on the properties of zinc coatings has been
of great attention for several years. The first experiments with improving the corrosion resistance of zinc
coatings enriched with magnesium can be dated back to 60ies of last century. The first commercial
coatings with significantly improved corrosion resistance, containing, in addition to zinc, a significant
amount of magnesium and aluminum were introduced in 1998 in Japan. One of such coatings is e.g. SUPER
DYMA coating (Zn-11%Al- 3%Mg-0,2%Si) made by Nippon Steel, and ZAM coating (Zn-6%Al-3%Mg), made
by Nisshin Steel Company. These coatings with excellent corrosion resistance were intended for the
construction industry. Their use in the automotive industry was cumbered by the fact that the addition of
Mg in the ZnAlMg coatings on one hand increased their corrosion resistance, but at the same time a high
content of Al in the coatings led to difficulties in spot welding. While these coatings have been extensively

55
used in Asia, European manufacturers continued in development of Zn-Al-Mg coatings that would both
significantly increase the resistance of steel to corrosion, and also would be suitable for use in the
automotive industry. In 2007, the efforts of European producers led to successful production of Zn-Al-Mg
coatings containing, beside zinc, also 1-2%Al and 1-2%Mg, by Corus. It was found that the coating allows
significant improvement of corrosion resistance, excellent paint adhesion; is suitable for deep drawing,
improves weldability and wear resistance. Compared to traditional zinc, i.e. GI (galvanized) coatings, this
coating does not stick to the forming tools, leading to galling, and compared to GA (Galvannealed)
coatings, this coating does not suffer from powdering and flaking during forming. Additional advantages
of zinc coating enriched by Al and Mg include better surface appearance (suppression of sags, wrinkles)
and improved yield (conversion rate) (at a given substrate thickness it covers by 4% more square meters
of material per ton of steel, with half coating thickness) . Currently, similar zinc coatings are also offered
by other steel companies, such as Thyssen Krupp, Voestalpine, ArcelorMittal and others. In 2010 the
development of alloyed zinc coating began in U. S. Steel Košice. In early 2011, this type of zinc coating was
patented and introduced to market under the name ZINKOMAG. The coating is produced in a zinc melt
containing 0.8 to 1.0% Mg and 0.8 to 1.0% Al.[22]

2.16 Corrosion behavior of galvanized, galvannealed and Zn55Al

coated interstitial free steels:

Zn is probably the most effective anticorrosion coating of carbon steels, acting simultaneously as a very
adherent barrier layer and providing galvanic protection. The approximately 350 mV potential difference
between the equilibrium potentials of E(Zn2+/Zn) and E(Fe2+/Fe) promotes the protection of occasionally
exposed steel surfaces, when the coating is damaged. The lifetime of a Zn coating depends on its slow and
homogeneous consumption, and increases if it is dissolved, mainly when the substrate is exposed.
Therefore, the study of the electrochemical behavior of Zn and Zn alloys in different media is important
to predict the behavior of Zn coated steels in applications, as in the automobile industry and in roofs and
facades. Specifically in the automobile industry, hot-dip Zn-based coatings are often applied to IF steels
due to the ductility necessary for deep drawing. Zn based coatings may be obtained by electrodeposition,

