Colloidal and Surface Phenomena of

Liquid Laundry Detergent

CE 457-527

Dr. Alexandridis
April 9, 2002

http://wwwcourses.sens.buffalo.edu/ce457_527/ce45
7_pro/g11_doc.htm

Daniel Boek
Erika Indivino
Katherine Marso
Karey Smollar

History and Background of Laundry Detergents

The method of cleaning clothes has changed greatly since its beginnings in ancient history.
The first form of laundering was purely mechanical. Clothes were beaten against rocks to
remove water-soluble stains. To remove the more difficult oily stains, additional
compounds needed to be added. This led to the first production of soap in the 15th
centuryi[1].

By combining animal or vegetable fats with aqueous sodium hydroxide soap is made.
Soaps are advantageous because they are made from biodegradable renewable resources.
Therefore, soaps are not polluting the environment. These factors are outweighed by the
negative affects of hard water and the cost of the raw materials. Soaps react with calcium
and magnesium ions in hard water leading to the formation of precipitates. Increased
household use of alkylbenzene sulfonates (ABS), a former compound used in laundering with
soaps, resulted in large bodies of water covered in foam. The synthesis of ABS is shown
below in Figure 1.

Figure1: Synthesis of ABSii[2]

These factors, as well as the commercialization of the Ziegler process leading to the
production of linear alkylbenzene solfonates, lead to the production of synthetic
detergentsiii[3].

The manufacture of synthetic detergents, commonly called laundry detergent, began in 1916
in Germany during WWI. The production of detergents in the United States took off after
WWII. The first detergents were used mainly for dishwashing and fine fabric laundering.
In 1946 the first all-purpose laundry detergent was produced using builders with
surfactantsiv[4]. Surfactants and builders became increasingly more complex as the
demand for better soil removal grew. The use of sodium triphosphate (STP), a very
effective builder, was restricted in the 1960s because it caused eutrophication in rivers.
Trisodium citrate, NaCit, is an effective, biologically degradable builder commonly used in
detergents todayv[5].

Figure 2: Chemical Structures of STP and NaCitvi[6]

New additives are continually being introduced to the detergent industry to keep up with
customer demand.

Liquid laundry detergent became popular in the U.S. in the 1970s. The USA holds the
largest market of liquid heavy-duty detergents (HDL) in the world. Liquid laundry
detergents usually do not contain bleaching agents and are best at removing oily stains at low
temperaturesvii[7]. Liquid laundry detergent is a huge industry in the United Stated.
Research has continued to develop detergents that would provide people with efficient
cleaning agents that are safe for the environment. The sale of liquid detergent has soared
over powdered detergent in the last decade. The two types have reached a 50/50 market
split in the U.S., whereas liquid detergent only holds 13% of the market in Europe.
Consumers find liquid detergents more convenient to use while giving better results in the
U.S. Liquid detergents are easier to measure and easier to apply directly to stains. The

liquid laundry detergent industry will continue to grow in the coming years and overtake that
of powdered laundry detergentsviii[8].

An interesting development in the industry is the introduction of tablets first marketed in

2000. Tablets are marketed towards students and the elderly for their convenience factor.
Tablets dissolve within seconds of hitting the water. Although they are new and fairly
expensive, with continual improvements in efficiency and production, tablets will also
become a strong competitor in the marketix[9].

There has been very little response to tablets in the U.S. In Europe, on the other hand,
tablets hold 25% of the market in some countries. This response lead to the introduction of
the sachet, or pouch, in April 2001. This new product delivers liquid laundry detergent
through a water-soluble polyvinyl alcohol skin. The pouch dissolves in minutes, leaving
behind no residue. These types of unit-dose products, such as tablets and pouches, are on
the very frontier of the detergent industry. It is a race to see which company can produce
the fastest dissolving, most easily dispensed detergent on the marketx[10].

Design considerations

Laundry detergent is a basic necessity for every household. Liquid laundry detergents must
have specific properties that will meet the needs of the general public.
Excellent soil removal is the main feature that consumers look for when choosing a
detergent. This is the central reason that people need any cleaning agent, to remove the
dirt.

