Freeze-Flame Nano

Capstone Design Project

Spring 2006

5/5/06

University of Oklahoma Chemical Engineering

KVTV Inc. Keshan Velasquez

Tyler Viani

1

Executive Summary

KVTV has developed a new phosphorus based flame retardant thermoplastic named Freeze Flame Nano. This flame retardant has been developed to revolutionize the building construction industry. Great Lakes Chemical, the former producer of pent-bromodiphenyl ether and octa-bromodiphenyl ether has recently stopped production of these two leading flame retardants. These brominated flame retardants have shown increased signs of bioaccumulation. Likewise, these retardants have banned because of their toxic byproducts: dioxins and furans. Freeze Flame Nano has none of the functional groups that cause toxins to exist in the environment. KVTV’s product is a coating that can be applied on the surface of a multitude of different woods, plastics and home furnishings. The thermoplastic product acts in the solid phase as a protective barrier that can withstand intense heat inputs. The barrier slows the release of potentially toxic and combustible vapors normally released from burning materials. Also, the phosphoric acid existing in the polymer blend serves to induce an added char barrier that further inhibits vapor release. KVTV created Freeze Flame Nano through researching modern flame retarding techniques. NASA has been studying the effects of thermosets and thermoplastic coatings on their re-entry vessels. Thermoplastics easily adhere to numerous surfaces and resist high heat inputs. Unlike thermosets, thermoplastics can be melted and remolded. Similarly, they have increased moduli of elasticity and lowered glass transition temperatures. Although the values have not been experimentally determined, it is expected that Freeze Flame Nano will have extremely low vapor pressures at high temperatures as well as have high enthalpies of vaporization, resulting in better flame retardancy. The flame retardant coating that KVTV is proposing consists of 50% polyvinyl alcohol, 15% phosphate, 3% Cloisite, and 32% water. A market analysis was performed to determine the demand that KVTV can capture. It was determined that the maximum demand that Freeze Flame Nano could capture would be 6.7 million pound per year. KVTV recommends that the production plant for Freeze Flame Nano be built in Corpus Christi, Texas. The total capital investment for this process is $1.7 million. The net present worth of this ten year venture is $15.3 million.

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Table of Contents 1.0 Introduction................................................................................................................... 6

1.1 Background............................................................................................................... 6 1.2 How Flame Retardants Work.................................................................................... 6 1.3 The Combustion Process........................................................................................... 7

1.3.1 Combustion of Hydrocarbons ............................................................................ 7 1.3.2 Combustion of Wood......................................................................................... 8 1.3.3 Combustion of Polymers.................................................................................. 10

1.4 Flame Retarding Pathways ..................................................................................... 11 2.0 Flame Retardant Families ........................................................................................... 14

2.1 Halogenated Flame Retardants ............................................................................... 14 2.2 Phosphorus Flame Retardants................................................................................. 15 2.3 Nitrogen Flame Retardants ..................................................................................... 17 2.4 Inorganic Flame Retardants .................................................................................... 17

3.0 The Flame Retardant Market ...................................................................................... 19 3.1 Global Market ......................................................................................................... 19 3.2 United States Market............................................................................................... 19 3.3 Flame Retardant Coatings....................................................................................... 19 3.4 Market Projections .................................................................................................. 20

4.0 Problem Statement ...................................................................................................... 21 5.0 Our Product................................................................................................................. 23

5.1 Pathway to Discovery ............................................................................................. 23 5.1.1 Statistical Method ............................................................................................ 23 5.1.2 Use of Thermoplastics ..................................................................................... 24

5.2 Synthesis Path ......................................................................................................... 25 5.3 Retarding Mechanism ............................................................................................. 28 5.4 Happiness................................................................................................................ 29

6.0 Business Model........................................................................................................... 36 6.1 Calculating Demand................................................................................................ 36

7.0 Business Plan .............................................................................................................. 41 7.1 Organizational Plan................................................................................................. 41

7.1.1 Company Description ...................................................................................... 41 7.1.2 Our Product...................................................................................................... 41 7.1.3 Plant Location .................................................................................................. 42 7.1.4 Management..................................................................................................... 42 7.1.5 Personnel.......................................................................................................... 42 7.1.6 Insurance .......................................................................................................... 43 7.1.7 Security ............................................................................................................ 43

7.2 Marketing Plan........................................................................................................ 43 7.2.1 Market Analysis ............................................................................................... 43 7.2.2 Market Trends.................................................................................................. 44 7.2.3 Marketing Strategy........................................................................................... 44

7.3 Financial Plan.......................................................................................................... 45 7.3.1 Financial Need ................................................................................................. 45 7.3.2 Cash Flow Statement ....................................................................................... 45 7.3.3 Projected Balance Sheet................................................................................... 46

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7.3.4 Break-Even Analysis ....................................................................................... 46 7.3.5 Risk Associated with Investing........................................................................ 47 7.3.6 Supporting Financial Documents..................................................................... 48

8.0 Conclusions and Recommendations ........................................................................... 51 8.1 Conclusions............................................................................................................. 51 8.2 Recommendations................................................................................................... 51

9.0 References................................................................................................................... 52 Appendix........................................................................................................................... 54

4

List of Tables Table Number Page Number Table 1: Zonal Analysis of Pyrolysis in Wood ………………………………………….9 Table 2: Zonal Analysis of Combustion in Wood ………………………………………9 Table 3: Lydersen Predicted Critical Constants ..............................................................23 Table 4: Relative weights assigned …………………………………………………….35 Table 5: Calculated demand over 10-year life cycle …………………………………...37 Table 6: Comparison of design scenarios and their effective NPW ……………………38 Table 7: Regret analysis results ………………………………………………………...39 Table 8: Equipment Specifications ……………………………………………………..39 Table 9: Target Consumers ……………………………………………………………..42 Table 10: Balance Sheet ………………………………………………………………...45 Table 11: Variability in Profit …………………………………………………………..47 Table 12: Total Capital Investment ..................................................................................47 Table 13: Total Annualized Cost ………………………………………………………..48

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List of Figures Figure Number Page Number Figure 1: General combustion reaction stoichiometry …………………………………7 Figure 2: Combustion of Isobutanol …………………………………………………...8 Figure 3: Pyrolysis and Combustion Pathway of Plastics …………………………….11 Figure 4: General Life-Cycle of a Fire ………………………………………………..12 Figure 5: Life Cycle of a Fire with Flame Retardant ………………………………….13 Figure 6: Initiation step for phosphate based flame retardants ………………………..15 Figure 7: Formation of polyphosphate barrier…………………………………………16 Figure 8: Esterification stage ………………………………………………………….16 Figure 9: Charring stage ……………………………………………………………….16 Figure 10: Global Market Breakdown …………………………………………………19 Figure 11: Chemical Structures of A) PBBs, B) PBDEs, C) HBCD, D) TBBPA …….21 Figure 12: Chemical Structure of A) Dioxin B) Furan ………………………………..22 Figure 13: Saponification of PVAc with NaOH to form PVOH ……………………...26 Figure 14: Polar mixing of PVOH and cloisite. ……………………………………….26 Figure 15: A) Polymer blend B) Legend ……………………………………………….27 Figure 16: Proposed process flow diagram …………………………………………….28 Figure 17: Flame retardant protection pathway ………………………………………...29 Figure 18: Overall happiness relative to changes in consumer attributes ………………31 Figure 19: Cash Balance for KVTV, Inc. ………………………………………………44 Figure 20: Break-Even Analysis ………………………………………………………..46 Figure 21: Risk Distribution ……………………………………………………………47

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1.0 Introduction

1.1 Background

Fire-related disasters have affected many and are a potential threat to any member in

society. According to the United States Fire Administration1, approximately 150,000 fires

were reported in 2004, and at least 2.5% of those fires resulted in civilian casualties.

Likewise, 76%2 of structural fires in 2001 resulted in varying residential property

damage. Over the past ten years, there has been an overall decrease in number of fires

reported per year, and an even greater decreasing trend in the amount of deaths resulting

from fire; therefore, the development and implementation of flame retardants can, on the

whole, help to maintain this decreasing trend. Since surveys show that most people claim

to feel safest from fire danger in their home, it seems only wise to develop better means

to protect them. Many products currently existing on the market have lessened the

impacts of fire damage, but with increasing need for fire prevention and safety at the job

and home has come an increased search for fire preventing/flame retarding

methods/products that are both extremely effective and environmentally friendly. The

ultimate driving force in the flame retardant industry is to save lives.

1.2 How Flame Retardants Work

Flame retardants work through a number of different mechanisms. The ultimate goal

is to decrease the potential of ignition or to delay the spread of a flame over the body of

material the retardant is protecting. This is accomplished by increasing the combusting

resistance of the materials to continue burning. Flame retardants are applied in a number

of different methods. They can be impregnated into plastics during processing, blended

with insulation materials during application, used as treatments on shingles and decks and

applied on the surface of materials as coatings or paints.

