UNIT-IV

4.1 Paints
4.1.1 Dried green paint

 Paint is any liquid, liquefiable, or mastic composition that, after application to a

substrate in a thin layer, converts to a solid film.

 It is most commonly used to protect, color, or provide texture to objects. Paint

can be made or purchased in many colors—and in many different types, such as
watercolor, artificial, etc.

 Paint is typically stored, sold, and applied as a liquid, but dries into a solid.

Components

Binder (or film former)

 The binder, commonly called the vehicle, is the film-forming component of paint.
It is the only component that must be present.

 Components listed below are included optionally, depending on the desired

properties of the cured film.

 The binder imparts adhesion and strongly influences properties such as gloss,
durability, flexibility, and toughness.

 Binders include synthetic or natural resins such as alkyds, acrylics, vinyl-acrylics,

vinyl acetate/ethylene (VAE), polyurethanes, polyesters, melamine resins,
epoxy, or oils.

 Binders can be categorized according to the mechanisms for drying or curing.

Although drying may refer to evaporation of the solvent or thinner, it usually
 refers to oxidative cross-linking of the binders and is indistinguishable from
curing.

 Some paints form by solvent evaporation only, but most rely on cross-linking
processes.

Pigment and Filler

 Pigments are granular solids incorporated in the paint to contribute color. Fillers
are granular solids incorporate to impart toughness, texture, give the paint
special properties, or to reduce the cost of the paint.

 Alternatively, some paints contain dyes instead of or in combination with

pigments.

 Pigments can be classified as either natural or synthetic. Natural pigments

include various clays, calcium carbonate, mica, silicas, and talcs. Synthetics
would include engineered molecules, calcined clays, blanc fixe, precipitated
calcium carbonate, and synthetic pyrogenic silicas.

 Hiding pigments, in making paint opaque, also protect the substrate from the
harmful effects of ultraviolet light. Hiding pigments include titanium dioxide,
phthalo blue, red iron oxide, and manyothers.

 Fillers are a special type of pigment that serve to thicken the film, support its
structure and increase the volume of the paint.

 Fillers are usually cheap and inert materials, such asdiatomaceous earth, talc,
lime, barytes, clay, etc.

 Floor paints that must resist abrasion may contain fine quartz sand as a filler.
Not all paints include fillers.

 On the other hand, some paints contain large proportions of pigment/filler and
binder.
  Some pigments are toxic, such as the lead pigments that are used in lead paint.
Paint manufacturersbegan replacing white lead pigments with titanium white
(titanium dioxide), before lead was banned in paint for residential use in 1978 by
the US Consumer Product Safety Commission.

 The titanium dioxide used in most paints today is often coated with
silica/alumina/zirconium for various reasons, such as better exterior durability,
or better hiding performance (opacity) promoted by more optimal spacing
within the paint film.

Additives

 Besides the three main categories of ingredients, paint can have a wide variety of
miscellaneous additives, which are usually added in small amounts, yet provide
a significant effect on the product.

 Some examples include additives to modify surface tension, improve flow

properties, improve the finished appearance, increase wet edge, improve
pigment stability, impart antifreeze properties, control foaming, control skinning,
etc.

 Other types of additives include catalysts, thickeners, stabilizers, emulsifiers,

texturizers, adhesion promoters, UV stabilizers, flatteners (de-glossing agents),
biocides to fight bacterial growth, and the like.

 Additives normally do not significantly alter the percentages of individual

components in a formulation.

Color changing paint

 Various technologies exist for making paints that change color.

 Thermochromic paints and coatings contain materials that change conformation
when heat is applied or removed, and so they change color.

 Liquid crystals have been used in such paints, such as in the thermometer strips
and tapes used in aquaria and novelty/promotional thermal cups and straws.
Photochromic paints and coatings contain dyes that change conformation when
the film is exposed to UV light, and so they change color. These materials are
used to make eyeglasses.

 Color changing paints can also be made by adding halochrome compounds or

other organic pigments.

 One patent cites use of these indicators for wall coating applications for light
colored paints. When the paint is wet it is pink in color but upon drying it
regains its original white color.

 As cited in patent, this property of the paint enabled two or multiple coats to be
applied on a wall properly and evenly.

 The previous coat/s having dried would be white whereas the new wet coat
would be distinctly pink.

