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SOLAR WATER PURIFICATION WITH PET BOTTLES COATED

WITH TITANIUM DIOXIDE USING IMPROVED BINDING AGENTS

BY

ERIC RICHARD MORGAN

B.S. UNIVERSITY OF MASSACHUSETTS, AMHERST, MA (2002)

SUBMITTED TO THE FACULTY OF THE ENERGY ENGINEERING PROGRAM IN

PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF

MASTER OF SCIENCE

ENERGY ENGINEERING, SOLAR

UNIVERSITY OF MASSACHUSETTS LOWELL

2008

Signature of
Author: ____________________________ Date: __________________

Signature of Thesis
Supervisor: ____________________________________________
Name Typed: _Dr. John J. Duffy_____________________________

Signature of Other Thesis Committee Members:

Committee Member Signature: ___________________________________________


Name Typed: _Dr. Christopher Niezrecki______________________

Committee Member Signature: ____________________________________________


Name Typed: _Dr. Ramaswamy Nagarajan_____________________
SOLAR WATER PURIFICATION WITH PET BOTTLES COATED

WITH TITANIUM DIOXIDE USING IMPROVED BINDING AGENTS

BY

ERIC MORGAN

ABSTRACT OF A THESIS SUBMITTED TO THE FACULTY OF THE

ENERGY ENGINEERING PROGRAM

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS

FOR THE DEGREE OF

MASTER OF SCIENCE

ENERGY ENGINEERING, SOLAR

UNIVERSITY OF MASSACHUSETTS LOWELL

2008

Thesis Supervisor: John J. Duffy, D.Sc.


Professor of Solar and Mechanical Engineering
Copyright © Eric Morgan, 2008

ii
Abstract

Solar water purification with polyethylene terephthalate (PET) bottles coated with the

photocatalyst TiO2 has been shown to be very effective. Replacements for perchloric

acid as a binding agent were sought. Through experiments, it was found that titanium

dioxide thin films could be deposited on the surface of PET bottles by creating a

suspension with distilled water, titanium dioxide and any of seven binding agents. The

photoactivity of each titanium dioxide thin film was compared by filling 500 ml PET

bottles with a mixture of distilled water and indicator dye indigo carmine and subjecting

them to solar radiation. The photocatalytic effectiveness of each thin film was determined

by measuring the temporal presence of indigo carmine using a spectrophotometer. It was

found that all thin films behaved in a similar fashion despite different masses of titania

being present on each bottle. Sodium acetate was found to be the best overall replacement

for perchloric acid because it performed as well as perchloric acid in photocatalytic

testing, is inexpensive, has a desirable safety rating, and can be manufactured in remote

areas with baking soda and vinegar.

iii
Acknowledgements

I would like to thank my friends at the Solar Lab in Lowell for their warmth and kindness

over the last several years. I would like to thank my friends and collaborators Manuel

Heredia and Robert Williams who enriched my solar water purification research on many

levels. I would like to thank John Duffy, my thesis advisor, for giving me the opportunity

to do this research. I would like to thank Christopher Niezrecki and Ramaswamy

Nagarajan as members of my thesis committee. I would like to thank my parents who

have supported me for as long as I can remember. I would like to thank my brother, Tom,

who spent long hours with me discussing the chemistry used in this thesis and even

longer hours editing my drafts. I would like to thank my wife, Frances, who encouraged

me throughout my graduate career in Lowell; your love and support enabled me to

complete this work.

iv
Table of Contents
Abstract .............................................................................................................................. iii
Acknowledgements ............................................................................................................ iv
Table of Contents ................................................................................................................ v
List of Figures ................................................................................................................... vii
List of Tables ..................................................................................................................... ix
1. Introduction ..................................................................................................................... 1
1.2 Objective ................................................................................................................... 4
1.3 Approach ................................................................................................................... 4
1.4 Organization .............................................................................................................. 5
1.5 Literature Review...................................................................................................... 6
1.5.1 UV Radiation ..................................................................................................... 6
1.5.2 SODIS ................................................................................................................ 9
1.5.3 Titanium Dioxide ............................................................................................. 11
1.5.4 Perchloric Acid ................................................................................................ 14
1.5.5 Advanced Oxidation Process ........................................................................... 15
2. Methodology ................................................................................................................ 19
2.1 Chemical Selection ................................................................................................. 19
2.2 Experimental Setup ................................................................................................. 27
2.2.1 Indigo Carmine ................................................................................................ 27
2.2.2 Beer-Lambert Law Analysis of Indigo Carmine ............................................. 30
2.2.3 Experimental Apparatus for Testing Indigo Carmine Decay .......................... 32
2.2.4 Standard Error in Chamber Measurements ...................................................... 34
2.2.5 Experimental Design ........................................................................................ 35
2.2.6 Bottles Used ..................................................................................................... 36
2.2.7 Coating Bottles................................................................................................. 38
2.2.7 Bottles Coated with Perchloric Acid................................................................ 39
2.2.8 Acceptable Coating – Visual and Practical Analysis ....................................... 39
3. Results and Discussion ................................................................................................. 41
3.1 – Phase I of Testing Chemicals ............................................................................... 41
3.1.1 Coated Bottles .................................................................................................. 42
3.1.2. Visual Evaluation of the Coated Bottles ......................................................... 54
3.1.3 Mass of Titania Film Before and After Rinsing .............................................. 56
3.2 Phase II – Testing the Bottles Under Actual Field Conditions ............................... 58

v
3.2.1 Procedure for Testing Bottles. ......................................................................... 58
3.2.2 Initial Durability Experiment on the Roof of Engineering Building, March 17,
2008........................................................................................................................... 59
3.2.3 Experiment – Photoactivity of Titania Coatings at 0oC with Low Solar
Insolation, Roof of Engineering Building, March 19, 2008 ..................................... 61
3.2.4 Experiment – Immersing Titania in Water for Two Weeks, May, 2008 ......... 63
3.2.5 Phase II Conclusions ........................................................................................ 64
3.3 Phase III – Evaluating the New Coatings against the Perchloric Acid Coatings.... 64
3.3.1 Bottle Effectiveness – Removing Indigo Carmine from Water ....................... 65
3.3.2 Preliminary Selection of Binding Agent .......................................................... 69
3.4 Coating Bottles Using Sodium Acetate Created from Baking Soda and Vinegar .. 72
3.4.1 Preparing Sodium Acetate ............................................................................... 72
3.4.2 Coating Bottles with BSVSA........................................................................... 75
3.4.3 Evaluating Baking Soda/Vinegar Sodium Acetate (BSVSA) ......................... 75
3.5 Bacterial Testing ..................................................................................................... 80
3.5.1 Serial dilutions and plating .............................................................................. 81
3.5.2 Coliscan® Method ........................................................................................... 84
3.5.3 Bacterial Testing Results ................................................................................. 85
3.6 Final Evaluation of Sodium Acetate as a Replacement for Perchloric Acid as a
Binding Agent. .............................................................................................................. 88
4. Conclusions .................................................................................................................. 90
5. Recommendations ....................................................................................................... 93
6. Bibliography................................................................................................................. 96
7. Appendix ..................................................................................................................... 100
7.1 Concerns ............................................................................................................... 100
7.1.1 Degree of Health Hazards .............................................................................. 100
7.1.2 Degree of Flammability Hazard..................................................................... 100
7.1.3 Degree of Instability Hazard .......................................................................... 101
7.1.4 All Chemicals Used and Their Ratings .......................................................... 102
7.2 TiO2 ...................................................................................................................... 103
8. Biographical Sketch of the Author ............................................................................. 105

vi
List of Figures
Figure 1 – The Electromagnetic Spectrum Covering Small Wavelength Gamma Rays to
Long Wavelength Radio Waves. (Treiman, 2005) ............................................................. 7
Figure 2 – Spectral Distribution of Sunlight and Molecular Absorption............................ 8
Figure 3 – Depiction of SODIS ........................................................................................ 10
Figure 4 – Photoreduction and Photooxidation with Titanium Dioxide
(www.davidonindustries.com, 2008) ................................................................................ 13
Figure 5 – Molecular Structure of EDTA ......................................................................... 23
Figure 6 – Molecular Structure of Tartaric Acid .............................................................. 23
Figure 7 – Molecular Structure of Bicine ......................................................................... 24
Figure 8 – Molecular Structure of Citric Acid .................................................................. 24
Figure 9 – Molecular Structure of Na3 Citrate .................................................................. 24
Figure 10 – Molecular Structure of Na2 EDTA ................................................................ 25
Figure 11 – Molecular Structure of L-Aspartic Acid........................................................ 25
Figure 12 – Molecular Structure of Sodium Dihydrogen Citrate ..................................... 25
Figure 13 – Molecular Structure of 4-Aminobutyric Acid ............................................... 25
Figure 14 – Molecular Structure of 4-Aminobenzoic Acid .............................................. 26
Figure 15 – Molecular Structure of Sodium Acetate ........................................................ 26
Figure 16 -- Molecular Structure of Indigo Carmine ........................................................ 28
Figure 17 -- Photodegredation Products and Reactions Showing the Activity of TiO2 on
Indigo and Indigo Carmine (Vauntier, Guillard, & Herrmann, 2001) .............................. 29
Figure 18 – Absorption Spectra for Indigo Carmine at Different Concentrations ........... 30
Figure 19 – Absorption as a Function of Concentration for Indigo Carmine .................. 31
Figure 20 -- Beer-Lambert Law for Indigo Carmine ........................................................ 32
Figure 21 – Experimental Setup for Measuring Optical Changes in PET Bottles............ 33
Figure 22 -- PET Chemical Structure, n Represents the Number of Repeating Monomers
........................................................................................................................................... 36
Figure 23 – Absorption and Transmission of UV Radiation in PET ................................ 37
Figure 24 – Spectra in the Experimental Chamber ........................................................... 38
Figure 25 – PET Bottle Covered with TiO2 Using EDTA................................................ 43
Figure 26 – PET Bottle Covered with TiO2 Using Tartaric Acid ..................................... 44
Figure 27 – PET Bottle Covered with TiO2 Using Bicine ................................................ 45
Figure 28 – PET Bottle Covered with TiO2 Using Na3 Citrate ........................................ 46
Figure 29 – PET Bottle Covered with TiO2 Using Sodium Acetate................................. 47
Figure 30 – PET Bottle Covered with TiO2 Using Na2 EDTA......................................... 48
Figure 31 – PET Bottle Covered with TiO2 Using L-Aspartic Acid ................................ 49
Figure 32 – PET Bottle Covered with TiO2 Using Sodium Dihydrogen Citrate .............. 50
Figure 33 – PET Bottle Covered with TiO2 Using 4-Aminobutyric Acid ........................ 51
Figure 34 – PET Bottle Covered with TiO2 Using 4-Aminobenzoic Acid....................... 52
Figure 35 – PET Bottle Covered with TiO2 Using Citric Acid ........................................ 53
Figure 36 – Side by Side Comparison of TiO2 Coatings. Coating Done January, 2008. . 54
Figure 37 – Original Six Solutions after 85 Days L-R: 4-Aminobenzoic Acid, Citric Acid,
4-Aminobutyric Acid, Sodium Acetate, Bicine, Sodium Dihydrogen Citrate ................. 55
Figure 38 – Initial and Final Mass of Titania on One Bottle ............................................ 57
Figure 39 – Mass of Titania Lost after First Rinse. .......................................................... 57

vii
Figure 40 – Normalized Mass of Titania Decrease after Rinsing ..................................... 58
Figure 41 – Bottles on the Roof of the Engineering Building during Testing March 17,
2008................................................................................................................................... 59
Figure 42 – Bottles coated with from L-R Perchloric acid 2%, Perchloric acid 4%,
Sodium Dihydrogen Citrate, 4-Aminobutyric Acid, No Coating, Citric Acid, 4-
Aminobenzoic Acid, Bicine and Sodium Acetate. Top: Bottles after 15 Minutes of
Exposure to Sunlight with Middle Bottle Unexposed. Bottom: Bottles after 30 minutes of
Sunlight with Middle Bottle Unexposed. Test Done March 17, 2008.............................. 60
Figure 43 -- Bottles Tested under Freezing Weather Conditions, Sitting in Slush.
Experiment: March 19, 2008 ............................................................................................ 62
Figure 44 -- Bottles after One Hour of Exposure to Diffuse Solar Radiation at 0°C.
Experiment: March 19, 2008 ............................................................................................ 62
Figure 45 -- Decay of Indigo Carmine after 2 Hours during Freezing Conditions........... 63
Figure 46 – Bottles after 2 Weeks of Immersion in Water ............................................... 64
Figure 48 – Indigo Carmine Absorption Spectra, March 26, 2008 .................................. 66
Figure 49 – Change in Absorption of Indigo Carmine for all Coated Bottles after 1 Hour
of Sun Exposure. Experiment Done on 3-26-2008. .......................................................... 66
Figure 50 – Indigo Carmine Absorption Spectra, April 1, 2008 ...................................... 68
Figure 51 – Decay of Indigo Carmine after One Hour of Sun Exposure. ........................ 68
Figure 51 – Preparing Sodium Acetate Using Baking Soda and Vinegar. ....................... 77
Figure 52 – Bottles Coated with BSVSA ......................................................................... 75
Figure 53 – Decay of Indigo Carmine in the Presence of BSVSA ................................... 77
Figure 54 – Mass of Titania Lost after First Rinse, Including BSVSA ............................ 77
Figure 55 Economics of Rinsing Bottles .......................................................................... 78
Figure 56 – Serial Dilutions of Bacteria for Counting Colonies. ..................................... 82
Figure 57 – Bacteria vs. Optical Density Curve for Determining CFUs .......................... 83
Figure 58 – Coliscan® Plates from Left to Right, No Coating, No Coating, Sodium
Acetate, Sodium Acetate; Top to Bottom, at 15 Minutes, 30 Minutes and 45 Minutes. .. 86
Figure 59 – Bacterial Death after 45 minutes of sun exposure. ........................................ 87
Figure 60 – Bacterial Death after 2 Hours of Sun Exposure Using the Binding Agents
BSVSA, Sodium Acetate, Perchloric Acid and No Coating. ........................................... 88