There are four major families of flame retardants currently existing on the market,

and each of the four categories retards the flame through a different mechanism. The

molecular structure of a flame retardant, the functional group arrangement and the

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thermodynamic properties determine whether it will resist higher temperatures, lessen the

release of combustible vapors, increase the level of char, or generically decrease the

spread of the flame.

1.3 The Combustion Process

A combustion reaction takes place when a combustible material in an oxygen rich

environment encounters a heat source. If the heat source’s intensity is large, the material

reaches an auto-ignition temperature and combusts. Since combustion reactions are

largely exothermic, both heat and combustible vapors are released at a high rate during

the process. If reaction conditions and the molecular energetics are conducive to

combustion, a material continues to degrade at elevated temperatures and release heat

until the material is consumed. One major feature of combustion is the occurrence of

pyrolysis, or the decomposition of organic material in the absence of oxygen. As a result

of pyrolysis, a combusting material can continue to burn in environments with relatively

low oxygen concentrations.

1.3.1 Combustion of Hydrocarbons

The combustion of hydrocarbons occurs predominately in the vapor phase. A vast

majority of unsubstituted alkanes, alkenes and alkynes readily exist as vapors at room

temperature, and they are often volatile species. In the presence of a significant amount of

oxygen and with substantial heat input, hydrocarbons ignite and propagate to other

molecules. The general form of a combustion reaction is shown in figure 1. A combustion

reaction results in a flame which propagates throughout the material and spurns further

burning of the material.

Figure 1: General combustion reaction stoichiometry

Longer and more substituted hydrocarbon molecules are not as volatile simple

hydrocarbons; therefore, they are less likely to move into the vapor phase and combust.

( ) )(2)(2)(2)( 224)( vapgggnm OHnCOmOnmHC ⎟

⎠⎞

⎜⎝⎛+→⎟

⎠⎞

⎜⎝⎛ +

+−−

8

Similarly, as hydrocarbon chains increase in size, dipoles are induced resulting in larger

Van der Waals interactions3 in the hydrocarbon mixture. Increased interactions further

stabilize the reactive system and decrease the probability that a combustion reaction

reaches completion.

Complete combustion occurs when an unsubstituted hydrocarbon is reacted to form

only CO2 and H2O vapors. When combusting substituted hydrocarbons, the products of

the reaction are stoichiometrically equivalent to that found in the original molecule. Take

for instance the combustion of isobutanol:

Figure 2: Combustion of Isobutanol

Sometimes when molecules induced dipole-dipole interactions are large enough and

there is insufficient energy to lead to complete combustion, a molecule may undergo

partial (incomplete) combustion. Incomplete combustion often results in toxic side

products, namely carbon monoxide.

1.3.2 Combustion of Wood

The combustion of wood is slightly more complex than that of hydrocarbon

combustion. Wood, in general, has much higher thermal resistances than many other

combustible materials. As a result, the burning of wood exhibits dynamic behavior. The

precursor to the ultimate combustion of wood is pyrolysis. Experiments performed reveal

that the pyrolysis pathway occurs via different temperature zones. Table 1 analyzes the

different zones that occur during pyrolysis and summarizes the behavior of wood within

each of the zones.

)(2)(2)(2)(104 546 vapggg OHCOOOHC +→+

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Table 1: Zonal Analysis of Pyrolysis in Wood

Zone Temperature Range, T(oC) Description A T < 200 1) Surface Dehydration

2) Release trace H2O/CO2 vapors

B 200 < T < 280 1) Pyrolysis continues, more H2O/CO2 emitted

2) Rxn remains endothermic

C 280 < T < 500 1) Rxn becomes exothermic, temperature rises sharply

2) Tars evolved, secondary rxns, pyrolysis continues

D T > 500 1) Carbonization ceases & char layer fully developes

2) H2O/CO2 vapors react with charcoal layer

Portions of the combustion and pyrolysis cycles overlap even though pyrolysis must

initiate the combustion cycle. The result of pyrolysis and combustion of wood is a

smoldering, charred ember existing at high temperatures. Table 2 illustrates the general

behavior of wood at different temperatures via zone analysis.

Table 2: Zonal Analysis of Combustion in Wood

Zone Temperature Range, T(oC) Description A T < 200 1) Steady loss of weight of material (char)

2) Exothermic oxidation reactions increase temp.

B 200 < T < 280 1) More gasses evolve, exothermic conditions reached

2) Heat re-radiated from vapors back to wood

C 280 < T < 500 1) Gas rate release increases sharply

2) Inhibiting char layer develops

D T > 500 1) Oxygen environment somewhat depleted

2) Glowing char embers

The physical properties of wood vary based upon their composition. For instance, balsa is

a porous, light-weight wood that has high surface area. Pine is much less porous, denser

wood that has low surface area. Balsa wood will be more reactive when subjected to

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elevated temperatures for shorter times, and pine wood can withstand elevated

temperatures for longer times. This results from the varying thermal resistances of the

respective materials.

1.3.3 Combustion of Polymers

The majority of polymers existing on the market consist of substituted hydrocarbons.

Much like the behavior of wood at elevated temperatures, plastics begin combusting

through pyrolysis. The behavior of polymers over broad temperature ranges is determined

in part by the connectivity of the polymer. During polymeric plastic formation, monomer

units are initially energized into radicals that propagate with other monomer units to

create the final polymer chain. The highly energetic monomer units add in a head-to-head

or head-to-tail fashion. Depending on the ratio of head-to-head to head-to-tail linkages

helps predict the behavior of the polymer at higher temperatures: more head-to-head

linkages result in more stable polymer slurries.

Polymeric plastic combustion occurs in the vapor phase. When a plastic is exposed to

increased temperatures, the plastic undergoes pyrolysis. Potentially combustible vapors

are slowly released at first. Since many polymers are substituted, the increase in

surrounding temperatures can cause variations in connectivity among the monomer units.

Often, these variations in connectivity result in an overall weakening of the polymer

structure and can encourage the release of more vapors and liquids, both flammable and

non-flammable. As the heat source persists, the temperature of the polymer increases

steadily. Volatile vapor release rates increase and hydrogen and hydroxide radicals

diffuse out of the material. The radicals can combine to propagate the flame spread. Re-

radiation from combusting vapors effectively increases the polymers’ temperature.

During this process a char layer forms on the surface of the plastic which serves to inhibit

flame spreading. If there is enough char barrier, the flame will slowly extinguish.

Otherwise, heat will continue to be released at higher rates and the pyrolysis-combustion

process continues. The flow chart in Figure 34 illustrates the overall process of pyrolysis

and combustion.

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Figure 3: Pyrolysis and Combustion Pathway of Plastics

1.4 Flame Retarding Pathways

A flame retardant behaves in a number of ways. Its main goal is to either increase the

overall resistance of the material to ignite or to delay the further spread of flames across

the material. The important fact to note is that flame retardants themselves are

combustible materials at certain temperatures; however, certain physical and structural

properties that flame retardants obtain effectively aid in retarding the flame’s spread or

resisting an initial ignition. As well as retard the flame, modern flame retardants are

specifically designed to decrease the production rate of harmful byproducts such as

carbon monoxide, hydrogen cyanide, soot, rogue char and debris. Certain fire testing

standards have been issued for various household appliances that require them have self-

extinguishing properties. Retarding additives are blended in mattresses and furniture

upholstery to prevent ignition from a common ignition sources like cigarettes. Likewise

high heat resistant coatings are applied to the surface of many electronics, computers,

stereos and cables, in the event of an electrical short. Altogether, the major goal of all

flame retardant research, development and production is to save lives, and this is

accomplished primarily by buying more time through lessening flame spread.

The life-span of a fire can be described in four main steps: initiation, propagation,

steady combustion, and termination5. Often, flames are initiated by a steady heat source

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and elevated to a certain temperature. Once the heated material becomes sufficiently

energized, the material combusts. This is known as the flash point of that material. After

the material has reached flash point and has begun combustion, potentially combustible

volatile vapors are released from the material and hurriedly propagate the spread of the

flame. The term steady combustion is used to describe the third, most lingering,

component of combustion. During this stage, the flame spreads rapidly, and the body of

material being burned has a relatively stable heat release rate. After this point, the fire

slows to the termination stage. Within this stage, the flame’s intensity is lessened or

essentially ceased due to a variety of reasons. The flame not existing in an environment

with enough oxygen to burn, combustible vapors are not being emitted as quickly as

during the steady combustion stage, or external flame prevention methods were employed

to quench the flame are a few of the potential means by which a flame terminates. Figure

4 illustrates the four-stage pathway of a fire.

Figure 4: General Life-Cycle of a Fire

When a flame retardant is added to a material via coating, impregnation or blending

the resulting behavior of the retarded material during intense heating is greatly stabilized.

Flame retardants increased heat capacity and increased resistance to high heat inputs

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change the behavior of the material under volatile conditions. This behavior is described

in Figure 5.