.Watercolors as applied with a brush

 Since the time of the Renaissance, siccative (drying) oil paints, primarily linseed
oil, have been the most commonly used kind of paints in fine art applications; oil
paint is still common today.

 However, in the 20th century, water-based paints, includingwatercolors and

acrylic paints, became very popular with the development of acrylic and other
latex paints. Milk paints (also called casein), where the medium is derived from
the natural emulsion that is milk, were popular in the 19th century and are still
available today.
  Egg tempera (where the medium is an emulsion of raw egg yolk mixed with oil)
is still in use as well, as are encaustic wax-based paints. Gouache is a variety of
opaque watercolor that was also used in the Middle Ages and Renaissance for
manuscript illuminations.

 The pigment was often made from ground semiprecious stones such as lapis
lazuliand the binder made from either gum arabic or egg white. Gouache, also
known as 'designer color' or 'body color' is commercially available today.

Application

 Paint can be applied as a solid, a gaseous suspension or a liquid. Techniques vary

depending on the practical or artistic results desired.

 As a solid (usually used in industrial and automotive applications), the paint is

applied as a very fine powder, then baked at high temperature.

 This melts the powder and causes it to adhere to the surface. The reasons for
doing this involve the chemistries of the paint, the surface itself, and perhaps
even the chemistry of the substrate (the object being painted).

 This is called "powder coating" an object.

 As a gas or as a gaseous suspension, the paint is suspended in solid or liquid

form in a gas that is sprayed on an object.

 The paint sticks to the object. This is called "spray painting" an object. The
reasons for doing this include:

 The application mechanism is air and thus no solid object touches the object
being painted;

 The distribution of the paint is uniform, so there are no sharp lines;

 It is possible to deliver very small amounts of paint;

  A chemical (typically a solvent) can be sprayed along with the paint to dissolve
together both the delivered paint and the chemicals on the surface of the object
being painted;

Product variants

 A collection of cans of paint and variants

 A huge collection of different kinds of spray cans, markers, paints and inks in the
underground graffiti shop.

 Primer is a preparatory coating put on materials before applying the paint itself.
The primed surface ensures better adhesion of the paint, thereby increasing the
durability of the paint and providing improved protection for the painted
surface.

 Suitable primers also may block and seal stains, or hide a color that is to be
painted over.

 Emulsion paints are water-based paints in which the paint material is dispersed
in a liquid that consists mainly of water.

 For suitable purposes this has advantages in fast drying, low toxicity, low cost,
easier application, and easier cleaning of equipment, among other factors.

 Flat Finish paint is generally used on ceilings or walls that are in bad shape. This
finish is useful for hiding imperfections in walls and it is economical in
effectively covering relatively great areas.

 However this finish is not easily washable and is subject to staining.

 Matte Finish is generally similar to flat finish, but such paints commonly offer
superiority washability and coverage.

 Eggshell Finish has some sheen, supposedly like that of the shell on an egg.
  This finish provides great washability, but is not very effective at hiding
imperfections on walls and similar surfaces.

 Eggshell finish is valued for bathrooms because it washable and water repellent,
so that it tends not to peel in a wet environment.

 Pearl (Satin) Finish is very durable in terms of washability and resistance to

moisture, even in comparison to eggshell finish.

 It protects walls from dirt, moisture and stains. Accordingly it is exceptionally

valuable for bathrooms, furniture, and kitchens, but it is shinier than eggshell, so
it is even more prone to show imperfections.

 Semi-Gloss Finish typically is used on trim to emphasise detail and elegance, and
to show off woodwork, such as on doors and furniture.

 It provides a shiny surface and provides good protection from moisture and
stains on walls. Its gloss does however emphasise imperfections on the walls and
similar surfaces.

 It is popular in schools and factories where washability and durability are the
main considerations.

 Varnish and shellac are in effect paints without pigment; they provide a
protective coating without substantially changing the color of the surface, though
they can emphasise the colour of the material.

.Failure of a paint

 The main reasons of paint failure after application on surface are the applicator
and improper treatment of surface.

Contamination
 Foreign contaminants added without the manufacturers consent can cause
various film defects.

Peeling/Blistering

Most commonly due to improper surface treatment before application and

inherent moisture/dampness being present in the substrate.

Chalking

 Chalking is the progressive powdering of the paint film on the painted surface.
The primary reason for the problem is polymer degradation of the paint matrix
due to exposure of UV radiation in sunshine and condensation from dew.