viii
List of Tables
Table 1 – Standard Error Measurements in Chamber ....................................................... 35
Table 2 – The Appearance of Each Titanium Dioxide Film on PET as well as the Ease of
Manufacturing and Color. ................................................................................................. 55
Table 3 – Decay of Indigo Carmine Absorptance for the Experiment Conducted on
3/26/2008 .......................................................................................................................... 67
Table 4 – Pricing and Hazard Information for Each Binding Agent ................................ 72
Table 5 – Median Lethal Dose for Each Binding Agent .................................................. 72
Table 6 – Molecular Weights of the Products and Reactants for Making Sodium Acetate.
........................................................................................................................................... 74
Table 7 – Masses Needed for a Stoichiometric Reaction Given Different Values of
Vinegar Acidity in Order to Produce Sodium Acetate. .................................................... 76
Table 8 – Bacterial Counts in CFU/100mL.(TNTC=Too Numerous to Count) ............... 88
Table 9 – All Chemicals Used in the Thesis and Their Ratings ..................................... 102

ix
1

1. Introduction

It is estimated that 1.8 million people die each year from diarrhoeal diseases,

eighty-eight percent of which are due to unsafe drinking water (World Health

Organization/UNICEF, 2005). Worldwide, 1.1 billion people (17% of global population)

lack access to safe drinking water and 2.6 billion people (42% of global population) lack

access to proper sanitation facilities (World Health Organization/UNICEF, 2005). These

are staggering numbers. In the age of technology we can and must work to reduce these

numbers and eradicate unnecessary illnesses and deaths. In order to do so work must be

done on global, national and local scales. This thesis aims to focus on the most local of

local scales – water treatment at the point-of-use.

While there are many methods of water purification, there are only a few that are

practical in remote rural areas of the world. Chlorination is practical for small

communities but is difficult to implement at the point-of-use. Pasteurization and boiling

are effective ways to eliminate bacteria, molds, yeasts and protozoa from drinking water.

Both methods require heating water to elevated temperatures – 65°C for pasteurization,

100°C for boiling – for short periods of time. Pasteurization can be done effectively in

remote areas using solar cookers (Ciochetti & Metcalf, 1984); boiling usually requires

burning biomass which is discouraged because it promotes the destruction of local forests
2

that are used for other purposes. Neither pasteurization nor boiling eliminates any

chemical contaminants – some of which cause severe health effects such as increased risk

of cancer, kidney and liver problems and nervous and reproductive system problems.

Slow sand filtration is considered to be an effective water purification technique for small

scale applications (Huisman & Wood, 1974). However, slow sand filtration requires a

large land area, manual cleaning of the filters and water with low turbidity levels. In

addition, organic pollutants such as bacteria and organic chemicals are not fully removed

from the water using this technique (National Drinking Water Clearinghouse, 2000).

As a response to the inadequacies of conventional water purification methods an

inexpensive process called Solar Water Disinfection (SODIS) was developed. SODIS can

reduce water-borne pathogens by filling plastic bottles (mainly polyethylene terephthalate

or PET) with water and exposing them to direct sunlight. SODIS is ideal for rural areas

because it requires only small volumes of water (<2 liters/bottle) and because it depends

only on sunlight for disinfection (EAWAG & SANDEC). SODIS is able to effectively

eliminate biological contaminants such as bacteria. However, it is not ideal for removing

chemical pollutants because it does so too slowly.

Advanced Oxidation Process (AOP) has been developed, in addition to SODIS, to

address the issue of water-borne bacterial pollutants as well as chemical pollution. AOP

uses titanium dioxide, or titania (TiO2), as a photocatalyst to reduce or oxidize organic

materials in water by creating super-radicals and peroxides from the water itself. The

superoxides and radicals act to destroy organic pollutants including both bacteria and

organic chemicals such as fertilizers, pesticides and herbicides that may be present in

drinking water.
3

Typically, colloidally suspended titania or titania bound to immersed surfaces is

used. The former method requires separation of the titania from the water after

purification, while the latter only requires a method for immobilizing the titania as a film.

Colloidal titania has been separated from water by microfiltration (Geissen & Xi, 2001)

and by flocculation due to aluminum chloride (Kagaya, Shimizu, Arai, & Hasegawa,

1999). Immobilization appears to be more efficacious for small villages because it does

not require microfiltration apparatuses or prolonged processes to recover flocculated

titanium dioxide particles.

Meitchtry et al. (2005) reported perchloric acid (pH 2.5) as an effective agent at

immobilizing TiO2 onto the polyethylene terephthalate surfaces. However, perchloric

acid in its pure form is categorized as a superacid with a pKa of -7. It is extremely

hazardous being both corrosive to skin and highly exothermic when in contact with

organic materials and is therefore undesirable to handle, especially by inexperienced

individuals. For this reason it is necessary to investigate the ability of other less toxic and

less hazardous acids to bind the titania to the PET.

The author, as part of the University of Massachusetts Energy Engineering

Program, has selected, evaluated and tested several alternatives to perchloric acid. The

alternatives are less toxic, and safer to work with than perchloric acid. In addition, the

chemicals selected are inexpensive and more readily accessible than perchloric acid in

developing countries.
4

1.2 Objective
The objectives of this thesis are the following:

1. Eliminate perchloric acid in the manufacturing process of titanium dioxide

coated bottles. The analysis will focus on several alternative chemicals and

their effectiveness at binding the titania to the surface of the PET.

2. Evaluate the alternative binding agents under field conditions. The binders and

titania should be compatible such that the titania does not affect the binder and

the binder does not affect the titania.

3. Analyze the mass of titania adhered to the bottles across all of the binding

agents. Determine the most cost effective binding agent.

4. Test the effectiveness of the new coatings at destroying the indicator dye indigo

carmine as well as the bacterium E. coli and compare the results to the

perchloric acid coating.

1.3 Approach
Criteria for the chemicals used to bind the titania to the PET were devised and

evaluated. Eleven organic chemicals were selected for preliminary testing based on

commercial availability and safety of handling. To determine the utility of the organic

acids as binding agents the PET was subjected to the titania-chemical suspension and the

film that was formed was examined for uniformity, durability and chemical activity.

Several possibilities including Tartaric Acid, L-Aspartic Acid, Trisodium Citrate, EDTA

and Disodium EDTA were discarded because the PET remained hydrophobic after
5

treatment with the suspension. The remaining chemicals were further investigated by

subjecting them to natural sunlight and ambient wind and temperature conditions

outdoors on a gravel roof (this will be referred to as “field conditions”) in the presence of

the indicator dye indigo carmine as well as the model bacteria E. coli.

1.4 Organization
Chapter two provides general background information on ultra violet (UV) radiation

and its effect on bacteria. SODIS is defined and described as a water purification

technique that uses UV radiation to eliminate bacteria and viruses. The Advanced

Oxidation Process (AOP) which uses titanium dioxide to treat water is introduced.

Background information about titania and its photochemical reactions is also established.

Chapter three introduces the experimental design; details the hazards of perchloric

acid; lists criteria for selecting appropriate alternative chemicals; describes the alternative

chemicals; and expounds the procedure for determining the suitability of the chemicals.

Chapter four reviews the results of testing the coatings under field conditions.

Chapter five discusses the conclusions of the experiments as well as suggests future

research in the field.


6

1.5 Literature Review

This section contains a discussion of the underlying science of solar water

purification as well as a review of solar water purification literature including SODIS and

the Advanced Oxidation Process (AOP) using titanium dioxide.

1.5.1 UV Radiation

Electromagnetic radiation is composed of discrete energy packets called photons.

Each photon propagates as a wave with two distinct, oscillating, mutually perpendicular

fields – the electric field and the magnetic field – that are both perpendicular to the

direction of propagation. The frequency (ν) of the radiation refers to the number of

oscillations that the fields go through each second; the wavelength (λ) of the radiation

refers to the length of one oscillation. Frequency has units of per second (1/s) and

wavelength has units of length, thus it can be inferred that the velocity (units of length

per second) must be frequency times wavelength, or Velocity = ν* λ. The velocity of

electromagnetic radiation – regardless of the frequency or wavelength – in a vacuum is a

constant, c, with a value of 2.9979*108 m/s. The energy of each photon is not the same

and is given by the relation:

hc
E = hν = (Equation 1)
λ

where h is Planck’s constant (6.626*10-34 J*s).

The electromagnetic spectrum (See Figure 1) categorizes photons having of

energies into separate spectral regions.


7

Figure 1 – The Electromagnetic Spectrum Covering Small Wavelength Gamma Rays to Long Wavelength Radio
Waves. (Treiman, 2005)

The electromagnetic radiation emitted by the sun covers much of the electromagnetic

spectrum and is referred to as the solar spectrum (Figure 2, red line). Some of the

radiation emitted by the sun is absorbed or reflected by the Earth’s atmosphere resulting

in reduced radiation at the Earth’s surface (Figure 2, blue line).


8

Figure 2 – Spectral Distribution of Sunlight and Molecular Absorption.

The spectra of the sun’s light at the surface of the sun (red) and at Earth’s surface (blue). The differences are due to
absorbed and reflected light in the Earth’s atmosphere. Absorbed light is due mainly to water, oxygen, ozone, and
carbon dioxide. (LEARN London Metroplitan University, 2004)

Ultraviolet radiation (UVR) is typically defined by the spectral region between

100 and 400 nm, although these values may vary slightly across disciplines. Of these,

UVR can be further categorized as UVA photons (400-320 nm) which are not absorbed

by ozone and constitute about 94% of the UV radiation incident on the Earth’s crust;

UVB photons (320-280 nm) which are only partially absorbed by ozone and constitute

about 6% of the UV radiation reaching the Earth’s crust; and UVC photons (280-100 nm)

which are strongly absorbed by ozone and thus do not reach the Earth’s crust in

abundance (Diffey, 2002). UVB photons, despite being fewer in number than UVA,

account for approximately eighty percent of biological damage, with UVA photons

responsible for twenty percent (Diffey, 2002).

It is thought that UV radiation inactivates pathogens by disrupting DNA

replication and/or causing mutations in DNA structures after cellular repair (Oates,
9

Shanahan, & Polz, 2003). UV also acts indirectly by creating superoxides (O2-) and

hydrogen peroxide (H2O2) from water (Gelover, Gomez, Reyes, & Leal, 2006; Oates,

Shanahan, & Polz, 2003). Furthermore, because water absorbs strongly in both the

infrared and red region of the spectrum the temperature increases when exposed to

sunlight. It has been shown that elevated temperatures (45-55o C) contribute to the

disinfection process (Joyce, G, Elmore-Meegan, & Conroy, 1996; EAWAG & SANDEC)

and that there is a synergistic effect of temperature and UV if, and only if, the water

temperature is above 45 oC (McGuigan, Joyce, Conroy, Gillespie, & Elmore-Meegan,

1998). Many pathogens can be inactivated at temperatures much lower than the boiling

point if exposed to UV light for a sufficient period of time (EAWAG & SANDEC).

1.5.2 SODIS
As a response to the inadequacies of conventional point-of-use water purification

methods Solar Water Disinfection (SODIS) was developed as an inexpensive alternative.

SODIS reduces pathogens by exposing water-filled plastic bottles (mainly polyethylene

terephthalate or PET) to sunlight. SODIS is primarily used to disinfect small volumes of

water (<2 liters/bottle) and depends only on sunlight for disinfection (EAWAG &

SANDEC), making it ideal for rural areas.


10

Figure 3 – Depiction of SODIS

(EAWAG & SANDEC)

There are, however, some crucial drawbacks. While SODIS may be effective at

reducing the levels of water-borne pathogens, it does nothing to mitigate inorganic or

organic chemical waste that may be present in water. In addition, several variables

including water turbidity (a measure of water clarity), total solar radiation, and ambient

air temperature affect the disinfection process. It has been also been suggested that the

efficacy of SODIS is related to the amount of dissolved oxygen in the water at the time of

treatment (Reed, 1997).

During periods of meteorological cloudiness it may be necessary to leave the

bottles outside for two days or more to ensure disinfection (Gelover, Gomez, Reyes, &

Leal, 2006). Even then, the water must be consumed immediately because remaining

pathogens could potentially incubate. A study by Rincon and Pulgarin (2004) showed

that using in SODIS bacterial levels dropped during periods of illumination but the

bacteria recovered during periods of darkness. Further, they showed that bacteria can
11

recover during periods of intermittent sunlight, as would be expected in real-life

applications. We must therefore conclude that while SODIS is effective under ideal

weather conditions, it may not be effective under poor weather conditions. Water storage

after SODIS could result in the regrowth of pathogens and contribute to illnesses or even

death.