56
thermal spraying or immersion in liquid metal baths (hot-dipping, HD) at temperatures around 450 °C.
The most common industrial HD Zn coatings used in Brazil are the galvanized iron or GI (Zn–0.2 wt.% Al),
galvalume or Al55Zn (55 wt.% Al, 43.5 wt.% Zn, 1.5 wt.% Si), and galvanneal or GA (obtained from GI by
annealing at temperatures from 490 °C to 540 °C), while galfan (Zn–5 wt.% Al) is most frequently used in
Europe and was not analyzed in this study. Hot dip Zn-based coatings (HD Zn) usually have Al or Si
additions to the metal bath that affect the structure of the obtained coatings and presumably their
corrosion behavior. Al is added to the Zn melt in the GI coating process at concentrations ranging from
0.15 to 0.25 wt.% to form a thin Fe2Al5/FeAl3 layer on the coating/steel interface to suppress the formation
of fragile Fe–Zn intermetallics and to reduce the Fe loss to the bath and consequent dross formation. The
final structure usually consists of a Fe2Al5 intermetallic layer containing Zn and of a dendritic η-phase.
Through the continuous process of GA production, the annealing treatment of GI immediately after
immersion in the metal bath and withdrawal allows reactions for the formation and growth of different
Fe–Zn intermetallics: γ-Fe3Zn10, γ1-Fe5Zn 21, δ-FeZn10, ζ-FeZn13 and an external layer of η not completely
consumed in the process. In the galvalume process circa 1.6 wt.% Si is usually added to the Al-rich Al–Zn
melt to prevent the strong exothermic reaction between the melt and the steel surface. The Si addition
and the higher Al content in the bath (55%) of the galvalume coating process result in a dendritic Zn-cored
α-Al microstructure with Zn rich η-phase and Si precipitates in the interdendritic region. According to the
literature, Zn in halide solutions suffers pitting corrosion. Therefore, it can be assumed, at least for
electrodeposited Zn that the protection of the steel substrate occurs by the localized corrosion of Zn.
Furman et al. verified that the pitting potential Epit in 0.1 mol/L NaCl for HD-Zn, galfan and Zn55Al coatings
has a stable value around −0.92 V (SCE) in the pH range from 4 to 10. For pH values outside these limits,
Epit assumes values as high as +0.15 V. The increase of [Cl-] from 0.1 to 0.9 mol/L at pH 7 shifts Epit nearly
linearly to more negative values, which was explained by means of Cl- competitive adsorption with other
anions that can protect the oxide surface, as nitrates and carbonates and the Cl- penetration into the
passive film at the film breakdown potential. The occurrence of pitting has also been reported for pure Zn
in Br-, I-, F-, ClO4-, SO42- and CH3COO-, as well as the usual positive shift of observed Epit with increasing
polarization sweep rate and, negative shift with increasing temperature Depending on the corrosion
conditions, different corrosion products have been proposed for the passivation of the Zn surface. Under
atmospheric conditions, amorphous Zn(OH)2 is formed on pure Zn, which is transformed into β-Zn(OH)2
and finally dehydrates to ZnO, while in chloride solutions the hydroxychloride, Zn5(OH)8Cl2, or the similar
mineral simonkolleite, Zn5(OH)8Cl2·H2O are assumed to form and passivate the Zn surface. It has been

57
reported that hydrochlorides, ε-Zn(OH)2 and ZnO also form on electroplated Zn and GI coatings, which,
after prolonged exposures will additionally form Zn hydroxycarbonates. .[23]

Fig. 15: SEM view of (a) GI, (c) GA and (e) Zn55Al coating surfaces and of the corresponding cross sections
(b, d, f).

58
2.17 Morphology and Corrosion Performance of Chromate
Conversion Coatings on Different Substrates:

The aqueous corrosion resistances of galvalume (FeAl+Zn) and steel galvanized (Fe-Zn) alloys, passivated
by immersion in chromating solution with different immersion times (0, 10, 30 y 60 s) are compared. The
electrochemical behaviour of various chromated and non-chromated coatings was investigated in 3 wt-%
NaCl solution using polarization techniques. For comparison, AISI 1010 carbon steel substrates were also
analyzed. The characterization measurements and polarization curves revealed that textural properties
of Fe alloys influence the growth of the films and both the cathodic and anodic reactions. An optimum
anticorrosive protection was obtained at 30 s. CCCs treatments inhibited the corrosion of zinc to a
significant degree, but less effectively than coatings formed with aluminium-zinc alloys. The difference in
the corrosion protection given by the two substrates types was attributed to the structural properties,
thickness coating, grain size and roughness observed, which affect oxygen diffusion. Zinc coatings are
predominantly used to improve the aqueous corrosion resistance of steel by two methods, barrier
protection and galvanic protection. In the barrier protection, the zinc coating which separates the steel
from the corrosion environment will first corrode before the corrosive environment reaches the substrate.
In addition, aluminium is added to provide an enhancement in the protective properties. In general,
aluminium coating offers better protection than zinc coating since aluminium itself carrying protective
oxide attacked very slowly. However, under certain mild conditions the attack of aluminium is too slow to
provide cathodic protection to steel and in such circumstances zinc coating is preferred. In view of limited
galvanic protection by aluminium, zinc alloyed with Al is used to enhance the corrosion resistance of zinc
coating on the steel surfaces. It is clear that considerable efforts are being made to improve the corrosion
resistance of zinc coatings by alloying and often by applying a compatible conversion coating treatments.
Chromate conversions coatings have been widely used for many engineering materials to provide improve
corrosion resistance, desirable surface finishes and paint adhesion characteristics. In spite of the fact, the
composition, structure and protective mechanism of such coatings are not well known up to now . The
morphology and the composition of a conversion coating play an important role in corrosion protection.
The properties of these coatings depend on the kind of substrate metal, the composition and structure of