Figure 5: Life Cycle of a Fire with Flame Retardant

This figure is somewhat misleading. It can be inferred, from quick inspection of the

figure, that a material’s overall temperature will decrease over time after the addition of a

flame retardant. However, the ignition temperature of the material is neither altered nor

increased substantially. Although it is difficult to accurately predict the dynamics of a

material under extreme heat conditions, it is safe to assume that the addition of a flame

retardant would have little-to-no adverse effects on the behavior of the system at

increased external temperatures.

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2.0 Flame Retardant Families

Some flame retardants cause a treated material to char thus inhibiting the pyrolysis

process. Others remove flammable gases by reacting with the hydrogen and hydroxide

radicals in the air. There are four primary substances which work to retard fire in

different ways. These families include halogenated, phosphorus, nitrogen and inorganic

flame retardants.

2.1 Halogenated Flame Retardants

Halogenated flame retardants are those that consist of one or more halogen atoms on

the flame retardant molecule. The effectiveness of the flame retardant increases with the

size of the halogen atom(s); however, fluorine and iodine are not used because they fail to

inhibit the combustion process. Fluorine is highly electronegative, thus its bonds with

carbon are too strong. Iodine is a relatively large halogen thus making its bonds with

carbon much weaker. Chlorine and bromine are both used in the flame retardant

industry. The reaction mechanism for halogenated flame retardant is shown below4:

When exposed to the flames, the bonds to the halogen atoms in the flame

retardant break and radicals are released.

RX → R· + X·

Then, the halogen radical reacts to form a halogen halide.

X· + RH → R· + HX

Next, the halogen reacts with the hydrogen and hydroxide radicals in the air to

form water.

HX + H· → H2 + X·

HX + OH· → H2O + X·

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The effectiveness of the halogen depends on the quantity and control of release of the

atoms. Bromine flame retardants are most commonly used because the bromine atoms

are released over a narrower temperature range. Therefore, there is an optimal

concentration of bromine radicals in the flame zone6.

Halogenated flame retardants are widely used due to relatively low production and

raw material costs. However, the effectiveness depends on quantity of halogen atoms

and on the control of halogen release. Halogenated flame retardants are not

biodegradable.

Some have been banned because of their toxic nature. Penta-bromodiphenyl ether

and octa-bromodephenyl ether, when burned were found to form trace amounts of side

products, dioxins and furans. Dioxins are classified by the EPA as class 1 carcinogens.

Class 1 carcinogens potentially cause cancer in humans. Dioxins are also known to have

adverse effects on the reproductive and developmental systems in humans. Exposure to

dioxins has led to infertility, suppressed immune systems, learning disabilities, diabetes,

and more7. Furans have been known to cause cancer in animals, and the FDA is currently

evaluating the effect on humans8.

2.2 Phosphorus Flame Retardants

Another family of retardants is the phosphorus containing ones. These act in the solid

phase as opposed to the halogenated which act in the gas phase. Phosphorus flame

retardants are particularly effective in plastics, such as cellulose, which contain a high

oxygen content4. The mechanism of phosphorus flame retardants is given below:

When heated, phosphates decompose to form polymeric phosphoric acid.

Figure 6: Initiation step for phosphate based flame retardants.

R CH2 CH2 PHeat

R CH CH2

O

+ P

O

HOR CH2 CH2 PHeat

R CH CH2

O

+ P

O

HO P

O

HO

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Figure 7: Formation of polyphosphate barrier

The phosphoric acid esterifies, dehydrates the oxygen-containing material, and causes

charring on the material it’s protecting.

Figure 8: Esterification stage

Figure 9: Charring stage

The chemical structure of char is not completely understood. It has been found to

be made of primarily of hydrogen and carbon. The chemical structure is

dependent upon the polymer from which it is created.

Phosphorus flame retardants can be used at lower concentrations than halogenated

flame retardants, but they tend to be more expensive the fore mentioned flame retardants.

This family of flame retardants is biodegradable and non-toxic.

2 P

O

HOHeat

OP

O

P

O

+ H2O2 P

O

HOHeat

OP

O

P

O

+ H2OP

O

HO P

O

HOHeat

OP

O

P

O

P

O

P

O

+ H2O

CH2 CH2 OP

O

P

O

+ CH2 CH2OP

O

P

O

O OHCH2 CH2CH2 CH2 OP

O

P

O

OP

O

P

O

P

O

P

O

P

O

P

O

+ CH2 CH2CH2 CH2OP

O

P

O

OP

O

P

O

P

O

P

O

O OH

+ HOHeat CH CH2 P

O

OP

O

P

O

CH2 CH2 O Charring+ HOHeat CH CH2 P

O

P

O

OP

O

P

O

CH2 CH2 O OP

O

P

O

OP

O

P

O

P

O

P

O

CH2 CH2 OCH2 CH2CH2 CH2 O Charring

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2.3 Nitrogen Flame Retardants

Another family of flame retardants is the nitrogen containing ones. The mechanism

for nitrogen flame retardants is not fully understood. It is known that nitrogen flame

retardants form cross-linked molecular structures that are relatively stable at high

temperatures. This works by physically inhibiting the pyrolysis process. This complex

structure promotes the formation of char. The release of nitrogen gas works to dilute the

flammable gases, thus reducing the flames. To be effective, nitrogen flame retardants are

often used in conjunction with other flame retardants or in high concentrations6.

2.4 Inorganic Flame Retardants

The final family of flame retardants is the inorganic family. There are a few different

inorganic substances that are effective at retarding flames in the temperature range that

plastics decompose, between 150 and 400°C4. The most commonly used flame retardant

is aluminum hydroxide. This hinders fire in three ways, and its mechanism is illustrated

below:

It decomposes into aluminum oxide and water at about 200°C.

2 Al(OH)3 → Al2O3 + 3H2O

The aluminum oxide forms a protective layer on the surface of the protected

material. The water, as steam, dilutes the flammable gas phase. Also, the

endothermic reaction absorbs heat energy cooling the material and slowing down

the pyrolysis process.

Magnesium Hydroxide is another inorganic flame retardant that acts in the same

mechanism as above; however it decomposes at higher temperatures (300°C). Boron

compounds act by releasing water and forming a protective glassy layer on material

surface. They can release boric acid to cause charring. While most inorganic flame

retards inhibit fire physically, antimony trioxide retards the flame chemically. It acts as a

catalyst in the breakdown of halogenated fire retardants. It reacts with the halogenated

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flame retardant to form antimony halogen compounds which are effective in removing H·

and OH· radicals4. Inorganic flame retardants can be relatively inexpensive; however

large concentrations are needed to be effective.

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3.0 The Flame Retardant Market

3.1 Global Market

Annually, more than two billion pounds of flame retardants are produced worldwide.

The primary use for flame retardants is in plastics. Textiles, paper and wood products,

adhesives and sealants, rubber products and coatings are all smaller divisions of the flame

retardant market9. The global market as of 2000 was valued at $2.1 billion. The

breakdown of the market is shown below10.

Figure 10: Global Market Breakdown

3.2 United States Market

The flame retardant market in the United States accounts for almost half of the global

market, with about one billion pounds produced nationwide. The US flame retardant

market is composed of over sixty suppliers. The value of the market is $1 billion9.

3.3 Flame Retardant Coatings

The flame retardant coating industry is relatively young, with the first patent being

issued in 1948. As of 1998, flame retardant paints and coatings made up 10% of the

phosphorus flame retardant family and were valued at $9 million7. Assuming that

coatings still make up 10% of the phosphorus market, the value of the flame retardant

coating market currently would be $27.6 million. The market is growing rapidly due to

an increase demand in specialty flame retardants.

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3.4 Market Projections

The demand for flame retardants in the United States is expected to increase 3.6% per

year and reach 1.1 billion pounds by 2008. The value of the market is supposed to

increase 5.9% annually to $1.3 billion. The average price for pound is increasing due to

an increase in the market of higher valued specialty flame retardants10.

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4.0 Problem Statement

With sharp increases in urban sprawl and increased reliance on fire prevention

methods, new flame retardant products are being researched and developed across the

globe. As a result of strict EPA standards and waste management regulations, the need

for effective, environmentally friendly flame retardants is at an all time high. A vast

majority of the formerly used halogenated flame retardants, specifically brominated ones,

are being phased out due to the potential health hazards that their side products can cause.

This family of flame retardants degrades into toxic byproducts including dioxins and

furans. The major concern arises from the high concentrations of brominated flame

retardants being sold currently and their geographic location, many of which are “found

far from the locations they are being used.”11 Figure 10 depicts the structure of four major

brominated flame retardants, whereas figure 11 reveals the structure of the their toxic side

products.

Figure 11: Chemical Structures of A) PBBs, B) PBDEs, C) HBCD, D) TBBPA12

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Figure 12: Chemical Structure of A) Dioxin B) Furan

One of the foregoing leaders in the flame retardant industry, Great Lakes Chemical,

has phased out production of two of their major selling brominated flame retardants,

penta-bromodiphenyl ether and octa-bromodiphenyl ether, effective in 2004 as a result of

noticeable recurrence and bioaccumulation in nature13. With a projected overall

increasing flame retardant demand over the next few years and a newly created gap in the

retardant market both domestically and internationally, the development of a marketable

highly versatile flame retardant is of high interest. This company, KVTV, intends to

develop an highly marketable, low cost and relatively versatile flame retardant. In the

same way, KVTV desires a product that has low bioaccumulation tendencies and is

biodegradable.