In order to increase the efficiency of the SODIS process, solar photocatalytic

disinfection (AOP) was developed using titanium dioxide (titania, TiO2) as a

photocatalyst. This method promises to increase the rate of disinfection of

microorganisms while eliminating organic pollutants, such as fertilizers herbicides and

pesticides. Titanium dioxide works much like SODIS in that it, too, generates hydroxyl

radicals, peroxides and superoxides. However, the photooxidation and photoreduction

capabilities of AOP are superior to those of SODIS for the destruction of E. coli bacteria

(Rincon & Pulgarin, Comparative evaluation of Fe3+ and TiO2 photoassisted processes

in solar photocatalytic disinfection of water, 2006; Duffy, et al., 2004; Gelover, Gomez,

Reyes, & Leal, 2006) and organic chemical effluents.

1.5.3 Titanium Dioxide

Titanium is a Group 4 transition metal in the periodic table, having the symbol Ti

and the atomic number 22. It is the fourth most abundant metal and the ninth most

abundant element (Carp, Huisman, & Reller, 2004) in the Earth’s crust comprising about

0.6% by mass (Zumdahl & Zumdahl, 2003). However, it is never found in its pure form

in nature. Instead, it is found as oxides in mineral form such as rutile (impure TiO2),

ilmenite (FeTiO3) and anatase (impure TiO2) (Zumdahl & Zumdahl, 2003; Carp,
12

Huisman, & Reller, 2004). Both rutile and anatase as well as one other – brookite – are

mineral forms of titanium dioxide (also titanium (IV) oxide or titania) differing only in

their crystalline configuration.

Titania is characterized as an n-type semiconductor due to oxygen vacancies

(Carp, Huisman, & Reller, 2004). This implies that the valence band of the material is

filled with electrons and that the conduction band has available space for these electrons.

Enough energy, as dictated by the band gap, must be provided for an electron to be

promoted to the conduction band from the valance band. This energy comes in the form

of photons whose energy is equal to the energy of the band gap. The bandgaps for rutile

and anatase titanium dioxide are 3.02 eV and 3.20 eV, respectively – corresponding to

wavelengths of 384 nm and 410 nm (Carp, Huisman, & Reller, 2004). If a photon

promotes an electron from the valence band to the conduction band a “hole” with a

positive charge is left in the valence band.:

(
TiO2 + hv → TiO2 ⋅ ecb− + holevb+ ) (Equation 2)

Once this occurs, the electron in the conduction band is available to reduce materials

while the hole in the valence band is available to oxidize materials. This is an essential

feature of titanium dioxide that will be exploited to reduce and oxidize both organic and

inorganic molecules.
13

Figure 4 – Photoreduction and Photooxidation with Titanium Dioxide (www.davidonindustries.com, 2008)

Often, recombination of the electron and the hole occurs and heat is given off, as

show in equation (3):

( )
TiO2 ⋅ ecb− + holevb+ recomb
→TiO2 + heat (Equation 3)
This reaction is responsible for the low quantum efficiencies of the photocatalyst.

However, the heat produced from the recombination increases the temperature of the

water and helps to inactivate or kill bacteria.

Several radicals that are responsible for photooxidation and photoreduction are

created in the process of absorbing a photon. The reactions that cause radicals and

peroxides are given below.

The superoxide radical is formed by the addition of a single electron:

O2 + ecb− ⇒ O2−• (Equation 4)


Hydrogen peroxide is formed during the reaction:

2O2−• + 2 H aq+ → H 2 O2 + O2 (Equation 5)


14

The OH radical is formed from either the reaction of water with an electron hole:

( )
H 2 O + TiO2 holevb+ → OH • + H + (Equation 6)
or through the reaction of a hydroxide ion with a hole:

( )
TiO2 holevb+ + OH adc

⇒ OH • + TiO2 (Equation 7)
It is evident from these reactions that the photoactivity of titania is critical to the

formation of these highly reactive species.

1.5.4 Perchloric Acid

Perchloric acid, HClO4, is a superacid with a pKa of -7. It is an extremely strong

oxidizer of organic compounds and can cause explosions due to intense exothermic

reactions. Furthermore, it is extremely corrosive and causes severe burns upon inhalation,

ingestion, skin contact or eye contact. Goggles, shields, lab coats, aprons, exclusive fume

hoods and proper gloves are recommended for anyone handling perchloric acid.

The bottle coating process involves mixing the aqueous perchloric acid with

titanium dioxide and pouring the solution into plastic bottles. The dangers of mixing the

perchloric acid with titanium dioxide are paramount; mistakes could not only affect those

directly working with perchloric acid but also, through inhalation or explosions,

bystanders. In remote villages in developing countries, proper laboratory equipment such

as fume hoods, showers and eyewashers may not be readily available. If exposed,

technicians – or those around them – may be hours from the nearest hospital or clinic.
15

Therefore, it is inadvisable for anyone in remote areas to handle, store or transport

perchloric acid.

When the solid salts of sodium perchlorate, ammonium, potassium, and perchloric

acid dissolve in water, the perchlorate anion (ClO4-) is produced (Motzer, 2001). The

perchlorate ion, being of a similar size to the iodide ion, can upset normal thyroid

function, and thus metabolism, in mammals (Urbansky, 2002). The threat of perchlorates

in the environment is, to date, unknown so the Environmental Protection Agency (EPA)

placed perchlorates on the Contaminant Candidate List in 1998. California passed the

Perchlorate Contamination Prevention Act of 2003 which implements best-management

practices for perchlorates (Perchlorate, 2007).

1.5.5 Advanced Oxidation Process

Photocatalysis by titanium dioxide, also known as an advanced oxidation process

(AOP, sometimes called solar photocatalytic disinfection or SPC-DIS), offers several

advantages over SODIS which make it very attractive for implementation in the field.

First, AOP is able to oxidize organic chemicals as well as organisms by producing

hydroxyl radicals (OH*), hydrogen peroxide (H2O2) and superoxide radicals (O2*).

Meichtry, et al., (2005) reported that photocatalytic degradation of 4-chlorophenol and

2,4-dichlorophenoxyacetic acid was possible; Duffy, et al., (2004) reported complete

photodegradation of isopropanol. It has also been shown that titanium dioxide is more

effective than SODIS at disinfecting water polluted with fecal and total coliforms

(Gelover, Gomez, Reyes, & Leal, 2006; Rincon & Pulgarin, Field solar E. coli

inactivation in the absence and presence of TiO2: is UV solar dose an appropriate


16

parameter for standardization of water solar disinfection?, 2004). AOP was able to

oxidize all total coliforms in fifteen minutes versus sixty minutes for SODIS alone.

Similar results held true for fecal coliforms. Most importantly, bacterial regrowth was

observed for SODIS for a period of seven days after disinfection, whereas AOP showed

no regrowth over this seven day timeframe. This indicates that most or all bacteria were

oxidized and were, therefore, unable to reproduce.

There are two main methods of implementing titanium dioxide as a photocatalyst

– suspension and immobilization. Suspension involves mixing the powered TiO2 with

water in reactors such that the TiO2 is uniformly distributed in the medium. Once

dispersed, the TiO2 is exposed to sunlight so that it can begin to create the reactive

radicals break down the organic matter in the water. Because the TiO2 powder is white,

the water will become turbid which will decrease the penetration depth of sunlight into

the water. However, the surface area of the titania will be large so as to generate more

radicals, thus offering more efficient disinfection. The main problem with this method is

that it requires separation of the titania from the water either by microfiltration or by

other means such as flocculation. Though there are several separation methods, they are

not practical for remote areas. For example, one microfiltration system involves using a

fine membrane, a pH meter, a pH controller, a peristaltic pump, a centrifugal pump and

other equipment to achieve separation (Geissen & Xi, 2001). Another example, this one

using aluminum chloride to achieve particle flocculation, uses a microfilter, hydrochloric

acid and a centrifuge to separate the coagulated titanium dioxide particles (Kagaya,

Shimizu, Arai, & Hasegawa, 1999). These processes are cumbersome and unrealistic to

implement in rural areas that have little access to outside help or resources.
17

Immobilization of TiO2 has been studied to avoid the issue of separation. Several

authors ( (Rincon & Pulgarin, Comparative evaluation of Fe3+ and TiO2 photoassisted

processes in solar photocatalytic disinfection of water, 2006; Lonnen, S, Kehoe, Al-

Touati, & McGuigan, 2005; Salih, 2003; Meichtry, et al., 2007), have reported on the

effectiveness of immobilized titania on both destroying pollutants and disinfecting water.

The process is promising for use in rural areas for several reasons. First, it uses less

titanium dioxide than conventional suspension reactors and is roughly forty times more

efficient by mass at killing bacteria than suspended titania (Rincon & Pulgarin, Field

solar E. coli inactivation in the absence and presence of TiO2: is UV solar dose an

appropriate parameter for standardization of water solar disinfection?, 2004). Second,

there are several methods for immobilizing the titania on plastics including using the use

of silicone adhesives similar to caulking (Lonnen, S, Kehoe, Al-Touati, & McGuigan,

2005) and using TiO2 in a perchloric acid solution (Meichtry, et al., 2007). The former

spreads a thin coating of black silicon on an acetate transparency sheet, covered with

powdered titanium dioxide and allowed to dry for 24 hours. The sheet is then shaken,

washed and dried overnight. The coated acetate is then trimmed and inserted into a PET

bottle. The latter uses perchloric acid as a binding agent, lets the bottle dry overnight and

then rinses off excess titania with distilled water.

Acetate strips are feasible for production in small communities for distribution to

remote areas. However, they may block UV light, leaving pockets of untreated water or

they may introduce contamination upon removal. Bottles coated using perchloric acid are

potentially dangerous to people and the environment due to the toxicity of perchloric acid
18

itself. If perchloric acid can be replaced with an equally efficient, low risk, inexpensive

binding agent, the technology can be an effective water purification tool.

Though immobilization of titania and the effectiveness of photocatalytic

disinfection have been studied there is a dearth of data showing the practical aspects of

these two techniques when utilized in field conditions. For example, SODIS has been

used and studied for many years so there is a wealth of information on the fate of the PET

bottles during use. However, because photocatalytic disinfection technology is inchoate

there is no equivalent data on the coated PET bottles that have been used in practice.

Recent research on a visual indicator that serves as a model for microbial

destruction has been conducted with promising results (Dubro, 2006). Indigo carmine has

been used because it is both non-toxic and, like bacteria and many organic molecules, is

sensitive to hydroxyl radicals. The benefits of indigo carmine are two-fold. First, because

it was shown to conservatively correlate with microbial destruction (Dubro, 2006) it can

be used in experiments as a substitute for the representative bacteria E. coli with little loss

of integrity. Second, it can be tested in “real-life” scenarios for possible adverse or

favorable interactions with the various immobilizing agents. There is no literature on the

interactions between the byproducts of photocatalytic degradation of indigo carmine and

the immobilizing agents proposed in this thesis. While the chemical analysis of such

reactions is beyond the scope of this thesis, it is important to be cognizant of the possible

side-reactions and take account of them during experiments.


19

2. Methodology

This chapter describes the criteria for selecting chemicals for experimentation and

the chemicals selected for experimentation. It also details the experimental setup

including the chamber used experimentation; the bottles used and the photo-sensitive dye

indigo carmine; the bottle coating process used for all bottles; and the definition of an

acceptable coating.

2.1 Chemical Selection


The focus will be on coating techniques and durability of PET bottles. Several

chemicals were selected for immobilizing the titanium dioxide onto PET bottles using

criteria proposed and detailed below. The coated bottles will be used repeatedly outside,

in ambient weather conditions so that the efficacy of the titanium dioxide coating can be

determined. The immobilized titanium dioxide must not flake off or otherwise dislodge

from the bottle’s surface after subjected to multiple stresses like filling and emptying,

squeezing or abrasion from contact with the ground or roof. If the titanium dioxide

remains immobilized further tests will be conducted to ensure that the advanced oxidation

process is effective. Specifically, it is necessary to measure the effectiveness of the

photocatalytic degradation of indigo carmine for each of the binding agents compared to
20

the perchloric acid coating. These parameters will provide an additional metric to

determine the overall feasibility of immobilized titanium dioxide in the field.

Given the hazards of working with perchloric acid it is incumbent on engineers to

find suitable alternatives. Because no underlying mechanism or attribute is given in the

literature for the use of perchloric acid to coat PET bottles, it is difficult to choose

substitutes with the necessary characteristics. The choice to use perchloric acid could

stem from a number of possibilities including:

• Perchloric acid oxidizes the PET and forms binding sites for the TiO2.

• There is an electrostatic reaction that occurs due between the perchloric acid,

the titania and the PET.

• The acidity of the perchloric acid affects the surface of the PET creating sites

for the titania to bind to.

The initial hypothesis was that the pH of the solution was an indicator of the

ability of the titania to bind to the plastic. For example, the lower the pH, the better the

agent would be. This approach offered a simple starting point for the choice of binding

agent.

Basic criteria were employed in order to select chemicals from the myriad of

possibilities that could achieve a coating similar to that of perchloric acid. The criteria

that needed to be met by the chemicals were as follows:

1. Safety in handling chemicals by trained individuals. It is assumed that non-ideal

laboratory conditions exist in developing nations and therefore chemicals should


21

be benign to both humans and their environment. The chemical should ideally be

safe to work with and not require redundant or excessive safe-handling equipment

such as fume hoods or gas masks.

2. The purified water needs to be potable. The chemicals used should be non-toxic to

humans.

3. The chemical needs to be both inexpensive and attainable to developing countries

where the technology will be used. The target end-users are those that do not have

potable water and likely have little income or money. In addition, the countries

that employ this technology are developing nations and have little money to spend

on programs of this stature.

4. Finally, the chemical needs to act to create a uniform thin film of titania on the

surface of the PET. This film should be durable and be able to withstand repeated

exposure to sunlight (UV) as well as repeated refills of water. It is not sufficient to

produce a coat in a plastic bottle if the coating is not durable.