Low sensitivity to water hardness is another crucial property of detergents. Many homes
only have hard water available. Hard water that contains high concentrations of calcium
and magnesium greatly decreases the effectiveness of soaps. The minerals react with the
soap to form a precipitates that are left on clothes. Detergents were introduced to
laundering applications to remove soils without leaving precipitates. Since most people
cannot afford to have a water softening system their home, it is important that detergents
avoid the formation of precipitates. Liquid laundry detergents contain builders that prevent
calcium and magnesium deposits when using hard water. Detergents must also have good
dispersion properties to ensure that the entire load of clothing is sufficiently cleaned.
Liquid detergents dissolve and spread much faster than powder detergents do in water. Soil
antiredeposition capability is also very important. Surfactants in the detergent must be
decided upon according to how well they keep soil from redepositing onto the clothing.
The soil from the clothing must be kept in suspension in the water until it can be rinsed
away. It is important that detergent has a high solubility in water. The purpose of using a
detergent is to overcome the surface tension of water so that soils can be removed. The
surfactants need to overcome the surface tension of water to ensure sufficient wetting
power. Liquid laundry detergents dissolve in water more quickly than powdered laundry
detergents, especially in cold water.

The amount of foam during washing has a psychological affect on whether detergent is or
isnt working. Too little foam indicates poor cleaning performance. Poor rinsing and
draining is also a result of too much foam. Liquid laundry detergents contain surfactants

that act as foaming agents to control this element of the detergent. Odor is another aspect to
be considered when thinking about consumer needs. Fragrances need to be added to cover
any chemical smell of the detergent. Perfumes are also added to differentiate one brand
from another. Detergents with low levels of fragrances are also produced for people who
are sensitive to perfumes. The color of the product should also be considered, but not too
excessively. On the other hand, the amount of toxicity to humans should be a major
concern. One cannot assume that every user of a household product pays strict attention to
warning labels or recommended safety precautions. Therefore, exposure through skin,
ingestion, and inhalation must be investigated whenever chemical products are put on the
market. Every compound included in liquid laundry detergents is extensively investigated
for its affects on humans.

Favorable environmental behavior is another important aspect that must be integrated into
liquid laundry detergent. Excess water containing additional energy (heat), soil from the
laundry, lint, dyes, finishing agents, and detergents is drained into the environmentxi[11].
The affects of these by-products on the environment need to be as minimal as possible. The
use of phosphates, one of the original compounds used in detergent, has been severely limited
due to their harmful affects on the environment. Companies continue research in the area
of environmental affects to ensure that detergents are not damaging the environment.

Convenience is a very important design consideration for detergent companies. Costumers

find liquid detergents easier to pour with a cap as opposed to scooping dry detergent out of a
boxxii[12]. All the above mentions aspects of detergent must be integrated into product
that can be sold in a very competitive market. There is a fine balance between creating an
efficient cleaning agent, keeping the costumers happy, and keeping the environment safe.

Components
The components of liquid laundry detergent are listed in Table 1xiii[13] below:

Table 1: Composition of liquid laundry detergent

Ingredients

Volume Percent

Anionic Surfactants
Nonionic Surfactants
Soaps
Builders
Solubilizers
Alcohols
Enzymes
Optical Brighteners
Stabilizers
Fragrances
Water

10 - 25
6 - 10
4-6
15 - 30
0-5
0-5
0 - 1.5
0.05 - 0.25
Trace amount
Trace amount
30-50

Surfactants

Surfactants are the most important components of liquid laundry detergents. Surfactants
are water-soluble surface-active agents that adsorb onto the surface of soil particles to
separate the soil from clothing. Surfactants remove oil by lowering the surface tension of
water, allowing the clothing surface to become wet.[1] Surfactants consist of a hydrophilic
and a hydrophobic portion. The hydrophobic component consists of an eight to eighteen
carbon hydrocarbon. Sources of these hydrocarbons are natural fats and oils, petroleum
fractions, synthetic polymers, and synthetic alcohols.

Surfactants are divided into three groups; anionic, nonionic and cationic. Anioinic surfactants
are the most abundant ingredient in liquid laundry detergent because they have proven to
show the most enhancing effects of removal of soil. Nonionic surfactants are used
primarily for their stabilization effects during detergency.

