Project report 2013

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SHEELA FOAM PRIVATE LIMITED




Project Report on:
Formulation and Characterization of EBT &
EDTA +METAL ION complexed Polyurethane
(PU) Foams
Submitted by:
ABHIJEET KUMAR
Roll No. 2K11/PS/001
B.Tech Polymer science and chemical technology
Delhi Technological University

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Acknowledgments
I sincerely thank Mr. Tushaar Gautam (COO) of Sheela Foam Pvt. Ltd. for allowing
me to carry out summer dissertation work at Sheela Foam XL Unit, Greater
Noida.
I also extend my gratitude to Dr. D K Chattopadhyay (AGM R&D) - my project
manager for his advice, moral support and continuous encouragement to take
challenge and complete my project work.
I would like to thank Capt. Dilip Mukherjee (Head HR and Admn. of North Zone)
for arranging my project and necessary administrative support.
I also take this opportunity to thank Mr. D. Balyan (AGM, Operation and
Technical) and Mr. P. Balyan (Executive Manager R&D) for their help and support
during the tenure of the project.
Last but not least, I am grateful to my parents, without whose support and
blessings it would have been impossible to carry out such research activity and
give the final conclusion of this chapter.






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Declaration
I hereby declare that the work reported in this report is original and carried out
by me under the supervision of Dr. Dipak Chattopadhyay at Sheela Foam R&D
centre, Greater Noida. The experimental findings of this report are not copied
from any other source, nor has the thesis been submitted to other place for the
award of any degree or diploma.



(Abhijeet kumar)

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Contents
1. Introduction
2. History
3. Chemistry
3.1. Polymerisation Reaction
3.2. Gas Producing Reaction
4. Basic Foam Components
4.1. Polyol
4.1.1. Polyol Preparation
4.2. Isocyanate
4.3. Fillers
4.4. Water
4.5. Surfactant
4.6. Catalysts
4.6.1. Amine Catalyst
4.6.2. Organometallic Catalyst
4.7. Chain Extenders and Cross Linkers
4.8. Additives
4.8.1. Colorants
4.8.2. UV Stabilizers
4.8.3. Flame Retardants
4.8.4. Plasticizers
4.8.5. Antistatic Agents
4.8.6. Compatibilizers
4.8.7. Bacteriostats
4.8.8. Cell Openers
4.9. Auxiliary Blowing Agents
5. Coordination chemistry principles of EBT, EDTA
6. Applications
6.1. Industrial Applications
6.2. Consumer Applications
7. Foam Calculations
8. Experimental Procedure
8.1Testing
8.1.1 Density Test
8.1.2 Indentation Force Deflection Test
8.1.3 Tension Test
8.1.4 Resilience Test
9. Formulations and Test Report/tables
10. Conclusions
11. References



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1. Introduction
Polyurethane is any polymer consisting of a chain of organic units joined by urethane
(carbamate) links. Polyurethane polymers are formed through step-growth polymerization by
the reaction of a monomer containing at least two isocyanate functional groups with another
monomer containing at least two hydroxyl (alcohol) groups in the presence of a catalyst.
Polyurethane products are often called "urethanes". They should not be confused with
the specific substance urethane, also known as ethyl carbamate. Polyurethanes are neither
produced from ethyl carbamate, nor do they contain it.

2. History of PU
The pioneering work on polyurethane polymers was conducted by Otto Bayer and his
co-workers in 1937 at the laboratories of I.G. Farben in Leverkusen, Germany.[1] They
recognized that using the polyaddition principle to produce polyurethanes from liquid
diisocyanates and liquid polyether or polyester diols seemed to point to special opportunities,
especially when compared to already existing plastics that were made by polymerizing olefins,
or by polycondensation.
Commercial production of flexible polyurethane foam began in 1954, based on toluene
diisocyanate (TDI) and polyester polyols. The invention of these foams was thanks to water
accidentally introduced in the reaction mix. These materials were also used to produce rigid
foams, gum rubber, and elastomers.
The first commercially available polyether polyol, poly (tetramethylene ether) glycol,
was introduced by DuPont in 1956 by polymerizing tetrahydrofuran. Less expensive
polyalkylene glycols were introduced by BASF and Dow Chemical in 1957. These polyether
polyols offered technical and commercial advantages such as low cost, ease of handling, and
better hydrolytic stability over polyester polyols and quickly replaced them in the manufacture
of polyurethane goods. In 1960 more than 45,000 tons of flexible polyurethane foams were
produced. The availability of chlorofluoroalkane blowing agents, inexpensive polyether polyols,
and methylene diphenyl diisocyanate (MDI) heralded the development and use of polyurethane
rigid foams as high performance insulation materials. Rigid foams based on polymeric MDI
(PMDI) offered better thermal stability and combustion characteristics than those based on TDI.
In 1967, urethane modified polyisocyanurate rigid foams were introduced, offering even better
thermal stability and flammability resistance compared to low-density insulation products.
The potential for polyols derived from vegetable oils to replace petrochemical-based
polyols began garnering attention beginning around 2004, partly due to the rising costs of
petrochemical feedstocks and partially due to an enhanced public desire for environmentally
friendly green products.