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5.0 Our Product

5.1 Pathway to Discovery

There are multiple potential pathways that can lead to the development of a new

flame retardant. With many pathways, however, there are even more technical and

consumer considerations to accompany each. Among these pathways include developing

a product based upon pure trial-and-error, laboratory research and development,

statistical prediction techniques and former conclusive research and experimentation with

existing products. While each of these respective methodologies has a certain level of

merit, each method of product development has varying sets of limitations. KVTV’s

product flame retardant was developed to have high thermal resistance, increased wood

charring effects and low vapor pressures at high temperatures. KVTV only examined two

of these product development techniques

5.1.1 Statistical Method

There is an abundance of statistical modeling techniques that relate the type of

functional groups on different molecules to the physical properties the molecule exhibits.

The Lydersen Method14 predicts the critical properties of non-hydrocarbon organic

compounds within reasonable levels of uncertainty. Estimating these values allows for

better predictions for vaporization enthalpies, saturation pressures and boiling points,

properties essential to developing effective flame retardants. For example, the critical

properties of acetic acid are known and tabulated in literature. A comparison of measured

and calculated critical values is shown in Table 3.

Table 3: Lydersen Predicted Critical Constants

Group

Description # ∆T ∆P ∆V Tr

calc/Trtable(K) Pr

calc/Prtable(bar) Vr

calc/Vrtable (L/mol)

Methyl 1 0.02 0.277 0.055

Alcohol 1 0.082 0.06 0.018

Carbonyl 1 0.04 0.29 0.06

Total 3 0.142 0.627 0.133

570/593

4% Error

72.3/57.8

25% Error

0.173/0.172

1.2% Error

24

The calculated reduced properties correspond closely to those experimentally determined.

The major problem surfaces when adding more groups to a non-hydrocarbon organic

chain. The estimation errors compound quickly resulting in calculated inaccuracies of

critical points. For example, tri-ethyl phosphate is claimed to have a predicted melting

point of 770K by the Lydersen Method; however, its recorded boiling point is

approximately 490K. The resulting error is nearly 37%.

5.1.2 Use of Thermoplastics

Thermosets, the precursor to thermoplastics, are more rigid non-melting class of

thermoplastics. They withstand high heat inputs and are relatively hard materials.

NASA’s development of high heat resistant thermosets to coat surfaces of fuel tanks and

engine encasings, areas that must withstand elevated temperatures, has switched from the

area of thermosets to that of thermoplastics15 because of their promising enhanced

durability and longevity.Thermoplastics16 are a class of materials that are deformable,

melt to liquid upon heating and dry to a solid when cooled. These classes of compounds

have increased heat resistant properties, moduli of elasticity and impact resistance.

Thermoplastics are a relatively modern technology that is increasingly being researched.

Because thermoplastics were known to have enhanced physical properties, the research

was directed at developing a similar thermoplastic that exhibited flame retardant

properties, that was biodegradable and that was non-toxic.

Substantial research17 has been performed on thermosets and thermoplastics to

determine their behavior as flame retardants. Hussein18 reports in his study of organo-

phosphorous and nano-clay additives to epoxy resins that the addition of even 7.5% and

3% phosphate can result in as much as 37% increase in time to material ignition. Similar

studies17 on vinyl ester resins reveal that the flash temperatures of the resins studied

increased by more than 3%. There are recorded studies concluding that thermoplastics

can be effectively used as flame retardants.

25

5.2 Synthesis Path

The flame retardant that KVTV developed is a thermoplastic material consisting of a

base substrate polymer, PVOH, to which nano-clay, phosphates and water are added. The

raw materials being used are polyvinyl acetate (PVAc), Cloisite ® Na+ 19, dimethyl-

methyl phosphonate20 and water. KVTV has cleverly named their product flame retardant

Freeze-Flame Nano. Freeze-Flame Nano is a product with estimated low vapor pressures

at high temperatures, relatively low volatility, increased boiling point temperatures and

high thermal resistance.

Varying the composition of raw materials alters the performance of the flame

retardant product. For instance, increasing cloisite concentrations results in higher

thermal resistances, whereas increasing phosphate concentrations results in a greater

degree of charring. Before these properties are evaluated, the product synthesis paths and

the product’s behavior when exposed to flame must be understood. KVTV’s first step in

flame retardant production involved the saponification of polyvinyl acetate using a strong

base. Experimentation with the saponification of PVAc21 with NaOH found it to be

highly selective toward the acetate group on PVAc; however, these experiments were

conducted with low base (NaOH) concentrations. To fully convert all the PVAc into

PVOH, a more concentrated base must be used. The reaction of PVAc with NaOH is

relatively mild with low estimated heats of dissociation. The reaction can occur at

temperatures ranging from 65oC to 95oC. Since the reaction is slightly exothermic, the

heat released during reaction elevates the temperature of the first reacting system (PVAc

with NaOH); however, since such large quantities are being produced, the heat gain is

considered negligible. Figure 12 illustrates the first step in the synthesis of Freeze-Flame

Nano. NaAc is a byproduct of the first reaction and can be sold at a reasonable cost.

26

Figure 13: Saponification of PVAc with NaOH to form PVOH

The second step in the reaction process is the heated blending of the PVOH with the

necessary amounts of cloisite. There are no required compositions of cloisite to make the

flame retardant work. This is addressed in subsequent sections. The key to creating the

final product is a result of complete mixing of the polymer and substrate slurry at

elevated temperatures less than 100oC. Complete mixing is essential to this reaction step

because it ensures that at any one point in time, there are equivalent amounts of polar

sites along the polymer chains available for positively charged cloisite molecules to bond.

as seen in figure X below. However, the alignment of the cloisite along the polymer chain

is not determined in the mixing stage but in the extrusion process. The alignment pattern

has pronounced effects on heat conduction into and across polymer coated surfaces.

Section 4.3 address these issues further.

Figure 14: Polar mixing of PVOH and cloisite.

+ NaOH(aq) + H—O—H C C

H

H H

OH

+ NaAc(aq) + H2O

C OCH3

C C

H

H H

O n n

+ NaOH(aq) + H—O—H C C

H

H H

OH

C C

H

H H

OH

+ NaAc(aq) + H2O

C OCH3

C C

H

H H

O nC OCH3

C OCH3

C C

H

H H

O n

C C

H

H H

O

C C

H

H H

O n n

C C

H

H H

OH

C C

H

H H

OH

+ N+

CH3

CH3

HTHT N+

CH3

CH3

N+

CH3

CH3

HTHT C C

H

H H

OH nδ-

N+

CH3

CH3

HTHT

……….

C C

H

H H

OH nδ-

N+

CH3

CH3

HTHT

……….

C C

H

H H

OH

C C

H

H H

OH nδ-

N+

CH3

CH3

HTHT N+

CH3

CH3

N+

CH3

CH3

HTHT

……….

27

Alcohol groups are attached to the polymer chain mostly in a head-to-tail fashion. When

the monomers combine in a head-to-head manner the resulting polar groups are more

concentrated and confined to one location on the chain. This does not necessarily have an

adverse effect on the complete mixing, but it may result in unprotected areas on the

material it’s protecting. Once the polymer is allowed to cure for a given length of time,

the resulting product is a molten slurry of polymer and clay.

This mixture is then extruded with the phosphate under high shear conditions in a

screw press extruder22 and either injection molded or cast into a large film (sheet). There

are advantages to both types of processing methods. The most pronounced effect is in

how the clay will align with the polymer. Injection molding tends to align the clay

parallel to the substrate, PVOH, adding heat resisting effects. Cast film molding,

however, often aligns the clay parallel to the substrate at the surface but becomes more

randomly dispersed toward the center of the sheet. Figure 15 depicts the random

dispersion of clay and phosphate in the product polymer blend.

Figure 15: A) Polymer blend B) Legend

The product can then be sold in sheets or pulverized into a powderous material and sold.

The final product has no well defined concentration of sites occupied by the phosphate

and the clay. If this were easily explainable, then it’s possible to assert that one could

easily manipulate the placement of the phosphate and clay; such is not the case. The final

step involves storing the flame retardant product. Final products are stored in large

horizontal containment vessels with enough capacity to hold one week’s worth of

product. Below is a proposed process flow diagram for our plant.

Polar Sites=

Clay=

Phosphate=

Polymer=

Polar Sites=

Clay=

Phosphate=

Polymer=

B A

28

Figure 16: Proposed process flow diagram

5.3 Retarding Mechanism

When exposed to elevated temperatures, the behavior of the system becomes quite

complicated. Initially, the coated material is exposed to a heat source of varying intensity.