Surfactants are chosen based on their sensitivity to water hardness. Certain surfactants such
as Linear Alkylsulfonate (LAS) show good detergency despite water hardness. The
surfactants exhibiting more sensitivity to water hardness are less effective regarding their
absorbance to fabrics and an increased production of surface film. Not one single
surfactant is capable of effectively removing all soil types on different types of fabrics.
Therefore, surfactant mixtures are proven to be most effective when considering a wide range
of solvent conditions and soil types.

The effectiveness of surfactants is proportional to the length of the chain. A high number
of carbon atoms in the surfactant molecule correspond to an increase in the number of
surfactants adsorbed. The type of hydrophilic group determines the classification of the
surfactant as anionic, nonionic, or cationic. The characteristics of surfactants cause the
hydrophobic component to be drawn together to form micelles. This allows the surfactants
to form a coating around a suspended material. A surfactant used to suspend a solid in
water is called a dispersant.[2]
Liquid laundry detergents contain larger amounts of anionic surfactants than ionic
surfactants. Anionic surfactants ionize in solution and have a negative charge. They are
good cleaning agents and create high sudsing. Some examples of anionic surfactants
are linear alkylbenzene sulfate, alcohol ethoxysulfates, alkyl sulfates and soaps. Nonionic
surfactants do not ionize in solution and therefore have no electrical charge. Cationic
surfactants ionize in solution to give a positive charge.

Anionic Surfactants

Anionic surfactants are the main component of liquid laundry detergents and found to be the
most active ingredient for the soil removal processxiv[14]. Some examples of the most
common type of anionic surfactants include sodium linear alkylsulfonate (LAS),
alkanesulfonates (SAS), and olenfinsulfonates (AOS).

The production of LAS originated from the former surfactant called Tertrsproplynenbenzene
sulfonate (TPS), which was used in the earlier stages of detergency to replace the use of
regular soaps. The structures of both molecules are similar, but the LAS molecule
eliminated the branching found on the TPS molecule. The straight chain structure of LAS
demonstrates more effective detergency due to its increasing solubility, greater level of
biodegradation, and less sensitivity to changing pH levels. LAS is shown below in Figure
3.

n + m = 710
Figure 3: Sodium linear alkylsulfonate (LAS)

TPS is shown below in Figure 4.

Figure 4: Tetrapropylenebenzenesulfonate (TPS)

Another type of anionic surfactant, Sodium Alkanesulfonate, has high solubility, fast wetting
properties, and chemical stability of alkali and acidsxv[15].
The production of SAS is formed by sulfooxidation and sulfochloronation process.

Figure 5: Secondary Alkanesulfonates (SAS)

The third type of anionic surfactant, Olenfinsulfate (OAS) is produced using the alkaline
hydrolysis process. This surfactant is unique because it exhibits less sensitivity to water
hardness. This effect can be dependent on the chain length of the hydrophobic portion of
the surfactant.

R1CH2CH=CH(CH2)nSO3Na Alkenesulfonates

Hydroxyalkanesulfonates

R1 = C8 C12

n = 1, 2, 3

R2 = C7 C13

m = 1, 2, 3

Figure 6: Olefinsulfonates (AOS)

The characteristics of these surfactants offer several advantages over one another. Due to the
fact that detergents must maintain satisfactory ability for removing various types soils, the
most effective type of surfactant used has proven to be a surfactant mixture. The
advantages of using surfactant mixtures include reduction of amount of detergent needed
during the detergency process and the reduced size of packaging.

Nonionic Surfactants

Nonionic surfactants are also an essential ingredient for liquid laundry detergents, but are
often found in a much smaller quantity as compared to anionic surfactants.
Both types of surfactants play different roles in detergency but work well in conjunction with
one another. The anionic surfactant plays an active role in the removal of the soil from the
surface of the fabric. The nonionic surfactants are used for the stability of solution. The
nonionic surfactants, depending on their structure, are commonly attracted to the outer most
part of the micelle and are used to help stabilize the micelle formations and reduce
redeposition of the treated soil back onto the fabric.

Builders

Builders play an important role in the effectiveness of liquid laundry detergents by enhancing
the affects of surfactants. Builders help remove water hardness and keep soils from
redepositing onto the clothing. The most common types of builders are phosphates,
silicates, carbonates and oxygen releasing materials. Phosphates are no longer used due to
their negative affect on the environment.