 The degree of chalking varies as epoxies react quickly while acrylics and
polyurethanes can remain unchanged for long periods.

 The degree of chalking can be assessed according to International Standard ISO

4628 Part 6 or 7 or American Society of Testing and Materials (ASTM) Method
D4214 (Standard Test Methods for Evaluating the Degree of Chalking of Exterior
Paint Films).

Cracking

 Cracking of paint film is due to the unequal expansion or contraction of paint

coats.

 It usually happens when the coats of the paint are not allowed to cure/dry
completely before the next coat is applied.

 The degree of cracking can be assessed according to International Standard ISO

4628 Part 4 or ASTM Method D661 (Standard Test Method for Evaluating Degree
of Cracking of Exterior Paints).
Erosion

 Erosion is very quick chalking.

 It occurs due to external agents like air,water etc. It can be evaluated using ASTM
Method ASTM D662 (Standard Test Method for Evaluating Degree of Erosion of
Exterior Paints).

Blistering

 Blistering is due to improper surface exposure of paint to strong sunshine. The

degree of blistering can be assessed according to ISO 4628 Part 2 or ASTM
Method D714 (Standard Test Method for Evaluating Degree of Blistering of
Paints).

Degradation

 The fungus Aureobasidium pullulans is one of the species prominent for

damaging wall paints.

Dangers

 Volatile organic compounds (VOCs) in paint are considered harmful to the

environment and especially for people who work with them on a regular basis.

 Exposure to VOCs has been related to organic solvent syndrome, although this
relation has been somewhat controversial.

 The controversial solvent 2-butoxyethanol is also used in paint production.

Suspension (chemistry)

 In chemistry, a suspension is a heterogeneous mixture containing solid particles

that are sufficiently large for sedimentation. Usually they must be larger than one
micrometer.
  The internal phase (solid) is dispersed throughout the external phase (fluid)
through mechanical agitation, with the use of certain excipients or suspending
agents. Unlike colloids, suspensions will eventually settle. An example of a
suspension would be sand in water.

 The suspended particles are visible under a microscope and will settle over time
if left undisturbed.

 This distinguishes a suspension from a colloid, in which the suspended particles

are smaller and do not settle.

 Colloids and suspensions are different from solutions, in which the dissolved
substance (solute) does not exist as a solid, and solvent and solute are
homogeneously mixed.

Technique monitoring physical stability

 Multiple light scattering coupled with vertical scanning is the most widely used
technique to monitor the dispersion state of a product, hence identifying and
quantifying destabilization phenomena.

 It works on concentrated dispersions without dilution. When light is sent

through the sample, it is back scattered by the particles.

 The backscattering intensity is directly proportional to the size and volume

fraction of the dispersed phase.

 Therefore, local changes in concentration (sedimentation) and global changes in

size (flocculation, aggregation) are detected and monitored.
Accelerating methods for shelf life prediction

 The kinetic process of destabilisation can be rather long (up to several months or
even years for some products) and it is often required for the formulator to use
further accelerating methods in order to reach reasonable development time for
new product design. Thermal methods are the most commonly used and consists
in increasing temperature to accelerate destabilisation (below critical
temperatures of phase inversion or chemical degradation).

 Temperature affects not only the viscosity, but also interfacial tension in the case
of non-ionic surfactants or more generally interactions forces inside the system.

4.1.1 Pigment
 A pigment is a material that changes the color of reflected or transmitted light as
the result of wavelength-selective absorption.

 This physical process differs from fluorescence, phosphorescence, and other

forms of luminescence, in which a material emits light.Many materials selectively
absorb certain wavelengths of light.

 Materials that humans have chosen and developed for use as pigments usually
have special properties that make them ideal for coloring other materials. A
pigment must have a high tinting strength relative to the materials it colors. It
must be stable in solid form at ambient temperatures.

 For industrial applications, as well as in the arts, permanence and stability are
desirable properties. Pigments that are not permanent are called fugitive.
Fugitive pigments fade over time, or with exposure to light, while some
eventually blacken.

 Pigments are used for coloring paint, ink, plastic, fabric, cosmetics, food and
other materials.
  Most pigments used in manufacturing and thevisual arts are dry colorants,
usually ground into a fine powder.

 This powder is added to a vehicle (or binder), a relatively neutral or colorless

material that suspends the pigment and gives the paint its adhesion.