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3. Chemistry of PU
Polyurethane chemistry is based on the reactions of isocyanates with active hydrogen-
containing compounds. Isocyanates are compounds having one or more of the highly reactive
isocyanate group (N=C=O). This group will readily react with hydrogen atoms that are
attached to atoms more electronegative than carbon.

Compounds of primary interest for polyurethane forming reactions are listed in the
table below:
Active Hydrogen Compound Typical Structure
Relative Reaction Rate Non-
catalysed at 25C
Primary aliphatic amine RNH2 100,000
Secondary aliphatic amine R2NH 20,000-50,000
Primary aromatic amine ArNH2 200 300
Primary hydroxyl RCH2OH 100
Water HOH 100
Carboxylic acid RCOOH 40
Secondary hydroxyl R2CHOH 30
Urea RNHCONHR 15
Tertiary hydroxyl R3COH 0.5
Urethane R = NHCOOR 0.3
Amide RCONH2 0.1

3.1. Polymerisation reaction
The polyurethane polymer-forming reaction occurs between an isocyanate and an
alcohol as follows:

This is an addition process for which the heat of reaction has been reported to be
approximately 24 kcal/mole of urethane. Depending on the choice of starting materials, the R
and R groups may also contain isocyanate or isocyanate-reactive groups respectively. When
extended to polyfunctional reactants, this reaction provides a direct route to cross-linked
polymers.
The hydrogen on the nitrogen atom of the urethane group is capable of reacting with
additional isocyanate to form an allophanate group as shown in the figure below:

The formation of allophanate is a high temperature, reversible reaction. If actually
formed in normal flexible foams, the allophanate linkage would serve to cross-link the polymer

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further. The catalysts generally used in foam formulations do not promote this reaction, and
temperatures greater than 110C are necessary for significant allophanate formation.
3.2. Gas producing reaction
To make foam, the polyurethane polymer must be expanded or blown by the
introduction of bubbles and a gas. A convenient source of gas is the carbon dioxide produced
from the reaction of an isocyanate group with water.

The intermediate product of this reaction is a thermally unstable carbamic acid, which
spontaneously decomposes to an amine and carbon dioxide. Diffusion of the carbon dioxide into
bubbles previously nucleated in the reacting medium causes the expansion of the medium to
make foam.
Blowing can also be achieved by the physical addition of a low-boiling nonreactive liquid
to a foam formulation. Historically, the most commonly used physical blowing agents were the
chlorofluorocarbons, urethane grade methylene chloride and trichloroethane. Vaporization of
these liquids by heat from the exothermic reactions produces gas molecules which diffuse into
nucleated bubbles and contribute to foam expansion.

4. Basic Foam Components
Flexible polyurethane foam recipes normally contain a host of ingredients selected to
aid in achieving the desired grade of foam.
Component Parts By Weight
Polyols 100
Inorganic Fillers 0 - 150
Water 1.5 - 7.5
Silicon Surfactant 0.5 - 2.5
Amine Catalyst 0.1 - 1.0
Tin Catalyst 0.0 - 0.5
Chain Extender 0 - 10
Cross Linker 0 - 5
Additive variable
Auxiliary Blowing Agent 0 - 35
Isocyanate 25 85




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4.1. Polyol
The polyol is a source of hydroxyl or other isocyanate reactive groups. Processing and
properties of the resultant foam can be markedly influenced by the choice of starting polyol
structure. Ninety percent of all flexible foams produced today are made from polyether type
polyols. These polyols may be broadly grouped into the following categories:
Polyoxypropylene diols.
Polyoxypropylene triols.
Polyoxypropylene tetrols and higher analogs.
Ethylene-oxide-capped diols, triols, tetrols and higher analogs.
Random and block polymers of the above in which the polyol is made with both
ethylene and propylene oxides. When the oxides are fed as a mixed feed, the products
are termed hetero polyols.
Graft or copolymer polyols which contain stable dispersions of a solid particulate
polymeric phase in the liquid polyol phase.
Cross-linkers which are typically short-chain polyfunctional molecules added to
increase load bearing or initial foam stability.
4.1.1. Polyol preparation
A polyether polyol is the polymeric reaction product of an organic oxide and an initiator
compound containing two or more active hydrogen atoms. The active hydrogen compound in
the presence of a base catalyst initiates ring opening and oxide addition, which is continued
until the desired molecular weight is obtained. If the initiator has two active hydrogens, a diol is
formed.

If a trifunctional initiator such as glycerine is used, oxide addition produces chain
growth in three directions, and a triol results.