With these criteria and the hypothesis that pH is a major factor in binding titania

two initial acids were chosen: acetic acid and phosphoric acid. Acetic acid is the

ingredient in vinegar that gives it the sour taste; phosphoric acid is used in colas to

provide a “bite” when consumed and in fertilizers. It should also be noted that acetic acid

is an organic acid while phosphoric acid, like perchloric acid, is a mineral acid. When

titania is illuminated with UV light it oxidizes organic compounds and therefore may

destroy the organic acids – a possible reason that perchloric acid – a mineral acid – was

chosen over organic acids.


22

Acetic acid and the phosphoric acid were each mixed with water and monitored

with a glass electrode pH probe until they reached pH 2.55 and 2.35 respectively. The pH

was verified with colorimetric pH paper. The procedure employed by Meichtry et al.

(2007) for coating bottles with perchloric acid was adapted for acetic acid and phosphoric

acid. In brief, titanium dioxide was added to the acidic solutions and the resulting agents

were poured into the PET bottles. The bottles were then rolled around so that the agents

could coat the inner walls.

Upon trying to coat the bottles, it was found that acetic acid at pH 2.55 left a

uniform, thin film similar to that of the perchloric acid coat, while the phosphoric acid at

pH 2.35 produced no coat at all.

The results nullified the hypothesis that the lower the pH the better the adherence

of the titania. In addition, it also showed that organic acids and mineral acids can both be

effective coating agents. However, the results inspired two other notable, but mutually

exclusive, hypotheses:

1. A pH close to 2.5 would produce a uniform coat.

2. The pH does not matter; the chemical reaction between the plastic, the titania and

the chemical dictates the adherence capabilities.

It seemed likely that the first hypothesis was false and the second one was true.

To test each hypothesis simultaneously several more organic chemicals were selected

using the aforementioned criteria. The eleven other chemicals selected for testing were as

follows:
23

1. Ethylenediaminetetraacetic acid (EDTA, Figure 5). This was chosen because it is

readily available. It is used as a preservative in foods, soft drinks, water softeners

and is considered non-toxic.

Figure 5 – Molecular Structure of EDTA

2. Tartaric Acid (Figure 6). This exists naturally in many fruits such as bananas and

grapes (wine, too) and can be considered non-toxic in small quantities.

Furthermore, this acid tests the hypothesis that pH is a determining factor of the

ability of a chemical to bind titania to PET.

Figure 6 – Molecular Structure of Tartaric Acid

3. N,n-Bis(2-Hydroxyethyl) glycine (Bicine, Figure 7). This was chosen because it

is readily available, nontoxic and is inexpensive.


24

Figure 7 – Molecular Structure of Bicine

4. Citric Acid (Figure 8). Citric acid occurs naturally in many fruits including

lemons, limes and oranges. It is readily available and non-toxic in dilute mixtures.

Figure 8 – Molecular Structure of Citric Acid

5. Trisodium Citrate (Figure 9). This is a sodium salt of citric acid. It is used as a

food preservative and is an ingredient in some drinks. It is relatively nontoxic and

readily available.

Figure 9 – Molecular Structure of Na3 Citrate

6. Disodium EDTA (Figure 10). This is a sodium salt of EDTA.


25

Figure 10 – Molecular Structure of Na2 EDTA

7. L-Aspartic Acid (Figure 11). This is a naturally occurring amino acid and is vital

to protein synthesis. It is readily available, inexpensive and non-toxic.

Figure 11 – Molecular Structure of L-Aspartic Acid

8. Sodium Dihydrogen Citrate (Figure 12). This is monobasic salt of citric acid.

Figure 12 – Molecular Structure of Sodium Dihydrogen Citrate

9. 4-Aminobutyric Acid (Figure 13).

Figure 13 – Molecular Structure of 4-Aminobutyric Acid

10. 4-Aminobenzoic Acid (Figure 14)


26

Figure 14 – Molecular Structure of 4-Aminobenzoic Acid

11. Sodium acetate (Figure 15). Sodium salt of acetic acid. Abundant, inexpensive

and a used as a preservative in some foods as well as a salt in others.

Figure 15 – Molecular Structure of Sodium Acetate

This list contains both acids and salts of acids. By selecting these chemicals the

hypothesis that a pH near 2.5 determines the adherence capabilities can be tested; the

hypothesis that pH does not matter is also tested because the salts of the acids exhibit a

wide range of pH values in water.

A simple procedure has been developed to determine the efficacy of each

chemical. Because the physical mechanism of binding the titania to the PET was

unknown the procedure adopted was that of trial-and-error. All chemicals obtained were

in their crystalline form.

The procedure was developed so that it is practical in remote locations and is outlined

below:

1. One quarter of a teaspoon of the chemical of interest was added to the bottle.
27

2. Water was added in increments. The hydrophobicity of the PET was visually

observed. If there existed any hydrophobicity no more water was added.

3. Titania was added slowly and in increments. The ability of the solution to coat the

PET was observed. If a coating formed no more titania was added. This was done

for each of the eleven chemicals.

It should be stressed that this procedure was crude but acted as a foundation and starting

point for designing other coating experiments. With this procedure, several chemicals

were completely eliminated as potential binding agents.

2.2 Experimental Setup

2.2.1 Indigo Carmine

Indigo carmine (Figure 16) is an organic dye also known as 5,5’-indigodisulfonic

acid sodium salt. It has the molecular formula C16H8N2Na2O8S2 and a molar mass of

466.36 g/mol. It is widely used in the textile industry for dying wool and cotton fabrics,

as well as in the chemical industry as a pH indicator. Indigo Carmine is sensitive to the

radicals produced by the photoexcitation of titania. Therefore, it can be used as a proxy

for the utility of the titanium dioxide at killing bacteria.

Figure 17 shows typical products and reactions from the photodegradation of

indigo carmine. It is noteworthy that complete mineralization of indigo carmine using

titanium dioxide yields only four chemicals – CO2, SO42-, NO3-, and NH4+.
28

Figure 16 -- Molecular Structure of Indigo Carmine


29

Figure 17 -- Photodegradation Products and Reactions Showing the Activity of TiO2 on Indigo and Indigo Carmine
(Vauntier, Guillard, & Herrmann, 2001)
30

2.2.2 Beer-Lambert Law Analysis of Indigo Carmine

To determine the concentration of indigo carmine in a treated solution, it was

necessary to construct a Beer-Lambert plot of the concentration as a function of

absorption. The absorption at 611 nm was determined for a series of known

concentrations of indigo carmine and the equation of the linear regression was found.

In brief, a 6.4 millimolar solution of indigo carmine was prepared in water and the

peak absorption value at 611 nm was recorded using a Spectra EPP 2100

spectrophotometer. The absorption was monitored over successive dilutions until the

limit of detection was reached (Figure 18).

Absorption vs. Wavelength for Indigo Carmine

2.50

.75g/L
Absorption (Arbitrary Units)

2.00
.375g/L

1.50 .1875g/L

.09375g/L

1.00
.046875g/L

0.50

0.00
500 550 600 650 700
Wavelength (nm)

Figure 18 – Absorption Spectra for Indigo Carmine at Different Concentrations


31

Beer-Lambert Law Plot for Indigo Carmine

3.50

3.00
Absorption (Arbitrary Units)

2.50

2.00

1.50

1.00

0.50

0.00
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50
Concentration (g/L)

Figure 19 – Absorption as a Function of Concentration for Indigo Carmine

The Beer-Lambert Law begins to break down above ~0.75 g/L of indigo carmine. The

linear region is plotted in Figure 20.


32

Absorption vs. Concentration for Indigo Carmine in Water

2.5
y = 3.2044x
Absorptance (Arbitrary Units)

R² = 0.9934
2

1.5

0.5

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Concentration (g/L)

Figure 20 -- Beer-Lambert Law for Indigo Carmine

The equation for the linear regression relates the absorption to the concentration

for any concentration of indigo carmine in water between zero 0.05 grams per liter and

0.80 grams per liter. The regression line is forced through zero because at zero

concentration there should be no absorptance.

2.2.3 Experimental Apparatus for Testing Indigo Carmine Decay

A sample chamber was constructed so that experiments could be carried out in a

uniform and reproducible manner (Figure 21). The chamber was build based on several

criteria that were chosen to reduce the variability between measurements. Specifically,

the chamber had to be opaque to outside light; easily opened and closed; have

controllable ultraviolet and visible spectra; a reflective interior; have a spectrophotometer


33

probe fixed at one point inside the chamber; have a platform so that position fluctuations

of the bottles are minimized.

With these criteria a box 15” high, 11” wide and 11.5” deep was constructed out

of ½” thick plywood with a removable ½” thick plywood door. A 3/8” hole for the

spectrophotometer’s probe was drilled in the center of one side of the box at 3” from the

bottom of the box’s exterior. On the opposite side, a 1” hole was drilled at 3” from the

bottom of the box’s exterior for a UV light that was wired into the box on the opposite

side from the probe. A small clear plastic platform was placed beneath the probe and

marked with a circle to indicate the sample bottle position. Finally, the interior was lined

with aluminum foil to improve the detection limits.

1. 2. 3. 4. 5 6. 7.
.

Figure 21 – Experimental Setup for Measuring Optical Changes in PET Bottles.


34

Experimental chamber for determining optical changes in bottles filled with indigo carmine. 1. Incandescent light

source. 2. UV light source. 3. Chamber and front cover. 4. Bottle on platform. 5. Optical probe in wall of chamber. 6.

Spectrophotometer. 7. Laptop running proprietary computer program.

2.2.4 Standard Error in Chamber Measurements

The consistency of the measurements in the chamber was evaluated using the dye indigo

carmine dissolved in water in PET bottles. The procedure for doing so is outlined below:

1. Fill one label-free PET bottle with 500 ml of distilled water and place it on the

platform in front of the probe.

2. Turn both the incandescent and UV lights on and take a reference measurement

using the spectrophotometer’s custom program.

3. Turn the lights off and take a “dark” measurement.

4. Remove the reference bottle and replace it with another PET bottle filled with 500

ml of distilled water and indigo carmine.

5. Measure the absorbance of the indigo carmine.

6. Record the peak measurement at a 610 nanometer wavelength.

7. Fully remove the bottle from the chamber and put back on the platform.

8. Repeat steps 5-6 24 more times for a total of 25 measurements.

This procedure was done with three different concentrations of indigo carmine and

tabulated in Microsoft Excel and presented in Table 1. Indigo carmine #1 had a

concentration of 0.130 g/L; indigo carmine #2 had a concentration of 0.095 g/L; indigo

carmine #3 had a concentration of 0.065 g/L.


35

Indigo Indigo Indigo


Carmine Carmine Carmine
#1 #2 #3
Average
Absorption 0.4137 0.305 0.2069
(A.U.)
StDev 0.0059 0.0059 0.0052
StErr 0.0012 0.0012 0.001
Table 1 – Standard Error Measurements in Chamber

The results show the average, standard deviation and standard error of

measurements. The standard deviation was within 2.5% of the average, indicating that the

technique was reproducible over the course of 25 measurements. The error is insensitive

to the concentration, suggesting that dilute solutions may be difficult to analyze.

2.2.5 Experimental Design

The effectiveness of each coating must be systematically evaluated using several

criteria to determine the best overall substitute for perchloric acid, and is broken down

into three distinct phases of testing. The initial phase of the experiments is designed to

test the ability of each chemical to immobilize the titanium dioxide on the surface of the

polyethylene terephthalate; the second phase tests each coating under realistic field

conditions and is designed to determine if there is a distinction between the different

coats that passed the initial test. The third phase of testing focuses on one coating that fits

several critical parameters and its performance compared to a perchloric acid coating.

The binding agent must have low health, fire and reactivity ratings as described in

the MSDS sheet. The titania must adhere strongly to the bottle (Phase I). The decay rates

of indigo carmine must be comparable to the bottles coated using the perchloric acid

solution (Phase II). The binding agent must be easily obtained in small rural areas or
36

developing nations where the technology is likely to be employed. The most suitable

coating, based upon the above criteria, will be recommended for implementation in the

field.

The approach adopted relies on the representative organic contaminant indigo

carmine degradation tests for water exposed to sunlight for a fixed time. Additionally, the

bacterium Escheria Coli (E. coli) was used as a model biological contaminant.

The experiments were performed during the Spring and Summer of 2008 on the

roof of the Engineering Building on the North Campus of the University of

Massachusetts Lowell.

2.2.6 Bottles Used

The bottles used were 500 ml Poland Springs water bottles which are made of

polyethylene terephthalate (PET), a polyester commonly used for water and soda bottles.

The monomer PET has the chemical formula C10H8O4 and is one component of the larger

polymer chain Figure 22.

Figure 22 -- PET Chemical Structure, n Represents the Number of Repeating Monomers

The bottles have nine ringed ridges and are clear and colorless. The transmittance and

absorbance spectra of PET were measured in using an EPP200 spectrophotometer from


37

StellarNet Inc. The bottles exhibit strong absorption in the 300 nm to 330 nm range, but

are weakly absorbing across the near-UV and visible region Figure 23.

Absorption and Transmission of UV Radiation in PET

0.80 100.00

90.00
0.70
80.00
0.60
Absorption (Arbitrary Units)

70.00

Transmittance (%)
0.50
60.00
Absorption
0.40 50.00
Transmittance
40.00
0.30
30.00
0.20
20.00
0.10
10.00

0.00 0.00
300 320 340 360 380 400
Wavelength (nm)

Figure 23 – Absorption and Transmission of UV Radiation in PET

Importantly, the PET bottle is able to transmit the majority of the light at 380 nm and 410

nm, which are required for photocatalytic destruction of organic materials by titania.

