CHAPTER - I

INTRODUCTION

Corrosion:

Corrosion is a natural process, which converts a refined metal to a more chemically-

stable form, such as its oxide, hydroxide, or sulfide. It is the gradual destruction of materials
(usually metals) by chemical and/or electrochemical reaction with their
environment. Corrosion engineering is the field dedicated to controlling and stopping
corrosion.

Many structural alloys corrode merely from exposure to moisture in air, but the
process can be strongly affected by exposure to certain substances. Corrosion can be
concentrated locally to form a pit or crack, or it can extend across a wide area more or less
uniformly corroding the surface. Because corrosion is a diffusion-controlled process, it
occurs on exposed surfaces. As a result, methods to reduce the activity of the exposed
surface, such as passivation and chromate conversion, can increase a material's corrosion
resistance. However, some corrosion mechanisms are less visible and less predictable

Effects of Corrosion:

Corrosion is also a chemical reaction in which metal reactions with atmospheric

moisture and oxygen gas to form metallic oxides. That is the reason, metals corrode quickly.
Metallurgy is the process of conversion of metallic ores to metal as metals are usually found
in combined state in nature.

Types of corrosion:

There are five general types of corrosion: galvanic, stress cracking, general, localized
and caustic agent corrosion. Galvanic corrosion is

extraordinarily common, and occurs when two metals with different electrochemical charges
are linked via a conductive path.

CORROSION TYPES AND PREVENTION:

 Uniform Corrosion. Uniform corrosion is considered an even attack across the surface
of a material and is the most common type of corrosion.
 Pitting Corrosion,

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  Crevice Corrosion,
 Inter granular Corrosion,
 Stress Corrosion Cracking (SCC) ,
 Galvanic Corrosion.

General Attack Corrosion:

Also known as uniform attack corrosion, general attack corrosion is the most common
type of corrosion and is caused by a chemical or electrochemical reaction that results in the
deterioration of the entire exposed surface of a metal. Ultimately, the metal deteriorates to the
point of failure. General attack corrosion accounts for the greatest amount of metal
destruction by corrosion but is considered as a safe form of corrosion, due to the fact that it is
predictable, manageable and often preventable.

Localized Corrosion:

Unlike general attack corrosion, localized corrosion specifically targets one area of
the metal structure. Localized corrosion is classified as one of three types:

Pitting

Pitting results when a small hole, or cavity, forms in the metal, usually as a result of
de-passivation of a small area. This area becomes anodic, while part of the remaining metal
becomes cathodic, producing a localized galvanic reaction. The deterioration of this small
area penetrates the metal and can lead to failure. This form of corrosion is often difficult to
detect due to the fact that it is usually relatively small and may be covered and hidden by
corrosion-produced compounds

 Crevice corrosion: Similar to pitting, crevice corrosion occurs at a specific location. This
type of corrosion is often associated with a stagnant micro-environment, like those found
under gaskets and washers and clamps. Acidic conditions or a depletion of oxygen in a
crevice can lead to crevice corrosion.
 Filiform corrosion: Occurring under painted or plated surfaces when water breaches the
coating, filiform corrosion begins at small defects in the coating and spreads to cause
structural weakness

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Galvanic Corrosion:

Galvanic corrosion, or dissimilar metal corrosion, occurs when two different metals
are located together in a corrosive electrolyte. A galvanic couple forms between the two
metals, where one metal becomes the anode and the other the cathode. The anode, or
sacrificial metal, corrodes and deteriorates faster than it would alone, while the cathode
deteriorates more slowly than it would otherwise.

Three conditions must exist for galvanic corrosion to occur:

 Electrochemically dissimilar metals must be present

 The metals must be in electrical contact, and
 The metals must be exposed to an electrolyte

Environmental Cracking:

Environmental cracking is a corrosion process that can result from a combination of

environmental conditions affecting the metal. Chemical, temperature and stress-related
conditions can result in the following types of environmental corrosion:

 Stress Corrosion Cracking (SCC)

 Corrosion fatigue
 Hydrogen-induced cracking
 Liquid metal embrittlement

Flow-Assisted Corrosion (FAC):

Flow-assisted corrosion, or flow-accelerated corrosion, results when a protective layer

of oxide on a metal surface is dissolved or removed by wind or water, exposing the
underlying metal to further corroding and deteriorate.

 Erosion-assisted corrosion
 Impingement
 Cavitation

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Inter granular corrosion:

Inter granular corrosion is a chemical or electrochemical attack on the grain

boundaries of a metal. It often occurs due to impurities in the metal, which tend to be present
in higher contents near grain boundaries. These boundaries can be more vulnerable to
corrosion than the bulk of the metal.

De-Alloying:

De-alloying, or selective leaching, is the selective corrosion of a specific element in

an alloy. The most common type of de-alloying is de-zincification of unstabilized brass. The
result of corrosion in such cases is a deteriorated and porous copper.

Fretting corrosion:

Fretting corrosion occurs as a result of repeated wearing, weight and/or vibration on an

uneven, rough surface. Corrosion, resulting in pits and grooves, occurs on the surface.
Fretting corrosion is often found in rotation and impact machinery, bolted assemblies and
bearings, as well as to surfaces exposed to vibration during transportation.

High-Temperature Corrosion:

Fuels used in gas turbines, diesel engines and other machinery, which contain
vanadium or sulfates can, during combustion, form compounds with a low melting point.
These compounds are very corrosive towards metal alloys normally resistant to high
temperatures and corrosion, including stainless steel. High-temperature corrosion can also be
caused by high-temperature oxidization, sulfidation, and carbonization.

Classification of Corrosion Process

Depending upon the nature of corrosion, and the factors affecting it, the corrosion
may be classified as follows.

(i) Chemical corrosion : Such corrosion, generally takes place when

(a) Reactive gases come in contact with metals at high temperatures e.g., corrosion in
chemical industry.

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(b) Slow dissolution of metal takes place when kept in contact with non conducting media
containing organic acids.

(ii) Bio-chemical corrosion or Bio-corrosion: This is caused by the action of

microorganisms. Soils of definite composition, stagnant water and certain organic products
greatly favour the bio-corrosion.

(iii) Electrochemical corrosion : It occurs in a gaseous atmosphere in the presence of

moisture, in soils and in solutions.

Mechanism of corrosion:

Corrosion Mechanism of Iron oxide (Rust) Formation. Now the final product is
familiarly called as “Rust”. Normally the acid solution containing

dissolved oxygen will be more corrosive than air free acids. Oxygen reduction simply
provides a new means of “electron disposal”.

Method of preventing corrosion :

Whatever your reason for wanting to stop and prevent the corrosion of metals, here
are some helpful ways to prevent corrosion of metals: Turn to non-corrosive metals such as
aluminium and stainless steel. Keep the area around the metal surface dry. Use drying agents
and
moisture barrier products.
Cost of corrosion
Huge investments are made to obtain metallic materials from the forms in which these
exist in nature such as oxides, sulphides and carbonates. The gradual destruction of materials
by electrochemical reaction with environments, has very grave consequences for the
industrial world. When these useful products undergo corrosion by exposure to environment,
all these investments are affects to a greater or lesser extent. Corrosion leads to a variety of
problems such as: leakage of products from pipe lines and storage tanks, contamination of
food products in metallic containers and equipments deterioration and collapse of structures
and cause hazards to human life. The losses to the society on account of these adversities can
be very great and it becomes an unavoidable necessity to invest on corrosion control
measures which cost a fraction of the losses that take place without corrosion control.
According to the National Associations of Corrosion Engineers – International India Section
(NACE), the annual direct cost of corrosion in India [56] may be 4% GNP (Gross Domestic

5
Product), which is estimated to be around Rs.80,000 core per annum on account
of corrosion. The solution to reduce this phenomenon loss is to ensure that industries take up
corrosion prevention as an important issue even at the design state. The losses due to
corrosion may be divided into direct and indirect.
Ways to Prevent Corrosion of Metal Parts:

 Design. Corrosion control begins at the engineering stage.

 Protective Coating. Coatings can provide a layer of protection against corrosion by
acting as a physical barrier between the metal parts and oxidizing elements in the
environment.
 Environmental Control
 Cathodic Protection
 Maintenance.
Body fluid:

Body fluids, bodily fluids, or biofluids are liquids within the bodies of living people.
In normal healthy men, the total body water is about 60% of the total body weight; it is
slightly lower in women. A 70 kg (160 pound) man, then, has 42 litres of water in his body.
This is divided between ICF and ECF in a two is one ratio. 28 litres are inside cells and 14
litres are outside cells. This ECF compartment is divided into the fluid between cells -
the interstitial fluid volume - and the vascular volume, also called the blood plasma volume.
The vascular volume is divided into the venous volume and the secreted arterial volume; and
the arterial volume has a conceptually useful but unmeasurable subcompartment called
the effective arterial blood volume. There are approximately 6 to 10 litres of lymph in the
body, compared to 3.5 to 5 litres of blood.

