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Solar Water Purification With Pet Bottles Coated With Titanium Dioxide Using Improved Binding Agents
Solar Water Purification With Pet Bottles Coated With Titanium Dioxide Using Improved Binding Agents
Solar Water Purification With Pet Bottles Coated With Titanium Dioxide Using Improved Binding Agents
BY
MASTER OF SCIENCE
2008
Signature of
Author: ____________________________ Date: __________________
Signature of Thesis
Supervisor: ____________________________________________
Name Typed: _Dr. John J. Duffy_____________________________
BY
ERIC MORGAN
MASTER OF SCIENCE
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
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
testing, is inexpensive, has a desirable safety rating, and can be manufactured in remote
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
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
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
lack access to safe drinking water and 2.6 billion people (42% of global population) lack
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
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
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).
inexpensive process called Solar Water Disinfection (SODIS) was developed. SODIS can
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
address the issue of water-borne bacterial pollutants as well as chemical pollution. AOP
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
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
Meitchtry et al. (2005) reported perchloric acid (pH 2.5) as an effective agent at
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
individuals. For this reason it is necessary to investigate the ability of other less toxic and
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:
coated bottles. The analysis will focus on several alternative chemicals and
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
3. Analyze the mass of titania adhered to the bottles across all of the binding
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
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
purification as well as a review of solar water purification literature including SODIS and
1.5.1 UV Radiation
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
constant, c, with a value of 2.9979*108 m/s. The energy of each photon is not the same
hc
E = hν = (Equation 1)
λ
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
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)
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
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
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
water (<2 liters/bottle) and depends only on sunlight for disinfection (EAWAG &
There are, however, some crucial drawbacks. While SODIS may be effective at
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
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
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.
pesticides. Titanium dioxide works much like SODIS in that it, too, generates hydroxyl
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,
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
(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
(
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
Often, recombination of the electron and the hole occurs and heat is given off, as
( )
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
Several radicals that are responsible for photooxidation and photoreduction are
created in the process of absorbing a photon. The reactions that cause radicals and
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
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,
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
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
advantages over SODIS which make it very attractive for implementation in the field.
hydroxyl radicals (OH*), hydrogen peroxide (H2O2) and superoxide radicals (O2*).
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
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
– 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
other equipment to achieve separation (Geissen & Xi, 2001). Another example, this one
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
Touati, & McGuigan, 2005; Salih, 2003; Meichtry, et al., 2007), have reported on the
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
there are several methods for immobilizing the titania on plastics including using the use
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
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
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
there is no equivalent data on the coated PET bottles that have been used in practice.
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
favorable interactions with the various immobilizing agents. There is no literature on the
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
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.
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
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
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
• 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 acidity of the perchloric acid affects the surface of the PET creating sites
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
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
2. The purified water needs to be potable. The chemicals used should be non-toxic to
humans.
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
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
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
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
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
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:
2. The pH does not matter; the chemical reaction between the plastic, the titania and
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
2. Tartaric Acid (Figure 6). This exists naturally in many fruits such as bananas and
Furthermore, this acid tests the hypothesis that pH is a determining factor of the
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.
5. Trisodium Citrate (Figure 9). This is a sodium salt of citric acid. It is used as a
readily available.
7. L-Aspartic Acid (Figure 11). This is a naturally occurring amino acid and is vital
8. Sodium Dihydrogen Citrate (Figure 12). This is monobasic salt of citric acid.
11. Sodium acetate (Figure 15). Sodium salt of acetic acid. Abundant, inexpensive
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
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
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
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
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
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,
titanium dioxide yields only four chemicals – CO2, SO42-, NO3-, and NH4+.
28
Figure 17 -- Photodegradation Products and Reactions Showing the Activity of TiO2 on Indigo and Indigo Carmine
(Vauntier, Guillard, & Herrmann, 2001)
30
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
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)
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)
The Beer-Lambert Law begins to break down above ~0.75 g/L of indigo carmine. The
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)
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
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
probe fixed at one point inside the chamber; have a platform so that position fluctuations
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
1. 2. 3. 4. 5 6. 7.
.
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.
