Handbook of Antimicrobial Coatings

Handbook of Antimicrobial Coatings

Atul Tiwari

Department of Mechanical Engineering, University of Hawaii at Manoa, Honolulu, HI, USA

Table of Contents

Cover image

Title page

Copyright

List of Contributors

1. Antimicrobial Coatings—Technology Advancement or Scientific Myth

1. Introduction

2. Current State of Work

3. The Industrial Product Analysis

4. Conclusion

2. Antimicrobial and Antifungal Treatments for US Army Applications

1. Introduction

2. Historical Perspective

3. Military Textile Treatments in the Modern Warfare Era

4. Recent US Army Textile Research Focus

5. Current Gaps and Needs

6. Conclusions

3. Polymer-Based Antimicrobial Coatings as Potential Biomaterials: From Action to Application

1. Introduction

2. Basic Concepts of Antibacterial Coating

3. Evaluation of Antimicrobial Properties

4. Basic Strategies and Testing Methods to Develop Effective Edible Antimicrobial and Antioxidant Coating

1. Introduction

2. Basic Strategies to Develop Effective Edible Antimicrobial and Antioxidant Coatings

3. Formulation of Edible Antimicrobial and Antioxidant Coatings

4. Preparation of Film-Forming Solutions

5. Basic Testing Methods of Antimicrobial and Antioxidant Coatings

6. Conclusions

5. Preparation and Antibacterial Properties of Reactive Surface Coatings Using Solar Energy Driven Photocatalyst

1. The Necessity of Novel Antibacterial Coatings

2. Photoreactive Surfaces

3. Antibacterial Feature of Photoreactive Coatings

4. Water-Repellent Self-Cleaning Surfaces with Photocatalytic Properties

6. Biological Characterization of Antimicrobial Coatings

1. Methods for the Determination of Efficacy of Biocidal Agents in Hard Surfaces

2. Qualitative Efficacy Testing

3. Analysis of Antimicrobial Activity of Nanoparticles

4. EPA Copper Test Surface Methodology

5. Effect of Chitosan–Copper Nanoparticles on Inhibition of Microbial Growth

6. Minimum Inhibitory Concentration and Minimum Bactericidal Concentration

7. Miscellaneous Techniques for Microbial Detection

7. Coating Technologies for Antimicrobial Textile Surfaces: State of the Art and Future Prospects for Textile Finishing

1. Antimicrobials for Textile Applications

2. Materials for Textile Coating

3. Antimicrobial Coating of Textile Materials

8. Formation of Antibacterial Paper Coated With Flavor and Essential Oils Encapsulated by Spray Drying

1. Introduction

2. Natural Bioactive Compounds as Antibacterial Agents

3. Development and Mechanisms of Antimicrobial Coating Systems

4. The Release of Antimicrobial Agents Based on Essential Oils

5. Formation of Antibacterial-Based Flavor by Spray Drying

6. Summary

9. Promising Antimicrobial Properties of Silicon-Based Thin-Film Coatings

1. Introduction

2. Amorphous Silicon–Oxygen Thin-Film Alloys

3. Bacterial Adhesion

4. Conclusions

10. Metallic Coatings on Fabrics for Antimicrobial Purposes

1. Introduction

2. Antimicrobial Reagent for Fabric

3. Metallization Process for Textile Finishing

4. Evaluation of Antimicrobial Textile

5. Remarks and Outlooks

11. Natural Antimicrobial Materials for Use in Food Packaging

1. Introduction

2. Natural Antimicrobials

3. Development of Antimicrobial Active Packaging Systems

4. Conclusions

12. The Sonochemical Coating of Textiles With Antibacterial Nanoparticles

1. Introduction

2. Why Sonochemistry?

3. Scientific and Practical Progress in Sonochemical Finishing of Textiles With Antibacterial Nanoparticles

4. Conclusion

13. Metamaterials for Antimicrobial Biofilm Applications: Photonic Crystals of Microspheres and Optical Fibers for Decontamination of Liquids and Gases