Saliva:

Saliva is a fluid substance formed in the mouths of animals, secreted by the salivary
gland. Human saliva comprises 99.5% water plus electrolytes, mucus, white blood
cells, epithelial cells (from which DNA, enzymes (such
as amylase and lipase), antimicrobial agents such secretory IgA and lysozyme. The enzymes
found in saliva are essential in beginning the process of digestion of dietary starches and fats.
These enzymes also play a role in breaking down food particles entrapped within dental
crevices, thus protecting teeth from bacterial decay. Saliva also performs a lubricative

6
function, wetting food and permitting the initiation of swallowing, and protecting the mucosal
surfaces of the oral cavity from desiccation.

Composition of saliva:

Produced in salivary glands, human saliva is 99.5% water,

including electrolytes, mucus, antibacterial compounds and various enzymes.

Electrolytes:

 2–21 mmol/L sodium (lower than blood plasma)

 10–36 mmol/L potassium (higher than plasma)
 1.2–2.8 mmol/L calcium (similar to plasma)
 0.08–0.5 mmol/L magnesium
 5–40 mmol/L chloride (lower than plasma)
 25 mmol/L bicarbonate (higher than plasma)
 1.4–39 mmol/L phosphate
 Iodine (mmol/L concentration is usually higher than plasma, but dependent variable
according to dietary iodine intake)
 Mucus (mucus in saliva mainly consists of mucopolysaccharides and glycoproteins)
 Antibacterial compounds (thiocyanate, hydrogen peroxide, and
secretory immunoglobulin A)
 Epidermal growth factor (EGF)

Various enzymes; there are three major enzymes found in saliva:

 α-amylase (EC3.2.1.1), or ptyalin, secreted by the acinar cells of the parotid and
submandibular glands, starts the digestion of starch before the food is even
swallowed; it has a pH optimum of 7.4
 Lingual lipase, which is secreted by the acinar cells of the sublingual gland; has
a pH optimum around 4.0 so it is not activated until entering the acidic environment
of the stomach
 Kallikrein, an enzyme that proteolytically cleaves high-molecular-weight kininogen
to produce bradykinin, which is a vasodilator; it is secreted by the acinar cells of all
three major salivary glands

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  Antimicrobial enzymes that kill bacteria
 Lysozyme
 Salivary lactoperoxidase
 Lactoferrin
 Immunoglobulin A

 Proline-rich proteins (function in enamel formation, Ca2+-binding,

microbe killing and lubrication)
 Minor enzymes include salivary acid phosphatases A+B, N-acetylmuramoyl-L-
alanine amidase, NAD(P)H dehydrogenase (quinone), superoxide
dismutase, glutathione transferase, class 3 aldehyde dehydrogenase, glucose-6-
phosphate isomerase, and tissue kallikrein (function unknown)
 Cells: possibly as many as 8 million human and 500 million bacterial cells per
mL. The presence of bacterial products (small organic acids, amines, and thiols)
causes saliva to sometimes exhibit foul odor
 Opiorphin, a pain-killing substance found in human saliva
 Haptocorrin, a protein which binds to Vitamin B12 to protect it against
degradation in the stomach, before it binds to intrinsic factor
Types of salivary gland:

 The parotid gland makes serous secretions only.

 The submandibular glands are mixed glands. They give serous and mucous
secretions.
 The sublingual glands make mucous only.

Fig1:schematic diagram of Salivary gland

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Daily salivary output:

There is much debate about the amount of saliva that is produced in a

healthy person per day; estimates range from 0.75 to 1.5 litres per day while it is generally
accepted that during sleep the amount drops to nearly zero. [3][6] In humans, the submandibular
gland contributes around 70–75% of secretion, while the parotid gland secretes about 20–
25% and small amounts are secreted from the other salivary glands.

Function:

Saliva contributes to the digestion of food and to the maintenance of oral hygiene.
Without normal salivary function the frequency of dental caries, gum disease
(gingivitis and periodontitis), and other oral problems increases significantly.

Lubricant:

Saliva coats the oral mucosa mechanically protecting it from trauma during eating,
swallowing, and speaking. Mouth soreness is very common in people with reduced saliva
(xerostomia) and food (especially dry food) sticks to the inside of the mouth.

Digestion:
The digestive functions of saliva include moistening food and helping to create a
food bolus. The lubricative function of saliva allows the food bolus to be passed easily from
the mouth into the esophagus. Saliva contains the enzyme amylase, also called ptyalin, which
is capable.

Saliva uses:

The digestive functions of saliva include moistening food, and helping to create a food
bolus, so it can be swallowed easily. Saliva contains the enzyme amylase that breaks some
starches down into maltose and dextrin. Thus, digestion of food occurs within the mouth,
even before food reaches the stomach.

Orthodontic wires:

An arch wire in orthodontics is a wire conforming to the alveolar or dental arch that
can be used with dental braces as a source of force in correcting irregularities in the position
of the teeth. An arch wire can also be used to maintain existing dental positions; in this case it
has a retentive purpose.

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Orthodontic arch wires may be fabricated from several alloys, most commonly stainless
steel, nickel-titanium alloy (Ni-Ti), and beta-titanium alloy (composed primarily
of titanium and molybdenum).

Fig:2 Orthodontic wire

Nickel-titanium (Ni -Ti) Arch wire:

Ni-Ti alloy was developed in 1960 by William F. Buehler who worked at the Naval
Ordinance Laboratory in Silver Springs, Maryland. The name Nitinol came from Nickel (Ni),
Titanium (Ti), Naval Ordinance Laboratory (nol). The first Nickel titanium (Ni-Ti)
orthodontic alloy, introduced by Andraeson. This alloy was based on the research done by
Buehler. Since their introduction, the wires made out of Ni-Ti alloys have become an
important part of orthodontic treatment. The composition of the wire has 55% Nickel and
45% Titanium. The first nickel-titanium orthodontic wire alloy was marketed by the Unitek
Corporation who are now known as 3M Unitek. These alloys have low stiffness, super
elasticity, high spring back, large elastic range and were brittle. The initial Ni-Ti wires did
not have shape-memory effect due to the cold-working of the wire. Thus these wires were
passive and were considered as an Martensitic-Stabilized alloy.

10
Fig3: Ni-Ti Arch wire

Stainless steel arch wire:

In 1929, stainless steel was introduced for the use of making appliances. This
was the first material that truly replaced the usage of noble alloys in Orthodontics. Steel wire
alloys, in comparison to the noble metals, were relatively cheaper. They also had better
formability and can be readily used to be soldered and welded for fabrication of complex
orthodontic appliances. The stainless steel alloys are of "18-8" austenitic type which
contain Chromium (17-25%) and Nickel (8-25%) and Carbon (1-2%). Chromium in this
stainless steel alloy forms a thin oxide layer which blocks the diffusion of oxygen into the
alloy and allow for the corrosion resistance of this alloy. Angle used stainless steel in his last
year practicing orthodontics. He used it as a ligature wire in his patient's mouth. At that
time, Emil Herbst was the main opponent of the Stainless steel based alloys. According to
him, he preferred using Noble alloys over stainless steel. By 1950, 300 series stainless steel
alloy was used by the majority of orthodontists in United States, as European Orthodontists
believed in using functional appliances such as Activator appliance with patient's
[Link] steel arch wires have high stiffness, low springness, corrosion
resistant, low range and good formability. They wires are often cheaper than the other arch
wires and can readily be used as "working" arch wires in an orthodontic treatment. Space
closure after extractions is often done by placing these arch wires in the mouth.

SS18/8:

The "grade" of stainless steel refers to its quality, durability and temperature
resistance. For example, 18/8 stainless steel is comprised of 18% chromium and 8% nickel.
304 grade stainless steel is also comprised of no more than 0.8%carbon and at least 50%
iron.

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Fig4: Stainless steel18/8 arch wires

Gold22:

Gold is a chemical element with symbol Au and atomic number 79, making it one of
the higher atomic number elements that occur naturally. In its purest form, it is a bright,
slightly reddish yellow, dense, soft, malleable, and ductile metal. Chemically, gold is
a transition metal and a group 11 element. It is one of the least reactive chemical elements
and is solid under standard conditions. Gold often occurs in free elemental (native) form,
as nuggets or grains, in rocks, in veins, and in alluvial deposits. It occurs in a solid
solution series with the native element silver (as electrum) and also
naturally alloyed with copper and palladium. Less commonly, it occurs in minerals as gold
compounds, often with tellurium (gold tellurides).