Due to their cylindrical shape, the PET bottles have a focusing effect when struck

with direct light. Therefore, when in the field, the bottles will focus the incoming

irradiation onto the surface perpendicular to the oncoming beam. The effects of this can

be seen in Figure 24. Because the sensor is on the back surface of the bottle and is

parallel to the incoming light, the water-filled bottle registers higher levels of light across

the spectrum.
38

Spectra for Testing Box

4.00E+03

3.50E+03
Empty
Relative Intensity (Arbitrary Units)

Box
3.00E+03
Plastic
2.50E+03 Bottle

Filled
2.00E+03
Plastic
Bottle
1.50E+03

1.00E+03

5.00E+02

0.00E+00
300 400 500 600 700 800
Wavelength (nm)

Figure 24 – Spectra in the Experimental Chamber

2.2.7 Coating Bottles

Meichtry et al (2007) expounded a method to coat bottles with a perchloric acid

solution, but no theoretical basis for the choice of acid was given. The method required

ultrasonicating the titania-perchloric acid solution for 30 minutes before coating. This

step was left out of the present work because it is not feasible for small rural villages.

The author of the present work, with guidance from Manuel Heredia Muñoz, devised

a method of coating the bottles using the new chemicals, water and the titanium dioxide

that is based on the method proposed by Meichtry et al (2007). The procedure proposed

was as follows:

1. Clean each bottle with distilled water and let dry, upside-down overnight.
39

2. Mix thoroughly 20 mL of deionized or distilled water with 2 grams of the binding

agent and 1.1 grams of titania powder (5% of solution by weight).

3. Pour some of the solution into a PET bottle and coat approximately one half of

the bottle with a uniform, thin film.

4. Dry the bottles upside-down for at least 24 hours.

5. Rinse the bottles with distilled water.

6. Repeat the above process to generate a total of two coatings.

7. Once dried, the bottles were filled with water and shaken vigorously to ensure that

any loose particles would be removed.

The coating process is untidy and not reproducible; it is impossible to manufacture all

bottle coatings in the same manner. For this reason, results for one experiment will

vary slightly between bottles with the same film type.

2.2.7 Bottles Coated with Perchloric Acid

PET bottles were coated with perchloric acid based on the procedure given above

for use in some of the experiments for this thesis. Two concentrations were used for the

experiments: a solution of 2 grams of titania in 100 grams of perchloric acid at pH 2.5

(called “2% perchloric” hereafter) and a solution of 4 grams of titania in 100 grams of

perchloric acid at pH 2.5 (called “4% perchloric” hereafter).

2.2.8 Acceptable Coating – Visual and Practical Analysis


40

The coating on the bottles is of utmost importance in this research. Therefore, an

acceptable coating on the bottles must be rigorously defined before the results can be

interpreted. There are three stages of coating the bottles – creating the first coat, rinsing

and drying, and producing the second coat. In this thesis, an acceptable coat can refer to

either the coat produced during the first step or the third step of the process.

An acceptable coating will be defined by many traits. First, the coating – either

wet or dry – must appear uniform to the naked eye – it should not contain splotches or

other irregularities. Second, it must not flake off or otherwise deteriorate during drying,

rinsing, soaking or exposure to UV light. The decrease in the mass of titania due to these

events should be at least comparable to the decrease in mass when perchloric acid is used.

Third, once the chemical, water and titania slurries have been prepared, coating the bottle

should be completed in a reasonable amount of time – under one minute per bottle would

be ideal. Fourth, the color of the coat should appealing to the user – white is ideal

because of its neutrality.


41

3. Results and Discussion

This chapter discusses the three phases of testing the binding agents. Phase I

concerns the immobilization of the titania on the surface of the PET with the twelve

binding agents; phase II concerns testing the coated bottles under field conditions; phase

III compares the experimental binding agents to perchloric acid using the photosensitive

dye indigo carmine. In addition, preparing bottles with sodium acetate created from

vinegar and baking soda and bacterial testing of the coated bottles are discussed.

3.1 – Phase I of Testing Chemicals

This chapter is divided into several sections due to the exploratory nature of this

work. The first section concerns the immobilization of the titanium dioxide onto PET

bottles by each of the chemicals or binding agents. Each chemical was given a pass/fail

test – those that produced acceptable coats progress to further testing; those that did not

were no longer part of the experimentation process. A visual evaluation of the acceptable

coats in both the short and long term is reported along with the pricing and hazard

information. The second section details the performance of the bottles when tested under

field conditions. The bottles are placed outside, under the sun and their ability to degrade
42

the organic dye indigo carmine is evaluated with a spectrophotometer inside a chamber

constructed by the author.

3.1.1 Coated Bottles

After mixing the chemicals with the titanium dioxide and water – as described in

the previous chapter – the resulting solution was put into the PET bottles. The bottles in

this experiment were coated completely on the inside. In practice, the bottles only half of

bottle’s inner face would be coated so that the bottle is not completely opaque to UV

light. The solution was rolled around inside the bottles until a suitable coating was

developed or until it became obvious that no coating was possible. It should be stressed

here that in the instances where the solution did not immobilize the titanium dioxide on

the PET a coating may still be possible with different concentrations of the chemical

agent or the titanium dioxide. These avenues were not pursued in this thesis. However, of

the eleven tested chemicals seven produced acceptable coats inside the bottle. The eleven

bottles are pictured both individually and together to give both a detailed look at each

coat and a comparison of each coat (Figures 25 to 35).


43

Figure 25 – PET Bottle Covered with TiO2 Using EDTA

1. EDTA produced a grainy, uniform coating.


44

Figure 26 – PET Bottle Covered with TiO2 Using Tartaric Acid

2. Tartaric acid produced no coating because the PET remained hydrophobic.


45

Figure 27 – PET Bottle Covered with TiO2 Using Bicine

3. Bicine produced a modest, uniform coating.


46

Figure 28 – PET Bottle Covered with TiO2 Using Na3 Citrate

4. Na3 Citrate produced no coating because the PET remained hydrophobic.


47

Figure 29 – PET Bottle Covered with TiO2 Using Sodium Acetate

5. Sodium Acetate produced a thin, uniform coating similar to perchloric or acetic

acid.
48

Figure 30 – PET Bottle Covered with TiO2 Using Na2 EDTA

6. Na2 EDTA produced no coating because the PET remained hydrophobic.


49

Figure 31 – PET Bottle Covered with TiO2 Using L-Aspartic Acid

7. L-Aspartic Acid produced no coating because the PET remained hydrophobic.


50

Figure 32 – PET Bottle Covered with TiO2 Using Sodium Dihydrogen Citrate

8. Sodium Dihydrogen Citrate produced a significant but thin coating.


51

Figure 33 – PET Bottle Covered with TiO2 Using 4-Aminobutyric Acid

9. 4-Aminobutyric Acid produced a uniform, grainy coat, similar to EDTA.


52

Figure 34 – PET Bottle Covered with TiO2 Using 4-Aminobenzoic Acid

10. 4-Aminobenzoic Acid produced a thin, slight coat.


53

Figure 35 – PET Bottle Covered with TiO2 Using Citric Acid

11. Citric acid produced a uniform coat similar to sodium acetate and acetic and

perchloric acids.

The results suggest that pH is not involved in determining the ability of the

solution to adhere the titania to the PET because the salt of acetic acid, sodium acetate, is

a base. Further, tartaric acid does not produce any coat at all – much like phosphoric acid.

This implies that the low pH effect hypothesis is false.


54

Figure 36 – Side by Side Comparison of TiO2 Coatings. Coating Done January, 2008.

Agents from left to right: Na3 Citrate, EDTA, Bicine, Sodium Acetate, 4-Aminobutyric Acid, Tartaric Acid, Na2 EDTA,

Citric Acid, Sodium Dihydrogen Citrate, 4-Aminobenzoic Acid, L-Aspartic Acid.

3.1.2. Visual Evaluation of the Coated Bottles

Eleven chemicals were tested for immobilizing the titanium dioxide on the PET

and of these, only seven produced acceptable coats. However, with subsequent testing

using the same procedure, EDTA failed to give consistent coatings. In some cases it

produced a thin coat similar to Bicine; in other cases it produced nothing. Because of this

inconsistency, EDTA was dropped from testing and will no longer appear in the analyses.

Table 2 shows a visual analysis of each of the coatings. Included are both short

term color and long term color. Figure 36 shows the bottles just after being coated; Figure

37 shows the solutions after eighty-five days of ambient indoor conditions. It is probably

that the 4-aminobenzoic acid turns brown because the titanium dioxide is reducing the

benzene ring (see Figure 14 for structure). This also happens – to a lesser extent – on the

coated bottle after a period of several weeks.


55

Comments Long Term


Film Short Term
Chemical and Time Color (85
Appearance Color (1 day)
days)
4- Somewhat
Thin,
Aminobenzoic difficult. 2 Light Brown Dark Brown
Splotchy
Acid minutes
Thin, Very
4-Aminobutyric
uniform Difficult. 3-4 White White
Acid
coating minutes.
Thin, Easy. Under
Bicine uniform 30 seconds. Slight yellow Slight Yellow
coating
Thin, Easy. Under
Citric Acid uniform 30 seconds. Slight Yellow Slight Yellow
coating
Thin, Easy. Under
uniform 30 Seconds.
Perchloric Acid Slight Blue Slight Blue
coating. Like
paint.
Sodium Slightly Easy. 30-60
seconds. White White
Acetate Splotchy
Sodium Thin, Difficult. 2-3
Dihydrogen uniform minutes. Slight Yellow Slight Yellow
Citrate coating

Table 2 – The Appearance of Each Titanium Dioxide Film on PET as well as the Ease of Manufacturing and
Color.

Figure 37 – Original Six Solutions after 85 Days L-R: 4-Aminobenzoic Acid, Citric Acid, 4-Aminobutyric Acid,
Sodium Acetate, Bicine, Sodium Dihydrogen Citrate
56

3.1.3 Mass of Titania Film Before and After Rinsing

To ascertain how much titania was present on the surface of the PET bottle

both before rinsing and after rinsing another experiment involving all of the binding

agents with the exception of 2% perchloric acid was performed. The experiment

was completed as follows:

1. Create new suspensions of each of the functional binding agents – 4-aminobutyric acid,

4-aminobenzoic acid, bicine, citric acid, 4% perchloric acid, sodium acetate, and sodium

dihydrogen citrate.

2. Weigh eight uncoated bottles three times using a Santorius Research R180D scale with

a precision of ±0.0001g.

3. Coat each of the bottles with the binding agents and dry with a hairdryer for 1 hour.

4. Weigh the coated bottles three times.

5. Rinse each bottle vigorously with 100 ml of distilled water.

6. Dry the rinsed bottles with a hairdryer for 1 hour.

7. Weigh the coated, rinsed bottles three times.

The results are plotted in Figure 39, Figure 40 and Figure 40.
57

Initial and Final Mass of Titania on One Bottle

Sodium Acetate
Binding Agent
Citric Acid After Rinse
Bicine Initial Mass
4-Aminobenzoic Acid
4-Aminobutyric Acid
NaH2 Citrate
4% Perchloric

0 0.1 0.2 0.3 0.4 0.5


Mass (g)

Figure 38 – Initial and Final Mass of Titania on One Bottle

Mass of Titania Lost after First Rinse

Sodium Acetate

Citric Acid

Bicine
Binding Agent

4-Aminobenzoic Acid

4-Aminobutyric Acid

NaH2 Citrate

4% Perchloric

0 0.01 0.02 0.03 0.04 0.05 0.06


Mass (g)

Figure 39 – Mass of Titania Lost after First Rinse.


58

Normalized Mass of Titania Decrease after Rinsing

0.98
4% Perchloric
0.96
NaH2 Citrate
0.94

0.92 4-Aminobutyric
Final/Initial Mass

Acid
0.9 4-Aminobenzoic
Acid
0.88 Bicine

0.86
Citric Acid
0.84
Sodium Acetate
0.82

0.8
Initial Mass After Rinse
Figure 40 – Normalized Mass of Titania Decrease after Rinsing

3.2 Phase II – Testing the Bottles Under Actual Field Conditions

The initial phase of testing was designed to evaluate the ability of each chemical

to immobilize titanium dioxide on PET. The chemicals used in the coating were all

organic. For this reason it was unknown if they would be able to endure the photo-

induced effects of the titanium dioxide. Testing the bottles under field conditions will

elucidate the utility of the binding agents and determine if the binding agent used greatly

affects the photoactivity of the coatings.

3.2.1 Procedure for Testing Bottles.


The procedure to determine the ability of each coating is as follows:
59

1. Four indigo carmine pills, each approximately 0.1 g, were dissolved in 1 gallon of

distilled water overnight.

2. 250 ml of the mixture was added to each bottle

3. Bottles were then put outside on the roof for 15 minutes, with the submerged

titanium dioxide coating facing the sky (i.e., the coated side of the bottle down).

Figure 41 – Bottles on the Roof of the Engineering Building during Testing March 17, 2008

4. Bottles were brought inside and photographed (Figure 42).

5. The bottles were brought back outside and steps 4-5 were repeated.

3.2.2 Initial Durability Experiment on the Roof of Engineering Building, March


17, 2008.

The bottles were placed on the roof of the Engineering Building on North Campus

of UMass Lowell during the afternoon of 3/17/2008. The bottles showed no visual
60

differences in the amount of coating after exposure to solar irradiation even though the

decay of the indigo carmine suggested that the titanium dioxide was producing radicals.