 A distinction is usually made between a pigment, which is insoluble in its vehicle

(resulting in a suspension), and a dye, which either is itself a liquid or is soluble in its
vehicle (resulting in a solution).

A colorant can act as either a pigment or a dye depending on the vehicle involved. In
some cases, a pigment can be manufactured from a dye by precipitating a soluble dye
with a metallic salt.

The resulting pigment is called a lake pigment.

The term biological pigment is used for all colored substances independent of their
solubility.

Physical basis

 A wide variety of wavelengths (colors) encounter a pigment. This pigment

absorbs red and green light, but reflects blue, creating the color blue.

 Pigments appear the colors they are because they selectively reflect and absorb
certain wavelengths of visible light.

 White light is a roughly equal mixture of the entire spectrum of visible light with
a wavelength in a range from about 375 or 400 nanometers to about 760 or 780
nm.

 When this light encounters a pigment, parts of the spectrum are absorbed by the
chemical bonds of conjugated systems and other components of the pigment.
  Some other wavelengths or parts of the spectrum are reflected or scattered. Most
pigments are charge-transfer complexes, like transition metal compounds, with
broad absorption bands that subtract most of the colors of the incident white
light.

 The new reflected light spectrum creates the appearance of a color. Pigments,
unlike fluorescent or phosphorescent substances, can onlysubtract wavelengths
from the source light, never add new ones.

Development of synthetic pigments

 The earliest known pigments were natural minerals. Natural iron oxides give a
range of colors and are found in many Paleolithic andNeolithic cave paintings.

 Two examples include Red Ochre, anhydrous Fe2O3, and the hydrated Yellow
Ochre (Fe2O3.H2O). Charcoal, or carbon black, has also been used as a black
pigment since prehistoric times.

 Two of the first synthetic pigments were white lead (basic lead carbonate,
(PbCO3)2Pb(OH)2) and blue frit (Egyptian Blue).

 White lead is made by combining lead with vinegar (acetic acid, CH3COOH) in
the presence of CO2.

 Blue frit is calcium copper silicate and was made from glass colored with a
copper ore, such as malachite. These pigments were used as early as the second
millennium BCE

Swatches

 Swatches are used to communicate colors accurately. For different media like
printing, computers, plastics, textiles; different type of swatches are used.

 Generally, the media which offers widest gamut of color shades is widely used
across different media.
Printed Swatches

 There are many reference standards providing printed swatches of color

shades. PANTONE, RAL, Munsell etc. are widely used standards of color
communication across different media like printing, plastics, and textiles.

Plastic Swatches

 Companies manufacturing color masterbatches and pigments for plastics offer

plastic swatches in injection molded color chips.

 These color chips are supplied to the designer or customer to choose and select
the color for their specific plastic products.

 Plastic Swatches are available in various special effects like pearl, metallic,
fluorescent, sparkle, mosaic etc.

 However, these effects are difficult to replicate on other media like print and
computer display.

 wherein they have created plastic swatches on website by 3D modelling to

including various special effects.

Computer Swatches

 Pure pigments reflect light in a very specific way that cannot be precisely
duplicated by the discrete light emitters in a computer display.

 However, by making careful measurements of pigments, close approximations

can be made. The Munsell Color System provides a good conceptual explanation
of what is missing.

 Munsell devised a system that provides an objective measure of color in three

dimensions: hue, value (or lightness), and chroma.
 Computer displays in general are unable to show the true chroma of many
pigments, but the hue and lightness can be reproduced with relative accuracy.

 However, when the gamma of a computer display deviates from the reference
value, the hue is also systematically biased.
4.1.2 Cleaning Agents
Soap

 A collection of decorative soaps, often found in hotels

 Two equivalent images of the chemical structure of sodium stearate, a typical

soap.

 In chemistry, soap is a salt of a fatty acid. Soaps are mainly used as surfactants
for washing, bathing, and cleaning, but they are also used in textile spinning and
are important components of lubricants.

 Soaps for cleansing are obtained by treating vegetable or animal oils and fats
with a strongly alkaline solution.

 Fats and oils are composed of triglycerides; three molecules of fatty acids are
attached to a single molecule of glycerol.

 The alkaline solution, which is often called lye (although the term "lye soap"
refers almost exclusively to soaps made with sodium hydroxide), brings about a
chemical reaction known assaponification.