Builders are also used to remove Ca2+ and Mg2+ ions which produce hardness of the wash
liquor. Calcium and magnesium form complexes with builders, diminishing the surfactant
interaction with calcium and magnesium. Trisodium citrate is the most common builder
used in todays laundry detergent. Trisodium citrate is shown in Figure 7.

Figure 7: Trisodium Citrate (NaCit)

In the absence of builders, hardness ions form complexes with soil. The complex can
redeposit onto the negatively charged fabric and soil interfaces. Zeolites are waterinsoluble builders of 10mm diameter and molecular formula Na2OAl2O3*4.5H2O. Calcium
and magnesium ions replace sodium ions from the zeolite crystals. Therefore, hardness
ions cannot form complexes in the wash liquor.

Redeposition Inhibitors

Micelles are negatively charged structures that can redeposit on neutral surfaces. For
example, synthetic fibers dont acquire a strong negative charge in water. Therefore, the
surface needs an electrostatic charge to keep negatively charged detergent micelles from
redepositing their soils on the fabric. These additives are known as redeposition
inhibitors. Sodium carboxymethyl cellulose (SCMC) is a polymer of molecular weight
from 20,000 to 500,000 that attaches itself to the fibers and adds to the negative charge.
SCMC can be seen in Figure 8 below.

Figure 8: SCMC Diagram

The types of detergent builders have changed over the years with increasing environmental
awareness. With tighter environmental restrictions, the uses of phosphates biulders in
detergents have been diminishing.

Enzymes

Protein stains from sources such as milk, cocoa, blood, egg yolk, and grass are resistant to
removal from fibers by enzyme-free detergents, particularly after stains are dried-on.
Chocolate, starch-based food stains, and greasy/fatty stains are particularly difficult to
remove in low-temperature washing. Proteolytic, amylolytic, and lipolytic enzymes are
usually capable of eliminating such soil during washing.
Commercial production of detergent enzymes experienced rapid expansion in recent years.
For example, by 1969 nearly 80 % of the detergents marketed in the Federal Republic of
Germany contained proteases as enzyme additives to detergents. Today's detergent
enzymes are perfectly safe. As a result, nearly all detergents produced in Europe, North
America, Japan and many other countries worldwide contain enzymes today. The
effectiveness of proteolytic, amylolytic, and lipolytic detergent enzymes is based on
enzymatic hydrolysis of peptide, glucosidic, or ester linkages, respectively.

Whitening agents

Fluorescent whitening agents (FWA), or optical brighteners, are added to liquid laundry
detergents to give laundry a much whiter appearance. FWAs are organic compounds that
convert invisible ultraviolet light into longer wavelength visible blue light. Optical
brighteners decrease the absorption of the blue radiation that gives clothes a yellowish tint.
Due to the fact that FWAs also exhibit reflectance in the visible region, a build up on the
fabric may also leave marks. FWAs are applied through a dyeing process.
Distyrylbiphenyl, stilbene, coumarin, and bis(benzoxazole) are the most common
brighteners. FWAs are evaluated on their stability (resistance to chemical change} and
fastness (chemical change after adsorption).

Soil Removal

Removal of Oily/Greasy Soil by Detergents

The removal of soil from clothing is primarily due to the wetting properties and interfacial
tensions between the washing liquid and the deposited soil. During the washing process,
the most significant interactions occur between the liquid (water) and the surfactant. Over
the time clothes are worn, oily/greasy soils are deposited and spread evenly on the
clothing. The ability of water to be in contact with oil is referred to as the measure of
wetting. The measure of wetting is useful when describing the contact angles, which are
responsible for the removal of the soil from the fabric.

The physical properties of water and the ingredients of the detergent are essential. The soil
that is present on clothing is apolar and the washing liquid is polar. In order for the
removal of the soil from the clothing to occur, there must be some sort of medium, which
causes a strong attraction between the two surfaces. Anionic surfactants allow for the
formation of the droplets, but nonionic surfactants create the attraction between the micelles.