The temperature profile across the coated barrier highly nonlinear, assuming a variable

heat source, with respect to distance across the retarding boundary layer. The temperature

of the protected material does encounter a substantial heat gain due to the relatively thin

flame retardant layer; however, thermal shock is prevented due to the ehanced heat

capacity of the Cloisite and its dispersion pattern as mentioned earlier. Correlations found

in the Handbook of Elastomers, Plastics and Composites23 predict increased thermal

conductivities based upon polymer filler orientation, and an example of how this is

determined can be found in the Appendix. As the surrounding conditions become more

volatile, the polymer coating gradually degrades creating infinitesimally small holes in

the polymer barrier. This allows excess heat to pass into the protected material in turn

causing the material to continue to heat unsteadily. Fortunately, the phosphates react via a

similar mechanism to that shown in figure(s) 6-9 to induce a char network across the

surface of the material inhibiting flame progression and intensity.

Tank 1 Tank 2

Storage

Tank

Pump 1Pump 2

L/L Sep.

Evaporator

Extruder

Conveyor

PVAc NaOH/H2O

NaAc

Cloisite

Phosphate

29

According to F. L. Browne, a chemist at the Forest Products Laboratory in the U.S.

Department of Agriculture24, “[flame retarding] wood and other cellulosic materials is

based on changing the pyrolysis mechanism from that of fast pyrolysis to that of slow

pyrolysis.” Fast pyrolysis tends to eject volatile and combustible gasses that can increase

wood burning. On the other hand, slow pyrolysis yields charcoal and vapors of low

flammability. Altering the mechanism from fast to slow pyrolysis is highly dependent to

the degree of char formation, which can be enhanced through phosphate char networks.

Few studies24 have been performed verifying the enhancement of char formation from

phosphates, but those that have examined char formation rates have found it to increase

flame retarding times and decrease flaming.If char formation is sufficient, then the wood

will glow and inevitably slow burning; however if the heat resistive properties of the

developed char layer are insufficient, then the wood will continue to combust. Figure 17

illustrates the basic behavior of the flame retardant.

Figure 17: Flame retardant protection pathway

5.4 Happiness

To accurately develop a marketable product, consumer preferences must be taken into

consideration. Being able to accurately identify what a consumer wants depends heavily

External heat source

Increasing surface temperature

More heat input

Surface formation of holes in polymer layer

Char barrier formation Combustible vapor

release High intensity

heat input Low intensity

heat input

30

on the type of product being developed; however, being able to accurately measure what

a consumer wants relates to the utility of the product. Utility25 is the measure of the

satisfaction gained from consuming or using a good or service. The goal is to somehow

relate consumer preferences to multiple properties of the product. By maximizing the

consumers’ utility, the true happiness value of the product can be estimated.

Based upon consumer surveys, it was possible to relate a consumers’ overall

happiness to characteristics of the product that can be altered to optimize happiness in the

final product. The major factors consumers consider when purchasing and using a flame

retardant were found to include: retardancy time, setting time, thickness, odor, effective

amount and toxicity. As well as the previous consumer considerations, KVTV has

included biodegradability as a measure of consumer’s utility and ultimately their

happiness. Happiness plots were then constructed to determine the effect that variations

in consumer factors would have on happiness. The list of figures below graphically

depicts relationship between consumer factors to overall happiness.

31

Retardancy Time

0

10

20

30

40

50

60

70

80

90

100

0 20 40 60 80 100 120 140 160 180 200

Time (sec)

% H

appi

ness

Setting Time

0

10

20

30

40

50

60

70

80

90

100

0 50 100 150 200 250 300

Setting Time (min)

% H

appi

ness

Thickness

0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7 8

# Applications

% H

appi

ness

Effective % Coated

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60 70 80 90 100

% Coated

% H

appi

ness

Figure 18: Overall happiness relative to changes in consumer attributes

The happiness relationships for odor, toxicity and biodegradability are somewhat

different in nature. For odor, overall happiness was associated to the type of odor

producing functional groups present in the flame retardant. The functional groups

considered were grouped into categories including hydrocarbons, alcohols/halogens,

carboxylic acids, ethers, aromatics, amines, ketones and mercaptans. Each functional

group was then assigned a numeric value ranging from 0 to 7, respectively, based upon

known odorous properties. For toxicity and biodegradability, a value of 0 or 1 was

assigned to the product: 0 for toxic non-biodegradable, 1 for non-toxic biodegradable or

any combination thereof. The next step involves relating the consumer defined properties

to the physical properties exhibited by the product. This is greatly accomplished by

defining models that alter physical properties based upon varying product compositions.

32

Retardancy time is interpreted as the duration of time between a material first being

introduced to the flame and its eventual ignition (combustion). As mentioned before, the

predominate manner to protect materials from burning is by forming surface char that

encourages slow pyrolysis, and few studies have been conducted on this phenomena. To

estimate the total retardancy time, a study24 of prolysis rates and char formation on

Douglas-Fir wood was used. This study measured the overall conversion of wood based

upon the mass of char formed and the mass of wood remaining after burning for different

time intervals.

,0

,0

chari

iii mm

mmX

−

−= Eqn. 1

Equation 1 shows the conversion of the wood based upon m0,i (the mass of component i

within the wood initially), mi (the mass of component i within the wood after burning for

a specific time interval), and mchar (the mass of char formed after burning for a specific

time interval). This conversion measurement can be related to retardancy time by

equation 2,

( )ni

RTE

ii XeA

dtdX avg

A

−=⎟⎟⎠

⎞⎜⎜⎝

⎛ −

1 Eqn. 2

which has been experimentally derived from burning wood. In this case, Ai is the

frequency factor, EA is the activation energy, R is the universal gas constant, Tavg is the

average temperature of the burning wood and n is the reaction order (assumed 1). Since

wood is comprised predominately of cellulose, lignin and hemicellulose, the overall

conversion can be represented by the fractional conversion of the wood components as

seen in equation 3, where wi’s are the mass fractions of the subcomponents in the wood,

and other terms are previously defined.

HH

TLL

TCC

TW

T wdtdXw

dtdXw

dtdX

dtdX

avgavgavgavg⎟⎠⎞

⎜⎝⎛+⎟

⎠⎞

⎜⎝⎛+⎟

⎠⎞

⎜⎝⎛=⎟

⎠⎞

⎜⎝⎛ |||| Eqn. 3

American Society for Testing and Materials, ASTM, standard for flame retarding time

has a threshold value 120 sec. This was our goal time, and by altering the composition of

phosphate the total retardancy time can be estimated assuming an allowable conversion

(15 % was assumed).

33

There are a number of factors to consider when evaluating the setting time of flame

retardant product. Setting time is a function of the flame retardants thickness, which, in

turn, is a function of the number of applications. The recommended number of

applications varies from 2 to 3 depending on the type of application required. To model

the time required to evaporate water from the product, a Gurney-Lurie26 approximation

was used.

0,,

,

AsA

AsA

CCCC

Y−−

= Eqn. 4

Y is the unaccomplished concentration change where CA,s, CA and CA,0 are the

concentrations of water at the surface of the coating, at the point measured and at the

reference point, a pre-defined depth beneath the retardant layer.

1xkDm

c

AB= Eqn. 5

This equation gives the relative resistance of the evaporating system, where DAB is the

diffusivity of water at a specified temperature, kc is the convective mass transfer

coefficient and x1 is the characteristic length or the thickness of the retarding layer.

1xxn = Eqn. 6

Here n represents the relative position of measurement. The value x is the point from the

surface where the measurement is made, and x1 is defined previously. In order to

determine the expected setting (drying) time, one more parameter must be included.

21x

tDX ABD = Eqn. 7

XD is a measure of the relative time required to dry, and t is the total time required. If Y,

m, n and the geometry of the drying surface is known, XD can be determined. From this

the total drying time can be estimated.

The third happiness model predicts overall happiness based upon the average number

of coats required by competitors. Most flame retardant vendors recommend a certain

number of applications, and the average of these values was used to estimate the point of

maximum happiness. The total number of applications necessary is proportional to the

thickness of the layer protecting the material. KVTV recommends anywhere from 2 to 3

34

coats with each coat being approximately 1mm thick. Deviations in the number of

applications effect the consumer’s happiness: more coats imply less happiness, etc.

The final happiness model relates overall happiness with respect to the effective

amount of flame retardant applied on the surface. Determining an effective amount

requires a basis material to be chosen. KVTV basis consists of a 10cm x 10cm x 2 cm

block of wood. Since there is an assumed thickness per coat and there is a basis volume,

the amount of flame retardant necessary to resist the flame can be calculated by

subtracting the total volume of the coated material from the total volume of the basis.

After all the models have been well defined, weights must be assigned to the

consumer properties. The weights can be assigned arbitrarily or can be based on

consumer preference. KVTV used a combination of both methods to determine the final

weights. The next stage requires the calculation of total happiness. The general equation

used to estimate consumer happiness is given by,

∑=i

ii yxH1 Eqn. 8

where xi are the assigned weights and yi are the normalized scores determined from the

consumer happiness models. The total sum of the weights must be equal to one. To

achieve the “perfect product,” or product with maximum happiness, the compositions of

KVTVs components are varied to produce the maximum happiness with the given

weights. Contrastingly, to achieve a marketable product, the compositions of the flame

retardant are varied in a manner that optimizes profit. Beta gives the ratio of happiness

between H2 the competitor’s happiness, and H1 KVTV’s happiness.