59
the coatings. On the other hand, the composition and structure of the coatings depend on the method
chromating the bath composition and parameters of the process. In our knowledge, there is little
information concerning the composition and characteristics of the coatings on the Fe-Zn and Fe-Zn+Al
alloys and there are many literatures on the various applications of the chromate conversion coating. In
the present article, an analysis of the effect of textural properties in the formation of chromate conversion
films on galvanized steel and galvalume substrates was realized. The corrosion resistance and
electrochemical behaviour for both substrates after different immersion times was evaluated and
compared with the performance of commercial carbon steel AISI-1010.[24]

2.18 Improvement the Corrosion Resistance for the Galvanized

Steel by Adding Sn:

Metals play an important role in our everyday life. Steel has always been the most favored and widely
used material because of their excellent strength, formability, the economics of production, and the ability
to recycle indefinitely. However, it tends to react with agents in the atmosphere to form stable bonds—
ferrous oxides and salts. The rate of these reactions depends on the nature and concentration of the
corrosive agents present in the environment. Hence, most of the energies and research have been
involved in reducing corrosion of steel. The most popular and most widely process used for corrosion
protection of steel is galvanizing. Enhancing life of galvanized products results in the reduction in
maintenance and replacement costs, thereby large savings in energy. The galvanized coating provides
protection to the substrate through the formation of a physical barrier, separating the corroding
atmosphere from the substrate, which is more commonly known as “barrier protection”, where Zn being
lower in the galvanic series than Fe, so it corrodes preferentially, thus protecting the substrate. In hot dip
galvanizing process, several parameters such as chemical composition of carbon steel and chemical
composition of coating bath could affect the microstructure and properties of coatings. Alloying elements
added to Zn bath induce differences in the morphology of coatings through interface reactions. To
improve the quality and the nature of the galvanized coating of Zn on steel, alloying elements, such as
lead, aluminum, nickel, and magnesium are added to the galvanized bath. Moreover, Zn-Pb, Zn-Al, Zn-Al-

60
Mg, and Zn-Fe alloys are widely used to improve the quality of the galvanizing coatings. These alloying
elements affect the crystallization, structure, and properties of the outer layer of the coatings. Depending
on the type and concentration of the alloying addition in the galvanizing bath, some differences were
induced in the crystallization process of the Fe-Zn phases. The study proves that the addition of lead to
the zinc in galvanizing bath promotes the formation of large, smooth surface spangles, which are having
a good sacrificial ability. However, the optimum lead content requirement in the bath is from 1.0% to
1.5%. It is also shown that the increase in chloride ion concentration reduces the effect of lead, but at a
lower concentration of chloride the effect of lead is observed specially at 1.5% Pb addition. A great
attention is considered with respect to the role of aluminum (Al) in a Zn galvanizing bath.The morphology
and the adherence of the layers of deposits were changed and depended on the Al wt% in the coating
bath. The synergy of the excellent properties of Zn and Al has already been very well exploited by
continuous galvanizers in commercial products like Galvalume (55 wt% Al) and Galfan (5 wt% Al), which
exhibit improved corrosion properties.It was found that, after adding Mg to the Zn-5Al coating, the
corrosion products of Zn-5Al-0.5Mg-0.08Si coating is very compact and fine in size and adhere on the
surface, so it can diminish the effect of the corrosion media. Also, Pb is an important additive for fluidizing
the bath, but it is dangerous for human health and sometimes is replaced by tin (Sn). It has been added
to give the galvanized coating improved spangle, brightness and ductility. Additionally, the presence of Sb
in the galvanizing bath has also led to improve the intergranular corrosion resistance. The literature at
present contains many reports about the effect of Al, Mg, Pb on Zn deposits, while, the reports about the
influence of Sn on hot dip Zn coating is very limited. Sn and Sb have little effect on Fe-Zn alloy formation,
but at high concentration, Sn and Sb promoted spangle formation. The goal of this research is to develop
a new approach to improve the corrosion resistance of the galvanized pieces.[25]

61
Figure 16: Cross section of galvanized layer formed from molten Zn bath containing different
concentration Sn operated at 460˚C for 40 sec

62
 CHAPTER 3

EXPERIMENTAL PROCEDURE

3.1 Sample Preparation:

Samples are need to be prepared for Thickness Measurement and Corrosion Test along with micro
hardness reading.First of all,three small sized samples were taken from the three Corrugated Iron Sheets
given (Galvanized,Galvalum and Colour coated).Metallurgical Sample Mounting Press of XQ-1 Model was
used to prepare samples for Thickness Measurement under Optical Microscope with the help of Bakelite
powder by rising it to 150⁰C temperature for melting and wheeled through Pressurization.