Figure 42 – Bottles coated with from L-R Perchloric acid 2%, Perchloric acid 4%, Sodium Dihydrogen Citrate,

4-Aminobutyric Acid, No Coating, Citric Acid, 4-Aminobenzoic Acid, Bicine and Sodium Acetate. Top: Bottles

after 15 Minutes of Exposure to Sunlight with Middle Bottle Unexposed. Bottom: Bottles after 30 minutes of

Sunlight with Middle Bottle Unexposed. Test Done March 17, 2008.
61

3.2.3 Experiment – Photoactivity of Titania Coatings at 0oC with Low Solar


Insolation, Roof of Engineering Building, March 19, 2008

The purposes of this experiment were to determine the photoactivity of the bottles

under freezing conditions with only diffuse insolation; to ascertain if the low

temperatures have an impact on the adherence of the titania film to the PET.

The titania coated bottles were placed on the roof of the Engineering Building on

North Campus of UMass Lowell during the afternoon of March 19, 2008 and the

degradation of indigo carmine was measured. At the time of the experiment the

temperature on the roof was 0oC and there were sleet and freezing rain for the duration of

the testing, during which, the water remained in the liquid phase.

All of the coatings showed greater than 60% reduction in indigo carmine

absorption after two hours. The 4-aminobutyric acid bottle exhibited the highest activity

and reduced the indigo carmine by more than 80% (Figure 45).

These results confirm that the high activity of the titania coated bottles is retained

irrespective of the binding agent used. Furthermore, the photoactivity was expected to be

sub-optimal due to low ambient temperature and overcast conditions.

The decay of the indigo carmine suggested that the titanium dioxide was producing

radicals (Figure 44, showing the bottles after one hour of solar irradiation). Although the

binding agents are all organic chemicals the radicals produced did not degrade the

coatings under freezing conditions. None of the bottles showed any visual deterioration

after two hours of exposure.


62

Figure 43 -- Bottles Tested under Freezing Weather Conditions, Sitting in Slush. Experiment: March 19, 2008

Figure 44 -- Bottles after One Hour of Exposure to Diffuse Solar Radiation at 0°C. Experiment: March 19, 2008
63

Decay of Indigo Carmine after 2 Hours during Freezing Conditions

1.00
Aminobenzoic Acid
0.90
Aminobutyric Acid
0.80 Bicine

0.70 Citric Acid

0.60 Sodium Dihydrogen


Citrate
Sodium Acetate
C/Co

0.50

0.40

0.30

0.20

0.10

0.00
0 20 40 60 80 100 120 140
Time (Min)
Figure 45 -- Decay of Indigo Carmine after 2 Hours during Freezing Conditions

3.2.4 Experiment – Immersing Titania in Water for Two Weeks, May, 2008

To purify drinking water, titanium dioxide coatings must remain submerged for

several hours. During this time it is possible that the water dissolves the coating and acts

to weaken it. The purpose of this experiment is to determine if water has a deleterious

effect on the coatings.

The bottles were filled with 250 ml of water and left to sit vertically for two

weeks indoors. This ensured that approximately half of the coating was in contact with

the water while the other half was not. Pictures were taken after the two week period so

that the top and bottom halves of the bottle could be compared visually (Figure 46). No

discernable differences were found between the two halves of any of the bottles. The

coatings were not affected by water for the two week period studied based on visual

comparisons.
64

Figure 46 – Bottles after 2 Weeks of Immersion in Water

3.2.5 Phase II Conclusions


The second phase of testing indicated that the coatings did not deteriorate when

exposed to either full sunlight or diffuse sunlight under freezing conditions. Significant

flaking would be expected if the photoactive titanium dioxide were oxidizing the organic

chemicals responsible for the immobilization. The coatings were also able to endure

submersion in water for two weeks – no visual evidence of coating detachment was found.

3.3 Phase III – Evaluating the New Coatings against the Perchloric Acid Coatings

The second phase of testing was designed to evaluate the ability of each film to

withstand actual outdoor conditions. Cold weather conditions, low insolation conditions

and hot, humid conditions were all used to evaluate the films. However, it is unknown

how well the films behave when compared to perchloric acid under the same conditions.

The chemicals used in the coating were all organic. For this reason it was

unknown if they would be able to endure the photo-induced effects of the titanium

dioxide. Testing the bottles under field conditions would elucidate the utility of the

binding agents and determine if the binding agent used greatly affects the photoactivity of

the coatings.
65

3.3.1 Bottle Effectiveness – Removing Indigo Carmine from Water

The purpose of this experiment is to evaluate the effectiveness of each of the

bottles at removing the dye indigo carmine from the water. The selected binding agents

will be compared to both the perchloric acid coating and a non-coated bottle.

One bottle from each of the six experimental binding agents was selected. A

solution of 0.06 g/L of indigo carmine in water was made and 250 ml of the solution was

put into each coated bottle. Absorption spectra were taken of the indigo carmine solution

before the bottles were placed in the sunlight (Figure 47, showing absorption spectra at

t=0). The bottles were then placed on the roof in direct sunlight on March 26, 2008 and

absorption measurements were taken every fifteen minutes to determine the

photodegradation rate of the indigo carmine dye (Figure 48, showing the absorption

spectra for t=15,30,45,60 minutes). More than 90% of the indigo carmine was degraded

after 1 hr of exposure in all coated bottles; the uncoated bottle degraded approximately 50%

of the dye. The “4% perchloric acid” coating showed the highest activity, degrading all

indigo carmine. Table 3 summarizes the decay rate of indigo carmine for each of the

coatings for this experiment.

The six binding agents were able to mineralize indigo carmine as well as

perchloric acid suggesting that the thickness of the coat – and therefore the film’s mass

for bottles with the same, or similar, coated areas – is not an important parameter in water

purification.
66

Indigo Carmine Absorption Spectra


0.20
0.18
0.16
Absorption (Arbitrary Units)

0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
500 550 600 650 700
Wavelength (nm)

Figure 47 – Indigo Carmine Absorption Spectra, March 26, 2008

Figure 48 – Change in Absorption of Indigo Carmine for all Coated Bottles after 1 Hour of Sun Exposure.

Experiment Done on 3-26-2008.


67

4- 4-
Time Citric NaH2 Perchloric Perchloric Sodium
None Aminobenzoic Aminobutyric Bicine
(min) Acid Citrate Acid 2% Acid 4% Acetate
Acid Acid

0 0.1927 0.1927 0.1927 0.1927 0.1927 0.1927 0.1927 0.1927 0.1927


15 0.1762 0.1321 0.1219 0.1321 0.1381 0.1198 0.1514 0.1406 0.1452
30 0.1452 0.0682 0.0642 0.0753 0.0806 0.0801 0.0845 0.0773 0.0999
45 0.1265 0.0379 0.0363 0.0296 0.0452 0.0325 0.0390 0.0345 0.0400
60 0.0960 0.0074 0.0079 0.0070 0.0069 0.0094 0.0112 0.0000 0.0105
Table 3 – Decay of Indigo Carmine Absorptance for the Experiment Conducted on 3/26/2008

A similar experiment to the one conducted on March 26th was conducted on April

1, 2008 in which two bottles from each of the six experimental binding agents were

selected. A solution with a concentration of 0.125 g/L of indigo carmine in water was

made and 250 ml of the solution was put into each coated bottle, including the bottle

coated in the presence of perchloric acid, and the uncoated bottle. Absorption spectra

were taken of the water-indigo carmine solutions before the bottles were placed in the

sunlight (Figure 49, showing the absorption spectra at t=0). The bottles were then placed

on the roof in direct sunlight and absorption measurements were taken every half-hour to

determine the photodegradation rate of the indigo carmine dye (Figure 50, showing the

absorption spectra for t=30 and t=60 min). While the uncoated bottle was able to degrade

only 20% of the indigo carmine in one hour, the coated bottles ranged from about 55% (2%

Perchloric) degradation to 80% (Sodium Acetate) degradation of the dye.


68

Indigo Carmine Absorption Spectra

0.40

0.35

0.30
Absorption (Arbitrary Units)

0.25

0.20

0.15

0.10

0.05

0.00
500 550 600 650 700
Wavelength (nm)

Figure 49 – Indigo Carmine Absorption Spectra, April 1, 2008

Decay of Indigo Carmine after 1 Hour of Sun Exposure

1.00

0.90

0.80

0.70

0.60 None
Aminobenzoic#2
Aminobenzoic#4
C/Co

0.50 Aminobutyric#1
Aminobutyric#2
Bicine#1
0.40 Bicine#2
Citric#2
0.30 Citric#3
NaH2#2
NaH2#3
0.20 Per2#1
Per4#1
Per4#2
0.10
SodiumAcetate#2
SodiumAcetate#3
0.00
0 10 20 30 40 50 60 70
Time (Min)
Figure 50 – Decay of Indigo Carmine after One Hour of Sun Exposure.
69

3.3.2 Preliminary Selection of Binding Agent

After testing the binding agents and comparing their results to perchloric acid, it

became obvious that all six of the chosen chemicals could be suitable replacements; the

differences between all tested agents – including perchloric acid – were not stark. They

were able to bind the titania to the surface of the PET; they endured UV irradiation under

both freezing and non-freezing conditions; in direct competition, under the same

conditions, they performed as well or better than perchloric acid at removing the dye

indigo carmine from water.

Other criteria, including health, flammability and instability hazards, price and

availability, must be considered when making the preliminary recommendation. Table 4

shows both the pricing and the hazards for the six chemicals and perchloric acid.

Perchloric Acid is listed for health as: “3 – Materials that, under emergency conditions,

can cause serious or permanent injury”; for instability it is listed as: “3 – Materials that in

themselves are readily capable of detonation or explosive decomposition but that require

a strong initiating source or must be heated under confinement before initiation”. All of

the other binding agents have values of less than three for each category. Therefore, using

those criteria, any of the chemicals would be a suitable replacement for perchloric acid.

Among the six chemical agents 4-aminobenzoic acid has the lowest overall

ratings. In Phase I experiments the 4-aminobenzoic acid coating was found to be slightly

brown in color; when stored it became a black color. To a person using the bottles this

would be aesthetically unpleasing. Chemically, the brown color probably indicates

destruction of the benzene ring which implies that another unknown chemical is being
70

produced. Due to the uncertainty of the chemical reaction and the unaesthetic appearance,

4-aminoebnzoic acid is eliminated as the most suitable of the six tested binding agents.

Four of the remaining five chemicals – 4-aminobutyric acid, bicine, citric acid,

and sodium acetate – have health ratings of 2 and flammability ratings of 1. The other –

sodium dihydrogen citrate – has a rating of 1 for health, flammability and instability.

It is difficult to compare the ratings of these five chemicals because the ratings are not

additive or commutative. Table 5 is introduced to further elucidate the toxicity of each of

the binding agents. Higher values indicate more benign chemicals; lower values indicate

caustic chemicals. It is clear that, using this criterion 4-aminobutyric acid is the least

toxic of the chemicals.

The economics and availability must also be considered. The target users are

those that have very little money and live in remote areas of the world. Thus, the ideal

chemical agent would be both inexpensive and able to be fabricated on site. Using Table

4 below, sodium acetate is the least expensive – by almost a factor of 7 compared to 4-

aminobutyric acid – of the five remaining chemical agents on a per mass basis.

The ease of coating the bottles with the different agents is also an important

criterion in selecting a successor to perchloric acid. Table 2 shows the duration and

relative difficulty of coating one bottle. Sodium dihydrogen citrate and 4-aminobutyric

acid were both difficult binding agents to work with, requiring several minutes for each

coated bottle, while bicine, citric acid and sodium acetate achieved coatings in under a

minute. The coatings that require less time to produce effectively save the users money in

labor costs.
71

Considering all of the aforementioned factors, sodium acetate is the best candidate

to replace perchloric acid for manufacturing PET bottles with titanium dioxide films.

Further, sodium acetate itself can be manufactured for a fraction of the cost of industrial

sodium acetate on site using the household products baking soda (sodium bicarbonate)

and vinegar (acetic acid). When combined, sodium bicarbonate and vinegar produce

carbon dioxide, water and sodium acetate. The process is benign, rapid and simple to

complete with the aid of a good scale.

Further testing should be done to ensure that the film created using sodium acetate

(either industrial or created with vinegar and baking soda) is as effective as perchloric

acid at destroying bacteria.


72

Chemical $/500g Health Flammability Instability

4-Aminobenzoic Acid 95.95 1 1 0

4-Aminobutyric Acid 280.59 2 1 0

Bicine 220.08 2 1 0

Citric Acid 71.12 2 1 0

Sodium Acetate 41.91 2 1 0

Sodium Acetate From


Vinegar and Baking 6 2 1 0
Soda

Sodium Dihydrogen
161.21 1 1 1
Citrate

Perchloric Acid 172.02 3 0 3

Table 4 – Pricing and Hazard Information for Each Binding Agent

Source: www.sciencelab.com

4- Sodium
4-Aminobutyric Citric Perchloric Sodium
LC50 Aminobenzoic Bicine Dihydrogen
Acid Acid Acid Acetate
Acid Citrate

Mouse
(Oral) 2850 12680 3750 5040 N/A 6891 5400
mg
Rat
(Oral) 6000 4950 N/A 3000 3279 3530 6730
mg
Table 5 – Median Lethal Dose for Each Binding Agent

3.4 Coating Bottles Using Sodium Acetate Created from Baking Soda and
Vinegar

3.4.1 Preparing Sodium Acetate


73

Sodium acetate can be easily made using two household products – sodium

bicarbonate (baking soda) and acetic acid (vinegar). The reaction is given by the

stoichiometric equation:

CH3–COOH + Na+[HCO3]– → CH3–COO– Na+ + H2O + CO2 Equation 8

The equation is balanced when all of the coefficients are the same for each reactant and

product. Therefore, it is straightforward to calculate how much sodium acetate will be

produced in a reaction of vinegar and baking soda. Starting with the molecular weights of

the four elemental constituents of the reaction the molecular weights of the compounds

can be found. See Table 6.