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These reactions are exothermic. Propylene oxide for example, releases approximately
22kcal/mole. Some of the commonly used initiators for the manufacture of flexible foam polyols
are listed in table:


4.2. Isocyanate
The isocyanate provides the source of NCO groups to react with functional groups from
the polyol, water and cross-linkers in the formulation. All the isocyanates used in the industry
today contain at least two isocyanate groups per molecule. The most commercially viable
methods of producing isocyanates involve the phosgenation of an amine as illustrated below:

Volume wise, aromatic isocyanates account for the vast majority of global diisocyanate
production. Aliphatic and cycloaliphatic isocyanates are also important building blocks for
polyurethane materials, but in much smaller volumes. There are a number of reasons for this.
First, the aromatically linked isocyanate group is much more reactive than the aliphatic one.
Second, aromatic isocyanates are more economical to use. Aliphatic isocyanates are used only if
special properties are required for the final product. For example, light stable coatings and
elastomers can only be obtained with aliphatic isocyanates. Even within the same class of
isocyanates, there is a significant difference in reactivity of the functional groups based on steric

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hindrance. In the case of 2,4-toluene diisocyanate, the isocyanate group in the para position to
the methyl group is much more reactive than the isocyanate group in the ortho position.
The two most important aromatic isocyanates are toluene diisocyanate (TDI) and
diphenylmethane diisocyanate (MDI). TDI consists of a mixture of the 2,4- and 2,6-
diisocyanatotoluene isomers. The most important product is TDI-80 (TD-80), consisting of 80%
of the 2,4-isomer and 20% of the 2,6-isomer. This blend is used extensively in the manufacture
of polyurethane flexible slab stock and moulded foam. TDI, and especially crude TDI and
TDI/MDI blends can be used in rigid foam applications, but have been supplanted by polymeric
MDI. TDI-polyether and TDI-polyester prepolymers are used in high performance coating and
elastomer applications.

4.3. Fillers
Finely divided inert inorganic fillers are often purposely added to foam formulations to
increase density, load bearing and sound attenuation. All other foam physical properties are
generally sacrificed. Depending on the nature of the filler, the overall cost of the final foam may
be reduced.
Typical fillers include the many grades of barium sulphate and calcium carbonate. Care
must be taken to dry the fillers or to know the precise water content available and factor that
data into the foam calculations. Normal concentrations used are from 20 to 150 parts per
hundred parts polyol. These fillers are heavy and will settle out of a polyol mixture unless
constant agitation is used.
Due to their abrasive nature, mineral fillers can also increase wear on machinery
components. Calcium carbonate fillers have a significant effect on the gelling reaction and
necessitate a re-balancing of the blowing and gelling reactions.

4.4. Water
Water is a source of active hydrogen. Only demineralised water should be used for foam
production. Isocyanate reacts with water to give carbon dioxide gas and polyurea molecules.
The gas diffuses into nucleated bubbles and aids in foam expansion. The polyurea molecules
enter into and contribute to the properties of the final polymer.

4.5. Surfactant
Almost all flexible polyurethane foams are made with the aid of nonionic, silicone-based
surfactants. In broad terms, surfactants perform several functions as shown below:
Lower surface tension,
Emulsify incompatible formulation ingredients,
Promote nucleation of bubbles during mixing,
Stabilize the rising foam by reducing stress concentrations,
Counteract the defoaming effect of any solids added to or formed; e.g., precipitated
polyurea structures, during the foam reaction etc.
Among these functions, stabilization of the cell-walls is the most important. By doing this,
the surfactant prevents the coalescence of rapidly growing cells until those cells have attained
sufficient strength through polymerization to become self-supporting. Without this effect,
continuing cell coalescence would lead to total foam collapse. Surfactants also help to control
the precise timing and the degree of cell-opening.

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4.6. Catalysts
Catalyst is a substance which changes the rate of reaction to some extent in either
direction. Polyurethane catalysts can be classified into two broad categories, amine compounds
and organometallic complexes.
4.6.1. Amine catalyst
Tertiary amines are the most commonly used flexible polyurethane foam catalysts.
Generally regarded as blowing catalysts, most amines also offer some contribution to the gelling
reaction. The catalytic activity of amines is due to the presence of a free electron pair on the
nitrogen atom. Steric hindrance about the nitrogen atom and the electronic effects of
substituent groups are the main factors influencing the relative catalytic activity of various
amines. In some foam systems, combinations of various amines are used in an attempt to
balance the gelling and blowing reactions so that the foaming process can be adequately
controlled.
The type and concentration of amine catalyst(s) can be selected to satisfy process
requirements such as cream times, rise profiles, gel times and even cure of the outer surface
skin. Choice of amine may also affect the foam properties such as airflow and load bearing
through influences on the primary and secondary foam reactions.
In general, requirements for good catalytic activity include:
A strong nucleophile capable of attacking the carbon of the isocyanate group.
Capable of readily forming an active hydrogen amine complex.
Soluble in water and forms stable hydrogen bonds with water.

