Proceedings of the International Symposium on

Sustainable Systems and Technologies, v2 (2014)

Hazard and Life Cycle Assessment of Titanium Dioxide Nanoparticles when Applied as
Antimicrobial Coatings in Textiles.

Zhimin Xie, zjxie@ucdavis.edu
Julie M. Schoenung, jmschoenung@ucdavis.edu

Department of Chemical Engineering & Materials Science
University of California, Davis

Abstract

Different methods have been developed to incorporate photocatalytic molecules like titanium
dioxide onto cotton fabrics. The process chemicals used to fabricate three types of titanium
dioxide coatings (nano-particle titanium dioxide, nitrogen doped titanium dioxide and nitrogen-
plus-silver iodide doped titanium dioxide) were evaluated by utilizing two hazard assessment
tools along with a life cycle assessment. Results from the GreenScreen and NanoRiskCat
assessments illustrate that the hazard traits of the three coatings were very similar and thus
there is no tradeoff between the efficiency and toxicity. The chemicals all obtained a
GreenScreen benchmark score of 2 or 1, which represents chemicals to be avoided. The NRC
ratings for the exposure-effects and hazardous-potential categories were the same of each of
the three coatings. The life cycle assessment (LCA) provided insight into the potential
environmental effects from the production process.











Proceedings of the International Symposium on Sustainable Systems and Technologies (ISSN 2329-9169) is
published annually by the Sustainable Conoscente Network. Melissa Bilec and Jun-Ki Choi, co-editors.
ISSSTNetwork@gmail.com.

Copyright 2014 by Zhimin Xie, Julie M. Schoenung Licensed under CC-BY 3.0.
Cite as:
Hazard and Life Cycle Assessment of Titanium Dioxide Nanoparticles when Applied as Antimicrobial Coatings in
Textiles. Proc. ISSST, Name of Authors. Doi information v2 (2014)



Introduction

One of the unique properties of titanium dioxide is that it can act as an antimicrobial under
particular conditions. When exposed to certain wavelengths of light, the titanium dioxide reacts
and forms superoxide ions and hydroxyl radicals that can oxidize/destroy various organic
compounds - (i.e., pollutants, bacteria, dyes, stains, etc.) to form carbon dioxide and water.
Because of this property, there are many practical applications for titanium dioxide coatings,
such as incorporating the coatings onto fabrics to make the fabric "self cleaning". Furthermore,
the incorporation of different chemicals into the coating changes the range of radiation
frequencies that can be absorbed, thus the antibacterial efficiency of titanium dioxide coatings
differs depending on other incorporated chemicals. Nitrogen doping decreases the band gap of
titanium dioxide, which makes the coating more reactive and photocatalytic. The energy gap for
titanium dioxide is 3.2 eV, but with nitrogen added, it becomes 2.93 eV, [2]. The addition of
silver iodide induces visible light activity and the energy gap becomes 2.86 eV, [2]. A review of
the literature indicates that there is limited information on the toxicity of the coatings themselves
and on the process chemicals. Thus, the main focus of the current investigation was to evaluate
the hazard traits of the process chemicals used to fabricate three different coatings with variable
efficiencies: pure nano-particle titanium dioxide, nitrogen doped titanium dioxide and nitrogen-
plus-silver iodide doped titanium dioxide.


Methodology

The first chemical hazard assessment tool used to assess the coatings was GreenScreen for
Safer Chemicals (GreenScreen), which is a tool that ranks chemicals based on 20 different
environmental and human health endpoints (e.g., carcinogenicity, skin sensitization, chronic
aquatic toxicity, etc). Toxicity data on the 20 endpoints were used to determine the ranking of
the chemicals: low, medium, high, or very high. These rankings in turn are used to determine a
benchmark scores. Benchmark scores range from 1 to 4: 1 means avoid, chemical of high
concern; 2 means use but find safer substitutes; 3 means use but there's still room for
improvement; and 4 means it's a preferred safer chemical. If the chemical passes the criteria
under Benchmark 1, it moves to benchmark 2 and so on.

For the second hazard assessment, the NanoRiskCat (NRC) for nanomaterials was used. The
NRC assesses the nanoparticles in five categories: exposure for professional end-users,
exposure for consumers, exposure for the environment, human hazards, and environmental
hazards. The five categories are then ranked low, medium, high, or unknown with the colors:
green, yellow, red, and grey, respectively. The NRC method is built on the principle that
exposure classifications can be determined by descriptive examples and explanations rather
than necessitating quantitative values, which can decrease the number of data gaps; but these
make the assessments a bit subjective. Figure 1 is an example from the appendix with
descriptive process methods and corresponding color coded hazard rankings.







Figure 1. Process descriptors found in the European REACH system.

In addition to GreenScreen and NRC, a comprehensive life-cycle assessment was also
completed. The goal of the life cycle assessment was to determine the potential environmental
impacts from producing the titanium dioxide coating. Since the production process of the
titanium dioxide coating is based on a lab scale, the scope of the assessment covers the
production process, whereas the end-of-life impacts/recycling of the fabric coating are not
covered. The energy, raw material consumption and waste (chemicals) from producing the
coating are considered but the inputs needed for reuse/disposal of the coated fabric are not
considered. The assessment starts with the mining of the ilmenite, goes through the titanium
dioxide coating production process, and ends with the coating of the cotton fabric. Inputs were
determined for each of the process steps: Titanium tetrachloride production, TIP production,
titanium dioxide nanocrystal formation, mixer, cotton fabric production, drying of fabric, coating
of cotton fabric, drying of coated fabric, rinse, and drying, [1]. Figure 2 depicts a flow diagram of
the different process steps.