Figure 27: Corrugated Iron Sheets

Figure 18: Mounted

Samples for thickness
measurement

Hardness of the samples were tested through Vickers Hardness Testing Machine at 2 Kgf force with dwell
time of about 10 seconds

63
3.2 Corrosion Test:
At First nine individual standard samples were taken at a dimensional area of about 1 square inch (three
from each given Corrugated Iron Sheets).Every single sample from different three (Galvanized,Galvalum
and Colour coated) Corrugated Iron Sheets was immersed altogether in Distilled water,Tap water and 1%
NaCl mild Saline water (adding 2gm NaCl in 200ml water) respectively in three separated Containers at
the same time.Data for weight loss and mass reading were taken and recorded repeatedly after 7 days
period through rust removal by washing and polishing.

Figure 19: Initial Setup for Corrosion Test

64
 Figure 20: Immersion in solution of C.I.Sheets

Figure 21: Visual Inspection of Corroded C.I.Sheets

65
 CHAPTER 4
EXPERIMENTAL RESULTS

4.1 Hardness measurement:

66
4.2 Corrosion Results:

4.2.1: sample weight measurement:

67
68
Figure 22: Wight Loss of Galvanized C.I.Sheet

69
Figure 23: Weight Loss Galvalume C.I.Sheet

70

70
Figure 24: Weight Loss of Colour coated C.I.Sheet

71
 4.3 Coating Thickness Observation

(Weeks)

72
73
74
75
 THICKNESS COMPARISON CHART
Galvanized Galvalum Colour Coated

28.24

22.05
21.06 17.95

20.25 20.55 14.05

13.5
15.1
16.76
12.35

12.6

Colour Coated

Galvalum

Galvanized

Before Immersion Distilled Water Tap Water Saline Water

Figure 28: Comparison of Coating Thickness

76
Figure 29: Thickness Variation of Galvanized C.I.Sheet before and after Immersion

77
Figure 30: Thickness Variation of Galvalume C.I.Sheet before and after Immersion

78
Figure 31: Thickness Variation of Colour coated C.I.Sheet before and after Immersion

79
 CHAPTER 5
CONCLUSION

In this study, the effects of coating thickness, corrosion resistance and weight loss of the Corrugated Iron Sheets of
Galvanized, Galvalume and Colour coated made from cold rolling were observed and analyzed. The following
consequences were visualized:

1. Three types of media (Distilled water, Normal Tap water and Saline water) were used to demonstrate the
corrosion behaviour and resistance to rust formation of Galvanized, Galvalum and Colour coated Corrugated
Iron Sheets. Non uniform coating thickness was observed on the ash side of the colour coated Corrugated
Iron Sheet.
2. From the obtained data, it can be concluded that the corrosion rate in salt water is higher than in normal
tap water (though rate of corrosion were drastically severe in the end in distilled water for Corrugated Iron
Sheets) due the presence of Chloride Cl- ions in salt water which increased the localized corrosion of the
sample.

80
 Reference
1.https://en.wikipedia.org/wiki/Sheet_metal

2.Yuji KUBO* Koji HANYA Shinji KODAMA, UDC 621 . 3 : 681 . 3 : 669 . 14 - 408 . 2

3. https://doi.org/10.1016/0376-4583(84)90145-6

4.FARID HANNA and NABIL NASSIF Central Metallurgical Research and Development Institute, National
Research Centre, Dokki, Cairo (Egypt)

5.https://www.pac-clad.com/interactive-pdfs/us-steel-galvalume-
steel/files/assets/common/downloads/publication.pdf

6. https://www.galvanizeit.org/uploads/publications/Zinc_Coatings.pdf

7. J. of the Braz. Soc. of Mech. Sci. & Eng. Copyright © 2009 by ABCM October-December
2009, Vol. XXXI, No. 4 / 319

8. J. H. Selverian M. R. Notis A. R. Marder, Journal of Materials Engineering June 1987, Volume 9, Issue 2,
pp 133–140

9.N. Coni [email protected] M. L. Gipiela [email protected] A. S. C. M. D’Oliveira