1. Introduction

2. UV Radiation Effects on Microorganisms

3. Nonlinear Models of Molecules Interaction With Short Pulse Radiation: A Review

4. Estimation of Decontamination Volume for Different Metamaterials

5. Conclusions

14. Metal Pigments as Antimicrobial Agent and Coating Additives

1. Introduction

2. Applications

3. Parameters and Influences

4. Conclusions

15. Antibiofilm Coatings

1. Biofilm Formation on Material Surfaces and Associated Challenges

2. Antibiofilm Coatings

3. Conclusions

16. Antimicrobial Coatings for Textiles

1. Introduction

2. Why Textiles Need Antimicrobial Coatings?

3. Polymeric Antimicrobial Coatings

4. Mechanism of Antibacterial Action

5. Coating Methods Used for Antibacterial Modifications of Textiles

6. Sustainability Issues in Antimicrobial Coatings of Textiles

7. Future Trends

8. Conclusions

17. Chitosan-Based Structures/Coatings With Antibacterial Properties

1. Introduction

2. Chitin and Chitosan: Origin, Structure, and Properties

3. Antimicrobial Systems Based on Chitosan

4. Perspectives for Chitosan Applications

18. N-Halamine-Based Antimicrobial Coatings

1. Introduction

2. N-Halamine Compounds

3. Applications of N-Halamine Coatings

4. Surface Coatings Based on Reactive N-Halamine Compounds

5. Surface Coatings Based on Nonreactive N-Halamine Compounds

6. Future Trends

19. Antimicrobial Coatings Based on Linseed Oil/TiO2 Nanocomposites

1. Introduction

2. Titanium Dioxide: Structure, Synthesis, Properties, and Applications

3. Preparation of AELO/Titanium Dioxide Nanocomposite Coatings

4. Characterization of the Nanocomposite Coatings

5. Conclusions

20. Antimicrobial Surface Modification of Polymeric Biomaterials

1. Introduction

2. Techniques for Surface Modification of Polymers

3. Grafting Techniques for Surface Modification

4. Surface Coatings and Films

5. Metal/Metal Nanoparticles Containing Coatings

6. Plasma Surface Modification: Sterilization and Antimicrobial Effect

21. Antibacterial Coatings on Medical Devices

1. Introduction

2. Current Strategies for Controlling Device-Related Infections

3. Antifouling Surfaces

4. Quorum-Sensing Inhibitors in Next Generation Antiinfective Coatings

5. Enzyme Coatings in Controlling Biofilm Infections

6. Antimicrobial Peptides

7. Phage Containing Antimicrobial Coatings

8. Antibacterial Lipids

9. Nanostructured Antibacterial Surfaces

10. Hybrid Coatings on Medical Devices

11. Conclusions

22. Antimicrobial Coating Development Based on Antimicrobial Peptides

1. Antimicrobial Peptides: Functions and Therapeutic Potential

2. Surface Immobilization of Antimicrobial Peptides

3. Antimicrobial Peptide–Controlled Release Surfaces

4. Concluding Remarks

23. Imparting Potential Antibacterial and Antifungal Activities to Water-Based Interior Paint Using Phytosynthesized Biocompatible Nanoparticles of Silver as an Additive—A Green Approach

1. Introduction

2. Materials and Methods

3. Results and Discussion

4. Summary and Future Perspective

24. Mechanism of Action of Tethered Antimicrobial Peptides

1. Introduction

2. The Mechanism of Action of Immobilized Peptides Can Be Complex

3. Concluding Remarks

Note Added in Proof

Index

Copyright

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List of Contributors

Shekhar Agnihotri,     Thapar University, Patiala, India

Abdellah Ajji,     CREPEC, Montreal, QC, Canada

Steven Arcidiacono,     US Army Natick Soldier Research, Development and Engineering Center, Natick, MA, United States