1

2

HH

=β Eqn. 9

Table 4 shows the weights used to determine the cost-effective product and the perfect

product.

35

Consumer Attribute Weight

Retardancy time 0.30

Thickness 0.15

Odor 0.15

Setting time 0.25

Effective amount 0.07

Biodegradability 0.04

Toxicity 0.04

Table 4: Relative weights assigned

For the cost-effective product the compositions are 50% PVOH, 15% Phosphorus,

3% Cloisite and 32% Water. For the perfect product the compositions are 50% PVOH,

27% Phosphorus, 3% Cloisite and 20% Water. These percentages were found using

excels solver function that altered initial composition guesses to a final composition that

produced the greatest happiness value. The percentages of our closest competitor, Firetect

WT-102 includes 18.4 % Polyvinylidine Chloride, 21.8 % Phosphate, 3.4 % Sodium salt

and 41.9 % Butyl Acetate. The happiness value, H1, for this cost-effective product is

0.868, whereas the competitor’s happiness value, H2, is 0.574. The optimal happiness was

roughly 0.930. The ratio of the competitor’s happiness value to KVTV’s happiness value

is given by β. For the cost-effective product, β=0.661, and for the perfect product,

β=0.617. Listed below are the weights KVTV assigned to the happiness model.

36

6.0 Business Model

6.1 Calculating Demand

Before KVTV can begin production on Freeze Flame Nano, it is important to

determine the demand for the product. The following equation relates the demand for

Freeze Flame Nano to the demand for KVTV’s main competitor, Firetect27, and their

flame retardant product WT-102.

⎟⎟⎠

⎞⎜⎜⎝

⎛= β

α

αβ2

12211 d

ddpdp Eqn. 10

β is the ratio of satisfaction given by Firetect’s product to the satisfaction given by

Freeze Flame Nano. α is a ratio of the consumers’ knowledge of both products. If α is

equal to one, this would imply an equal knowledge of both products. This number will

vary with time and is related to the extent of advertising. Before this product is out on

the market, at year 0, α is equal to zero. KVTV assumes that this number will increase

each year until it reaches a maximum of 0.8 at year 10. This is due to the fact that no

matter how aggressively Freeze Frame Nano is advertised, there is a portion of the

market that cannot be attained. When α was made any higher than 0.8, the demand for

Freeze Flame Nano did not increase.

KVTV must also take into consideration the budget constraints of the consumer. The

following equation shows that consumers cannot spend more money on flame retardants

than they have, and Y is the total budget that consumers have to spend on flame

retardants.

2211 dpdpY += Eqn. 11

Solving these two equations for d2, the demand for Firetect’s WT-102, and setting

them equal to each other gives the equation for determining the demand for KVTV’s

Freeze Flame Nano. β

α

βα

−

⎟⎟⎠

⎞⎜⎜⎝

⎛−⎟⎟

⎠

⎞⎜⎜⎝

⎛⎟⎟⎠

⎞⎜⎜⎝

⎛=

1

2

11

21

211 p

dppY

ppdd

Eqn. 12

This equation gives d1 as a function of d1 (Φd1), so to find the demand for each year a

graphical method was employed. First, the demand was varied and Φd1 was calculated.

37

The solid curve below shows how this function changes with demand. Next, the line d1 =

d1 was put on the same graph as shown by the dashed line. Where these two functions

intersect is at the demand for Freeze Flame Nano at that particular year. The example

below shows the demand for year 4 of this process.

Year 4

0

1,000,000

2,000,000

3,000,000

4,000,000

5,000,000

6,000,000

7,000,000

8,000,000

9,000,000

0 1,000,000 2,000,000 3,000,000 4,000,000 5,000,000 6,000,000

d1

phi (

d1)

This function, Φd1, will change for each year because the value of α changes as does

the budget that the consumer has to spend on flame retardants. This method was used for

each year and the demand found for each year is shown in the table below.

Table 5: Calculated demand over 10-year life cycle

Year Demand (lb/year)

1 19,000

2 930,000

3 3,900,000

4 4,900,000

5 5,300,000

6 5,500,000

7 5,800,000

8 6,000,000

9 6,300,000

10 6,700,000

38

6.2 Regret Analysis

It is not economically feasible for KVTV to rebuild the production plant each year to

meet the demand for that particular year. Therefore, before building can occur, a

decision must be made as to which capacity the plant will be built. To do this a regret

analysis is performed. A regret analysis shows how much money could be made by

building the plant at a certain capacity in comparison to how much could be made by

building at another capacity. Three designs were taken into account for this analysis.

The first design consists of building for the maximum capacity of 3.9 million pounds per

year which is the demand at year 3. The second design is for the demand at year 6, 5.5

million pounds per year. The final design is to build for maximum capacity at year 10,

6.7 million pounds per year. The net present worth (NPW) of each design was calculated

under three different scenarios. One scenario is that the prices of all byproducts, raw

materials, equipment, and utility costs remain the current prices. This is called the

“medium” scenario. The “low” scenario would be when all of these prices are 15%

below the current prices, and the “high” scenario would be when these prices are 15%

higher than current prices. To calculate the net present worth the following equation was

used.

TCIiSVWC

iCFNPW

nn

n −++

++

= ∑=

10

10

1 )1()1( Eqn. 13

The NPW for each design under each scenario is given in the table below. The next

table shows the regret which is the NPW for that design and scenario subtracted from the

maximum NPW that could have been obtained in that scenario.

39

Table 6: Comparison of design scenarios and their effective NPW

NPW Low Med High Average

Design 1 $ 3,604,323

$ (1,271,019) $ (6,146,351) $ (1,271,016)

Design 2 $18,887,671

$12,583,641 $ 6,279,608 $12,583,640

Design 3 $22,003,977

$15,314,316 $ 8,624,652 $15,314,315

Max $22,003,977

$15,314,316 $ 8,624,652

Table 7: Regret analysis results

Regret Low Med High Max Regret

Design 1 18,399,653

16,585,335

14,771,004

18,399,653

Design 2 3,116,306

2,730,675

2,345,044

3,116,306

Design 3 0 0 0 0 Minimax 0

Since there was no regret in using the third design, KVTV has decided to build its

plant for the maximum capacity of 6.7 million pounds per year. The capacity of the

major equipment used is shown in the table below, along with the cost for that piece of

equipment. The total equipment cost with piping was found to be $310,000.

Table 8: Equipment Specifications

Component Capacity Equipment Cost

Tank 1 7.2 m3 $40,000

Tank 2 4.1 m3 $25,000

Pump 1 4.9 kW $7,000

Pump 2 0.6 kW $5,000

Settler 6.8 m3 $76,000

Evaporator 3.2 m3 $25,000

Extruder 0.7 m3 $47,000

Storage 85 m3 $40,000

40

The total capital investment, which is calculated using the equipment cost, was calculated

be $1.7 million. A distribution of the NPW that could be attained by using design 3 with

a 15% standard deviation is shown below. The maximum NPW attainable was found to

be $23.8 million, while the minimum is $6.9 million. The average NPW was found to be

$15.3 million.

41

7.0 Business Plan

7.1 Organizational Plan

7.1.1 Company Description

KVTV, Inc. is a small, Texas-based flame retardant supplier. The mission of KVTV

is to provide a non-toxic, biodegradable flame retardant and excellent service to its

customers. The short term goals of KVTV are to provide a flame retardant that is

effective, easily applicable, odor-free, and non toxic to constructions companies

throughout our region of the United States, and to capture 3% of the current flame

retardant market. To ensure a consistent supply, KVTV has established a relationship

with Science Lab Chemicals and Laboratory Equipment in Houston, Texas and with

DuPont in La Porte, Texas. KVTV will remain a regional supplier for the first ten years.

The long term goals of KVTV are to expand nationally. After establishing a loyal

consumer base with local construction companies, KVTV will begin to supply flame

retardant to companies nation-wide.

7.1.2 Our Product

KVTV will primarily sell a flame retardant called Freeze Flame Nano (FFN). FFN is

a phosphorus-based, non-toxic, biodegradable flame retardant coating. FFN is a mixture

of phosphate, nano-clay, polymer, and water. Our basic supply will consist of polyvinyl

acetate(PVAc), sodium hydroxide, Cloisite (a silica based nano-clay), and phosphoric

acid. Approximately 2 million pounds per year of PVAc are needed, while our supplier,

DuPont, produces 135 million pounds per year. Similarly, Science Lab also produces an

excess amount of sodium hydroxide and phosphoric acid. The nano-clay will be

provided by Rockwood. KVTV will first obtain the polyvinyl vinyl acetate needed for

FFN by the saponification of PVAc with sodium acetate. Then, a predetermined amount

of phosphoric acid and nano-clay will be added to the polymer slurry to yield Freeze

Flame Nano. This slurry will be pumped to an extruder and then stored. One week’s

supply of FFN will be stored. FFN will be packaged and then shipped by truck all over

42

the region. FFN will be sold by the gallon. The primary industry for FFN is the

construction industry; however, it can also be used to coat plastics and electronics.