[email protected] P. V. P. Marcondes [email protected] Universidade Federal do Paraná – UFPR Caixa
Postal 19011

10.P. Pokorny, J. Kolisko, L. Balik – Czech Technical University – Klokner Institute, Prague, Czech Republic
P. Novak – University of Chemistry and Technology, Prague, Czech Republic METALURGIJA 55 (2016) 1,
115-118

11.S. Aslanlar et al. / Materials and Design 28 (2007) 2–7

12.https://d1uj7t3vxtt0z2.cloudfront.net/Documents/Technical%20Bulletins/Expansion%20Properties%
20of%20Metal.pdf

13.https://www.galvanizeit.org/uploads/publications/Zinc_Coatings.pdf

14.J. Strutzenberger, J. Federl: Metall. Trans. A, 1998, vol. 29A’ pp. 631-646

15.Barbara A. Shaw and Robert G. Kelly, The Electrochemical Society Interface • Spring 2006

81
16.Gareth Hinds from the original work of J G N Thomas, ELECTROCHEMISTRY OF CORROSION/BM

17.Sully J R, Taylor D. W, Electrochemical Methods of Corrosion Testing, Metals Hand Book. Vol 13, 1987.

18.IJASR International Journal of Academic and Scientific Research ISSN: 2272-6446 Volume 2, Issue 4
(November-December 2014), PP 01-07

19.https://nzic.org.nz/ChemProcesses/metals/8J.pdf

20.MATERIALS SCIENCE AND ENGINEERING – Vol. II – Fundamental Aspects of Corrosion of Metallic

Materials - P. Marcus and V. Mauric

21.https://www.galvanizeit.org/uploads/publications/Galvanized_Steel_Inspection_Guide.pdf

22.Juraj GRABAN, Mária KOLLÁROVÁ, Peter ZIMOVČÁK, Ivor KUČERA, Viera KOHÚTEKOVÁ, František
HOLLÝ U. S. Steel Kosice, s.r.o., Kosice, Slovak Republic, EU

23.A. Pritzel dos Santos a, S.M. Manhabosco a , J.S. Rodrigues a,b , L.F.P. Dick a, ⁎ a Laboratório de
Processos Eletroquímicos e Corrosão (Eletrocorr), Depto. Metalurgia, Universidade Federal do Rio Grande
do Sul (UFRGS), Av. Bento Gonçalves, 9500, Bl. 4–75, Porto Alegre 91501-970, Brazil b Instituto Federal
Sul Rio Grandense, Campus Charqueadas, Rua General Balbão, n° 81, Bairro Centro, Charqueadas, RS CEP
96475-000, Brazil

24.Miguel Antonio Domínguez-Crespo,1* Edgar Onofre-Bustamante,2 Aidé Minerva Torres-Huerta1, and

Francisco J. Rodríguez-Gómez2 1 Grupo de Ingeniería en Procesamiento de Materiales CICATA, Instituto
Politécnico Nacional. Unidad Altamira. Km 14.5, Carretera Tampico-Puerto Industrial Altamira. C. P.
89600. Altamira, Tamps. México. 2 Facultad de Química, Departamento de Metalurgia. Edificio D,
Universidad Nacional Autónoma de México, Ciudad Universitaria, 04510 México D.F

25. Z. Abdel Hamid1, *, S. S. Abd El Rehim2, A. Abou Shama3, M. Ebrahim3 1 Central Metallurgical
Research & Development Institute (CMRDI), Cairo, Egypt 2 Chemical Department, Faculty of Science, Ain
Shams University, Cairo, Egypt 3 Physics Department, Faculty of Science, Ain Shams University, Cairo,
Egypt

26. http://www.corrosionclinic.com/types_of_corrosion/crevice_corrosion.htm

27. J Environ Anal Toxicol, an open access journal ISSN: 2161-0525 Volume 7 • Issue 1 • 1000422

82
28.https://www.researchgate.net/publication/238074163_Corrosion_resistance_of_commercial_roofin
g_sheets_to_acid_rain_water_in_Eleme_Rivers_Nigeria

29.

30. International Journal of Science and Engineering Investigations, Volume 5, Issue 54, July 2016

31.

32. https://en.wikipedia.org/wiki/Corrugated_galvanised_iron

33. https://www.azom.com/article.aspx?ArticleID=14933

34. J Environ Anal Toxicol, an open access journal ISSN: 2161-0525

35.

36.

37.

38.

39.

40.

83
84
85
86