 In this reaction, the triglyceride fats are first hydrolyzed into free fatty acids, and
then these combine with the alkali to form crude soap, an amalgam of various
soap salts, excess fat or alkali, water, and liberated glycerol (glycerin).

 The glycerin is a useful by-product, which can be left in the soap product as a
softening agent, or isolated for other uses.

 Soaps are key components of most lubricating greases, which are usually
emulsions of calcium soap or lithium soaps and mineral oil.

 These calcium- and lithium-based greases are widely used. Many other metallic
soaps are also useful, including those of aluminium, sodium, and mixtures of
them.
  Such soaps are also used as thickeners to increase the viscosity of oils. In ancient
times, lubricating greases were made by the addition of lime to olive oil

Mechanism of cleansing soaps

 Structure of amicelle, a cell-like structure formed by the aggregation of soap

subunits (such as sodium stearate):

 The exterior of the micelle is hydrophilic (attracted to water) and the interior is
lipophilic (attracted to oils).

Action of soap

 When used for cleaning, soap allows insoluble particles to become soluble in
water and then be rinsed away.

 For example: oil/fat is insoluble in water, but when a couple of drops of dish
soap are added to the mixture, the oil/fat apparently disappears.

 The insoluble oil/fat molecules become associated inside micelles, tiny spheres
formed from soap molecules with polar hydrophilic (water-attracting) groups on
the outside and encasing a lipophilic (fat-attracting) pocket, which shields the
oil/fat molecules from the water making it soluble.

 Anything that is soluble will be washed away with the water. Synthetic
detergentsoperate by similar mechanisms to soap.
Effect of the alkali

 The type of alkali metal used determines the kind of soap product. Sodium
soaps, prepared from sodium hydroxide, are firm, whereas potassium soaps,
derived from potassium hydroxide, are softer or often liquid.

 Historically, potassium hydroxide was extracted from the ashes of bracken or

other plants. Lithium soaps also tend to be hard—these are used exclusively in
greases.

Effects of fats

 Soaps are derivatives of fatty acids. Traditionally they have been made from
triglycerides (oils and fats).

 Triglyceride is the chemical name for the triesters of fatty acids and glycerin.
Tallow, i.e., rendered beef fat, is the most available triglyceride from animals. Its
saponified product is called sodium tallowate.

 Typical vegetable oils used in soap making are palm oil, coconut oil, olive oil,
and laurel oil.

 Each species offers quite different fatty acid content and, hence, results in soaps
of distinct feel.

 The seed oils give softer but milder soaps. Soap made from pure olive oil is
sometimes called Castile soap or Marseille soap, and is reputed for being extra
mild.

 The term "Castile" is also sometimes applied to soaps from a mixture of oils, but
a high percentage of olive oil.
Liquid soap

 Liquid soap was not invented until the 1800s; in 1865, William Shepphard
patented a liquid version of soap. In 1898, B.J. Johnson developed a soap (made
of palm and olive oils); his company introduced "Palmolive" brand soap that
same year.

 This new brand of the new kind of soap became popular rapidly, and to such a
degree that B.J. Johnson Soap Company changed its name to Palmolive.

 At the turn of the Twentieth century, Palmolive was the world's best-selling
soap.

 As a detergent, liquid soap tends to be more effective than flake soap, and tends
to leave less residue on skin, clothes, and surfaces (e.g., wash basins).

 Liquid soap also works better for more traditional/non-machine washing

methods, such as using a washboard.

Soap-making processes

 The industrial production of soap involves continuous processes, such as

continuous addition of fat and removal of product. Smaller-scale production
involves the traditional batch processes.

 The three variations are: the 'cold process', wherein the reaction takes place
substantially at room temperature, the 'semiboiled' or 'hot process', wherein the
reaction takes place near the boiling point, and the 'fully boiled process', wherein
the reactants are boiled at least once and the glycerol is recovered.

 There are two types of 'semiboiled' hot process methods. The first is the ITMHP
(in the mold hot process) and the second is the CPHP (crockpot hot process).
Typically soapmakers choose the hot process methods if they wish to reduce the
cure time to a three-day air dry process.
  Most soapmakers, however, continue to prefer the cold process method.

 The cold process and hot process (semiboiled) are the simplest and typically
used by small artisans and hobbyists producing handmade decorative soaps. The
glycerine remains in the soap and the reaction continues for many days after the
soap is poured into moulds.

 The glycerine is left during the hot-process method, but at the high temperature
employed, the reaction is practically completed in the kettle, before the soap is
poured into moulds.