Gold is resistant to most acids, though it does dissolve in aqua regia, a mixture of nitric
acid and hydrochloric acid, which forms a soluble tetrachloro aurate anion. Gold is insoluble
in nitric acid, which dissolves silver and base metals, a property that has long been used
to refine gold and to confirm the presence of gold in metallic objects, giving rise to the
term acid test. Gold also dissolves in alkaline solutions of cyanide, which are used
in mining and electroplating. Gold dissolves in mercury, forming amalgam alloys, but this is
not a chemical reaction.

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Fig:5 Gold22k orthodontic wire

Rio (Ingredient):

Sugar, acidity regulator vitamins, DMH, permitted food colours, natural flavours and
add natural identifical flavouring substance (apple).Apple flavour used in Rio soft drink
power present of malic [Link] rich source ascorbic and malic acid .Apple cider vinegar,
produced fermentation of apple juice also contains acetic acid sour taste of the product.

Fig 6: Rio soft drink powder

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 CHAPTER - II

REVIEW OF LITERATURE

Effect of fruit juices and chloride ions on the corrosion behavior of orthodontic arch
wire [1].

Electrochemical and surface analytical study on the corrosion behavior of AISI

316L stainless steel orthodontic arch wire in different fruit juices was carried out. The
electrochemical parameters were measured after immersing the wires for approx. 24 h in
artificial saliva (AS) containing different fruit juices and separately in fruit juices with 1%
Nacl in AS. All the fruit juices used in this study increased the rate of corrosion process in
AS in the presence or absence of salt. Addition of 1% Nacl to the AS, all experiments
exhibited pitting. Solanum lycopersicum (Tomato) and Durio zibethinus (Amra) are rated as
most detrimental to the surface followed by Prunus domestica Linn. (Plum) juice. SEM
Micrographs of the specimens show formation of blisters onto the steel surface which are
remnants of passive film.

Comparative assessment of the corrosion process of orthodontic arch wires made of

stainless steel, titanium–molybdenum and nickel–Titanium alloys[2].

The phenomenon of corrosion of orthodontic appliances is of interest to both

clinicians and researchers dealing with the issue of biocompatibility of medical materials.
The oral cavity, due to its temperature fluctuations, changing pH, high humidity, action of
mechanical forces and the presence of microorganisms is a favorable environment for
degradation of dental materials. This article presents the comparative assessment of the
intensity of corrosion of orthodontic arch wires made of alloy steel, nickel–titanium and
titanium–molybdenum alloys in laboratory conditions. Corrosion resistance examinations
were carried out by means of the impedance and the potentio dynamic method using an
Autolab PGSTAT100 potentiostat/galwanostat (Eco Chemie B.V., Holand) with FRA2
module, in non-deaerated artificial saliva solution at 37 °C. An analysis of the impendence
method's data showing that the highest corrosion resistance is observed for Ni-Ti arches (3M,
USA), while the lowest resistance for SS arches (3M, USA). These observations were
confirmed by the data obtained from potentio dynamic tests; it was observed that the average
corrosion current density [Icor] was the lowest for nickel–titanium arch wires (3M, USA) and
averaged 2.50 × 10−3 μA/cm2. The highest Icor corrosion current was observed in the case
of steel wires from the same manufacturer and averaged 4.96 × 10−2 μA/cm2.
14
corrosion of metal orthodontic brackets and arch wires caused by fluoride-containing
products: Cytotoxicity, metal ion release and surface roughness [3].

The aims of this study were to determine the cytotoxicity, metal ion release and
surface roughness of metal orthodontic appliances after immersion in different fluoride
product solutions. Materials and methods: Twelve sets of 20 brackets and four tubes were
ligated with three types of arch wires: stainless steel, nickel-titanium, and beta-titanium. The
samples in each arch wire group were divided into three subgroups and immersed in solutions
of fluoride toothpaste,1.23% acidulated phosphate fluoride (APF), or artificial saliva without
fluoride as a control group. The immersion times were estimated from the recommended time
of using each fluoride product for 3 months. The samples were immersed in cell culture
medium for 7 days. Primary gingival fibroblast cell viability was determined by an MTT
assay. Metal ion (nickel, chromium, iron, and molybdenum) release and surface roughness
were measured by inductively coupled plasma mass spectroscopy and a noncontact optical 3-
dimensional surface characterization and roughness measuring device, respectively. The
bracket and wire surface morphology was observed using scanning electron microscopy. The
data were analysed by Two-way ANOVA. Results: In the APF groups, the four metal ion
levels and surface roughness of the brackets and arch wires significantly increased, while cell
viability significantly decreased, especially in the TMA subgroup. The SEM results showed
that the brackets and wires in the APF groups demonstrated more lines and grooves compared
with the other groups. Conclusion: Using APF gel during orthodontic treatment with fixed
metal appliances should be avoided.

Assessment of corrosion behavior in artificial saliva of wires for orthodontic

applications [4].

The aim of this study, the corrosion behavior of Ti-Ni Cu in artificial saliva
(pH5.35) at 37oC was assessed by the use of electrochemical methods. Ti50Ni43Cu7(at%)
used in this study were made from ingots prepared by the vacuum arc melting (VAM)
method. The furnace was purged with argon gas during melting. All melted ingots were then
homogenized at 800oC for 3.6 ks. Open circuit potential (OCP) was monitored at 3.6 ks
followed by potentiodynamic techniques. The results showed that all chemical composition
of orthodontic wires by EPMA were Ti, Ni, Cu, Cr, Fe and Mn. Surface roughness was
measured in order to ensure that TiNiCu and SS was significant difference which might affect
corrosion resistance. It was seen that TiNiCu orthodontic wires, presented a good corrosion

15
resistance, compared to the stainless steel, probably due to the formation of a protective oxide
film mainly constituted by titanium oxide.

Evaluation of corrosion behavior in artificial saliva of 2507 and 2205 duplex stainless
steel for orthodontic wires before and after heat treatment[5].

The present study investigates comparison between corrosion behavior of 2507

and 2205 DSS in artificial saliva for orthodontic wires. The heat treatment is necessary for
2507 and 2205 duplex stainless steel to remove or dissolve intermetallic phases, removed
segregation and to relieve any residual thermal stress in DSS which may be formed during
production processes. The corrosion behavior of a 2507 and 2205 DSS in artificial saliva was
studied by SEM, HV test and potentio dynamic measurements. The results indicate that the
corrosion resistance mainly depends on presence of secondary phases (sigma phase) and
ferrite /austenite ratio, it’s revealed that the corrosion resistance of 2507 DSS higher than
2205 DSS in artificial saliva at 37 °C

Metal release profiles of orthodontic bands, brackets, and wires: an in vitro study
[Schwermetallfreisetzungsprofile aus kieferorthopädischen Bändern Brackets und
Drähten: Eine In-vitro-Untersuchung] Open Access [6].

The present study evaluated the temporal release of Co Cr, Mn, and Ni from
the components of a typical orthodontic appliance during simulated orthodontic treatment.
Materials and methods: Several commercially available types of bands, brackets, and wires
were exposed to an artificial saliva solution for at least 44 days and the metals released were
quantified in regular intervals using inductively coupled plasma quadrupole mass
spectrometry (ICP-MS, Elan DRC+, Perkin Elmer, USA). Corrosion products encountered on
some products were investigated by a scanning electron microscope equipped with an energy
dispersive X-ray microanalyzer (EDX). Results: Bands released the largest quantities of Co,
Cr, Mn, and Ni, followed by brackets and wires. Three different temporal metal release
profiles were observed: (1) constant, though not necessarily linear release, (2) saturation
(metal release stopped after a certain time), and (3) an intermediate release profile that
showed signs of saturation without reaching saturation. These temporal metal liberation
profiles were found to be strongly dependent on the individual test pieces. The corrosion
products which developed on some of the bands after a 6-month immersion in artificial saliva
and the different metal release profiles of the investigated bands were traced back to different
attachments welded onto the bands. Conclusion: The use of constant release rates will clearly

16
underestimate metal intake by the patient during the first couple of days and overestimate
exposure during the remainder of the treatment which is usually several months long. While
our data are consistent with heavy metal release by orthodontic materials at levels well below
typical dietary intake, we nevertheless recommend the use of titanium brackets and
replacement of the band with a tube in cases of severe Ni or Cr allergy.