Nury Ardila,     CREPEC, Montreal, QC, Canada

Hermawan D. Ariyanto,     Kagawa University, Miki-cho, Japan

Mounia Arkoun,     CREPEC, Montreal, QC, Canada

Shafrina Azlin-Hasim,     University College Cork, Cork, Ireland

Maria Bădiceanu,     National Institute for Lasers, Plasma and Radiation Physics (INFLPR), Magurele, Romania

Jaya Bajpai,     Govt. Autonomous Science College, Jabalpur, India

Anil K. Bajpai,     Govt. Autonomous Science College, Jabalpur, India

Arnau Bassegoda,     Universitat Politècnica de Catalunya, Terrassa, Spain

Sergiu Bazgan,     Academy of Sciences of Moldova, Chisinau, Republic of Moldova

Cara Both,     Niederrhein University of Applied Sciences, Moenchengladbach, Germany

Idris Cerkez,     Bursa Technical University, Bursa, Turkey

Anupama Chaturvedi,     Flora Coatings, Center for Entrepreneurial Innovations, Phoenix, AZ, United States

Ying-Hung Chen,     Feng Chia University, Taichung City, Taiwan

Malco Cruz-Romero,     University College Cork, Cork, Ireland

Enda Cummins,     University College Dublin, Dublin, Ireland

Imre Dékány,     University of Szeged, Szeged, Hungary

Navneet K. Dhiman,     Thapar University, Patiala, India

Ana M. Díez-Pascual,     Alcalá University, Madrid, Spain

Nicolae Enaki,     Academy of Sciences of Moldova, Chisinau, Republic of Moldova

Shaun Filocamo,     US Army Natick Soldier Research, Development and Engineering Center, Natick, MA, United States

Aharon Gedanken,     Bar-Ilan University, Ramat Gan, Israel

Thomas Grethe,     Niederrhein University of Applied Sciences, Moenchengladbach, Germany

Mohammad M. Hassan,     AgResearch Limited, Christchurch, New Zealand

Ju-Liang He,     Feng Chia University, Taichung City, Taiwan

Marie-Claude Heuzey,     CREPEC, Montreal, QC, Canada

Kristina Ivanova,     Universitat Politècnica de Catalunya, Terrassa, Spain

László Janovák,     University of Szeged, Szeged, Hungary

Anika Joßen,     Niederrhein University of Applied Sciences, Moenchengladbach, Germany

Joseph P. Kerry,     University College Cork, Cork, Ireland

Susanna S.J. Leong,     Singapore Institute of Technology, Singapore, Singapore

Kaiyang Lim,     Singapore Institute of Technology, Singapore, Singapore

Boris Mahltig

University of Applied Sciences Niederrhein, Mönchengladbach, Germany

Niederrhein University of Applied Sciences, Moenchengladbach, Germany

Pietro Mandracci,     Politecnico di Torino, Turin, Italy

Rajarathinam Manjumeena,     New Horizon College of Engineering, Bangalore, India

Cristian N. Mihailescu,     National Institute for Lasers, Plasma and Radiation Physics (INFLPR), Magurele, Romania

Ion N. Mihailescu,     National Institute for Lasers, Plasma and Radiation Physics (INFLPR), Magurele, Romania

Biswajit Mishra,     University of Nebraska Medical Center, Omaha, NE, United States

Michael A. Morris,     Trinity College Dublin, Dublin, Ireland

Federico Mussano,     Università di Torino, Turin, Italy

Elisabeth Nagy,     University of Szeged, Szeged, Hungary

Pranav Nawani,     Washington State University, Spokane, WA, United States

Tze L. Neoh,     Kagawa University, Miki-cho, Japan

Tatiana Paslari,     Academy of Sciences of Moldova, Chisinau, Republic of Moldova

Ilana Perelshtein,     Bar-Ilan University, Ramat Gan, Israel

Nina Perkas,     Bar-Ilan University, Ramat Gan, Israel

Laura Place,     US Army Natick Soldier Research, Development and Engineering Center, Natick, MA, United States