7.1.3 Plant Location

The location of the Freeze Flame Nano production plant will be Corpus Christi,

Texas. The raw material suppliers are located in Texas, which keeps shipping cost low.

The land in Corpus Christi is also relatively inexpensive. KVTV, Inc. has acquired a 5.8

acre lot for $300,000. The price of land in Houston, Texas was also looked into. It was

found to be $3 per square foot. An equivalent lot in Houston would therefore be about

$750,000. The total shipping costs of raw materials to the plant in Corpus Christi are

approximated at $120,000 per year. Shipping to and from Houston would only be

$90,000 per year, but over the ten year life span of this process only $300,000 would be

saved in shipping by building in Houston. Therefore, Corpus Christi was chosen. Also,

there is high demand for flame retardants in the southwestern portion of the United

States. Freeze Flame Nano could be easily shipped from the Corpus Christi plant to

construction companies in Houston, Dallas, or Kansas City.

7.1.4 Management

KVTV will be managed by two partners, Keshan Velasquez and Tyler Viani. Tyler

Viani will be the Operational Manager. His responsibilities include process and product

improvements, as well as future product discovery. Keshan Velasquez will be the

Financial Manger. Her responsibilities include strategic planning, budgeting, data

management, and continual marketing analysis. There will also be a process manager

and three process engineers who will oversee daily operations. The projected total

income for all management is $400,000 per year.

7.1.5 Personnel

KVTV will consist of twelve operators. The production of FFN will call for four

operators per shift, and two shifts per day. The average wages of the operators will be

approximately $24 per hour. Operators will be allowed to work up to 40 hours a week.

As KVTV expands, more operators will be added as needed.

43

7.1.6 Insurance

KVTV will obtain commercial property insurance, liability insurance, and flood and

hail insurance from the Texas Department of Insurance. All employees will be given the

option of life and health insurance through Primerica Life. This will cost KVTV

approximately $60,000 per year.

7.1.7 Security

KVTV is dedicated to the security of its employees and assets. The production plant

of KVTV will be continuously monitored by ADT. Inventory of all raw materials and

product will be taken every three months to ensure against theft.

7.2 Marketing Plan

7.2.1 Market Analysis

The United States flame retardant market accounts for half of the global market,

which amounts to one billion pounds of flame retardant being produced in the U.S. per

year. The flame retardant coating market accounts for over $10 million per year. KVTV

will at first target the construction industry in the Midwest region of the United States.

The target consumers are shown in the table below, along with their regional offices.

Table 9: Target Consumers

Consumer Regional Office Locations

Turner Construction Co. Dallas, TX; Houston, TX; Kansas City, MO;

Denver, CO

Hansel Phelps Construction Co. Austin, TX

J E Dunn Construction Co. Dallas, TX; Houston, TX; Fort Worth, TX;

Topeka, KS; Kansas City, MO; Denver, CO;

Colorado Springs, CO

Centex Construction Dallas, TX; Houston, TX; Plano, TX;

Oklahoma City, OK; Lawton, OK; Goldsby, OK

44

There are several flame retardant coating producers in the United States. Some

companies produce a flame retardant additive that is mixed into a gallon of paint. The

major competitors of KVTV for this type of flame retardant include Flame Guard,

Fireshield, and RoscoFlamex. Other flame retardants are sold by the gallon, like Freeze

Flame Nano. Our major competitors from this type of flame retardant include Flame

Stop, Firetect, and Contego International.

7.2.2 Market Trends

The demand for flame retardants is expected to increase 3.8% annually. Consumers

are increasingly concerned with fire resistance as shown by the decreasing number of fire

reported annually. The average price of flame retardants is expected to increase due to an

increase in the consumer demand for specialty flame retardants. The value of the flame

retardant market will therefore increase 5.9% per year.

7.2.3 Marketing Strategy

The fixed capital investment (FCI) for this process was calculated as a percentage of

equipment cost. The FCI was found to be $1.5 million, and the total capital investment

(TCI) is $1.7 million. The NPW for FFN was calculated to be $15.3 million. The return

on investment which is profit divided by total capital investment was found to be almost

250%. The NPW and ROI were also calculated for the “perfect” flame retardant, which

is the product with the compositions of phosphoric acid, nano-clay, polyvinyl alcohol,

and water that provided the maximum happiness. These values were determined to be

$13.6 million and 200% respectively.

Freeze Flame Nano will be sold directly from the plant located in Corpus Christi, TX

and also on the KVTV website. To ensure that a quality flame retardant is delivered to

the consumer, an employee of KVTV will measure the effectiveness of one batch of FFN

per day before the product is packaged. FFN will be packaged by the gallon.

The price of FFN is comparable to the costs of other flame retardant in the market.

The price will start at $6.19 per pound in 2006 and increase between 8 and 10¢ per year.

The average price of flame retardants currently on the market is $6.29 per pound. KVTV

will introduce its product at a price below the market average to maintain a competitive

advantage. KVTV will also offer discounts for large orders.

45

7.3 Financial Plan

7.3.1 Financial Need

The owners of KVTV will invest an initial $200,000 into the FFN production process.

However, this only accounts for a portion of the total capital investment required. To

obtain the additional $1.5 million needed, KVTV will seek financing from the Small

Business Administration. This money will cover the purchasing of land, and start up

costs for the plant. This money will be paid back by 2011.

7.3.2 Cash Flow Statement

The cash flow of each year for the first ten years of production was calculated by

subtracting the annualized fixed cost from the annual revenue from the selling of FFN

and sodium acetate, the byproduct of the saponification process. The varying demand for

FFN provides for a varying flow of cash in and out of the company. The following figure

shows the projected cash flow for the first ten years of production as well as the overall

cash balance.

$(20,000,000)

$(10,000,000)

$-

$10,000,000

$20,000,000

$30,000,000

$40,000,000

$50,000,000

2006

2007

2008

2009

2010

2011

2012

2013

2014

2015

2016

Cash FlowCash Balance

Figure 19: Cash Balance for KVTV, Inc.

46

7.3.3 Projected Balance Sheet

The projected balance sheet for KVTV is given below. Table 10: Balance Sheet Pro Forma Balance Sheet Assets Current Assets FY 2007 FY 2009 FY 2011 Cash $5,000,000 $65,000,000 $93,000,000Accounts Receivable $11,400,000 $25,400,000 $9,400,000Other Current Assets $300,000 $300,000 $300,000Total Current Assets $16,700,000 $90,700,000 $102,700,000 Long-Term Assets $610,000 $610,000 $610,000Depreciation $68,500 $137,000 $205,500Total Long-Term Assets $241,500 $173,000 $104,500Total Assets $17,241,500 $91,173,000 $103,104,500 Liabilities and Capital Current Liabilities Accounts Payable $121,500 $5,948,000 $4,050,000Current Borrowing $300,000 $600,000 $600,000Other Current Liabilities $0 $10,000,000 $1,967,500Long-Term Liabilities $30,000 $300,000 $300,000Total Liabilities $451,500 $16,848,000 $6,917,500 Paid-in Capital $170,000 $170,000 $170,000Retained Earnings ($25,000,000) ($84,200,000) ($93,300,000)Total Capital ($24,830,000) ($84,030,000) ($93,130,000)Total Liabilities and Capital

($25,281,500) ($100,878,000) ($100,047,500)

Net Worth ($8,040,000) ($9,705,000) $57,000

7.3.4 Break-Even Analysis

To determine how long in will take to repay all loans and investments, a break-even

analysis was done. The projected cash balance for each year is compared to the total

47

capital investment. When the two are equal, the plant is said to break-even. This plant is

expected to break even by 2011. The analysis is shown graphically below.

$(30,000,000)

$(20,000,000)

$(10,000,000)

$-

$10,000,000

$20,000,000

$30,000,000

$40,000,000

$50,000,000

2008 2010 2012 2014 2016

Series1Linear (Series1)

Figure 20: Break-Even Analysis

7.3.5 Risk Associated with Investing

To determine the risk involved in investing in Freeze Flame Nano, a risk assessment

was conducted using @risk. The prices in all raw material, equipment cost, and utility

cost were varied by 15%. The figure bellows shows a graphical representation of the risk

involved. Table 8 shows the mean, maximum, and minimum of the profit that can be

obtained.

48

Distribution for Design 3 NPW/J27

Mean = 1.531434E+07

X <=1897093695%

X <=116964535%

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

6 12 18 24

Values in Millions

Val

ues

in 1

0^ -7

Figure 21: Risk Distribution

Table 11: Variability in Profit

Mean $15.3 million Min $6.9 million Max $23.8 million

7.3.6 Supporting Financial Documents

The following table shows the total capital investment for the FFN plant. All costs

were taken to be a percentage of the total equipment cost.