Ion release and galvanic corrosion of different orthodontic brackets and wires in
artificial saliva [7].

To investigate the galvanic corrosion of brackets manufactured by four

different companies coupled with stainless steel (SS) or nickel-titanium (Ni-Ti) wires in an
artificial saliva solution. Materials and methods: A total of 24 mandibular central incisor Roth
brackets of four different manufacturers (American Orthodontics, Dentaurum, Shinye, ORJ)
were used in this experimental study. These brackets were immersed in artificial saliva along
with SS or NiTi orthodontic wires (0.016", round) for 28 days. The electric potential
difference of each bracket/wire coupled with a saturated calomel reference electrode was
measured via a voltmeter and recorded constantly. Corrosion rate (CR) was calculated, and
release of ions was measured with an atomic absorption spectrometer. Stereomicroscope was
used to evaluate all samples. Then, samples with corrosion were further assessed by scanning
electron microscope and energy-dispersive X-ray spectroscopy. Two-way analysis of
variance was used to analyze data. Results: Among ions evaluated, release of nickel ions
from Shinye brackets was significantly higher than that of other brackets. The mean potential
difference was significantly lower in specimens containing a couple of Shinye brackets and
SS wire compared with other specimens. No significant difference was observed in the mean
CR of various groups (p > 0.05). Microscopic evaluation showed corrosion in two samples
only: Shinye bracket coupled with SS wire and American Orthodontics bracket coupled with
NiTi wire. Conclusion: Shinye brackets coupled with SS wire showed more susceptibility to
galvanic corrosion. There were no significant differences among specimens in terms of the
CR or released ions except the release of Ni ions, which was higher in Shinye brackets.

Corrosion resistance of an SS 316l alloy in artificial saliva in presence of a sparkle fresh

toothpaste [8].

People are implanted with orthodontic wires made of different materials, to regulate their
teeth. The various toothpastes that they use during the course of the treatment may have a
corrosive effect on these materials. Hence, the main objective of this study was to evaluate

17
the corrosion behaviour of an SS 316L alloy in artificial saliva in the presence of a sparkle
fresh toothpaste. An electrochemical study has been used to investigate the corrosion
behaviour of this alloy. Scanning electron microscopy (SEM) imaging gave the
morphological data for the sample; however, by using X-ray spectroscopy in conjunction
with SEM (EDAX), the elemental composition was determined. Further, the analysis of the
protective film formed on the metal surface was done using UV-visible absorption and
fluorescence spectra. The corrosion resistance of the SS 316L system in various solutions
decreases in the following order: AS+ toothpaste> toothpaste>AS. For AS+ toothpaste
system, LPR= 1813475 Ohm cm2; Icorr = 2.464 x10-8A/cm2; Rct =14961 Ohm cm2; Cdl=
3.4088 x10-10 F/cm2 and impedance = 4.397 log z/Ohm. The high corrosion resistance
offered by the toothpaste is due to the formation of a protective film. It confirmed that the
active principles of the toothpaste ingredients have co-ordinated with the SS 316L metal ions
through their polar atoms to form a complex.

Evaluation of frictional resistance and surface characteristics after immersion of

orthodontic brackets and wire in different chemical solutions: A comparative in
vitrostudy Open Access [9].

To evaluate the changes of static and kinetic frictional forces between the
brackets and wires following exposure to a soft drink, acidic food ingredient, and acidulated
fluoride prophylactic agents. Materials and Methods: Two types of Roth prescription
mandibular incisor brackets were used: 3M Unitek Victory stainless steel (SS) brackets (n =
40) and Transcend 6000 polycrystalline alumina (PCA) brackets (n = 40) as well as eighty
0.019 × 0.025" dimension ortho technology SS wires of 50 mm length each. Subsequently,
brackets tied with SS wires divided into eight subgroups (n = 10) and were immersed in
vinegar (pH = 3.5 ± 0.5), Pepsi ® (pH = 2.46), Colgate Phos-Flur mouth rinse (pH = 5.1), and
artificial saliva (control group pH = 7) for 24 h. Changes in surface morphology under
scanning electron microscope ×1000, surface roughness (Ra) with surface profilometer
(single bracket and single wire from each subgroup), and frictional resistance using universal
testing machine were evaluated. Results: Highest mean (standard deviation) static frictional
force of 2.65 (0.25) N was recorded in Pepsi ® followed by 2.57 (0.25) N, 2.40 (0.22) N, and
2.36 (0.17) N for Vinegar, Colgate Phos-Flur mouth rinse, and artificial saliva groups,
respectively. In a similar order, lesser mean kinetic frictional forces obtained. PCA brackets
revealed more surface deterioration and higher frictional force values than SS brackets. A
significant positive correlation was observed between frictional forces and bracket slot

18
roughness (r = 0.861 and 0.802, respectively, for static and kinetic frictional forces, p < 0.001
for both) and wire roughness (r = 0.243 and 0.242, respectively, for static and kinetifrictional
forces, p < 0.05 for both). Conclusions: Findings may have long-term implications when
acidic food substances are used during fixed orthodontic

treatment. Further, in vivo studies are required to analyze the clinical effect of acidic
mediums in the oral environment during orthodontic treatment.

Corrosion resistance of SS 316 L alloy in artificial saliva in the presence of a soft drink
[10].

Corrosion resistance of orthodontic wires made of SS 316 L alloy in artificial

saliva in the absence and presence of a soft drink namely sprite has been evaluated by
polarisation study, when corrosion resistance increases, the linear polarisation resistance
value increases and the corrosion current value decreases, the present study reveals that; the
corrosion resistance of SS 316 L alloy decreases in the following order; sprite only > sprite +
Artificial saliva > Artificial saliva. It is concluded that people who have been implanted with
orthodontic wires made of SS 316 L alloy need not dither to take the soft drink sprite orally.

An evaluation of two types of nickel-titanium wires in terms of micromorphology and

nickel ions’ release following oral environment exposure [11].

This study aimed to compare superelastic and heat-activated nickel-titanium

orthodontic wires’ surface morphology and potential release of nickel ions following
exposure to oral environment conditions. Methods: Twenty-four 20-mm-length distal cuts of
superelastic (Ni-Ti Force I®) and 24 20-mm-length distal cuts of heat-activated (Therma-Ti
Lite®) nickel-titanium wires (American Orthodontics, Sheboygan, WI, USA) were divided
into two equal groups: 12 wire segments left unused and 12 segments passively exposed to
oral environment for 1 month. Scanning electron microscopy and atomic force microscopy
were used to analyze surface morphology of the wires which were then immersed in artificial
saliva for 1 month to determine potential nickel ions’ release by means of atomic absorption
spectrophotometer. Results: Heat-activated nickel-titanium (Ni-Ti) wires were rougher than
superelastic wires, and both types of wires released almost the same amount of Ni ions. After
clinical exposure, more surface roughness was recorded for superelastic Ni-Ti wires and heat-
activated Ni-Ti wires. However, retrieved superelastic Ni-Ti wires released less Ni ions in
artificial saliva after clinical exposure, and the same result was recorded regarding heat-

19
activated wires. Conclusions: Both types of Ni-Ti wires were obviously affected by oral
environment conditions; their surface roughness significantly increased while the amount of
the released Ni ions significantly declined.

Estimation of release of nickel and chromium by Indian made orthodontic appliance in

saliva [12].

With increasing use of Indian made orthodontic materials, need was felt to know
nickel and chromium release from these material. Materials and Methods: This study was
conducted on simulated appliances consisting of brackets (022”Roth, Modern orthodontics,
Ludhiana, India), from second premolar to central incisor, buccal tube and 0.019×0.025- inch
SS arch wires secured with SS ligatures. Immersion was done in artificial saliva. Samples
were analysed to using Atomic Absorption Photospectrometer (GVC ScientificEquipment
Pvt. Ltd Australia) at AES Laboratories (P) Ltd., Noida India on 1st, 7th, 14th and 28th day.
Results: SPSS (ver 17, Inc., Chicago, Illinois, USA) was used toperform the statistical
analysis. Descriptive statistics i.e. median and 25 and75 percentiles were used. Peak nickel
release was on 7th day and subsequently declined over 14th and 28th day. The peak level of
chromium concentration was on 14th day, which declined thereafter. Conclusion: Average
daily release of nickel and chromium over a period of one month was 97.368 μg/day and
47.664 μg/day respectively. The estimated release rates were approximately 32% and 16% of
the reported average daily dietary.

Susceptibility to corrosion of laser welding composite arch wire in artificial saliva of

salivary amylase and pancreatic amylase[13].