The inventory data collected for the assessment was obtained through databases found on
GaBi. The production of titanium dioxide requires multiple steps with different chemical
reactions; it starts with the chlorination of ilmenite, producing tetrachloride, which is use to make
titanium IV tetraisopropoxide, then titanium dioxide. Since most of the process steps were not
common industrial process, they were not found in the database thus, certain inputs had to be
calculated manually. Given that the process is in a lab scale, the inputs were calculated based
on one mole of starting material and the rest of the inputs/outputs were adjusted accordingly.
This could result from tracking the inputs and outputs incorrectly in the plan. In Gabi, there can
be elementary flows (which are all flows that enter or leave the system as a natural flow from/to
the environment) and non-elementary flows (which are inputs/outputs that stays within the
system and can be used in other process steps); these flows then can be tracked in Gabi. The
results were verified by extracting all the data for each of the environmental hazard endpoints
and adding each of the endpoints from all the different process steps to get a total number.






















Figure 2. Process Plan from GaBi.


Results and Discussion
From GreenScreen, benchmark scores were found for the chemicals used in the production
processes. Most of the chemicals had a benchmark score of either 1 or 2, so the three
processes are very similar in terms of hazard and toxicity. The benchmark scores result
primarily from high-concern rankings for the human health group II/II* endpoints (i.e., skin/eye
irritation). Figure 3 shows the final benchmark scores of the chemicals. The benchmark U
corresponds to uncertainty due to insufficient toxicity data.








Figure 3. GreenScreen
results.










Results from the NRC show that each coating process had the same overall rankings, with the
exposure for professional end-users, exposure for consumers, human hazards, and
environmental hazards ranked at high concern, and the exposure for the environment at
medium concern. Figure 4 provides a summary of the NRC assessment of N-TiO
2
.




Figure 4.NRC results summary for N-TiO
2
.


A balance was calculated using the GaBi tool, but many of the hazard endpoints had values of
zero, meaning that the production process had no effect on that specific hazard category; for
example, the result for water depletion was zero even though water was used during the
production process. It could be because the amount used was not large enough to affect the
outcome, but when the process was scaled up by a factor of one thousand, the results were still
the same. Different scenarios were developed and analyzed; this was done by changing the
amount of starting material (e.g., instead of one mole, 1000 moles was used instead). When the
amount of starting material increased, most of the environmental impact increased by the same
ratio. If the input values were doubled, the endpoint toxicity values would do the same. The
results showed that the endpoint values were consistently proportional to the amount of starting
material.


The graph in Figure 5 shows the total quantity of the different hazardous endpoints. Results
show that most of the toxicity numbers were from two main process steps. The two steps that
influenced the final endpoint data were the titanium tetrachloride production and TIP production;
other process steps had minimal effect on the overall environmental and human health
endpoints. In addition, other inputs that would have been considered if the process was on an
industrial scale were omitted in the assessment because the process is lab scale based. For
instance, the cost and environmental impacts from transportation were not included in the
analysis. Moreover, industrial size equipment would also be more efficient than lab scale
equipment, so even when the assessment is scaled up it's not a perfect representation of what it
would be if coatings were manufactured industrially.



Figure 5. LCA results.



Conclusions
Green Screen results showed that the different coatings had the same toxicity levels and the
benchmark scores for all the chemicals were 2 or 1 - chemicals to avoid. The exposure
categories (professional, consumer, and environmental) and potential hazardous effects (human
and environment) were identical based on NRC results. Since both GreenScreen and the NRC
established that the three coatings have similar hazard ratings, the coating preference should
be determined by efficiency and not toxicity.





Acknowledgements:
The authors acknowledge Professor Alissa Kendall for helping with the LCA and providing the
GaBi program, and the Wasson Scholarship for funding the project.





2.84E-08
0.336
0.000146 0.004536
0.14
0.00504 0.00672 7.39E-07
9.24
5.98E-05 2.25E-06
0.073 0.12848
6.525499
0.465051
0.030689
0.00E+00
1.00E+00
2.00E+00
3.00E+00
4.00E+00
5.00E+00
6.00E+00
7.00E+00
8.00E+00
9.00E+00
1.00E+01


References

[1] Gupta, Kamal K., Manjeet Jassal, and Ashwini K. Agrawal. "Sol-gel Derived Titanium Dioxide
Finishing of Cotton Fabric for Self Cleaning." Indian Journal of Fibre & Textile Research 33.Dec
(2008): 443-50. Print.

[2] Wu, Deyong, and Mingce Long. "Realizing Visible-Light-Induced Self-Cleaning Property of
Cotton through Coating N-TiO2 Film and Loading AgI Particles." Applied Materials &
Interfaces 3.12 (2011): 4770-774. Print.\