Surfactants concentrate at water-liquid, water-gas, or water-solid interfaces because the

hydrophobic and hydrophilic properties of the surfactant are satisfied. One nonionic
surfactant molecule has an apolar hydrocarbon polymer tail and a polar head group. The
following diagram depicts a single surfactant. Another type of surfactant, ionic surfactants,
have static charges associated with their head groups.

Figure 9:Nonionic SurfactantMolecule

Oil
Figure10 below displays the alignment of surfactant molecules at an interface between oil
and water.

Water

Figure 10:Oil-Water Interface

interface

Before surfactants are added to

the oil-water system, the oil-water interactions are very weak. As the surfactant molecules
replace water at the oil-water interface, the attraction between water and the head group
increases. Likewise, the attraction between the polymer chain and oil also increase. The
new attractions decrease the soil-water interfacial surface tension.

The water, soil, and fabric interfaces are shown below in Figure 11.

Figure 11:Contact Angle inWater-Soil-Fabric System

The Young equation describes the overall shape of a droplet of oil at the three-component
interface. The Young equation is


(1)
where is the surface tension at the corresponding interfaces and is the contact angle in
Figure 11 above. After surfactants are added to the system the fabric-water and soil-water
interfacial tensions approach zero (FW and SW = 0). The interfacial tension between soil and
fabric remains constant, therefore, FS FW. The Young equation now gives
cos 0. Solving for the contact angle, 900. This contact angle means that the area
of contact between soil and fabric reduces to zero. Figure 12xvi[16] shows this mechanism
of detergency, called roll-up.

Figure 12:Complete Removal ofOil Droplets by Roll-up

Without surfactants, part of the soil droplet can be removed from the fabric by mechanical
agitation. The Young equation now yields a positive value for cos , resulting in a positive
contact angle less than 900. As the area of contact is reduced, the oil droplet pinches off
and leaves some oil residue. This process is illustrated in Figure 13xvii[17].

Figure 13:Partial Removal ofOil Droplets by Agitation Without Surfactant

At high concentrations, detergents form micelles in aqueous solution. Micelles dissolve the
fatty stains. The inner section of the micelle contains hydrophobic polymer chains and
oil. Micellar size and shape can vary, depending on surfactant type, temperature, and the
presence of salts. The packing properties of surfactants are dependent upon cross-sectional
surface area of the headgroups (a0 ), the volume (v ) of the hydrocarbon chains, and the
maximum length, (lc ), of the chains. The packing parameter is dimensionless where
p=v/aolc. The packing parameter determines the geometry of the surfactants. The
possible shapes are shown in Figure 14xviii[18].
Figure 14: Geometry of Surfactants

As seen above in Figure 14, for p < 1/3, the surfactant forms a cone shape. Therefore, the
corresponding micelle is spherical. The truncated cone surfactant shape is valid for
1/3 < p < , forming a rod-like micelle. If < p <1, the surfactant is cylindrical in shape
and a bilayer is formed.

Spherical micelles in the presence of an aqueous salt solution form a multilamellar

structure. The multilamellar structure is formed because the salt ions are attracted to the
surfactant headgroups. The repulsive forces between headgroups are minimized. Figure
15 below shows the difference of headgroup area with and without salt ions present

Figure 15: a) Oil with Water, b) Oil with Water and Salt Ions

The packing parameter now takes on the bilayer shape. A continuous lamellar phase of
bilayer aggregates is formed (shown in Figure 16xix[19] below).

Figure 16:Continuous LamellarLiquid Crystalline

Phase

Several bilayers pack around each other to form multalamellar vesicles, or lamellar
droplets. Lamellar droplets form from the continuous lamellar liquid crystalline phase even
though they are metastable. Mechanical agitation dissolves sodium citrate and induces the
formation of lamellar droplets. Although the continuous lamellar liquid crystalline phase is
more thermodynamically stable, spontaneous curvatures of the bilayers are favored in the
presence of a surfactant mixture. Bilayers form multilamellar vesicles to minimize
interactions between hydrocarbon chains and solvent that would be present at the edges of the
crystalline structure.