In this study, laser-welded composite arch wire (CAW) with a copper interlayer
was exposed to artificial saliva containing salivary amylase or pancreatic amylase, and the
resultant corrosion behavior was studied. The purpose was to determine the mechanisms by
which salivary amylase and pancreatic amylase contribute to corrosion. The effects of
amylase on the electrochemical resistance of CAW were tested by potentiodynamic
polarization measurements. The dissolved corrosion products were determined by ICP-OES,
and the surfaces were analyzed by SEM, AFM and EDS. The results showed that both
exposure to salivary amylase and pancreatic amylase significantly improved the corrosion
resistance of CAW. Even isozyme could have different influences on the alloy surface. When
performing in vitro research of materials to be used in oral cavity, the effect of α-amylase

20
should be taken into account since a simple saline solution does not entirely simulate the
physiological situation.

Reliability performance of titanium sputter coated Ni-Ti arch wires: Mechanical

performance and nickel release evaluation [14].

The present research was aimed at developing surface coatings on Ni-Ti arch wires capable
of protection against nickel release and to investigate the stability, mechanical performance
and prevention of nickel release of titanium sputter coated Ni-Ti arch wires. Coated and
uncoated specimens immersed in artificial saliva were subjected to critical evaluation of
parameters such as surface analysis, mechanical testing, element release, friction coefficient
and adhesion of the coating. Titanium coatings exhibited high reliability on exposure even for
a prolonged period of 30 days in artificial saliva. The coatings were found to be relatively
stable on linear scratch test with reduced frictional coefficient compared to uncoated samples.
Titanium sputtering adhered well with the Ni-Ti substrates at the molecular level, this was
further confirmed by Inductive coupled plasma emission spectroscopy (ICPE) analysis which
showed no dissolution of nickel in the artificial saliva. Titanium sputter coatings seem to be
promising for nickel sensitive patients. The study confirmed the superior nature of the
coating, evident as reduced surface roughness, friction coefficient, good adhesion and
minimal hardness and elastic modulus variations in artificial saliva over a given time period.

Comparison of chemical properties and Ni release of stainless steel and nickel titanium
wires [15].

This study aimed to determine the composition and corrosion resistance of

stainless steel and nickel titanium (NiTi) archwires and to compare Ni released from
simulated standard fixed orthodontic appliances ligated with stainless steel and NiTi wires in
artificial saliva at pH 5.14 and pH 6.69. in 4 weeks at 37°C. Materials and Method: Two
commercial rectangular wires, 0.016 × 0.022" in size were studied, one Ormco stainless steel
wire and another Ormco nickel titanium wire. Their composition was analyzed by an energy
disporsive X-ray spectrometer (ESC) and their corrosion resistance was evaluated by a
potentio dynamic polarization technique. For Ni release, the twenty-eight simulated fixed
appliance sample sets were used, each corresponding to one half-maxillary arch. The samples
were divided in 2 groups (14 sets per group). The first one was ligated to Ormco stainless
steel arch wires and the other one to Ormco Ni-Ti arch wires with elastomeric ligatures. Half
sets of each group were immersed in 50 ml artificial saliva at pH 5.14 and the other half were

21
immersed at pH 6.69. Ni release was quantified using flame atomic absorption
spectrophotometry. Statistical analysis of variance (t-test) was determined on days 1, 4, 7, 9,
14, 21 and 28 comparing the amount of Ni released between groups. Results: Stainless steel
wire was composed of Ni, Cr, Si, Mn and Fe while the nickel titanium wire was composed of
Ti, Ni and Cr. Ni-Ti wire has more percentage of Ni and therefore has less corrosion
resistance than stainless steel wire. For Ni release, stainless steel and Ni-Ti continuously
increased at the time intervals for both pH levels. For group one, stainless steel wire had more
Ni release at pH 5.14 and for the other group, Ni-Ti wire had more Ni-release at pH 6.69. At
4 weeks, the Ni release of one half-maxillary arch was 1.383 ppm (1383 μg/l) at pH 5.14 and
1.079 ppm (1078 μg/l) at pH 6.69 for stainless steel wire while it was 1.221 ppm (1221 μg/l)
at pH 5.14 and 1.267 ppm (1267μg/l) at pH 6.69 for Ni-Ti wire. No significant difference was
found in the amount of Ni release from stainless steel and Ni-Ti wires at pH 5.14 and pH 6.69
in the different time intervals except on day 1 wherein the stainless steel arch wire was
significantly different (p<0.05) at pH 5.14 and pH 6.69. Conclusions: The Ni-Ti wire had
more Ni contain and less corrosion resistance than stainless steel wire. Stainless steel had
more Ni release at pH 5.14 than pH 6.69 but Ni-Ti had greater Ni release at pH 6.69 than pH
5.14

Corrosion resistance of 3M nickel-titanium arch wires and damon copper-nickel-

titanium arch wires in different artificial saliva with different fluoride and pH [16].

In the fluorine-containing acidic environment, it is unclear whether Damon

copper nickel- titanium arch wire can have a corrosion resistance similar to conventional
nickel-titanium arch wire and whether copper ion will affect its corrosion resistance.
OBJECTIVE: To evaluate the corrosion resistance of 3M nickel-titanium arch wires and
Damon copper-nickel-titanium arch wires in artificial saliva with different fluoride and pH.
METHODS: Potentiodynamic polarization curves of 3M nickel-titanium arch wires and
Damon copper-nickel-titanium arch wires were measured in four kinds of artificial saliva
(pH=7; pH=7, 0.2% fluoride; pH=7, 0.5% fluoride; pH=5, 0.5% fluoride). Then, the
corrosion potential, corrosion current density and polarization resistance were acquired, and
scanning electron microscope was used for morphological observation after corrosion.
RESULTS AND CONCLUSION: In neutral (pH=7) artificial saliva, 0.2% fluoride ions
added could shift up the Damon specimen polarization curve, increase the corrosion cerrent
density and reduce the polarization resistance (P < 0.05); under the scanning electron
microscope, corrosion was observable on the specimen surface. But 3M specimen

22
polarization curve did not move, corrosion current density and polarization resistance
substantially unchanged (P > 0.05), and no significant corrosion was produced. When
fluoride concentration was increased to 0.5%, the polarization curves of two kinds of the
specimens moved, the corrosion cerrent density increased, the polarization resistance
decreased (P < 0.05), and there was significant presence of corrosion on the specimen
surface. When pH=5, corrosion phenomenon was more pronounced. These findings suggest
that low concentrations fluoride cannot affect corrosion resistance of 3M arch wire, but can
reduce the corrosion resistance of Damon arch wire; high concentrations of fluoride and acid
can both reduce their corrosion resistance. In addition, the corrosion resistance of 3M arch is
stronger than that of Damon arch wire.

Degradation of orthodontic wires under simulated cariogenic and erosive conditions

[17].

This study examined the effect of cariogenic and erosive challenges (CCs and
ECs, respectively) on the degradation of copper-nickel-titanium (CuNiTi) orthodontic wires.
Sixty wire segments were divided into four treatment groups and exposed to CCs, ECs,
artificial saliva, or dry storage (no-treatment control). CC and EC were simulated using a
demineralizing solution (pH 4.3) and a citric acid solution (pH 2.3), respectively. Following
treatment, the average surface roughness (Ra) of the wires was assessed, and friction between
the wires and a passive self-ligating bracket was measured. CuNiTi wires subjected to ECs
exhibited significantly higher Ra values than did those that were stored in artificial saliva. In
contrast, surface roughness was not affected by CCs. Finally, friction between the treated
wires and brackets was not affected by ECs or CCs. Our results indicate that CuNiTi
orthodontic wires may suffer degradation within the oral cavity, as ECs increased the surface
roughness of these wires. However, rougher surfaces did not increase friction between the
wire and the passive self-ligating bracket.

Effect of titanium nitride/titanium coatings on the stress corrosion of nickel-titanium

orthodontic archwires in artificial saliva[18].