Table 12: Total Capital Investment

Description of Cost % of Purchased Equipment

Total Cost

Direct Costs Purchased equipment 100 $310,000 Installation 53 $164,300 Instrumentation and controls 29 $89,900 Piping 34 $105,400

49

Electrical Systems 11 $31,400 Buildings (incl. services) 32 $99,200 Yard Improvements 13 $40,300 Service Facilities 60 $186,000 Total Direct Cost 330 $1,023,000

Indirect Costs Engineering and Supervision 35 $108,500 Construction expenses 37 $114,700 Legal expenses 5 $15,500 Contractor Fee 21 $65,100 Contingency 40 $124,000 Total Indirect Costs 138 $427,800 Table 4: Continued Fixed Capital Investment 469 $1,453,900 Working Capital (15% of TCI) 75 $232,500 Total Capital Investment 544 $1,686,400

The total annualized cost for 2016 is calculated below. A basis for estimation is also

given.

Table 13: Total Annualized Cost

Description of Cost Basis for Estimate Cost ($/yr) Manufacturing Cost Direct Production Cost + Fixed Charges + Plant

Overhead Cost $103,267,000

Direct Production Cost

Raw Material

Polyvinyl Acetate $1.41/lb at 15,313,000 lb/yr $21,590,000 Water $0.00024/lb at 4,053,000 lb/yr $973 Sodium Hydroxide $10/lb at 6,005,000 lb/yr $60,050,000 Phosphate $1.60/lb at 1,982,000 lb/yr $3,170,000 Cloisite $3.18/lb at 396,000 lb/yr $1,260,000 Operating Labor 4 employee/shift 2shift/day pay is $28.00/hr $787,000 Direct Supervision and Clerical

15% operating labor $118,000

Utilities $188,000 Laboratory Charges 15% of Operating labor $118,000 Patents and Royalties 1% of Total Annualized Cost $1,095,000Sub-total $88,480,000

50

Fixed Charges

Depreciation Calculated Separately

Property Taxes 2% of FCI $29,000 Insurance 1% of FCI $175,000 Financing 10% of fixed capital investment $146,000 Advertising $9,600,000Sub-total $9,950,000

Overhead costs 60% of Labor, Supervision, and Maintenance $992,000

General Expenses

Administration costs 20% of Labor, Supervision, and Maintenance $198,000 Distribution and Marketing Costs

5% of Total Annualized Cost $5,474,000

Research and Development

4% of Total Annualized Cost $4,379,000

Sub-total $10,051,000 Total Annualized Cost Manufacturing Cost + General Expenses $109,473,000

51

8.0 Conclusions and Recommendations

8.1 Conclusions

• Freeze Flame Nano is a durable, heat resistant, char-inducing flame retardant.

• It will bind to multiple surfaces, especially porous wood, because of the

polymer’s polar nature.

• KVTV believes Freeze Flame Nano will benefit the construction industry the

most as well as benefit a certain portions of the plastics and electronics industries.

8.2 Recommendations

• KVTV would like to find a closer and possibly a less costly source of polyvinyl

acetate.

• KVTV hopes to research a cheaper alternative to PVAc that has same

environmentally friendly qualities as PVAc.

• Rigorous ASTM standardized lab-scale tests must be performed on Freeze Flame

Nano to determine its true performance.

• KVTV should try to research adding a color line to their product Freeze Flame

Nano

52

9.0 References 1 United States Fire Administration. National Fire Statistics. Accessed March 2006. www.usfa.fema.gov/statistic/national/ 2 Virnbaum, L and Staskal, D. 2004. “Brominated Flame Retardants: Cause for Concern?” Environmental Health Perspectives Vol. 112: 9-17. (BFR Cause for Concern PDF). 3 The Combustion of Alkanes and Cycloalkanes. Jim Clark 2003. Accessed March 2006. <http://www.chemguide.co.uk/organicprops/alkanes/oxygen.html> 4 Troitzsch, J.H. “Overview of Flame Retardants: Fire and Fire Safety, Markets and Applications, Mode of Action and Main Families, Role in Fire Gasses and Residue.”Chemistry Today. February 1998. Vol. 16 (Overview of Flame Retardants PDF). 5 Kesner, Miri. Teaching about Flame Retardants. A Joint Israeli-Dutch Project. Science Teaching Department, The Weizmann Institute of Science, Rehovot, Israel. Accessed March 2006. <http://jchemed.chem.wisc.edu/HS/Journal/Issues/2001/ Jan/clicSubscriber/V78N01/p41.pdf> 6 EFRA. The European Flame Retardants Association. “Protecting Lives, Property and the Environment.” Accessed January 2006. <http://www.cefic-efra.com/> (cefic-eftra PDF) 7 ActionPA. “Dioxin Homepage.” Last Modified January 29, 2005. Accessed March 2006. <http://www.ejnet.org/dioxin/> (dioxin PDF) 8 U.S. Food and Drug Administration. “Questions and Answers on the Occurrence of Furan in Food.” May 7, 2004. Accessed March 2006. <http://cfsan.fda.gov/~dms/furanqa.html> (furan PDF) 9 Freedonia Group. “Demand to Grow 3.6% per Annum through 2008.” Flame

Retardants Report. January 2001. (Demand to Grow 3.6% PDF) 10 Lerner, Ivan. “FR Market Down but not Out: Albemarle Stays the Course.” Chemical Market Reporter. December 10, 2001. Page 12. (FR Market Down but Not Out PDF) 11 Birnbaum, L and Staskal, D. “Brominated Flame Retardants: Cause for Concern?” Environmental Health Perspectives. Vol. 112: 9-17. (BFR Cause for Concern PDF). 12 Perry, Robert H. Green, Don W. Perry’s Chemical Engineer’s Handbook. 7th Edition. McGraw-Hill 1997.

53

13 Tulio, Alex. Great Lakes to Phase Out Flame Retardants. Provided by Dr. Miguel Bagajewicz (Provided Article PDF). 14 Perry, Robert H. Green, Don W. Perry’s Chemical Engineer’s Handbook. 7th Edition. McGraw-Hill 1997. 15 Composites and Advanced Materials. U.S. Centennial of Flight Commission. Dwayne A. Day. Accessed March 2006 <http://www.centennialofflight.gov/essay/ Evolution_of_Technology/composites/Tech40.htm> 16 Thermoplastics. Accessed March 2006. <http://en.wikipedia.org/wiki/ Thermoplastics > 17 Mazali, Cristiana A. Ittner and Maria Isabel Felisberti. “Vinyl Ester Resin Modified With Silicone-Based Additives: II. Flammability Properties.” Instituto de Quimica, Universidade Estadual de Campinas, SP Brazil. Wiley InterScience. April 8, 2005. 18 Hussein, M. et al. “Effect of Organo-Phosphorus and Nano-Clay Materials on th Thermal and Fire Performance of Epoxy Resins.” School of Physics and Materials Engineering, Monash University, Clayton, Australia. Wiley InterScience. May 13 2003. 19 Southern Clay Products, Inc. Gonzales, Tx. 20 Chemistry Webbook. <http://webbook.nist.gov/chemistry/> 21 Kumakura, Rie and Kazuo Yamaura. “Gel-Spinning of Partially Saponificated Poly(vinyl alcohol). Faculty of Textile Science and Technology, Shinshu University, Japan. September 1999. 22 Polymer Extrusion. Ralph Bridge. University of Connecticut. Accessed March 2006. < http://www.salspolymer.com/sources/Polymer%20Extrusion.htm> 23 Harper, Charles A. Handbook of plastics, elastomers, and composites. 4th Ed. New York : McGraw-Hill, c2002.

24 Browne, F. L. “Theories of the Combustion of Wood and its Control.” Forest Products Laboratory, U.S. Department of Agriculture. <http://www.fpl.fs.fed. us/documnts /fplmisc/rpt2136.pdf> 25 Utility. Accessed March 2006. < http://en.wikipedia.org/wiki/Utility> 26 Welty, James R. et al. Fundamentals of Momentum, Heat, and Mass Transfer. 4th Edition. John Wiley & Sons, Inc. Copyright 2001. 27 Firetect flame retardant. <http://www.firetect.com/>

54

Appendix

Lydersen Calculations:

[ ]

[ ][ ]∑

∑

∑∑

∆+=

∆+=

∆−∆+=

Vc

P

c

TT

bc

V

MP

TT

04.0

34.0101325.0

567.0

2

2

Where ∆T, ∆P, and ∆V are the sum of the group contributions as found in Perry’s 7th, and

Tb is the normal boiling point and M is the molecular mass of acetic acid.

Pump Work Calculations:

( )cpipe

eqpipefo gD

LLVfzgVPW

++∆+

∆+

∆=

22

22ρ

Heater Duty Calculations:

TmCQ P ∆=

Economic Calculations:

( ) ( )TCI

iWCVCF

iCF

NPWn

kn

Snk

k −+

+++

+= ∑

−

=

1

1 11