Material of Construction
Material of Construction
Material of Construction
Samanta 1
CHAPTER 8
Material of Construction
Syllabus:
General study of composition, corrosion, resistance. Properties and applications of the materials of construction with
special reference to stainless steel and glass.
A number of equipment are used in the manufacture of pharmaceuticals, bulk drugs, antibiotics, biological products etc.
A wide variety of materials are used.
Classification of material of construction:
Material of construction
Metals Non-metals
1. Chemical factors
Whenever a chemical substance is placed in a container or equipment the chemical is exposed to the material of
construction of the container or equipment. Therefore, the material of construction may contaminate the product
(contamination) or the product may destroy the material of construction (corrosion).
Contamination of product:
Iron contamination may change the color of the products (like gelatin capsule shells), catalyze some reactions
that may enhance the rate of decomposition of the product.
Leeching of glass may make aqueous product alkaline. This alkaline medium may catalyze the decomposition
of the product.
Heavy metals such as lead, inactivate penicillin.
Corrosion of material of construction:
The products may be corrosive in nature. They may react with the material of construction and may destroy it.
The life of the equipment is reduced.
Extreme pH, strong acids, strong alkalis, powerful oxidizing agents, tannins etc. reacts with the materials,
hence some alloys having special chemical resistance are used.
2. Physical factors
Strength
The material should have sufficient physical strength to withstand the required pressure and stresses.
Iron and steel can satisfy these properties. Tablet punching machine, die, upper and lower punch sets are
made of stainless steel to withstand the very high pressure.
Glass, though has strength but are brittle.
Aerosol container must withstand very high pressure, so tin plate container coated with some polymers
(lacquered) are used.
Plastic materials are weak so they are used in some packaging materials, like blister packs.
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Mass
For transportation light weight packaging materials are used. Plastic, aluminium and paper packaging
materials are used for packing pharmaceutical products.
Wear properties
When there is a possibility of friction between two surfaces the softer surface wears off and these materials
contaminate the products. For example during milling and grinding the grinding surfaces may wear off and
contaminate the powder. When pharmaceutical products of very high purity is required ceramic and iron
grinding surfaces are not used.
Thermal conductivity
In evaporators, dryers, stills and heat exchangers the materials employed have very good thermal conductivity.
In this case iron, copper or graphite tubes are used for effective heat transfer.
Thermal expansion
If the material has very high thermal expansion coefficient then as temperature increases the shape of the
equipment changes. This produces uneven stresses and may cause fractures. So such materials should be used
those are able to maintain the shape and dimension of the equipment at the working temperature.
Ease of fabrication
During fabrication of an equipment, the materials undergo various processes such as casting, welding, forging
and mechanization etc. For example glass and plastic may be easily moulded in to containers of different
shape and sizes. Glass can be used as lining material for reaction vessels.
Cleaning
Smooth and polished surfaces makes cleaning easy. After an operation is complete, the equipment is cleaned
thoroughly so the previous product cannot contaminate the next product. Glass and stainless steel surfaces can
be smooth and polished, hence are easy to clean.
Sterilization
In the production of parenteral, ophthalmic and bulk drug products all the equipment are required to be
sterilized. This is generally done by introducing steam under high pressure. The materials must withstand this
high temperature (1210C) and pressure (15 pounds per square inch). If rubber materials are there it should be
vulcanized to withstand the high temperature.
Transparency
In reactors and fermentors a visual port is provided to observe the progress of the process going on inside the
chamber. In this case borosilicate glass is often used.
In parenteral and ophthalmic containers the particles, if any, are observed from with polarized light. The walls
of the containers must be transparent to see through it. Here also glass is the preferred material.
3. Economic factors
Initial cost of the equipment depends on the material used. Several materials may be suitable for construction from
physical and chemical point of view, but from all the materials only the cheapest material is chosen for construction of
the equipment.
Materials those require lower maintenance cost are used because in long run it is economical.
CORROSION
Definition: Corrosion is defined as the reaction of a metallic material with its environment, which causes a measurable
change to the material and can result in a functional failure of the metallic component or of a complete system.
THEORY OF CORROSION
1. Corrosion reaction on single metal
A single piece of metal (e.g. Fe) when comes in contact with acid
(e.g. HCl ) small galvanic cells may be set up on the surface.