The purpose of this investigation was to develop titanium nitride (TiN)/titanium

(Ti) coating on orthodontic nickel-titanium (Ni-Ti) wires and to study the stress corrosion of
specimens in vitro, simulating the intra-oral environment in as realistic a manner as possible.
TiN/Ti coatings were formed on orthodontic Ni-Ti wires by physical vapor deposition
(PVD). The characteristics of untreated and TiN/Ti-coated Ni-Ti wires were evaluated by

23
measurement of corrosion potential (Ecorr), corrosion current densities (Icorr), breakdown
potential (Eb), and surface morphology in artificial saliva with different pH and three-point
bending conditions. From the potentiodynamic polarization and SEM results, the untreated
Ni-Ti wires showed localized corrosion compared with the uniform corrosion observed in the
TiN/Ti-coated specimen under both unstressed and stressed conditions. The bending stress
influenced the corrosion current density and breakdown potential of untreated specimens at
both pH 2 and pH 5.3. Although the bending stress influenced the corrosion current of the
TiN/Ti-coated specimens, stable and passive corrosion behavior of the stressed specimen was
observed even at 2.0 V (Ag/AgCl). It should be noted that the surface properties of the Ni-Ti
alloy could determine clinical performance. For orthodontic application, the mechanical
damage destroys the protective oxide film of Ni-Ti; however, the self-repairing capacity of
the passive film of Ni-Ti alloys is inferior to Ti in chloride-containing solutions. In this study,
the TiN coating was found able to provide protection against mechanical damage, while the
Ti interlayer improved the corrosion properties in an aggressive environment.

New Ni-free superelastic alloy for orthodontic applications [19].

A potential new Ni-free Ti alloy for biomedical applications was assessed in

order to investigate the superelastic behavior, corrosion resistance and the biocompatibility.
The alloy studied was Ti19.1Nb8.8Zr. The chemical composition was determined by X-ray
microanalysis, the thermoelastic martensitic transformation was characterized by high
sensitivity calorimeter. The critical stresses were determined by electromechanical testing
machine and the corrosion behavior was analyzed by potentiostatic equipment in artificial
saliva immersion at 37 C. The results were compared with six different NiTi orthodontic
archwire brands. The biocompatibility was studied by means of cultures of MG63 cells. Ni-
free Ti alloy exhibits thermoelastic martensitic transformation with M s = 45 C. The phase
present at 37 C was austenite which under stress can induce martensite. The stress-strain
curves show a superelastic effectth physiological critical stress (low and continuous) and a
minimal lost of the recovery around 150 mechanical cycles. The corrosion resistance
improves the values obtained by different NiTi alloys avoiding the problem of the Ni adverse
reactions caused by Ni ion release. Cell culture results showed that adhered cell number in
new substrate was comparable to that obtained in a commercially pure Ti grade II or beta-
titanium alloy evaluated in the same conditions. Consequently, the new alloy presents an
excellent in-vitro response. The corrosion resistance of composite arch wire laser-welded

24
by Ni-Ti shape memory alloy and stainless steel wires with Cu interlayer in artificial
saliva with protein [20].

In this paper, the corrosion resistance of laser-welded composite arch wire (CoAW) with Cu
interlayer between NiTi shape memory alloy and stainless steel wire in artificial saliva with
different concentrations of protein was studied. It was found that protein addition had a
significant influence on the corrosion behavior of CoAW. Low concentration of protein
caused the corrosion resistance of CoAW decrease in electrochemical corrosion and
immersion corrosion tests. High concentration of protein could reduce this effect

Surface roughness changes on β-Titanium Orthodontic wires after corrosion in various

artificial saliva solutions [21].

β-Titanium orthodontic wires are exposed to three different artificial corrosive

environments, modified Fusayama, modified Fusayama with 0.1 % NaF addition, and
modified Fusayama with 1.7 % H3PO4addition, which are similar to the oral cavity
conditions. Corrosion behaviours of wires are observed by using weight loss method and
scanning electron microscope observations. Afterwards, surface roughness of wires is
investigated in details. Consequently, it is determined that corrosion rate of β-titanium wires
exposed to the modified Fusayama solutions with H3PO4addition is higher because of the
acidity of this saliva. Furthermore, maximum increase in surface roughness and skewness are
observed in the same environment. Hydrogen embrittlement of titanium is also an important
factor for the corrosion of wires

Evaluation of ionic degradation and slot corrosion of metallic brackets by the action of
different dentifrices [22].

To evaluate the in vitro ionic degradation and slot base corrosion of metallic
brackets subjected to brushing with dentifrices, through analysis of chemical composition by
Energy Dispersive Spectroscopy (EDS) and qualitative analysis by Scanning Electron
Microscopy (SEM). Methods: Thirty eight brackets were selected and randomly divided into
four experimental groups (n = 7). Two groups (n = 5) worked as positive and negative
controls. Simulated orthodontic braces were assembled using 0.019 x 0.025-in stainless steel
wires and elastomeric rings. The groups were divided according to surface treatment: G1
(Máxima Proteção Anticáries®); G2 (Total 12®); G3 (Sensitive®); G4 (Branqueador®);
Positive control (artificial saliva) and Negative control (no treatment). Twenty eight brushing
cycles were performed and evaluations were made before (T0) and after (T1) experiment.
25
Results: The Wilcoxon test showed no difference in ionic concentrations of titanium (Ti),
chromium (Cr), iron (Fe) and nickel (Ni) between groups. G2 presented significant reduction
(p < 0.05) in the concentration of aluminium ion (Al). Groups G3 and G4 presented
significant increase (p < 0.05) in the concentration of aluminium ion. The SEM analysis
showed increased characteristics indicative of corrosion on groups G2, G3 and G4.
Conclusion: The EDS analysis revealed that control groups and G1 did not suffer alterations
on the chemical composition. G2 presented degradation in the amount of Al ion. G3 and G4
suffered increase in the concentration of Al. The immersion in artificial saliva and the
dentifrice Máxima Proteção Anticáries® did not alter the surface polishing. The dentifrices
Total 12®, Sensitive® and Branqueador® altered the surface polishing.

Corrosion behavior of titanium wires: An in vitro study [23].

Teeth and restorations are subjected continuously to degradation in hostile

physical and chemical environments, resulting in corrosion. Component of liquid or solid is
an important factor influencing the corrosion of metallic appliances placed in the oral cavity.
Aims: To study in vitro corrosion of titanium wires immersed in solutions of toothpaste and
chocolate in artificial saliva. Materials and Methods: Immersion test and electrochemical
studies using different parameters, including corrosion potential (E corr ), cathodic Tafel
constant (c), anodic Tafel constant (a), corrosion current (I corr ), polarization resistance (R
p ), and corrosion rate of titanium wires, were done in solutions of artificial saliva containing
Colgate toothpaste and Amul chocolate. Photomicrographs were also taken. Results: The
results showed degradation of titanium wires by electrochemical attack when they were
placed in the hostile electrolytic environments provided in the experiments. Surface analysis
of titanium wires showed pitting and localized attacks on the surface. Pitting corrosion was
found in the titanium wires.

Release of metal ions from orthodontic appliances: An in vitro study [24].

In this paper, we report the results of an in vitro experiment on the release of metal ions from
orthodontic appliances composed of alloys containing iron, chromium, nickel, silicon, and
molybdenum into artificial saliva. The concentrations of magnesium, aluminum, silicon,
phosphorus, sulfur, potassium, calcium, titanium, vanadium, manganese, iron, cobalt, copper,
zinc, nickel, and chromium were significantly higher in artificial saliva in which metal
brackets, bands, and wires used in orthodontics were incubated. In relation to the maximum
acceptable concentrations of metal ions in drinking water and to recommended daily doses,

26
two elements of concern were nickel (573 vs. 15 μg/l in the controls) and chromium (101 vs.
8 μg/l in the controls). Three ion release coefficients were defined: α, a dimensionless
multiplication factor; β, the difference in concentrations (in micrograms per liter); and γ , the
ion release coefficient (in percent). The elevated levels of metals in saliva are thought to
occur by corrosion of the chemical elements in the alloys or welding materials. The
concentrations of some groups of dissolved elements appear to be interrelated

Surface roughness changes and corrosion on nickel titanium orthodontic wires

compared to stainless steel wires in various artificial saliva [25].

Nickel titanium shape memory alloy and stainless steel orthodontic wires were
exposed to three different artificial saliva solutions which are modified Fusayama, modified
Fusayama with 1g/1 NaF addition and modified Fusayama with 1.7% H3PO4addition. Under
conditions similar to oral cavity temperature, corrosion behaviours were observed by using
weight loss method and by macro surface photographic observations. Also, surface roughness
of wires were investigated and compared. Consequently, it was determined that corrosion
rates of all NiTi wires exposed to the modified Fusayama solutions with NaF addition are
higher because of galvanic interaction of NiTi and hydrogen embrittlement of titanium. Also,
surface roughness of NiTi wires were increased in modified Fusayama solution with NaF
addition

Effect of Cu and Co additions on corrosion behavior of NiTi alloys for orthodontic

applications [26].