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
2. Turn both the incandescent and UV lights on and take a reference measurement
4. Remove the reference bottle and replace it with another PET bottle filled with 500
7. Fully remove the bottle from the chamber and put back on the platform.
This procedure was done with three different concentrations of indigo carmine and
concentration of 0.130 g/L; indigo carmine #2 had a concentration of 0.095 g/L; indigo
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
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
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.
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
Massachusetts Lowell.
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
The bottles have nine ringed ridges and are clear and colorless. The transmittance and
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.
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)
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
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)
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
3. Pour some of the solution into a PET bottle and coat approximately one half of
7. Once dried, the bottles were filled with water and shaken vigorously to ensure that
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
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
(called “2% perchloric” hereafter) and a solution of 4 grams of titania in 100 grams of
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
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.
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
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
acid.
48
Figure 32 – PET Bottle Covered with TiO2 Using Sodium Dihydrogen Citrate
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.
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,
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
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
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
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.
The results are plotted in Figure 39, Figure 40 and Figure 40.
57
Sodium Acetate
Binding Agent
Citric Acid After Rinse
Bicine Initial Mass
4-Aminobenzoic Acid
4-Aminobutyric Acid
NaH2 Citrate
4% Perchloric
Sodium Acetate
Citric Acid
Bicine
Binding Agent
4-Aminobenzoic Acid
4-Aminobutyric Acid
NaH2 Citrate
4% Perchloric
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
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
1. Four indigo carmine pills, each approximately 0.1 g, were dissolved in 1 gallon of
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
5. The bottles were brought back outside and steps 4-5 were repeated.
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
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
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
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
1.00
Aminobenzoic Acid
0.90
Aminobutyric Acid
0.80 Bicine
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
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
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
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
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
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
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
500 550 600 650 700
Wavelength (nm)
Figure 48 – Change in Absorption of Indigo Carmine for all Coated Bottles after 1 Hour of Sun Exposure.
4- 4-
Time Citric NaH2 Perchloric Perchloric Sodium
None Aminobenzoic Aminobutyric Bicine
(min) Acid Citrate Acid 2% Acid 4% Acetate
Acid Acid
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%
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)
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
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
Other criteria, including health, flammability and instability hazards, price and
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
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
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
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
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
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
Bicine 220.08 2 1 0
Sodium Dihydrogen
161.21 1 1 1
Citrate
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
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:
The equation is balanced when all of the coefficients are the same for each reactant and
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
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
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)
Table 7 – Masses Needed for a Stoichiometric Reaction Given Different Values of Vinegar Acidity in Order to Produce Sodium Acetate.
77
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
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
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.
The photoreactivity of films created with sodium acetate has been studied in this
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
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
carmine using the BSVSA bottles and an uncoated bottle is shown in Figure 53 below.
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
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)
BS/Vinegar
Sodium Acetate
Citric Acid
Binding Agent
Bicine
4-Aminobenzoic Acid
4-Aminobutyric Acid
NaH2 Citrate
4% Perchloric
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
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
of 6.8%.
80
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
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
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
1. Using the sterile 9mL broth-filled pipettes from above, put 1mL of E.Coli broth
2. Transfer 1mL of solution from the newly-formed 10mL pipette into an unused 9
mL pipette.
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.
10. To get the number of bacteria in the undiluted solution multiple the average
of each dilution.
12. Plot a transmission versus CFU curve so that the transmission spectra is correlated
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
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
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
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
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
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
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
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)
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
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
Figure 60 – Bacterial Death after 2 Hours of Sun Exposure Using the Binding Agents BSVSA, Sodium Acetate,
Perchloric Acid and No Coating.
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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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
3 - Materials that, under emergency conditions, can cause serious or permanent injury.
residual injury.
0 - Materials that, under emergency conditions, would offer no hazard beyond that of
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
temperatures before ignition can occur. Materials under this degree would not under
normal conditions form hazardous atmospheres with air, but under high ambient
1 – Materials that must be preheated before ignition can occur. Materials in this degree
require considerable preheating, under all ambient temperature conditions, before ignition
0 – Materials that will not burn under typical fire conditions, including intrinsically
decomposition but that require a strong initiating source or must be heated under
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
0 – Materials that in themselves are normally stable, even under fire conditions.
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
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
listed:
b. May cause damage to the following organs: lungs, upper respiratory tract.
inhalation.
edema.
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
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
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
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
Apera Ethanol Technology – that will enable sustainable ethanol production using only