 This simple and quick process is employed in small factories all over the world.

Cold process

The lye is dissolved in water.

 Even in the cold soapmaking process, some heat is usually required; the
temperature is usually raised to a point sufficient to ensure complete melting of
the fat being used.

 The batch may also be kept warm for some time after mixing to ensure the alkali
(hydroxide) is completely used up.

 This soap is safe to use after about 12–48 hours, but is not at its peak quality for
use for several weeks.

 Cold-process soapmaking requires exact measurements of lye and fat amounts

and computing their ratio, using saponification charts to ensure the finished
product does not contain any excess hydroxide or too much free unreacted fat.

 Saponification charts should also be used in hot processes, but are not necessary
for the “fully boiled hot-process” soaping.

 The lye is dissolved in water.

  Then oils are heated, or melted if they are solid at room temperature. Once the
oils are liquefied and the lye is fully dissolved in water, they are combined. This
lye-fat mixture is mixed until the two phases (oils and water) are fully
emulsified.

 Emulsification is most easily identified visually when the soap exhibits some
level of “trace”, which is the thickening of the mixture. (Modern-day amateur
soapmakers often use a stick blender to speed this process).

 There are varying levels of trace. Depending on how additives will affect trace,
they may be added at light trace, medium trace, or heavy trace. After much
stirring, the mixture turns to the consistency of a thin pudding. “Trace”
corresponds roughly to viscosity.

 Essential oils and fragrance oils can be added with the initial soaping oils, but
solid additives such as botanicals, herbs, oatmeal, or other additives are most
commonly added at light trace, just as the mixture starts to thicken.

 The batch is then poured into moulds, kept warm with towels or blankets, and
left to continue saponification for 12 to 48 hours. (Milk soaps or other soaps with
sugars added are the exception.

 They typically do not require insulation, as the presence of sugar increases the
speed of the reaction and thus the production of heat.)

 During this time, it is normal for the soap to go through a “gel phase”, wherein
the opaque soap will turn somewhat transparent for several hours, before once
again turning opaque.

Hot processes

 Hot-processed soaps are created by encouraging the saponification reaction by

adding heat to speed up the reaction.
 In contrast with cold-pour soap which is poured into moulds and for the most
part only then saponifies, hot-process soaping for the most part saponifies the
oils completely and only then is poured into moulds.

 In the hot process, the hydroxide and the fat are heated and mixed together at
80–100 °C, a little below boiling point, until saponification is complete, which,
before modern scientific equipment, the soapmaker determined by taste (the
sharp, distinctive taste of the hydroxide disappears after it is saponified) or by
eye; the experienced eye can tell when gel stage and full saponification has
occurred.

 Beginners can find this information through research and classes. Tasting soap
for readiness is not recommended, as sodium and potassium hydroxides, when
not saponified, are highly caustic.

 An advantage of the fully boiled hot process in soapmaking is the exact amount
of hydroxide required need not be known with great accuracy.

 They originated when the purity of the alkali hydroxides were unreliable, as
these processes can use even naturally found alkalis, such as wood ashes and
potash deposits.
Purification and finishing

 In the fully boiled process on an industrial scale, the soap is further purified to
remove any excess sodium hydroxide, glycerol, and other impurities, colour
compounds, etc.

 These components are removed by boiling the crude soap curds in water and
then precipitating the soap with salt.

 At this stage, the soap still contains too much water, which has to be removed.
This was traditionally done on chill rolls, which produced the soap flakes
commonly used in the 1940s and 1950s. This process was superseded by spray
dryers and then by vacuum dryers.

 The dry soap (about 6–12% moisture) is then compacted into small pellets or
noodles. These pellets or noodles are then ready for soap finishing, the process of
converting raw soap pellets into a saleable product, usually bars.

 Soap pellets are combined with fragrances and other materials and blended to
homogeneity in an amalgamator (mixer).

 The mass is then discharged from the mixer into a refiner, which, by means of an
drill, forces the soap through a fine wire screen.

 From the refiner, the soap passes over a roller mill (French milling or hard
milling) in a manner similar to calendering paper or plastic or to making
chocolate liquor.

 The soap is then passed through one or more additional refiners to further
plasticize the soap mass.