The aim of this study is to investigate effect of Cu and Co additions on corrosion

behavior of NiTi shape memory alloys for orthodontic application. Ni50.649.4, Ti49Ni46Cu5
and Ti50Ni47Co3 (at%) alloys were prepared. The specimens were melted by arc-melting
furnace and homogenized at 800°C for 3.6 ks. Transformation temperatures were analyzed by
differential scanning calorimeter (DSC). The corrosion behavior was assessed
electrochemically in artificial saliva (pH 5.35) at 37°C. Open circuit potential (OCP) was
monitored 3.6 ks followed by potentiodynamic techniques. The results show that all of
specimens revealed transformation temperature close to oral temperature which may be
utilized as orthodontic wire. Surface roughness was measured in order to ensure that there is
no significant difference which might affect corrosion resistance. It is seen that by adding Co
and Cu into NiTi alloys, the corrosion potential (Ecorr) and pitting corrosion potential (E
break) increase resulting in lower corrosion rate. Conceivably, Co and Cu additions

27
considerable affect the corrosion behavior of NiTi alloys by improving corrosion resistance in
artificial saliva.

Influence of topographical features on the fluoride corrosion of Ni-Ti orthodontic arch

wires [27].

Different manufacturing processes of Ni-Ti arch wires respond differently to

corrosion due to the surface conditions involved. In this study, several topographical features
and their influence upon fluoride corrosion were studied. Four topographies (smooth, dimple,
scratch, and crack) according to the main surface defect were characterized (n = 40). Static
corrosion tests were performed in artificial saliva with fluorated prophylactic gel (12500
ppm) for 28 days. The surface was characterized by SEM and laser confocal microscopy.
Standard electrochemical corrosion (open circuit potential, corrosion potential and corrosion
current density) was performed. Statistical analysis was carried out using the ANOVA test (α
≤ 0.05). An increase was observed in the surface defects and/or roughness of the cracked and
scratched surfaces. These defects produced an important increase in corrosion behavior. The
best surfaces for the orthodontic arch wires were the smooth and dimpled surfaces,
respectively. The increase in defects was independent of roughness. Manufacturing processes
that produce surface cracks should be avoided in orthodontic applications.

An in vitro study of resistance to corrosion in brazed and laser-welded orthodontic

appliances [28].

Many orthodontic appliances comprise a number of elements soldered together.

This technique is known as brazing and has now been in use for over thirty years, although
today laser welding is increasingly widespread. Biocompatibility of alloys contained in
orthodontic appliances has become a hotly-debated issue and previous studies have shown
that it depends on the products of alloy corrosion and their effects on the oral cavity. The
present study is intended to compare the corrosion resistance of stainless steel when
traditionally soldered - i.e, brazed - and when laser-welded. Samples comprising stainless
steel band strips and Remanium® wire were soldere d together traditionally (i.e. brazed) and
laser-welded and were then left in artificial saliva for 7 days at 37±1 degrees . Corrosion was
studied by: a) SEM observation of sample surface morphology before (TO) and after
standardized immersion test (Tl); b) X-ray micro analysis (EDAX). SEM observation of the
brazed samples showed surface corrosion, which was not visible in the laser-welded samples.
Our study shows that laser-welded samples have superior resistance to corrosion

28
Galvanic corrosion between various combinations of orthodontic brackets and arch
wires [29].

The purpose of this study was to compare galvanic currents generated by

different combinations of commonly used brackets and arch wires. Methods: As-received
stainless steel, nickel-titanium, and beta-titanium wires were coupled to stainless steel and
titanium brackets in an artificial saliva medium. The galvanic current and amount of charge
transferred for each pair were monitored with a zero resistance ammeter for 10 hours.
Results: Two-way analysis of variance (ANOVA) showed a significant difference in charge
and galvanic currents when factored for type of bracket (P <0.001), but no significant
difference between them when factored by type of wire (P >0.05). Specifically, a brazed
stainless steel bracket was significantly greater in charge transferred and 10-hour galvanic
current than metal injection molded stainless steel and titanium brackets (P <0.001), which
were not different from each other (P >0.05). Conclusions: The method of bracket
manufacturing might be of equal or more relevance to galvanic corrosion susceptibility than
bracket composition.

Comparison of friction force between corroded and noncorroded titanium nitride

plating of metal brackets [30].

Titanium nitride (TiN) plating is a method to prevent metal corrosion and can
increase the surface smoothness. The purpose of this study was to evaluate the friction forces
between the orthodontic bracket, with or without TiN plating, and stainless steel wire after it
was corroded in fluoride-containing solution. Methods: In total, 540 metal brackets were
divided into a control group and a TiN-coated experimental group. The electrochemical
corrosion was performed in artificial saliva with 1.23% acidulated phosphate fluoride (APF)
as the electrolytes. Static and kinetic friction were measured by an EZ-test machine
(Shimadazu, Tokyo, Japan) with a crosshead speed of 10 mm per minute over a 5-mm stretch
of stainless steel archwire. The data were analyzed by using unpaired t test and analysis of
variance (ANOVA). Results: Both the control and TiN-coated groups' corrosion potential
was higher with 1.23% APF solution than with artificial solution (P <0.05). In brackets
without corrosion, both the static and kinetic friction force between the control and TiN-
coated brackets groups showed a statistically significant difference (P <0.05). In brackets
with corrosion, the control group showed no statistical difference on kinetic or static friction.
The TiN-coated brackets showed a statistical difference (P <0.05) on kinetic and static

29
friction in different solutions. Conclusion: TiN-coated metal brackets, with corrosion or
without corrosion, cannot reduce the frictional force

30
 CHAPTER - III

AIM AND SCOPE

Need of present study

The present work is undertaken to investigate the corrosion behaviour of

orthodontic wires made of Ni-Ti, SS18/8 and gold22 alloys in artificial saliva in the absence
and presence of 500ppm of Rio by electrochemical studies. Such as polarisation studies.
Such as polarisation study and Ac impedance spectra.

31
 CHAPTER - IV

MATERIALS AND METHODS

Artificial saliva was chosen as the electrolyte, Open to the atmosphere at 37º[Link] test
solution used was the artificial saliva from Fusayama and Meyer B. Its Composition is shown
in table-1. The test solution has to be used shortly after preparation because of urea’s
instability.

Composition Quantity gL -1
Kcl 0.4 gm
Nacl 0.4 gm
Cacl2.2H2O 0.906 gm
NaH2PO4.2H2O 0.690 gm
Na2S.9H2O 0.005 gm
Urea 1 gm
Table -1: Composition of artificial saliva
Orthodontic Wires:
The orthodontic wire Ni-TiL stainless steel was chosen for the present study. The
composition of wire is given in Table2-a.

Nickel 55%
Titanium 45%

Table2-a: Composition of Ni-Ti

The first nickel-Titanium orthodontic wire alloy was marked by the Unitek Corporation Who
are now known as 3M Unitek.

The orthodontic wire SS18/8L stainless steel was chosen for the present study. The
composition of wire is given in Table2-b.

32
 Carbon 0.08%
Manganese 2%
Chromium 18-20%
Nickel 8-10.5%
Iron Bal
Silicon 1%
Phosphorous 0.045%
Sulfur 0.03%

Table2-b: Composition of SS18/8

The orthodontic wireGold22L stainless steel was chosen for the present study. The
composition of wire is given in Table2-c

Metal Composition
Gold 91.6%
Silver 5%
Copper 2%
Zinc 1.33%

Table2-c: Composition of Gold22k

Nutrition information approx value for 100g

Energy 333.3kcal
Protein 0.8g
Fat 0.3g
Carbohydrate 81.9g
Table :2-d Composition of the Rio

Rio (Ingredient):

Sugar, acidity regulator vitamins, DMH, permitted food colours, natural flavours and
add natural identifical flavouring substance (apple).

33
Polarization study:

Polarization methods were often used for laboratory corrosion testing. These
techniques can provide useful information regarding the corrosion mechanisms and
susceptibility of specific materials. Polarization studies were vestigated in a CHI
Electrochemical workstation/analyzer, model [Link] was provided with automatic IR
compensation facility. The Ni-TiL alloy was used as working electrodes, the other two
electrodes the were saturated calomel electrode (SCE) as a reference electrode and platinum
foil as the counter electrode. A time interval of 5 to10 minutes was given for the system to
attain a steady state of open circuit potential. The working electrode and platinum electrode
were immersed in artificial saliva in the absence and presence of Rio. From the polarization
study corrosion parameters such as corrosion potential (E corr ), corrosion current (I corr ),
Tafel slopes (ba and bc) and linear polarization resistance (LPR) were calculated. During the
polarization study, the scan rate (V/s) was 0.01 Hold time at Ef(s) was zero and quiet time(S)
was tw

Fig-7:Schematic diagram of CHI Electrochemical workstation assembly

AC Impedance Spectra:

An AC impedance spectrum [electrochemical impedance spectra] has been used to

confirm the formation of a protective film on the metal surface. The instrument used for
polarization study was used to record AC impedance study also the same. A CHI
electrochemical impedance analyzer (model 660A) was used for AC impedance
measurements. A time interval of 5 to 10 minutes was
given for the system to attain its open-circuit potential. The real part (z’) and imaginary part

34
(z’’) of the cell impedance were measured in ohms at various frequencies (f). The values of
the charge transfer resistance R t and the double layer capacitance C dl were calculated from
Nyquist plots. Impedance log(z/ohm) value was calculated from Bode plots.