Each galvanic cell consists of (i) anode regions and (ii) cathode
regions.
Reaction at anode: Fe on the iron leaves two electrons to the metal
and itself becomes Fe++ ion. Fe++ ion is soluble in water, so it is
released in the medium. Thus the iron surface is corroded.
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Reaction at cathode: The released electron is conducted through the metal piece into cathode region. Two electrons are
supplied to two protons (H+ ) to form two atoms of H. Hydrogen atoms are unstable, hence two H atoms will combine
to form a molecule of stable H2. In the absence of acid , water itself dissociates to generate H+ ion.
2H+ + 2e H2 Hydrogen (H2) forms bubbles on the metal surface. If the rate of hydrogen
formation is very slow then a film of H2 bubbles will be formed that will slow down the cathode reaction, hence the rate
of corrosion will slow down. If the rate of hydrogen production is very high then hydrogen molecules cannot form the
film on the surface. So the corrosion proceeds rapidly.
4. Velocity
When corrosive medium moves at a high velocity along the metallic surface, the rate of corrosion increases due to:
Corrosion products are formed rapidly and washed away rapidly to expose new surface for corrosion reaction.
Accumulation of insoluble films on the surface is prevented.
The corrosion is rapid in the bends in the pipes, propellers, agitators and pumps.
5. Surface films
Thin oxide films are formed on the surface of stainless (rusting). These films absorbs moisture and increases the
rate of corrosion.
Zinc oxide forms porous films. Fluid medium can enter inside and thus corrosion continues. Nonporous films of
chromium oxide or iron oxide prevent corrosion.
Grease films protect the surface from direct contact with corrosive substances.
TYPE OF CORROSION
1. Fluid corrosion: General
When corrosion is generally confined to a metal surface as a whole, it is known as general corrosion. This corrosion
occurs uniformly over the entire exposed surface area. E.g. Swelling, cracking, softening of plastic materials.
(b) Pitting corrosion: On metal surface small holes or pits are created due to local corrosion and these pits increase in
size rapidly. In the pits the metals dissolves rapidly especially by chlorine and chloride ions.
(c) Stress corrosion: Certain area of metal may be subjected to thermal, mechanical or chemical stresses. The surface
area becomes anode and acts as corrosion area.
(d) Fretting corrosion: Equipment showing high vibrations destroys the surface of metal (e.g. steels balls in ball-
bearing) by mechanical hitting.
(e) Corrosion fatigue: Cyclic stress breaks the protective film, so corrosion increases.
PREVENTION OF CORROSION
Following methods may be adopted for preventing or reducing corrosion:
1. Material selection
(a) Pure materials have less tendency towards pitting, but they are expensive and soft. Therefore, only aluminium can
be used in pure form.
(b) Improved corrosion resistance can be obtained by adding corrosion resistant elements. For example inter-granular
corrosion occurs in stainless steel. This tendency can be reduced by addition of small amount of titanium.
(c) Nickel, copper and their alloys are used in non-oxidizing environment, whereas chromium containing alloys are
used in oxidizing environment.
(d) Materials those are close in electrochemical series should be used for fabrication.
(e) Corrosive materials are taken with suitable material of construction:
Corrosive material Suitable material
Nitric acid Stainless steel
Hyfrofluoric acid Monel metal
Distilled Water Tin
Dilute sulphuric acid Lead
Caustic Nickel
3. Coating or lining
Corrosion resistant coating may be applied on metal surface to improve corrosion resistance. It also separates the metal
from corrosive environment.
(a) Organic coating are used as lining in equipment such as tanks, piping,
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FERROUS MATERIAL
Cast Iron, Steels, Stainless Steels
Cast Iron
This iron consists of carbon more than 1.5%. Different proportions of carbon gives different properties of the steel.
Properties:
1. Cast iron is resistant to concentrated sulfuric acid, nitric acid and dilute alkalis.
2. Cast iron is attacked by dilute sulfuric acid, dilute nitric acid and dilute and concentrated hydrochloric acid.
3. Cast iron has low thermal conductivity.
4. It is not corrosion resistance hence it is alloyed with Silicon, Nickel or Chromium to produce corrosion resistacnce.
5. It is brittle so it is tough to machine.
Applications:
1. It is used as supports for plants.
2. Thermal conductivity is low hence used as the outer wall of steam jacket.
3. It is cheap hence used in place of more expensive materials by coating with enamel or plastic.
Stainless Steel
Stainless steel is an alloy of iron usually of nickel and chromium.