Aurelia Profir

Academy of Sciences of Moldova, Chisinau, Republic of Moldova

Moldova State University, Chisinau, Republic of Moldova

Maike Rabe,     Niederrhein University of Applied Sciences, Moenchengladbach, Germany

Carmen Ristoscu,     National Institute for Lasers, Plasma and Radiation Physics (INFLPR), Magurele, Romania

Anamika Singh,     Govt. Autonomous Science College, Jabalpur, India

Robert Stote,     US Army Natick Soldier Research, Development and Engineering Center, Natick, MA, United States

David Joseph Sullivan,     University College Cork, Cork, Ireland

Szabolcs P. Tallósy,     University of Szeged, Szeged, Hungary

Fikret Terzioglu,     Niederrhein University of Applied Sciences, Moenchengladbach, Germany

Atul Tiwari

Flora Coatings, Center for Entrepreneurial Innovations, Phoenix, AZ, United States

Pantheon Chemical Inc., Phoenix, AZ, United States

Anuj Tripathi,     Bhabha Atomic Research Centre, Mumbai, India

Tzanko Tzanov,     Universitat Politècnica de Catalunya, Terrassa, Spain

Hayriye Ünal,     Sabanci University Nanotechnology Research and Application Center, Istanbul, Turkey

Dana Walters,     Washington State University, Spokane, WA, United States

Guangshun Wang,     University of Nebraska Medical Center, Omaha, NE, United States

Ahmet Yemenicioğlu,     Izmir Institute of Technology, Izmir, Turkey

Hidefumi Yoshii,     Kagawa University, Miki-cho, Japan

1

Antimicrobial Coatings—Technology Advancement or Scientific Myth

Atul Tiwari, and Anupama Chaturvedi     Flora Coatings, Center for Entrepreneurial Innovations, Phoenix, AZ, United States

Abstract

The demand of new antimicrobial products is increasing due to the increase in spread of infections and reduction in the effectiveness of the existing industrial products. It is, however, extremely difficult to develop a universal product that could regulate or stop the entire infectious occurrence. Companies are claiming to produce or develop new products that would help in limiting the spreading of infectious microbes. An enormous amount of work has been conducted in both the academic and industrial sectors on understanding the origin and possible regulations of the health hazards through microbes. This chapter discusses the volume of work that has been accomplished so far in the area of antimicrobial products development. An attempt has been made to summarize the utility of various marketed commercially available products along with their associated in-depth chemistry. Due to the proprietary nature of the information out of the commercial products, a limited technical investigation was accomplished.

Keywords

Antimicrobial products; Chemistry; Drug delivery; Infections; Regulations; Research

1. Introduction

The household cleaning products have been incorporating antibacterial/antimicrobial agents for past several decades, and they have achieved overwhelming success in gaining the confidence of the consumers. The incredible success of the antibacterial household products can be attributed to the dual mode of action of the chemistry inherited in the formulations. On application of products, the medicinal chemistry could efficiently kill 99.9% of the pathogens; remnant could be wiped out through the cleaning action of the surfactants in the formula. This cleaning action is, however, temporary and pathogens return to the treated surface almost instantaneously. An extended permanent treatment to such microbes-infected surfaces is highly desirable. This article will highlight some of the chemical ingredients that are available to the formulation chemists for their products. This article is mere representation of chemical components based on the assessment of the author and does not promote or compare the suitability of one product over another. The following chapters in this book will be describing the use of such chemical ingredients in greater detail.

2. Current State of Work

The most legitimate question is that why paint and coating industry cannot have solutions similar to household cleaner industry. An extensive work is going in both academia and industrial sector. The search of term Antimicrobial AND Coatings between years 2007–16 resulted into 2882 documents. In past 10  years, there has been a linear trend in the increment of number of publications with value reaching four times in year 2016 to that in year 2007 (Fig. 1.1). The most number of publications appeared in the United States (30%) followed by China (12.7%), India (11.2%), Germany (9.7%), and United Kingdom (7.0%) with small number of articles written in close collaborations between these countries. Nearly 47% articles were published in Materials Science followed by approximately 27% in Chemistry. Chemical engineering and other engineering disciplines accounted for about 47.7% published articles. It is interesting to note that both the science and engineering disciplines are equally interested in this area.