Traditional amine catalysts have been tertiary amines such as triethylenediamine (TEDA, also
known as 1,4-diazabicyclo[2.2.2]octane), dimethylcyclohexylamine (DMCHA), and
dimethylethanolamine (DMEA).
4.6.2. Organometallic catalyst
The polymer forming or gellation reaction between the isocyanate and a polyol is
promoted by organometallic catalysts. Of the many metals available, tin compounds are the
most widely used. These compounds act as Lewis acids and are generally thought to function by
interacting with basic sites in the isocyanate and polyol compounds.
For flexible slabstock foam, dibutyl tin diluarate (DBTDL), stannous octoate (tin II 2-
ethyl hexoate) are the preferred gelling catalyst. Special handling is necessary since the
compound is easily hydrolyzed and oxidized in the presence of water and tertiary amines. In a
given slabstock foam formulation, varying the concentration of stannous octoate will produce
the typical results as shown below:


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4.7. Chain Extenders and Cross Linkers
Chain extenders (f=2) and crosslinkers (f=3 or greater) are low molecular weight
hydroxyl and amine terminated compounds that play an important role in the polymer
morphology of polyurethane fibers, elastomers, adhesives, and certain integral skin and
microcellular foams. The elastomeric properties of these materials are derived from the phase
separation of the hard and soft copolymer segments of the polymer, such that the urethane hard
segment domains serve as cross-links between the amorphous polyether (or polyester) soft
segment domains. This phase separation occurs because the mainly non-polar, low melting soft
segments are incompatible with the polar, high melting hard segments. The soft segments,
which are formed from high molecular weight polyols, are mobile and are normally present in
coiled formation, while the hard segments, which are formed from the isocyanate and chain
extenders, are stiff and immobile. Because the hard segments are covalently coupled to the soft
segments, they inhibit plastic flow of the polymer chains, thus creating elastomeric resiliency.
Upon mechanical deformation, a portion of the soft segments are stressed by uncoiling, and the
hard segments become aligned in the stress direction. This reorientation of the hard segments
and consequent powerful hydrogen bonding contributes to high tensile strength, elongation,
and tear resistance values. The choice of chain extender also determines flexural, heat, and
chemical resistance properties.

4.8. Additives
Additives are the chemicals which enhances the properties of the existing product to
some extent. Various additives may be incorporated into a foaming system to impart specific
desired properties. Some of the more common additives used in flexible foams are as follows:
4.8.1. Colorants
Many flexible foam products are color coded during manufacture to identify product
grade, to conceal yellowing, or to make an appealing consumer product. The historical method
of coloring foam was to blend in traditional pigments or dyes. Typical inorganic coloring agents
included titanium dioxide, iron oxides and chromium oxide. Organic pigments originated from
the azo/diazo dyes, phthalocyanines and dioxazines, as well as carbon black. Typical problems
encountered with these colorants included high viscosity,abrasive tendencies, foam instability,
foam scorch, migrating color and a limited range of available colors.
4.8.2. UV Stabilizers
All polyurethanes based on aromatic isocyanates will turn dark shades of yellow upon
aging with exposure to light. The yellowing is a surface event that is not a problem for most
foam applications. Light protection agents, such as hydroxybenzotriazoles, zinc dibutyl
thiocarbamate, 2,6-ditertiary butylcatechol, hydroxybenzophenones, hindered amines and
phosphites have been used to improve the light stability of polyurethanes.
4.8.3. Flame Retardants
Low-density, open-celled flexible polyurethane foams have a large surface area and high
permeability to air and thus will burn given the application of sufficient ignition source and
oxygen. Flame retardants are often added to reduce this flammability, at least as it is measured
by various specific, often small-scale tests, conducted under controlled laboratory conditions.
The choice of flame retardant for any specific foam often depends upon the intended service
application of that foam and the attendant flammability testing scenario governing that
application. Aspects of flammability that may be influenced by additives include the initial
ignitability, burning rate and smoke evolution. The most widely used flame retardants are the
chlorinated phosphate esters, chlorinated paraffins and melamine powders.