74

Mol. Wt.
Compound
(g/mol)

CH3COOH 60.052

NaHCO3 84.008

CH3COOHNa 83.042

CO2 44.01

H 2O 18.016

Table 6 – Molecular Weights of the Products and Reactants for Making Sodium Acetate.

Using the molecular weights, Equation 8 can be rewritten in terms of mass rather than in

terms of moles. Rounding to the nearest whole number, Equation 8 becomes:

60g CH3–COOH + 84 g Na+[HCO3]– → 83g CH3–COO– Na+ + 18g H2O + 44g CO2 Equation 9

This equation gives the mass ratios for each reactant and product which can then be used

to calculate sodium acetate yield given an acetic acid concentration in vinegar. For

simplicity, the balance of the vinegar is assumed to be water, though sugars and other

acids do exist and may affect the reaction. Table 7 shows how the concentration of acetic

acid in vinegar changes the amount of sodium bicarbonate needed in the reaction as well

the amounts of the products. Because the procedure for making the solution to coat the

bottles with titanium dioxide requires a 1:10 ratio of sodium acetate to water both the

ratio of sodium acetate to water and the change in water to achieve a 1:10 ratio are also

calculated. Negative values for the change in water imply that water must be removed

from the solution in order to achieve the proper ratio; positive values indicate water must
75

be added. Figure 51 plots the amount water required against the concentration of acetic

acid in vinegar, with the y-intercept being the optimal acetic acid concentration in vinegar

– about 6.8%.
76

Sodium Sodium
Acetic Acetic Acid Carbon Change
Bicarbonate Acetate Water Sodium
Acid % Vinegar Present Dioxide in H20
Added Generated Generated Acetate/H20
in (g) (CH3COOH) Generated for 10:1
(NaHCO3) (CH3COOHNa) (H2O) (g) Ratio
Vinegar (g) (CO2) (g) Ratio
(g) (g)

1 750 7.5 10.49 10.37 5.50 744.75 0.014 -639.83

2 750 15 20.98 20.74 10.99 739.50 0.028 -529.66

3 750 22.5 31.48 31.11 16.49 734.25 0.042 -419.49

4 750 30 41.97 41.49 21.99 729.00 0.057 -309.32

5 750 37.5 52.46 51.86 27.48 723.75 0.072 -199.15

6 750 45 62.95 62.23 32.98 718.50 0.087 -88.99

7 750 52.5 73.44 72.60 38.48 713.25 0.102 21.18

8 750 60 83.94 82.97 43.97 708.00 0.117 131.35

Table 7 – Masses Needed for a Stoichiometric Reaction Given Different Values of Vinegar Acidity in Order to Produce Sodium Acetate.
77

Figure 51 – Preparing Sodium Acetate Using Baking Soda and Vinegar.


Vinegar

Sodium Acetate wa
wass prepared in the laboratory using the above analyses. Pure

baking soda and vinegar were obtained from a supermarket. However, the author was

only able to find vinegar with 5% acidity instead of the optimal 6.8% acidity. As can be

seen in either Figure 51 or Table 7 the sub-optimal


optimal vinegar will result in more water than

has been previously used.

Seventy five grams of vinegar was measured and poured into a flask; 5.246 grams

of baking soda was weighed and reacted with the vinegar generating sodium acetate,

water and carbon dioxide. The resulting solution was slightly more diluted with water

than the solution made with industrial sodium acetate. The total time to make the sodium

acetate was under 10 minutes.


75

3.4.2 Coating Bottles with BSVSA


Four PET bottles were coated using the same technique expounded in section

2.2.7., they are shown in Figure 52. The resulting coat was very similar to that of the

industrial sodium acetate – splotchy, with irregularities, but covering the entire wall.

The bottles were rinsed after the coat was applied to remove any excess titania.

Figure 52 – Bottles Coated with BSVSA

3.4.3 Evaluating Baking Soda/Vinegar Sodium Acetate (BSVSA)

The photoreactivity of films created with sodium acetate has been studied in this

thesis. Therefore, no further comparisons involving the photoreactivity of films created

with sodium acetate or other binding agents are necessary. However, experiments were
76

performed to test the ability of the film to withstand field conditions, and to degrade

indigo carmine in water. The primary concern is that, because the BSVSA coating was

done using a “sub-optimal” vinegar, it is possible that the coating will not be attached as

well as the other agents. To test this hypothesis the method of section 2.2.3 was adopted;

the photodegradation of indigo carmine was also measured at half-hour increments for a

total of one hour to confirm the photoreactivity of the film.

The four coated bottles were each filled with 250 ml of distilled water with an

indigo carmine concentration of 0.122 g/L and placed on the roof of the Engineering

Building at UMass-Lowell on May 6, 2008. The decay of indigo carmine was measured

using a spectrophotometer in the experimental chamber. A plot of the decay of indigo

carmine using the BSVSA bottles and an uncoated bottle is shown in Figure 53 below.

The four bottles showed significant decreases in indigo carmine concentration

compared to the uncoated bottle. However, excessive flaking was noted on each of the

bottles. The suspended titania certainly acted to purify the water more efficiently than the

immobilized titania, thus skewing the results.


77

Decay of Indigo Carmine in the Presence of Titanium Dioxide


Immobilized with Sodium Acetate Made from Baking Soda and
Vinegar
1

0.9 No Coat
0.8 Sodium
Acetate #1
0.7
Sodium
Acetate#2
0.6
Sodium
C/Co

Acetate#3
0.5
Sodium
0.4 Acetate#4

0.3

0.2

0.1

0
0 10 20 30 40 50 60
Time (Min)

Figure 53 – Decay of Indigo Carmine in the Presence of BSVSA

Mass of Titania Lost after First Rinse

BS/Vinegar

Sodium Acetate

Citric Acid
Binding Agent

Bicine

4-Aminobenzoic Acid

4-Aminobutyric Acid

NaH2 Citrate

4% Perchloric

0 0.01 0.02 0.03 0.04 0.05 0.06


Mass (g)

Figure 54 – Mass of Titania Lost after First Rinse, Including BSVSA


78

The results suggest that BSVSA loses a large fraction of titania during the initial

rinse – nearly 25% by mass of the titania film. However, because BSVSA is so

inexpensive the amount of money lost is actually smaller than that of perchloric acid.

Figure 55 shows the economics of rinsing the bottles. The monetary values are based

on those given in Table 4.

Investment Lost per Bottle after One Rinse


BS/Vinegar
Sodium Acetate
Citric Acid
Bicine
4-Aminobenzoic Acid
4-Aminobutyric Acid
NaH2 Citrate
4% Perchloric

0 0.005 0.01 0.015 0.02 0.025


Investment Lost ($)

Figure 55 Economics of Rinsing Bottles

BSVSA has been found to be an effective immobilizer of titanium dioxide on PET. There

are several drawbacks including significant flaking of the titania into the drinking water.

While all of the other binding agents exhibited flaking to some extent, it was clearly more

prevalent in BSVSA. It would be advantageous to either purchase a more acidic vinegar


79

of 6.8%.
80

3.5 Bacterial Testing

In order to fully test the effectiveness of the bottles, it is not sufficient to simply

use the decay of indigo carmine as an indicator. Bacteria are a central problem in

contaminated water; if the bottles are unable to eliminate the bacteria from the water the

bottles would be considered ineffective. To test for the destruction of bacteria the number

of colony forming units (CFUs) per milliliter of contaminated water first needs to be

determined.

Escheria Coli (E. coli) bacteria were used during the experiments because they are

considered in the literature to be an indicator bacteria. That is, their behavior is similar to

the behavior of numerous other bacteria.

There are several steps that need to be done in order to accurately count the CFUs

in a given volume of water. The first step is to make a nutrient broth in which the E. coli

can grow; the second step is to make sterile agar plates on which the plated E. coli can

grow; the third step is to incubate the bacteria overnight so that enough are present for

serial dilutions; the fourth step is to measure the absorbance or transmittance of the

bacteria in a spectrophotometer at a given wavelength; the fifth step is to plate the serial

dilutions of the bacteria, wait 24 hours and then visually count the CFUs on the plates.

Each of these procedures has several associated steps all of which are outlined below.
81

3.5.1 Serial dilutions and plating

Serial dilutions are used to count bacteria when the concentration of bacteria is

too high to count in a particular volume. One bacterium will spawn one CFU when on an

agar plate. Assuming the bacteria are not proximate on that plate the CFUs will appear to

the naked eye and can easily be counted. The procedure for counting the bacteria for the

serial dilution is as follows:

1. Using the sterile 9mL broth-filled pipettes from above, put 1mL of E.Coli broth

into one of the pipettes.

2. Transfer 1mL of solution from the newly-formed 10mL pipette into an unused 9

mL pipette.

3. Continue until the last pipette is reached.


82

4.
Figure 56 – Serial Dilutions of Bacteria for Counting Colonies.

(Kirkman, 1996)

5. Take 1mL of solution from each pipette and put onto agar plate.

6. Using a sterile spreader, spread the bacteria around each agar plate and cover.

7. Repeat steps 4-5 two more times for a total of three plates for each dilution – 24

total.

8. Incubate at 37°C for 24 hours.

9. Count the CFUs on each plate, if applicable.

10. To get the number of bacteria in the undiluted solution multiple the average

number of CFUs by the dilution factor.

11. Using a Spectronic 20 (Spec20) machine measure the absorbance or transmission

of each dilution.

12. Plot a transmission versus CFU curve so that the transmission spectra is correlated

with the number of CFUs/mL.


83

Figure 57 – Bacteria vs. Optical Density Curve for Determining CFUs

Once constructed, the optical density curve can be used to determine the

concentrations of bacteria in any pure sample of that particular bacterium. To do this, the

Spec 20 is used to find the optical density; the colony forming units are determined with

Figure 48. Since the graph was created using the nutrient broth agar as a medium it is not

useful for bacterial dilutions of wa


water.
ter. In addition, the titanium dioxide water purification

method cannot realistically be used with nutrient broth agar so the utility of the graph in

Figure 48 extends only to the initial reading. Another enumeration method must be

implemented to count the bacteria once they are dispersed in the distilled water in the

PET bottles. To enumerate the E. coli coliforms in water the Coliscan® Membrane

Filtration Method was used. For detailed information on the method refer to (Micrology

Labs, 2005).. A brief description of the method is given below.


84

3.5.2 Coliscan® Method

The Coliscan® method is an Environmental Protection Agency approved method

of testing drinking water for the presence or absence or E. coli or total coliforms. Further,

the ability to enumerate each is afforded. The testing requires an incubation time of 24

hours and has a detection limit of 1 CFU/sample.

A 100 ml water sample is filtered through a 0.45 um pore size membrane that is

47 millimeters in diameter, leaving the bacteria onto the gridded surface. Plates are

prepared with a growth medium and the filters are placed inside, inverted and incubated

at 35 C for 24 hours. The E. coli colonies will appear as blue/purple dots; other coliforms

will appear as pink/magenta dots.

The procedure for testing the water using the Coliscan® technique is similar to

testing with indigo carmine. First, the E. coli sample is taken from the incubator, put into

a cuvette and measured with the Spec 20. A 2 mL sample is then taken from the cuvette

and put into the PET bottles which are filled with 500 mL of distilled water. The bottles

are then put outside on the roof of the Engineering Building for a predetermined amount

of time, with the submerged titanium dioxide coating facing the sky. After a time, the

bottles are brought indoors so that the Coliscan® method can be performed. To do so,

100 mL of water is filtered from each bottle and the resulting filters were plated in dishes,

filled with 2 mL of nutrient broth. The bottles are again placed on the roof for a

predetermined amount of time and the Coliscan® process is repeated. When finished, all

dishes are inverted and incubated for 24 hours.


85

3.5.3 Bacterial Testing Results

On June 2, 2008 an experiment was performed on the roof of the Engineering

Building to determine the photodegredation of bacteria using the titania thin film created

with sodium acetate. The experiments were done for a total of 45 minutes with four

bottles – two bottles having no coating and two bottles having a sodium acetate coating.

The Spec 20 was used to determine the initial bacterial count but the absorptance was too

low to be of value. When plated with the Coliscan® method, the bacteria were too

numerous to count. This indicates that the initial bacterial concentration was greater than

10 CFU/mL but less than 5,000,000 CFU/ml.

After being subjected to sunlight, the bottles were ennumerated for bacteria with

the Coliscan® method every 15 minutes. Pictures of the non-coated and sodium-acetate-

coated plates are shown for 15 minute increments in Figure 58; Figure 59 summarizes the

results.
86

Figure 58 – Coliscan® Plates from Left to Right, No Coating, No Coating, Sodium Acetate, Sodium Acetate; Top
to Bottom, at 15 Minutes, 30 Minutes and 45 Minutes.

The test results demonstrate that the sodium acetate film is able to degrade the bacteria
better and more quickly than the uncoated bottle.
87

Bacterial Death after 30 Minutes of Sun Exposure

Concentration/Initial Concentration 1
0.9
0.8
0.7
0.6 None #1

0.5
None #2
0.4
0.3
Sodium
0.2 Acetate #2

0.1 Sodium
Acetate #3
0
0 5 10 15 20 25 30 35

Time (Min)

Figure 59 – Bacterial Death after 45 minutes of sun exposure.