The presence of bilayers within a salt solution gives rise to the formation of multilameller
(multi-bilayer) structures due to strong osmotic forces. Multibilayers are
thermodynamically favored within a salt solution (i.e. sodium citrate) when the area of the
hydrophilic head groups are reduced. Although the multilamellar bilayers are more
thermodynamically stable, spontaneous curvature of these bilayers is favored in the presence

of a surfactant mixture. This spontaneous curvature gives rise to the formation of the multilamellar droplets. The Gibbs energy of a two-component bilayer is minimized by the
formation of the lamellar droplet. Figure 17xx[20] shows a lamellar droplet.

Figure 17: Lamellar Droplets

Many multilamellar vesicles phase separate. In stable conditions interlamellar repulsive

forces are present. Flocculation occurs if interlamellar attractive forces are strong. Van
der Waals forces are present, causing lamellar droplet flocculation. Counterion
concentration increases in the intralamellar region. Osmotic flow of solvent into the
intralamellar region takes place to keep the bilayers separated. Poor solvents increase
flocculation unless decoupling polymer is present, thus causing steric repulsion.

Flocculation of lamellar droplets causes phase separation. In the presence of electrolytes

(salts) water is a poor solvent. The hydrophilic portion of the nonionic surfactant decreases
in length because of this poor solvency. Therefore, intralamellar droplet volume
decreases. Decoupling polymer, comprised of a hydrophilic backbone and hydrophobic
side chains, is added to the solution and attaches to the lamellar droplet surface. The side
chains attract to the oily portions of the exterior bilayers (of the droplet) and the backbones
dissolve in the water solvent. Figure 18xxi[21] displays three scenarios: good solvent, bad
solvent, and bad solvent with decoupling polymer. Steric repulsions between the
decoupling polymers causes the droplets to repel, and no flocculation occurs.

Figure 14:a) Good Solvent, b)Poor Solvent, c) Poor Solvent with Decoupling
Polymer

Figure 18: a) good solvent, b) poor solvent, c) poor solvent with decoupling polymer

Particulate Soil

The removal of particulate soil is based on the DLVO Theory. The potential energy must
be overcome in order to removal the soil from the clothing fiber. Potential Energy graphs
demonstrate the potential energy as a function of distance from the garment.

Calculated potential energy of attractionPAand repulsionPRas a function of the distance

of aparticle from a fabric, along with the resultant potentialP;predictions based on the
DLVO theory
DLVO computational parameterz = 4

Figure 19: Potential Energy versus Distance

The smaller the potential energy, the easier it is to remove the solid particle. Although a
soil already in the washing liquor is less likely to be redeposited on the clothing if the
potential barrier is large.

Bi-layers are first created due to attractive Van der Waals forces when no electrical double
layer exists. The formation of bi-layer structures causes the free energy of the system to be
reduced. As a result of the greater stability of the bi-layer, it takes a considerable amount of
energy (mechanical energy) to introduce contact between the lamellar droplet and the
substrate. This is important when considering anti-redeposition of the soil.

The presence of calcium ions in solution also is relevant to the potential energy theory. The
Schulze-Hardy rule discusses the how water hardness causes the compression of the double
layer. At high concentrations the calcium ions may induce more attractive forces causing
flocculation, which would lead to less efficient detergency.

In addition to surface potential, the electrical charge of the surfactant and the fibers of the
clothing are also important. Generally, the soil/pigment and fiber both have has a negative
charge, which can be altered depending on the pH of the solution. The following diagram
(Figure 20) shows that changes in pH and its effect on potential energy of different fabric
types.

Figure 20: Potential of various fibers as a function of pH [66]

a) Wool; b) Nylon; c) Silk; d) Cotton; e) Viscose

Although pH can enhance the performance of the detergency it is not good enough to create
repulsive forces for steric stabilization. As more and more anionic surfactants are absorbed,
the negative charge on the surface increases. Therefore the dispersing power of the
pigments is also increased, which results in reduction of redeposition of removed soil.

The most effective soil removal therefore occurs at high surfactant concentrations where
there is the greatest negative charge. When the laundry goes through the rinse cycle, charge
reversal takes place creating a neutral environment. This environment of electrical
neutrality is avoided because it would enhance redeposition of the soil or pigment. For this
reason, anionic surfactants are used instead of cationic surfactant for the effective detergency.