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4.8.4. Plasticizers
Nonreactive liquids have been used to soften a foam or to reduce viscosity for improved
processing. The softening effect can be compensated for by using a polyol of lower equivalent
weight, so that a higher cross-linked polymer structure is obtained. These materials increase
foam density and often adversely affect physical properties.
4.8.5. Antistatic Agents
Some flexible foams are used in packaging, clothing and other applications where it is
desired to minimize the electrical resistance of the foam so that buildup of static electrical
charges is minimized. This has traditionally been accomplished through the addition of
ionizable metal salts, carboxylic acid salts, phosphate esters and mixtures thereof. These agents
function either by being inherently conductive or by absorbing moisture from the air. The
desired net result is orders of magnitude reduction in foam surface resistivity. Problems with
permanence of the effect and corrosion of electronic components led to the development of
STATURE static control additive technology. Polyurethane foams containing the patented
STATURE additive provide reliable, noncorrosive static protection regardless of humidity
conditions.
4.8.6. Compatibilizers
Compatibilizers are special molecules that allow two or more nonmiscible ingredients to
come together and give one clear, homogeneous liquid phase. Many such molecules are known
to the polyurethane industry. Known classes of compatibilizer compounds include: amides,
amines, hydrocarbon oils, phthalates, polybutylene glycols, and urea.
4.8.7. Bacteriostats
Under certain conditions of warmth and high humidity, polyurethane foams are
susceptible to attack by micro-organisms. When that is a concern, additives against bacteria,
yeast or fungi are added to the foam during manufacture.
4.8.8. Cell-openers
In some polyurethane foams it is necessary to add cell-openers to obtain foam that does
not shrink upon cooling. Known additives for inducing cellopening include silicone-based
antifoamers, waxes, finely divided solids, liquid perfluocarbons, paraffin oils, long-chain fatty
acids and certain polyether polyols made using high concentrations of ethylene oxide.
4.9. Auxiliary blowing agents
Auxiliary blowing agents may be used in a foam formulation to aid in attaining densities
and softness not obtainable with conventional water isocyanate blowing chemistry. Auxiliary
blowing agents function by absorbing heat from the exothermic reactions, vaporizing and
providing additional gas useful in expanding the foam to a lower density. Since they are
nonreactive and contribute nothing to the polymer structure, such blowing agents give softer
foams than those blown to the same density with only water. Because the auxiliary blowing
agent acts as a heat sink, higher total catalyst package levels are generally needed to maintain
adequate cure of the foam.





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5. Coordination chemistry principles OF EBT, EDTA:-
5.1) Eriochrome black-T

Molecular Formula: C20H12N3NaO7S

Average mass: 461.379913 Da

Monoisotopic mass: 461.029358 Da

IUPAC name
Sodium 3-hydroxy-4-[(E)-(1-hydroxy-2-naphthyl)diazenyl]-7-nitro-1-
naphthalenesulfonate

Figure 1 EBT
5.1.1 complexation of EBT with metals
Eriochrome Black T is a complexometric indicator that is part of the complexometric
titrations, e.g. in the water hardness determination process. It is an azo dye, Eriochrome is a
trademark of Ciba-Geigy. In its protonated form, Eriochrome Black T is blue It turns red
when it forms a complex with calcium, magnesium, or other metal ions, that is why the
polyurethane foams formed by using EBT as complexating agent are blue in colour.
EBT forms complex with metal ions such as copper,nickel,calcium.



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5.2) Ethylene DiaminE Tetra Acetic Acid :-

Molar mass: 292.24 g/mol

Formula: C10H16N2O8

IUPAC ID: 2,2',2'',2'''-(Ethane-1,2-diyldinitrilo)tetraacetic acid

Density: 860.00 kg/m

Melting point: 237 C

Soluble in: Water

Figure 2 EDTA


Ethylenediaminetetraacetic acid, widely abbreviated as EDTA, is
an aminopolycarboxylic acid and a colourless, water-soluble solid. Its conjugate base is
named ethylenediaminetetraacetate. It is widely used to dissolve limescale. Its
usefulness arises because of its role as a hexadentate ("six
toothed") ligand and chelating agent, i.e. its ability to "sequester" metal ions such as
Ca2+ and Fe3+. After being bound by EDTA, metal ions remain in solution but exhibit
diminished reactivity. EDTA is produced as several salts, notably disodium EDTA and
calcium disodium EDTA.



xvi
5.2.1) complexation of EDTA with metals
In coordination chemistry, EDTA4 is a member of the aminopolycarboxylic acid family
of ligands. EDTA4 usually binds to a metal cation through its two amines and four
carboxylates. Many of the resulting coordination compoundsadopt octahedral geometry.
Although of little consequence for its applications, these octahedral complexes
are chiral. The anion [Co(EDTA)] has been resolved into enantiomers. Many complexes
of EDTA4 adopt more complex structures due to (i) the formation of an additional
bond to water, i.e. seven-coordinate complexes, or (ii) the displacement of one
carboxylate arm by water. Ferric complex of EDTA is seven-coordinate. Early work on
the development of EDTA was undertaken by Gerold Schwarzenbach in the
1940s. EDTA forms especially strong complexes with Mn(II), Cu(II), Fe(III), Pb (II) and
Co(III).