Another test was conducted on June, 7, 2008 with uncoated bottles, bottles coated

with sodium acetate, sodium acetate made with baking soda and vinegar and perchloric

acid. All bottles were given high doses of the E. Coli bacterium and subjected to two

hours of sun exposure. The results are tabulated in Table 8. The blue cast on the top plate

in Figure 60 indicates that the initial bacterial concentration was too numerous to count

(TNTC) with the Coliscan® method. The initial bacteria count was measured with the

Spec 20 at an absorptance of 0.12, corresponding to an initial bacterial count of

24,000,000 CFU/ml. After one hour, when plated, the sodium acetate, non-coat, and

perchloric acid coat were still too numerous to count; only the film produced with sodium

acetate made from vinegar and baking soda could be counted. After two hours, both the

sodium acetate and the sodium acetate made from vinegar and baking soda had degraded
88

all of the bacteria; the perchloric acid coating and the non-coating had still not degraded

the bacteria to detectable levels.

Time Perchloric Sodium


None BSVSA
(hr) Acid Acetate
0 TNTC TNTC TNTC TNTC
1 TNTC TNTC TNTC 967
2 TNTC TNTC 0 0
Table 8 – Bacterial Counts in CFU/100mL.(TNTC=Too Numerous to Count)

Figure 60 – Bacterial Death after 2 Hours of Sun Exposure Using the Binding Agents BSVSA, Sodium Acetate,
Perchloric Acid and No Coating.

3.6 Final Evaluation of Sodium Acetate as a Replacement for Perchloric


Acid as a Binding Agent.

Sodium Acetate performed well in all of the experimental testing done in this

thesis. The coating it produced was white and slightly splotchy but easy to manufacture;

it was able to withstand freezing and high insolation conditions; it was able to degrade
89

indigo carmine as well or better than many of the other binding agents; it retained a

reasonable coating after rinsing; it is inexpensive and relatively non-toxic; it is able to

mineralize bacteria better than the perchloric acid coating in preliminary testing.

However, its value lies in the fact that, unlike the other tested binding agents, it

can be manufactured in rural villages in developing countries using only two household

products – baking soda and vinegar. When made from these household products the

sodium acetate costs approximately twelve dollars per kilogram produced – enough to

coat approximately 2500 bottles.


90

4. Conclusions

The original objectives of the thesis as defined in Section 1.2 were accomplished.

Perchloric acid can be eliminated from the manufacturing process by any of the six

binding agents – bicine, citric acid, sodium acetate, sodium dihydrogen citrate, 4-

aminobenzoic acid and 4-aminobutyric acid. The six binding agents are less toxic than

perchloric acid and they performed in a similar manner to perchloric acid with regard to

indigo carmine destruction, thereby making them suitable alternatives in the

manufacturing process.

The six binding agents were evaluated under field conditions such as freezing

temperatures, high temperatures, high insolation and low insolation. All agents performed

effectively in each of the conditions. No significant flaking was observed. This implies

that, although each binding agent was organic, the titania film did not destroy the

molecules that adhered it to the PET.

During the testing procedure, several of the titania films were eliminated because

they performed similarly to other agents but were more caustic. Others were eliminated

for aesthetic or practical reasons. Sodium acetate was the final recommendation for

replacing perchloric acid because it is much less toxic than perchloric acid, it is

inexpensive and it can be fabricated using baking soda and vinegar.


91

The mass of the titania adhered to the side of the bottles for each binding agent

offers unique insight into the economics of coating bottles as well as the photocatalytic

process of the films. Figure 54 shows the mass of titania lost after the first rinse; Figure

48 and Figure 50 show that all of the films produced by the binding agents are effective

at destroying indigo carmine. Because the coated area of each of the bottles is

approximately the same it can be concluded that very thin films such as those produced

by sodium dihydrogen citrate work as well as thick films such as perchloric acid because

the photocatalytic activity occurs only on the surface of the film exposed to direct

insolation. This further implies that opaque films are unnecessary and not economically

worthwhile because additional titania strata do not aid photocatalytic water purification.

Phases I and II of testing indicated that the titania and the binding agents were

photocatalytically stable and therefore, compatible. This further implied that the

mechanism that binds the titania to the PET is not affected by the radicals produced by

the titania. Perhaps this points to the formation of a molecular bond between the PET, the

titanium dioxide and the binding agent.

Phase III of the testing showed that extremely thin titania films could be as

effective, or more effective than the films produced using perchloric acid. These thin

films can be produced using the simple ingredients baking soda and vinegar which

greatly adds to their value.

It is clear that many villagers would not have ready access to perchloric acid.

Therefore, they would depend on an outside organization to produce the bottles. Because

both vinegar and baking soda can be purchased in supermarkets, the ability to create

titania films on bottles shifts from an organization to an individual. This approach


92

empowers the individuals using the technology – an outcome that was the main focus of

this work.
93

5. Recommendations

It is imperative that, if new binding agents are to be employed in the field, the

purity of the water that they produce should be evaluated. This would involve testing for

the presence of various chemicals and microorganisms in the water. Specifically, because

the binding mechanisms for the titania and the PET are unknown the absence of toxic

chemicals produced by the reaction should be verified.

The mixtures of the binding agents, titania and water were based on previous

work by Meichetry et al (2007) and have not been optimized. Many of the binding agents

that were discarded because they failed to produce a coating may be acceptable if the

proportions in the mixture were changed. Work should be done to optimize each of the

mixtures of binding agent, titania and water for the best coating. As an example, using

EDTA as a binding agent worked well one time but then failed upon subsequent attempts.

The reasons for the failure and the success are not understood.

New research should center on the ability of each of the new binding agents to

destroy indigo carmine given a specific dose of UV light and a specific volume of water

already purified. The research conducted in this thesis focused on comparisons between

bottles all given the same UV dose, but offered little about the projections of the volume

of water each coat could purify. The tests for this are not straightforward, but they can be

achieved with a spectrophotometer and a pyranometer. Once complete, this investigation


94

could provide an economic analysis of the cost of purifying a given volume of water. The

economic analysis in this thesis tacitly assumes that each binding agent will endure the

same volume of water. This need not be the case.

Indigo carmine was used as a photosensitive organic dye in this research. It has

been proposed (Dubro, 2006) to use it as a visual indicator for water purification. It was

found during the construction of the Beer-Lambert plot for indigo carmine in water that

the limit of detection of indigo carmine using a spectrophotometer was less

than .046875g/L but above .0234475g/L. The limit of detection with the naked eye is

probably worse than that of the spectrophotometer. The concentration of dye and its

effects on human health should be investigated further if indigo carmine is to be used in

the field.

Figure 17 should offer some guidance for future research on this topic.

Sodium acetate prepared using baking soda and vinegar was used as a binding

agent for titania and PET. Testing on the Baking Soda/Vinegar sodium acetate (BSVSA)

in this thesis was not extensive. The experiments focused on the ability of BSVSA to act

as a binding agent. It was determined that using BSVSA is possible but did not determine

the extent to which it is. Experimenting with different concentrations of vinegar (5%

acidity vs. 7% acidity) would be worthwhile. Carrying out comparative experiments with

perchloric acid and the other binding agents would also be useful.

As mentioned in previous chapters, thirteen chemicals were tested and seven were

successful binding agents. This is a good success rate. A knowledgeable chemist or

materials scientist could likely devise many more chemicals or combinations of


95

chemicals that would emulate the ones presented here. Research should focus on why

certain chemicals are able to bind the titania to the plastic while others fail to do so.

Pilot studies involving solar water purification using bottles coated with sodium

acetate should be carried out in areas that are currently using SODIS or AOP. Regions

that are employing the AOP using perchloric acid as a binding agent are of particular

interest. The studies would offer insight into the advantages and disadvantages of using

the coated bottles under actual field, operating and cultural conditions. Further

comparisons of sodium acetate and perchloric acid would be beneficial.


96

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7. Appendix

7.1 Concerns
The National Fire Protection Association (NFPA – see http://www.nfpa.org) produced a

document entitled “Review NFPA 704: Standard System for the Identification of the

Hazards of Materials for Emergency Response, 2007” which helps to quantify how

dangerous various chemicals are in terms of health, flammability and instability. The

ratings are given below:

7.1.1 Degree of Health Hazards


4 – Materials that, under emergency conditions, can be lethal.

3 - Materials that, under emergency conditions, can cause serious or permanent injury.

2- Materials that, under emergency conditions, can cause temporary incapacitation or

residual injury.

1 - Materials that, under emergency conditions, can cause significant irritation.

0 - Materials that, under emergency conditions, would offer no hazard beyond that of

ordinary combustible materials.

7.1.2 Degree of Flammability Hazard

4 – Materials that rapidly or completely vaporize at atmospheric pressure and normal

ambient temperature or that are readily dispersed in air and burn easily.
101

3 – Liquids and solids that can be ignited under almost all ambient temperature

conditions. Materials in this degree produce hazardous atmospheres with air under almost

all ambient temperatures, or though unaffected by ambient temperatures, are readily

ignited under almost all conditions.

2 – Materials that must be moderately heated or exposed to relatively high ambient

temperatures before ignition can occur. Materials under this degree would not under

normal conditions form hazardous atmospheres with air, but under high ambient

temperatures or under moderate heating could release vapor in sufficient quantities to

produce hazardous atmospheres with air.

1 – Materials that must be preheated before ignition can occur. Materials in this degree

require considerable preheating, under all ambient temperature conditions, before ignition

and combustion can occur.

0 – Materials that will not burn under typical fire conditions, including intrinsically

noncombustible materials such as concrete stone and sand.

7.1.3 Degree of Instability Hazard

4 – Materials that in themselves are readily capable of detonation or explosive

decomposition or explosive reaction at normal temperature and pressure.

3 – Materials that in themselves are readily capable of detonation or explosive

decomposition but that require a strong initiating source or must be heated under

confinement before initiation.

2 – Materials that readily undergo violent chemical change at elevated temperatures and

pressures.
102

1 – Materials that in themselves are normally stable but that can become unstable at

elevated temperatures and pressures.

0 – Materials that in themselves are normally stable, even under fire conditions.

7.1.4 All Chemicals Used and Their Ratings

Chemical Health Flammability Instability

Perchloric Acid 3 0 3

Titanium Dioxide 1 1 0

Sodium Acetate 2 1 0

Acetic Acid 3 2 2

Phosphoric Acid 3 0 0

Citric Acid 2 1 0

Tartaric Acid 2 1 0

L-Aspartic Acid 1 1 0

Trisodium Citrate 1 1 0

Trisodium Citrate 1 1 0

Sodium Dihydrogen
1 1 1
Citrate

Bicine 2 1 0

Sodium Bicarbonate 1 0 0

4-aminobutyric Acid 2 1 0

Disodium EDTA 1 1 0

EDTA 1 0 0

4-aminobenzoic acid 1 1 0

Table 9 – All Chemicals Used in the Thesis and Their Ratings

Source: www.ScienceLab.com Retrieved 6-19-2008


103

7.2 TiO2

The Material Safety Data Sheet (MSDS) for titanium dioxide (CAS# 13463-67-7)

identifies several health hazards that need to be considered if titania is to be used for

water purification. Under Section 11 – Toxicological Information – the following are

listed:

1. Chronic Effects on Humans

a. Mutagenic for mammalian somatic cells

b. May cause damage to the following organs: lungs, upper respiratory tract.

c. Slightly hazardous in case of skin contact (irritant), of ingestion, of

inhalation.

d. Heavy occupational dust exposures may cause chronic rhinitis, chronic

bronchitis, impaired pulmonary function, resemblance of silicosis without

any fibrosis, functional change in trachea or bronchi, chronic pulmonary

edema.

2. Acute Potential Health Effects

a. May cause gastrointestinal (digestive) tract irritation with nausea,

vomiting and diarrhea. It is not absorbed following ingestion. No hazard is

expected in normal industrial use.

b. Nuisance dust. May be harmful if inhaled. Causes respiratory tract

irritation. May affect respiration and blood.


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In addition, under Section 10 – Stability and Reactivity Data – titania is listed as being

incompatible with acids and “slightly reactive to reactive” with metals. Although it does

not list the acids with which it is incompatible.

The thrust of water purification using titanium dioxide is to alleviate or eliminate

some of the diseases that accompany unclean water. As mentioned, many of the

waterborne diseases cause life-threatening diarrhea in both children and vulnerable adults.

If titania, too, causes diarrhea upon ingestion it is possible that the chemical will do more

harm than good. For this reason it is imperative that the immobilized titania does not

dislodge and get ingested.


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8. Biographical Sketch of the Author

Eric Morgan was born in Lynn, Massachusetts on November 10, 1978. Eric

attended the University of Massachusetts at Amherst and received his B.S. degree in

Mathematics in 2002. From 2002 to 2004 Eric worked as a middle school teacher before

enrolling at the University of Massachusetts, Lowell to pursue a Master’s degree in

Energy Engineering with a concentration in solar energy. During this time Eric

volunteered with the Village Empowerment Project – Peru where he helped to install PV

panels, water pumps and solar water heaters in small villages throughout the Huarmey

Valley.

Eric is currently pursuing a Doctoral degree at the Wind Energy Center at the

University of Massachusetts at Amherst. Recently, he has helped to found a company –

Apera Ethanol Technology – that will enable sustainable ethanol production using only

wind power as an energy source for distillation.