Figure 1.1  Statistical analysis of academic involvement in research and development related to antimicrobial coatings in last 10   years (i.e., between years 2007–16). The data were searched on Scopus and plots were regenerated.

More than 76% of these articles appeared as research papers in journals or trade magazines followed by 9.4% as review papers and 8.6% as conference papers. The research publications from United States demonstrated an inclination toward the work related to silver metals. China on the other hand showed exceptional growth in the number of publications per year with majority of the articles from materials science discipline. Approximately, 26% of these articles from China were written in collaboration with foreign countries and majorly with United States. Similarly, about 17% of the articles from India were published with collaboration between different countries. The articles from India discussed about the use of silver, chitosan, and herbal products as sustained released antimicrobial substances in coatings. This clearly demonstrates that there has been fair deal of research and development collaboration on this topic among global academic institutions.

The confined patent search analysis for the terms Antimicrobial AND Coatings between years 2007–16 informed that more than 15000 patents have been granted in the past 10  years. It means that more than 1000 patents were awarded each year in the last decade. The figure shows that more than 65% of these patents were filed in US patent office, while close to 18% were in European patent office. The Australian patent office has received the third highest number of applications. As demonstrated in Fig. 1.2, there has been close to fourfold increment in the number patents awarded in the past 10  years. More than 2500 patents were awarded on this subject in year 2016 indicating toward the incredible demand of such materials.

Figure 1.2  Statistical analysis of patents granted on antimicrobial coatings in last 10   years (i.e., between years 2007–16). The data were searched through The Lens ( www.lens.org ) and plots were regenerated.

It is interesting to note that when search was confined for technology classes/subclasses A61L; A01N; C08G; C08L; and C09D, which are focused only on the solid coatings and related tests, the number of granted patents reduced to only 446. This suggests that most of the patents were filed on antimicrobial chemical ingredients rather than antimicrobial coatings.

3. The Industrial Product Analysis

The staggering customer demands have motivated the industrial sector to constantly look for new effective antimicrobial products. Most of the companies are marketing several antimicrobial coatings that offer numerous promising attributes. This section briefly describes such products and their possible active chemical ingredients responsible for the antimicrobial actions. Readers are encouraged to self-verify the chemical entities in the commercial products described below.

The AkzoNobel markets Interlux product Micron as antifouling coatings for boat and ship hulls. This product is a combination of copper, copper oxide, zinc oxide, and carbon black. The SilverSan product from PPG is a formula containing silver in polyester, epoxy, or hybrid powder coating technology. This product claims a slow release of Ag+ ions through an ion-exchange mechanism in the presence of atmospheric moisture that interacts with the Na+ in microbes making them neutral species. The BASF product Irgaguard B6000 has been registered with environmental protection agency. Irgaguard B6000 is a solid material formed of silver (1.18%) and zinc zeolite (2.58%) and can be added between 1  wt% and 5  wt% in finished products to achieve an adequate microbial protection.

Agion Active XL from Sciessent is a dual action product for textiles that functions as antimicrobial as well as odor absorber. The product is based on silver ions and zeolite, passes ISO 17299-3 criteria, and works through an ion-exchange mechanism. The bad odor–creating molecules are attracted and subsequently absorbed in the silver zeolite network where they are disintegrated through various modes of action. Dow chemical manufactures several biocides such as Silvadur, Bioban, Amical, Dowicide, Vinyzene IT, and DOWICIL QK-20. Some of these products utilize active ingredient such as 2,2-dibromo-3-nitrilopropionamide commonly known as DBNPA in concentration of 5  wt% and 20  wt%. This compound effectively imparts product a broad-spectrum control over fungi, yeast, bacteria, cyanobacteria (blue-green algae), and the true algae. The product SILVADUR relies on silver ions in a certain concentration that does not harm human and environment. BIOBAN IPBC 100 contains 98% w/w 3-Iodo-2-propynylbutylcarbamate (IPBC) as an active ingredient as a broad-spectrum preservative and dry film fungicide. This product when used in water borne or solvent borne paint or coating provides excellent protection in both indoor and outdoor environments.