CHAPTER - V

RESULTS AND DISCUSSION

Analysis of Potentio dynamic Polarization Curves

Polarization study has been used to investigate the formation of the protective
film, which formed on the metal surface during corrosion process. If corrosion resistance
increases, the linear polarization resistance (LPR) value increases and corrosion current
decreases. corrosion parameter are given in table3. These parameters are such as corrosion
potential (E corr ), corrosion current (I corr ), Tafel slopes (ba and bc) and linear polarization
resistance (LPR).

Table 3:

System Ecorr Bc ba LPR Icorr

2
mV Vs A/cm
mV/decade mV/ Ohm cm2
SCE
decade

AS -317 209 227 9877504 4.799x10-9

AS+Rio500ppm -666 213 260 249487360 2.046x10-10

Corrosion resistance of Ni-Ti alloy in artificial saliva in the absence and presence of
500ppm of Rio.

35
 (a)

(b)

Fig:8 Polarisation curves of Ni-Ti alloy immersed in various test solution a)As,
b)As+500ppmRio

36
Ni-Ti system:

When Ni-Ti is immersed in artificial saliva the corrosion potential is -317 mV Vs

SCE. When Rio is added corrosion potential shifts to cathodic side-317 to -666 mV Vs SCE.
This indicates that the cathodic reaction is controlled predominantly. The LPR value
increases from 9877504 to 249487360-ohm cm2. But the corrosion current decrease from
4.799x10-9 to

2.046x10-10A/[Link] indicates that in presence 500ppm of Rio the corrosion resistance Ni-
Ti alloy increases.

Implication:

People having Ni-Ti orthodontic wire need not hesitate to take Rio solution orally.

Table 4:

System Ecorr bc ba LPR Icorr

mV Vs SCE mV/decade mV/decade Ohm cm2 A/cm
2

AS -381 178 206 6564196 6.338x10-9

AS+Rio500ppm -335 220 253 7865321 6.517x10-9

Corrosion resistance of SS18/8 alloy in artificial saliva in the absence and presence of
500ppm of Rio.

37
 (a)

(b)

Fig:9 Polarisation curves of SS18/8 alloy immersed in various test solution a)As,
b)As+500ppmRio

38
SS18/8 system:

When SS18/8 is immersed in artificial saliva the corrosion potential is -381 mV Vs

SCE. When Rio is added corrosion potential shifts to anodic side-381 to -335 mV Vs SCE.
This indicates that the anodic reaction is controlled predominantly. The LPR value increases
from 6564196 to 7865321-ohm cm2. But the corrosion current decrease from 6.338x10 -9 to
6.517x10-9A/[Link] indicates that in presence 500ppm of Rio the corrosion resistance
SS18/8 alloy increases.

Implication:

People having SS18/8 orthodontic wire need not hesitate to take Rio solution orally.

Table 5:

System Ecorr bc ba LPR Icorr

mV Vs SCE mV/decade mV/decade Ohm cm2 A/cm
2

AS -024 182 211 11030318 3.860x10-9

AS+Rio500ppm -822 166 011 26458386 2.321x10-9

Corrosion resistance of Gold22 alloy in artificial saliva in the absence and

presence of 500ppm of Rio.

39
 (a)

(b)

Fig:10 Polarisation curves of Gold22K immersed in various test solution a)As,

b)As+500ppmRio

40
Gold22 system:

When Gold22 is immersed in artificial saliva the corrosion potential is -024 mV Vs

SCE. When Rio is added corrosion potential shifts to cathodic side-024 to -822 mV Vs SCE.
This indicates that the cathodic reaction is controlled predominantly. The LPR value
increases from 11030318 to 26458386-ohm cm2. But the corrosion current decrease from
3.860x10-9 to 2.321x10-9A/[Link] indicates that in presence 500ppm of Rio the corrosion
resistance Gold22 alloy increases.

Implication:

People having Gold22 orthodontic wire need not hesitate to take Rio solution orally.

Analysis of AC Impedance Spectra:

The Ac impedance spectra of orthodontic wires made of Ni-Ti in artificial saliva

in the absence and presence of Rio, is shown in figures. The corrosion parameters charge
transfer resistance, such as double layer capacitance and impedance values are given in table
6.

Table 6:

Phase angle
System Rt Cdl Z
Ohm cm2 F/cm2 Impedance Z/ohm

AS 452400 1.1273x10-11 7.001 90.79

As+Rio500ppm 1078000 4.7309x10-12 6.146 74.66

Corrosion resistance of Ni-Ti alloy in artificial saliva in the absence and presence of
500ppm of Rio.

41
 (a)

(b)

Fig:11 AC impedance curve of Ni-Ti alloy immersed in various test solution. a)As,
b)As=500ppmRio.

When Ni-Ti alloy is immersed in artificial saliva the R t value is 452400. When 500ppm of
Rio is added the Rt value increases from 452400 to [Link] value decreases from

42
1.1273x10-11 to [Link] value increases 7.001 to 6.146. This indicates that in
presence 500ppm of Rio the corrosion resistance Ni-Ti alloy increases.

Implication:

People having Ni-Ti orthodontic wire need not hesitate to take Rio solution orally.

Table 7:

System Rt Cdl Z Phase angle

ohm cm2 F/cm2 Impedance (Z/ohm)

AS 629970 8.0956x10-12 5.940 72.78

AS+Rio500ppm 14731100 3.462xx10-13 7.121 174.6

Corrosion resistance of SS18/8 alloy in artificial saliva in the absence and presence of
500ppm of Rio.

(a)

43
 (b)

Fig:12 AC impedance curve of SS18/8 alloy immersed in various test solution. a)As,
b)As=500ppmRio.

When SS18/8 alloy is immersed in artificial saliva the R t value is 629970. When 500ppm of
Rio is added the Rt value increases from 629970 to [Link] value decreases
from8.0956x10-12to 3.462 [Link] value increases from 5.940 to 7.121. This
indicates that in presence 500ppm of Rio the corrosion resistance SS18/8 alloy increases.

Implication:

People having SS18/8 orthodontic wire need not hesitate to take Rio solution orally.

Table 8:

System Rt Cdl Z Phase angle

Ohm cm2 F/cm2 Impedance (Z/ohm)

AS 298720 1.7072x10-11 5.983 69.86

AS+Rio500ppm 1549760 3.2906x10-12 6.389 78.22

Corrosion resistance of Gold22 alloy in artificial saliva in the absence and

presence of 500ppm of Rio.

44
 (a)

(b)

Fig:13 AC impedance curve of SS18/8 alloy immersed in various test solution. a)As,
b)As=500ppmRio.

45
When Gold22 alloy is immersed in artificial saliva the R t value is 298720. When 500ppm of
Rio is added the Rt value increases from 298720 to [Link] value decreases
from1.7072 x10-11to 3.2906 [Link] value increases from 5.983 to 6.389. This
indicates that in presence 500ppm of Rio the corrosion resistance Gold22 alloy increases.

Implication:

People having Gold22 orthodontic wire need not hesitate to take Rio solution orally.

CHAPTER - VI

CONCLUSION

Corrosion resistance of orthodontic wires made of Ni-Ti, SS18/8 and gold22 in artificial
saliva in the absence and presence of 500ppm Rio has been evaluated by electrochemical
study. Such has polarisation and Ac impedance spectra.

The study leads to the following conclusion:

 In presence of 500ppm of Rio corrosion resistance of Ni-Ti alloys in artificial

saliva increases.
 In presence of 500ppm of Rio corrosion resistance of SS18/8 alloys in artificial
saliva increases.
 In presence of 500ppm of Rio corrosion resistance of gold22 alloys in artificial
saliva increases.
 People having orthodontic wire Ni-Ti, SS18/8 and also gold22 need not hesitate
to take Rio solution orally.

46
 CHAPTER – VII

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