Complexing agents show similar effects to anionic surfactants. Complexing agents

undergo specific attraction to surfaces, which demonstrate a distinct delocalized charge. The
benefit of using complexing agents is that they can be specifically absorbed unlike anionic
surfactants, which are absorbed at all hydrophobic surfaces. By adding complexing agents

to the washing solution, the absorption of the anionic surfactant on the metal oxides is
diminished. Although the opposite is true at surface of the fiber, the absorption is
enhanced by the electrolyte nature of the complexing agent. Due to the fact that multiple
soil types exist on the surface of the soiled clothing, the specificity of the complexing agent
and the surfactant provide complementary functions to the fabrics.

The role of the nonionic surfactant for the removal of particulate soils is similar for other soil
types. The nonionic surfactant does not affect the surface charge but enhances surface
absorption. The nonionic surfactant shows significant absorption at the hydrophobic
surface. The hydration of the nonionic surfactants is important when considering
redeposition. As the amount of hydrated spheres that surround the substrate increases,
interference is created which reduces Van der Waals forces, thereby reducing
redepositionxxii[22].

Calcium-Containing Particulate Soil

Calcium containing particulate soils is common on textile fabric surfaces. The problem with
these soils is that they are not very soluble. As the hardness of the water increases, the
solubility is minimized. Although this is true, the calcium ions can show some solubility
when using distilled water as the washing solvent. This small amount of solubility can
cause the break up of the calcium-containing solid on the fabric until the extent of the
calcium is absorbed in the washing solution

Types of Fabrics

The type of fabric being washed determines the type of soil removal. One example can be
demonstrated between textile fabrics, which contain calcium ions, and synthetic fibers, which
have low calcium content. The major difference between these fabrics is their
wettability due to their degree of hydrophobic and hydrophilic nature.xxiii[23] As a
result, the complexing agents also react differently with each type of soil.
Sodiumtriphosphate, a common complexing agent, shows enhancing effects to the removal of
soil from both synthetic and cotton garments. The efficiency is more dependent on the
hydrophilic/hydrophobic nature of the fabric. One example is that the effect of sodium
triphosphate enhancing the removal of soils from hydrophilic fibers such as poylamide or
polyacrylonitrile, but shows minimal effects when considering hydrophobic textile fibers.
Although soil removal is specific to the fabric type, these effects can complement each other
when considering the detergency of fabric blends in the presence of soil mixture.

Processing

The manufacturing process for liquid laundry detergent is very complex. First, the
surfactants, builders, and other additives are mixed and dried so that they form a compact
powder. The resulting dried powder is then added in particulate form to either a batch or
continuous reactor, where it comes into contact with the agitated liquid medium. This
liquid must be able to suspend not only the detergent particulate, but other additives that may
be desired such as bleaching agents, bleaching activators, and detergent buildersxxiv[24].
A schematic of the process follows.

Figure 21: Manufacture of liquid detergentxxv[25]

Packaging

The three main purposes of packaging are to protect the product so that its quality does not
change between manufacture and purchase, to supply information about the detergent to the
consumer, and to make handling easier. There are many factors companies must consider
when packaging liquid laundry detergent. The selection of packaging materials involves
taking into account product compatibility, cost, safety, waste, and appeal. Advances in
plastics have made the goal of environmentally conscious packaging more easily
obtainable. Convenience is also a very important issue. The size and shape of the bottle
must be well thought-out so that consumers like the design and want to use the product
again. Cheskin Research conducted a telephone survey of 200 people, where each person
was asked to rate the importance of certain package features. The following figure shows
what consumers notice.

Most Useful Package Attributes

Percent Stating

(Sample Size = 200)

Figure 22: Important package featuresxxvi[26]

Typical bottles for liquid detergent are recyclable plastic. Companies such as Procter &
Gamble have been gradually adding recycled material to their plastic in order to cut down on
waste. These bottles generally contain 25% recycled plastic. Smaller bottles containing a
concentrated detergent solution are very popular. This results in less solid waste because
the same amount of laundry can be done with a smaller container. Concentrated detergents
use less chemicals per load of wash as well. Another way detergent manufacturers
reduce waste is by selling refillable containers. This concept was introduced in the early
1990s. A consumer purchases a larger container initially, and then buys refills that range
65-90% smaller than the original container.