The Alista powder coating from DuPont contains elemental silver that is ionically bonded to biocompatible zeolite. This product has been developed by Agion Technologies. Similar to other products, silver ions from Alista are released from inorganic aluminosilicate carrier through unique absorption and exchange mechanism. The atmospheric moisture drives the slow and controlled release of silver ions enabling the product to perform over prolonged period. Sherwin-Williams has partnered with Lintech for the promotion of Microban antimicrobial coatings. Microban is a combination of polyvinylidene difluoride coating matrix along with silver as an active ingredient. Microban technology offers protection from odor producing bacteria and from the deterioration of the coating from mold and mildew. The silver-based particles on contacting with microbes do not allow the reproduction of microbes by interfering with metabolism and disrupting/damaging the cell walls. Moreover, active ingredient interferes with the conversion of nutrients into energy thereby inhibiting the reproduction process. Similar to few other manufacturers, Dunmore offers Agion- based DUN-SHIELD antimicrobial coating technology. This technology offers long-term protection from bacterial growth, mildew, and fungi.

Troy Corporation offers Mergal 530, a fast-dissipating broad-spectrum biocide with reduced environmental effects. The active ingredient 2,2-dibromo nitropropionamide (DBNPA) is completely soluble in water and offers protection within 5  min and complete protection within 30  min. The active ingredient has been approved for the indirect food contact application by the US food and drug administration (FDA). DBNPA is temperature sensitive, clear colorless to amber liquid, and can be used along with other ingredients such as biostatic benzisothiazolinone (BIT). Ashland offers Nuosept, Nuosept BMc 412 and Bodoxin TG for the preservation of water treatment/cooling system, fuel, and metalworking fluids. The active ingredient in Nuosept 14 product is 3:1 liquid mixture of 5-chloro-2-methyl-2H-isothiazolin-3-one (CMIT) and 2-methyl-2H-isothiazol-3-one (MIT). The Nuosept BMc 412 contains another ingredient 1,2-benzisothiazol-3(2H)-one (also known as BIT) along with CMIT and MIT while Bodoxin TG is in-can preservative containing a combination of an aliphatic hemiacetal and BIT.

Similarly, Lonza Arch offers series of wet-state preservatives for broad-spectrum performance against spoilage organism. Their Proxel range of products are primarily based on BIT, sodium pyrithione (NaPT), 2-bromo-2-nitropropane-1,3-diol (BNP), zinc pyrithione (ZPT), and MIT while Dantogard range is based on DMDM hydantoin along with MDM Hydantoin. Company also offers Vantocil, which is an aqueous solution of poly(hexamethylene biguanide) hydrochloride (PHMB). Moreover, Company also offers dry film biocides for long term preservation from fungi, yeast, and algae. The Omacide range of products contains 3-iodo-2-proponyl-n-butylcarbamate (IPBC), while Densil range contains Diuron, ZPT, n-butyl-1,2-benzisothiazolin-3-one (BBIT), and chlorothalonil (CTL). Company also provides fast-acting biocides for plant hygiene in the trade name of Reputain containing BNP and 2,2-dibromo-3-nitrilopropionamide (DBNPA).