6. Applications
Polyurethanes are one of the most versatile materials today. They have many uses
worldwide:

6.1. Industrial Applications
Flexible Foam: Flexible polyurethane foam's versatility of form and function can be seen in
bedding, furniture, automotive interiors, carpet underlay and packaging. Foam can be created in
almost any variety of shape and firmness. In addition, it's light, durable, supportive and
comfortable.
Rigid Foam: Rigid polyurethane and polyisocyanurate foams form one of the world's most
popular, energy-efficient and versatile insulations. It significantly cuts fuel and construction
costs while making commercial and residential properties safer, better utilized and more
comfortable around the globe.
Thermoplastic Polyurethane: Thermoplastic polyurethane (TPU) offers a myriad of physical
property combinations and processing applications. It's highly elastic, flexible and resistant to
abrasion, impact and weather. TPU's can be colored or fabricated in a wide variety of methods,
and their use increases a product's overall durability.

xvii
Coatings, Adhesives, Sealants and Elastomers: Polyurethane coatings make a product look
better and last longer. Polyurethane adhesives provide strong bonding advantages.
Polyurethane sealants provide tighter seals. Polyurethane elastomers can be molded into almost
any shape, are lighter than metal, offer superior stress recovery and can be resistant to many
environmental factors.
6.2. Consumer Applications
Apparel: When scientists discovered that polyurethanes could be made into fine threads, they
were combined with nylon to make more lightweight, stretchable garments. Over the years,
polyurethanes have been improved and developed into Spandex fibres, polyurethane coatings,
and thermoplastic elastomers.
Appliance: Polyurethanes are an important component in major appliances consumers use
every day. In 2004, appliance manufacturing represented a 468 million pound market for
polyurethanes in North America, about 6 percent of total polyurethane consumption.
Automotive: Polyurethanes are used throughout your car - in familiar places like the foam that
makes your car seats comfortable, as well as a few places you might not expect.
Building & Construction: Today's homes demand high-performance materials that are strong,
yet lightweight; that perform well, yet are easily installed; and that are durable, but also
versatile. With well over 1.5 million new homes being constructed in the U.S. each year,
building-material quality and performance must be exceptionally reliable, which is why builders
are consistently turning to polyurethane.
Coatings, Adhesives, Sealants and Elastomers: The spectrum of polyurethane use in coatings,
adhesives, sealants and elastomers not only advances traditional manufacturing methods, it also
substantially expands the lifetime of a host of products.
Composite Wood: Some of today's modern materials are a combination of synthetic and natural
materials. Polyurethanes play a major role in today's modern materials such as in composite
wood.
Electronics: Often referred to as potting compounds, non-foam polyurethanes are frequently
used in the electrical and electronics industries to encapsulate, seal and insulate fragile,
pressure sensitive microelectronic components, underwater cables and printed circuit boards.
Flooring: Either as a foam underlay or on top as a coating, polyurethanes can make the floors
we walk on every day more durable, easier to maintain and more aesthetically pleasing.
Furnishings: Polyurethane, mostly in the form of flexible foam, is the one of the most popular
materials used in home furnishings in places such as furniture, bedding and carpet underlay.
Marine: Boating as a pastime and a sport is increasingly popular. According to recent surveys,
more than 70 million Americans enjoy boating each year.
Medical: Polyurethanes are commonly used in a number of medical applications including
catheter and general purpose tubing, hospital bedding, surgical drapes, wound dressings, as
well as in a variety of injection moulded devices.
Packaging: Polyurethane packaging foam (PPF) provides cost-effective, custom form-fitting
cushioning to uniquely and securely protect items that need to stay safely in-place during
transit.
RIM: Car bumpers, electrical housing panels, and computer and telecommunication equipment
enclosures are some of the parts produced with polyurethanes via Reaction Injection Molding
(RIM).
Waterborne Polyurethane Dispersions: Waterborne Polyurethane Dispersions (PUDs) are
coatings and adhesives that use water as the primary solvent

xviii
7. Foam Calculations
A-Side: The isocyanate-containing material.
B-Side: The polyol-containing material, usually a blend of polyol, chain extenders, cross-linker,
water, catalysts and surfactants.
Functionality: The functionality of a B-side foam ingredient is the number of isocyanate
reactive sites on a molecule. For polyols, an average functionality is generally used.

Acid Number: A number arising from a wet analytical method to determine the amount of
residual acidic material in a polyol. It is reported in the same units as hydroxyl number.
Hydroxyl Number (OH Number): A number arising from a wet analytical method for the
hydroxyl content of a polyol; it is the milligrams of potassium hydroxide equivalent to the
hydroxyl content in one gram of polyol or other hydroxyl compound.

where 56.1 is the atomic weight of potassium hydroxide and 1000 is the number of milligrams
in one gram of sample.
The OH number for each lot of polyol is provided by the manufacturer. Polyols are
sometimes characterized by quoting the weight percentage of hydroxyl groups. Conversion to
hydroxyl number is accomplished by:

where the number 33 is obtained by reduction of constants. For a mixture of polyols, the
hydroxyl number of the mixture (OHm) is given by:

Equivalent Weight of a Polyol: The weight of a compound per reactive site.