For pharmaceutical use stainless steel contains 18% chromium and 8% nickel. This steel is called 18/8 stainless steel.
Properties:
1. It is heat resistant
2. Corrosion resistant
3. Ease of fabrication
4. Cleaning and sterilization is easy.
5. Has good tensile strength.
6. During heat welding the corrosion resistant properties of stainless steel may be reduced du to deposition of carbide
precipitate at the crystal grain boundaries. This steel is stabilized by addition of minor quantities of titanium,
molybdenum or niobium.
Applications:
1. Storage and extraction vessels, evaporators and fermenting vessels.
2. Small apparatus like funnels, buckets, measuring vessels.
3. Sinks and bench tops.
4. In penicillin production plant nearly all equipment are made of stainless steel.
ALUMINIUM
Properties:
1. Pure aluminium is soft and more corrosion resistant than its alloys. Small percentages of manganese, magnesium
or silicon produces strong, corrosion resistant aluminium alloys (e.g Duralumin)
2. It is attacked by mineral acids, alkali, mercury and its salts.
3. It is resistant to strong nitric acid.
4. It is resistant to acetic acid due to the formation of a gelatinous surface film of aluminium subacetate.
5. Low density hence lighter.
Applications:
1. The salts of aluminium is colorless and non-toxic to microorganisms, hence used for fermenting vessels for
biosynthetic production of citric acid, gluconic acids and streptomycin.
2. Used for making extraction and absorption vessels in preparation of antibiotics.
3. Storage vessels of acetic acid and ammonia.
4. Plants for nitric acid is used.
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5. Because of its lightness large containers such as drums, barrels, road and rail tankers are made with aluminium.
GLASS
Preparation of glass:
Glass is composed principally of sand (silica - SiO2), soda-ash (Na2CO3 - sodium carbonate) and lime-stone (Ca CO3-
calcium carbonate).
Glass made from pure silica consists of a three-dimensional network of silicon atoms each of which is surrounded by
four oxygen atoms an in this way the tetrahedra are linked together to produce the network.
Glass prepared from pure silica require very high temperature to fuse, hence soda-ash and lime is used to reduce the
melting point.
(i) glass made of pure silica has network (Fig-1)
Properties:
(a) It is very hard and
(b) chemically resistant but
(c) melting point very high so it is very difficult to mould.
(ii) Glass made of pure silica + Na2O (Fig.-2)
(valency of Na = 1)
Properties:
(a)Structure is less rigid so low
m.p. and easier to mould
(b) the glass is too rapidly attacked
by water and NaOH is leached out of the glass.
(iii) Pure silica + CaO (or BaO, MgO, PbO and ZnO) (Fig.-3)
(valency of Ca, Ba, Mg, Pb, Zn = 2)
Properties:
(a) divalent oxides do not break the network
of pure silica, but only push the tetrahedron
apart. It is more rigid than soda-silica network.
(b) Since the bond is more stronger, hence chemical reactivity is lowered.
Disadvantages:
Physical aspect
1. They are brittle and break easily.
2. They may crack when subject to sudden changes of temperatures.
3. They are heavier in comparison to plastic containers.
4. Transparent glasses gives passage to UV-light which may damage the photosensitive drugs inside the container.
Chemical aspect
5. Flaking: From simple soda-lime glass the alkali is extracted from the surface of the container and a silicate rich
layer is formed which sometimes gets detached from the surface and can be seen in the contents in the form of
shining plates known as flakes and in the form of needles they are known as spicules. this is a serious
problem, specially in parenteral preparations.
6. Weathering: Sometimes moisture is condensed on the surface of glass container which can extract some weakly
bound alkali leaving behind a white deposit of alkali carbonate to remain over there, further condensation of
moisture will lead to the formation of an alkaline solution which will dissolve some silica resulting in loss of
brilliance from the surface of glass called weathering.
To prevent weathering, the deposited white layer of alkali carbonates should be removed as early as possible
by washing the containers with dilute solution of acid and then washing thoroughly with water.