4. Conclusion

The global demand of antimicrobial coatings has been increasing in leaps and bounds due to the exponential increase and transmission of life-threatening diseases. The paint and coating companies are in rush to introduce their products in the highly competitive market. Although, companies are offering promises to impart desired functional attributes to the users, yet the success of the currently available products has been limited due to insufficient time devoted in the testing and analysis of the active ingredients in the coating material. Most of the currently available products that offer protection against microbial attack are majorly inclined toward the use of silver compounds. The slow antimicrobial activity and associated toxicity with silver compounds have motivated researchers to find safer alternate. The development of universal antimicrobial coating for the indoor and outdoor use is still a challenging task due to the associated health and safety issues. Identification of safer antimicrobial agent and its incorporation into long-lasting coating matrix is high desirable.

Acknowledgments

Authors are grateful to the Centre for Entrepreneurial Innovations for providing us the necessary facility for the research and development. Although, best efforts are given while extracting the meaningful information from the Technical Data Sheets (TDS) and Safety Data Sheets (SDS) provided by the manufacturers, yet, authors do not claim for the accuracy of the content. This article is written to educate and motivate readers to work on this area of significant importance. The information provided by the manufacturers is gratefully acknowledged. This research was partially funded by the National Science Foundation through SBIR grant # 1721411, United States.

2

Antimicrobial and Antifungal Treatments for US Army Applications

Steven Arcidiacono, Laura Place, Robert Stote, and Shaun Filocamo     US Army Natick Soldier Research, Development and Engineering Center, Natick, MA, United States

Abstract

The US Army has been battling against microbial and fungal degradation since its founding in 1775. Advances in small molecule treatments provided some level of protection for Army materiel since WWII, but issues with supply, long-term Soldier health and environmental concerns led to research on alternatives. Synthetic polymers emerged as the primary replacement to treated cotton canvas, successfully supplanting it in most of the shelter components. However, recent evidence suggests that fungal growth on synthetics could still be a problem, and with a greater emphasis on personalized Soldier health, research, and development on antimicrobial and antifungal treatments for military textiles is experiencing a resurgence. Novel technologies in shelters, uniforms, and Soldier health, as well as new testing protocols, will be necessary to protect Soldiers and continue to field a strong and effective fighting force.

Keywords

Antifungal; Antimicrobial; Narrow versus broad spectrum; Shelters; Soldier; Uniforms; US Army

1. Introduction

Since its inception, the US Army has been fighting more than one enemy, not only against opposing combatants but also logistics to supply Soldier equipment. Buildup, distribution, and sustainment have been challenging issues to overcome in every conflict, and the maintenance of existing supplies was central to fielding an effective fighting force. This includes all types of Army gear, from armaments to textiles. The use of natural materials such as cotton, wool, wood, etc. for shelters, uniforms, backpacks, and other Soldier essentials have made textile degradation from microorganisms a particular concern. Although the 20th century saw advances in treatments and the advent of synthetic polymers, similar challenges exist in today's US Army that were present in 1775. In this chapter, we provide a historical perspective on advances in military textile treatments designed to combat microbial degradation, a description of efforts currently ongoing to address these issues, and a summary of research and development gaps that exist as the US Army shifts focus to new combat environments in other regions of the world.

2. Historical Perspective

Supply of Soldier materiel for the US Army has been a primary concern since its founding in 1775. Very little textile manufacturing in the colonies exists at the outset of hostilities, making procurement of uniforms and tents extremely difficult throughout the Revolutionary War. While colonial governments and ordinary citizens did what they could to keep the fledgling Army in the field, it was virtually impossible to provide every Soldier with proper provisions. This was compounded by the British blockade, which made it very challenging to obtained adequate amounts of cloth for new supplies. Thus it was imperative to maintain the existing supplies as best as possible. General Washington was an early proponent of diligent maintenance of materiel (including tents and clothing), and one of his first orders was designed to address this. At the end of the 1775 campaign, he ordered all tents be turned into the Quartermaster for cleaning and mending, which eventually became an established practice. Unfortunately, Army discipline was not yet in force at the beginning of the war, and the men regularly ignored Washington's orders. Instead, inspections would find Army materiel such as tents standing uninhabited and in a disgraceful and ruinous situation, such as tents tossed together in a heap while wet, resulting in loss due to rot [1]. Due to limited supply and inflation, prices skyrocketed throughout the war for any type of suitable cloth. Out of desperation and necessity, the Continental Congress encouraged colonial legislatures to provide incentives for the establishment of domestic production of finished textiles to help support the war effort. This is one of the first documented examples of the challenges associated with bacterial/fungal degradation for the US Army.