Environmental Considerations

In order to create the most marketable product, the detergent industry must keep up with
changing societies. The trend toward more environmentally friendly washing machines has
forced detergent manufacturers to adjust and compensate for these changes. New washing
machines pose problems because they use less water, energy, and the temperature of the
water is lower. If the industry does not meet its past standards for new technologies and
concerns, consumers will be dissatisfied.

Water consumption is a major concern worldwide. This needs to be addressed by detergent

producers because laundry contributes to water usage. Niall Fitzgerald, chairman of
Unilever, voiced his concern: By 2025, two-thirds of our village (the earth) will be living
with water stress, meaning that they wont even have enough for safe drinking water
and sanitation-never mind enough for a wash load.xxvii[27] His priorities for the future
of detergents include minimizing the amount of water necessary for washing, the ability to
wash with poor water quality such as cold water, gray water, and salt water.

Market Sales

There are several types of laundry detergents on the market currently. There are powders,
tablets, liquids, and different types of fragrances, pre-treatments, and boosters. The leading
style of detergent is liquid, with sales surpassing that of powders for the first time in 1998.
According to Information Resources, Inc., Chicago, for the 52 weeks ending on October 7,
2001, $3 billion of liquid detergent was sold, as opposed to $1.8 in powders. The
popularity of liquid detergent is attributed to its convenience. Dispensing and measuring
the liquid is thought to be much easier than using a cumbersome box of powder.

Additionally, liquids dissolve easier in water than powder detergents. Speculators claim
powder detergents have a market only because it is cheaper per load of laundry to use
powder. The top three manufacturers of liquid laundry detergent have been the same for
the past two years. In descending order, they are Procter & Gamble, Lever Brothers, and
Dialxxviii[28].

The leading brand of liquid detergent is Tide, and it has held this top position for several
years. The sales for the year until October 7, 2001 were $1 billion according to Information
Resources, Inc. This figure means that Tide controls over 33% of the entire liquid
laundry detergent market in the United Statesxxix[29]. Other top brands include All,
Purex, Wisk, Xtra, and Cheer. There are virtually no middle-tier brands of
detergent because consumers either tend to buy for quality (more expensive liquid varieties),
or price (inexpensive powders). The following chart shows the market breakdown by
brandxxx[30].

F
igure 23: Detergent Marketxxxi[31]

Endnotes

i[1] http://www.ub.rug.nl/eldoc/dis/science/j.kevelam/c1.pdf
ii[2] ibid
iii[3] ibid
iv[4] http://www.sdahq.org

v[5] http://www.ub.rug.nl/eldoc/dis/science/j.kevelam/c1.pdf
vi[6] ibid
vii[7] http://www.mrw.interscience.wiley.com/ueic/ull_search_fs.html

viii[8] http://www.ub.rug.nl/eldoc/dis/science/j.kevelam/c1.pdf
ix[9] http://www.happi.com/current/Jan024.htm
x[10] McCoy, Michael. Soaps and Detergents. Chemical &Engineering News 21

January 2002: 21-28

xi[11] http://www.mrw.interscience.wiley.com/ueic/ull_search_fs.html
xii[12] http://www.ub.rug.nl/eldoc/dis/science/j.kevelam/c1.pdf
xiii[13] ibid
xiv[14] http://www.mrw.interscience.wiley.com/ueic/ull_search_fs.html

xv[15] http://www.mrw.interscience.wiley.com/ueic/ull_search_fs.html
xvi[16] http://www.ub.rug.nl/eldoc/dis/science/j.kevelam/c1.pdf
xvii[17] ibid

xviii[18] ibid
xix[19] ibid
xx[20] ibid
xxi[21] ibid
xxii[22] ibid
xxiii[23] http://www.mrw.interscience.wiley.com/ueic/ull_search_fs.html
xxiv[24] United States Patent number 6,277,804.

http://patft.
uspto.gov

xxv[25] http://www.ballestra.com/ps_deter.htm#liquid
xxvi[26] http://www.cheskin.com/who/press/release_19980929.doc
xxvii[27] http://www.happi.com/current/Jan024.htm
xxviii[28] ibid
xxix[29] ibid
xxx[30] McCoy, Michael. Soaps and Detergents. Chemical &Engineering News 21
January 2002: 21-28