 Immediately before extrusion, the mass is passed through a vacuum chamber to

remove any trapped air.
  It is then extruded into a long log or blank, cut to convenient lengths, passed
through a metal detector, and then stamped into shape in refrigerated tools. The
pressed bars are packaged in many ways.

 Sand or pumice may be added to produce a scouring soap. The scouring agents
serve to remove dead cells from the skin surface being cleaned.

 This process is calledexfoliation. Many newer materials that are effective, yet do
not have the sharp edges and poor particle size distribution of pumice, are used
for exfoliating soaps.

4.2 Detergent
 A detergent is a surfactant or a mixture of surfactants with "cleaning properties
in dilute solutions."

 These substances are usuallyalkylbenzenesulfonates, a family of compounds that

are similar to soap but are more soluble in hard water, because the polar
sulfonate (of detergents) is less likely than the polar carboxyl (of soap) to bind to
calcium and other ions found in hard water.

 In most household contexts, the term detergent by itself refers specifically to

laundry detergent or dish detergent, as opposed to hand soap or other types of
cleaning agents.

 Detergents are commonly available as powders or concentrated solutions.

Detergents, like soaps, work because they are amphiphilic: partly hydrophilic
(polar) and partly hydrophobic (non-polar).

 Their dual nature facilitates the mixture of hydrophobic compounds (like oil and
grease) with water. Because air is not hydrophilic, detergents are also foaming
agents to varying degrees.
4.2.1 Chemical classification of detergents
Detergents are classified into three broad groupings, depending on the electrical
charge of the surfactants.

Anionic detergents

 Typical anionic detergents are alkylbenzenesulfonates. The alkylbenzene portion

of these anions is lipophilic and the sulfonate is hydrophilic.

 Two different varieties have been popularized, those with branched alkyl groups
and those with linear alkyl groups.

 The former were largely phased out in economically advanced societies because
they are poorly biodegradable.[2] An estimated 6 billion kilograms of anionic
detergents are produced annually for domestic markets.

 Bile acids, such as deoxycholic acid (DOC), are anionic detergents produced by
the liver to aid in digestion and absorption of fats and oils.

Cationic detergents

 Cationic detergents are similar to the anionic ones, with a hydrophobic

component, but, instead of the anionic sulfonate group, the cationic surfactants
have quaternary ammonium as the polar end.

 The ammonium center is positively charged.

Non-ionic and zwitterionic detergents

 Non-ionic detergents are characterized by their uncharged, hydrophilic

headgroups.

 Typical non-ionic detergents are based on polyoxyethylene or a glycoside.

Common examples of the former include Tween, Triton, and the Brij series.
  These materials are also known as ethoxylates or PEGylates and their
metabolites, nonylphenol.

 Glycosides have a sugar as their uncharged hydrophilic headgroup. Examples

include octyl thioglucoside and maltosides.

 HEGA and MEGA series detergents are similar, possessing a sugar alcohol as
headgroup.

 Zwitterionic detergents possess a net zero charge arising from the presence of
equal numbers of +1 and −1 charged chemical groups. Examples include
CHAPS.

Major applications of detergents

Laundry detergents

 One of the largest applications of detergents is for washing clothes. The

formulations are complex, reflecting the diverse demands of the application and
the highly competitive consumer market.

 In general, laundry detergents contain water softeners, surfactants, bleach,

enzymes, brighteners, fragrances, and many other agents.

 The formulation is strongly affected by the temperature of the cleaning water

and varies from country to country.

Fuel additives

 Both carburetors and fuel injector components of Otto engines benefit from
detergents in the fuels to prevent fouling. Concentrations are about 300 ppm.

 Typical detergents are long-chain amines and amides such as

polyisobuteneamine and polyisobuteneamide/succinimide.[3]

Biological reagent
  Reagent grade detergents are employed for the isolation and purification of
integral membrane proteins found in biological cells.

 Advancements in the purity and sophistication of detergents have facilitated

structural and biophysical characterization of important membrane proteins such
as ion channels also the disrupt membrane by binding LPS.,transporters,
signaling receptors, and photosystem II.

4.2.2 Soapless soap

 Soapless soap refers to a soapfree liquid cleanser with a slightly acidic pH.
Soapless soaps are used in an array of products.

Borax-based washing detergent

Sulfonic acid

 A sulfonic acid (or sulphonic acid) refers to a member of the class of

organosulfur compounds with the general formula RS(=O)2–OH, where R is an
organic alkyl or aryl group and the S(=O)2–OH group a sulfonyl hydroxide.