Since polyols have a molecular weight distribution, an average equivalent weight is
calculated. These calculations are done using the product analysed hydroxyl (OH) content and
acid number:

For most polyols in use today, the acid number is very low and may be omitted. If the
acid number is larger than about 1.0, it should be factored into the above equation.


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Equivalent Weight of an Isocyanate: The weight of an isocyanate compound per isocyanate
site. This is calculated from the analyzed isocyanate (NCO) content.

where 42 is the atomic weight of the NCO group.
Equivalent Weight of an Isocyanate Blend: For foam systems using a blend of different
isocyanates, the net equivalent weight of the blend is given by:

Equivalent Weight of Water: Water reacts with 2 isocyanate groups and thus the equivalent
weight is given by:

Isocyanate Index: The ratio of the equivalent amount of isocyanate used relative to the
theoretical equivalent amount times 100.

The calculation procedure for a foam formulation is:
1. Determine the parts of each polyol. Total parts polyol should equal 100.
2. Determine the parts of other B-side components per 100 parts polyol.
3. Sum the parts of all B-side materials to get the total formula weight.
4. Record the equivalent weight of each B-side component from the above calculations or from a
listing of typical equivalent weights.
5. Calculate the equivalents of each B-side component.

6. Sum the reactive equivalents of each B-side component to get the total B-side equivalents.
7. Record the isocyanate equivalent weight.
8. Select the desired isocyanate index.
9. Calculate the isocyanate parts required.

Amount of water is determined as:




xx

8. Experimental Procedure
The other constituents of the 32 g/cm
3
PU foam calculated based on per 100 parts of
polyol in the foam formulation are shown below:
Isocyanate = 38 parts
Water = 3.0 parts
Amine Catalyst = 0.18 parts
Tin Catalyst = 0.14 parts
Silicon Surfactant = 1.2 parts

The following steps were adopted in order to have cured PU foams:

Step I: Desired quantity of isocyanate is weighed in a vessel and kept aside.
Step II: The required quantity of polyol for each sample is taken in another vessel.
Step III: Required amount of water, amine catalyst, tin catalyst and silicon surfactant are
added to the polyol mixture prepared in Step II. The formulation is mixed
thoroughly with the help of an electric stirrer.
Step IV: After mixing the formulation for about 25-30 seconds isocyanate is added to it and
the mixing is continued for another 8-10 seconds.
Step V: The thick liquid obtained at the end of Step IV is immediately poured into a
cardboard box mould.
Step VI: At the end of Step V, foam start rising because of the polyol and isocyanate
reaction. This process is known as foaming. The time taken by the foam to rise to
maximum height i.e., foam rise time is recorded.
Step VII: Foam prepared in Step VI is kept for 24-36 hours for curing process.

After all the samples were prepared and cured they were cut into blocks of equal
dimensions for testing.












xxi
8.1. Testing
The following tests were performed on each foam sample for comparison of their properties:
1. Density Test
2. Indentation Force Deflection Test
3. Tension Test
4. Resilience Test
8.1.1 Density Test

Fig. 1. Density determination apparatus.
The density measurement is an apparent or bulk density, not the true polymer density.
This physical property is important because of its parallel relationship with both cost and load
bearing. High densities generally result in higher costs and improved load-bearing properties. In
the test, a representative sample is carefully measured and accurately weighed (Fig. 1). The
density, normally reported in pounds per cubic foot or kilograms per cubic meter is simply the
sample weight divided by its volume.
8.1.2 Indentation Force Deflection (IFD) Test

Fig.2. Determining the hardness of PU foam in Universal Tensile Testing Machine
The indentation force deflection test (IFD) is a measurement of the loadbearing
properties of foam. In this test the force required to depress a circular plate into the foam is
measured. Two types of measurements are important: the indentation resulting from a specified
force and the force required to reach a specified indentation. Experience has shown that these
measurements can vary depending on the temperature and relative humidity conditions under
which the foam was made. The results of foam hardness are taken at 50% compression.


22
8.1.3 Tension Test (Tensile Strength)

The tension test measures the strength of foam under tension and gives information about
the foams elasticity. Samples for the test are generally die-cut and are dog bone or dumbbell
shaped. The sample is pulled at a constant rate until it breaks. The force recorded at the
breaking point is the tensile strength of the foam, generally reported in kilopascals. The
maximum extension of the sample as a percentage of its original length is the elongation at
break.
8.1.4 Resilience Test

The resilience of foam is measured in a ball rebound test. The test consists of dropping a
steel ball on a foam sample and visually measuring the height of rebound. Results from this test
have been correlated to overall cushion comfort.