 A sulfonic acid can be thought of as sulfuric acid with one hydroxyl group
replaced by an organic substituent.

 The parent compound (with the organic substituent replaced by hydrogen) is the
hypothetical compoundsulfurous acid. Salts or esters of sulfonic acids are called
sulfonates.

Preparation

 Ball-and-stick model of methane sulfonic acid.

 Sulfonic acid is produced by the process of sulfonation. Usually the sulfonating

agent is sulfur trioxide.
  A particularly large scale application of this method is the production of
alkylbenzenesulfonic acids:

RC6H5 + SO3 → RC6H4SO3H

 In this reaction, sulfur trioxide is an electrophile and the arene undergoes

electrophilic aromatic substitution.

 Thiols can be oxidized to sulfonic acids:

RSH + 3/2 O2 → RSO3H

 Certain sulfonic acids, such as perfluorooctanesulfonic acid are prepared by

electrophilic fluorination of preformed sulfonic acids. The net conversion can be
represented simplistically:

C8H17SO3H + 17 F2 → C8F17SO3H + 17 HF

Properties

 Sulfonic acids are much stronger acids than the corresponding carboxylic acids.
p-Toluenesulfonic acid, with a pKa of -2.8, is about a million times stronger acid
than benzoic acid, with a pKa of 4.2.

 Similarly, methanesulfonic acid, pKa = -1.9, is also about one million times
stronger acid than acetic acid. Because of their polarity, sulfonic acids tend to be
crystalline solids.

 They are also usually colourless and nonoxidizing, which is convenient. Because
of their high acidity, sulfonic acids are often soluble in water or exhibit
detergent-like properties.

 The structure of sulfonic acids is illustrated by the prototype, methanesulfonic

acid.
  The sulfonic acid group, RSO2OH features a tetrahedral sulfur centre, meaning
that sulfur is at the center of four atoms: three oxygens and one carbon.

 The overall geometry of the sulfur centre is reminiscent of the shape of sulfuric
acid.

Detergents and surfactants

 Nafion, a polymeric sulfonic acid useful in fuel cells.

 Sodium dodecylbenzenesulfonate, an alkylbenzenesulfonate surfactantused in

laundry detergents.

Applications

 Although both alkyl and aryl sulfonic acids are known, most of the applications
are associated with the aromatic derivatives.

 Detergents and surfactants are molecules that combine highly nonpolar and
highly polar groups.

 Traditionally, soaps are the popular surfactants, being derived from fatty acids.
Since the mid-20th century, the usage of sulfonic acids has surpassed soap in
advanced societies.

 For example, an estimated 2 billion kilograms of alkylbenzenesulfonates are

produced annually for diverse purposes.

 Lignin sulfonates, produced by sulfonation of lignin are components of drilling

fluids and additives in certain kinds of concrete.

 Sulfonic acids can be converted to esters. This class of organic compounds has
the general formula R-SO2-OR.

 Sulfonic esters such as methyl triflateare considered good alkylating agents in

organic synthesis.
  Such sulfonate esters are often prepared by alcoholysis of the sulfonyl chlorides:

RSO2Cl + R'OH → RSO2OR' + HCl

 Sulfonyl halide groups occur when a sulfonyl functional group is singly bonded
to a halogen atom.

 They have the general formula R-SO2-X where X is a halide, almost invariably
chloride. They are produced by chlorination of sulfonic acids using thionyl
chloride and related reagents.

Displacement

 Although the C-SO3H bond is strong, the (aryl)C-SO3 bond can be cleaved by
certain nucleophiles. Of historic and continuing significance is the α-sulfonation
of anthroquinone followed by displacement of the sulfonate group by other
nucleophiles, which cannot be installed directly.

 An early method for producing phenol involved the base hydrolysis of sodium
benzenesulfonate, which can be generated readily from benzene.

C6H5SO3Na + 2 NaOH → C6H5OH + Na2SO3 + H2O

Environmental concerns

 Sulfonic acid derivatives are generally not derived from natural precursors and
tend to biodegrade slowly.

 Some, such as perfluorooctanesulfonic acid, have been detected in the serum of

humans.
 This should be not surprising as all organic fluorine compounds have extreme
stability, and low to zero biodegradability.

 Many are intended to withstand harshest chemical conditions, for example

teflon. The nonfluorinated sulfonic acids tend to have low toxicities.