23
9. Formulations and Test Reports/Tables:-
9.1. Polyols
Polyester Polyol Trade Name OH Value Viscosity(cp at
25C)
Polyol A VORANOL 3322 56
Polyol B FLEXTER Z-013 (UFLEX) 55 660-700
Polyol C FLEXTER Z-015(UFLEX) 245 5000-8000
Polyol D FLEXTER Z-019(UFLEX) 56 1000
Polyol E DIEXTER G-175 54 8800 10200

9.2. Catalysts&Surfactants
Chemical Name Trade Name Nature
Tin Catalyst Niax D-19 Catalyst
Amine Catalyst Lupragon N-600 (BASF) Catalyst
Silicon L-618 Surfactant

9.3. Others
Water Tap Water
Isocynate Toluene Diisocynate (BASF)







24
9.4 series of formulation
In the series, one polyol is used, Polyol A (VORANOL 3322), Formulations are
shown below (Density: 32 g/cc, Water: 3.5pph, EBT, EDTA, DMG):
Series of formulation:-
POLYOL TDI AMINE SILICON TIN
250 100 0.14 1.2 0.04

EBT NICKEL
PHOSPHATE
CALCIUM
PROPIONATE
COPPER
SULPHATE
CALCIUM
CARBONATE
0.1 0.19 0.11 0.216 0.059
0.3 0.59 0.332 0.259 0.162
0.6 1.18 0.66 0.510 0.32

EDTA DMG NICKEL PHOSPHATE
(with DMG)
CALCIUM
CARBONATE
(with edta)
0.1 0.1 0.39 0.06
0.3 0.3 1.2 0.201
0.6 0.6 2.36 0.403




25



S.NO EBT+METAL EDTA+METAL %
ELONGATION
PERMIABILITY TENSILE
STRENGTH
1 Ebt+nickel(0.1)

180 30 0.87
2 Ebt+nickel(0.3)

186 28 0.76
3 Ebt+nickel(0.6)

195 25 0.68
4 Ebt+calcium(0.1)

102 20 0.92
5 Ebt+calcium(0.3)

119 24 0.67
6 Ebt+calcium(0.6)

158 28 1.25
7 Ebt+copper(0.1)

211.4 25 1.05
8 Ebt+copper(0.3)

226 27 1.03
9 Ebt+copper(0.6)

232.3 30 1.03
10 Ebt+caco3(0.1)

145.7 43 0.83
11 Ebt+caco3(0.3)

163 41 0.91
12 Ebt+caco3(0.6)

205.7 40 1.29
13

Edta+caco3(0.1) 201.3 34 1.17
14

Edta+caco3(0.3) 203 31 1.00
15

Edta+caco3(0.6) 199 30 1.30

26
9.5. Observations :-
All the foams are prepared using polyol A (voranol 3322) and other components as
shown in the table.
All the foams have density of 32 g/cc, the foams which are prepared using EBT have
following properties
1) colour- violet
2) rough surface
3) closed cell (dense)
4) surface has pores
On the other hand, the foams prepared using EDTA have
1) smooth surface
2) white in color
3) Good tensile properties and % elongation
The foams prepared using dimethyl glyoxime with nickel phosphate get shrinked and
ultimately collapsed.
As we increase the concentration of complexating agent the foam shows closed cell
structure, increased tensile properties, and high resilience.

10. Conclusions
The mechanical properties like tensile strength and elongation of the foam increased
with the addition of glycerol, tween20 and span20 to the mother foam.
Constant improvement in the tensile strength and elongation could be improved with
increase in the concentration of glycerol and tween20 up to 30% addition in the polyol
after which formulating the foams became next to impossible.
The foams obtained using these cross-linkers were softer than the mother foam.
The foam samples observed total foam shrinkage and partial shrinkage depending on
the concentration of cross-linkers used with same concentration of tin catalyst.
The corrective measures taken to prevent shrinkage were:
o Decrement in tin concentration to prevent shrinkage,
o Increment in amine concentration to increase the blowing for cell opening, and
o Increment in silicone oil concentration to provide strength to the foam.
The TOES and A-TEOS also increased the crosslinking and further resulting in the
closed cell structures and shrinkage in some cases.
The samples are yet to be tested for thermal stability using TGA and DSC. It is expected
that the use of TEOS and A-TEOS will improve the thermal stability of the mother foam
manifold.





27
11. References
Dow Polyurethanes - Flexible Foam 2
nd
edition, Editors Ron Harrington and Kathy Hock.
Huntsman The Polyurethanes Book, Editors David Randall and Steve Lee, Publisher
John Wiley and Sons Ltd.
K. C. Frisch and S. L. Reegen Advamces in Urethane Science and Technology Vol. 1.
Technomic Publishing Co.
Gunter Oertel Polyurethane Handbook. Hanser Publishers.
George Woods Flexible Polyurethane Foams. Applied Science Publishers.
www.en.wikipedia.org/wiki/Polyurethane
www.polyurethane.org