Logistical challenges aside, the US Army in those first years also had to contend with a fundamental lack of knowledge of the causes of materiel degradation. Since all textiles at this time were made from natural fibers, breakdown was an ever-present issue for armies throughout the world. Although bacteria and fungi were already known to the scientific community, their biochemistry, and how they impact the surroundings, would not be widely studied until the 20th century. Therefore, protection of the Soldier from the environment was the primary driving force of textile advancement for the Army in the 19th century. With the invention of vulcanized rubber in the 1840s, durable waterproofing of textiles soon became a reality. For example, gum blankets, as they were known during the American Civil War, were made of cotton and were coated with rubber (or resin) on one side [2]. They were lightweight, and proved useful for protecting a Soldier from the wet ground, as a waterproof shelter, and as a poncho to keep a Soldier and his knapsack dry during marches in wet and/or muddy conditions. These blankets were provided to every Union soldier and would be one of the prized items they carried [2]. The rubberized treatment of some of the Soldier materiel had the added (albeit unintentional) benefit of a slower rate of decay due to biological metabolism. Research in the early 20th century showed that although there are species of bacteria and fungi that can use natural rubber as a carbon source, the degradation rate is quite slow, reaching 30.9% weight loss after 5  years in a controlled environment [3].

3. Military Textile Treatments in the Modern Warfare Era

3.1. New Combat Theaters (1900–45)

Although natural waxes and oils were also available for waterproofing, rubberized fabrics were considered more durable for Army applications and were used when available into the 20th century. The use of cotton canvas (duck) for tents and other equipage was still prevalent at this time, and until WWII there were no major issues with rot or mildew, because the US Army presence in jungle environments to that point was limited. In addition, during peacetime, storage and maintenance discipline was well controlled, so there was no biological deterioration concern with these items. The advent of WWII severely impacted the availability of natural rubber and some natural oils due to blockades and treacherous passage. This necessitated a dual approach to imparting waterproof properties to materials: development of synthetic rubber, and use of existing waxes, resins, and lacquers. These materials, even with chemical advancements, were still highly susceptible to fungal growth and degradation. Indeed, the environmental conditions of the Pacific theater caused quick deterioration of Army cloth materiel within a few days. This prompted the Quartermaster Corps to demand an investigation of treatments to preserve Army equipage [4]. The primary method used to evaluate potential solutions was the soil burial test, a standard test still in use today as Antifungal Test AATCC 30.

The Army Corps of Engineers had some success against degradation of sandbags through the incorporation of copper soaps (naphthenate and stearate) (Fig. 2.1). Unfortunately, the incorporation of these types of compounds into cotton duck proved incompatible with the water-repellent finishes applied to the equipage. Other copper-containing compounds, including ammoniacal copper salts and copper 8-hydroxy quinolinate (Cu-8), received attention during the war effort, even as the demand for copper skyrocketed as the war continued to expand. While these types of copper compounds gave excellent soil burial results, there were issues with undesirable color changes or treatment permanency. The industrial partners working with ammoniacal copper compounds were successful in changing the dye formulation to account for the color change, which allowed a higher loading of the fungicide in the coating. The addition of a secondary inhibitor, 2,2′-dihydroxy-5,5’-dichlorodiphenylmethane (G-4), to the formulation in December 1944 created a very potent fungicidal treatment. However, consistent shortages throughout the war of the most effective inhibitors required continual research on alternative solutions from multiple industrial partners [4].

Small organic molecules applied on their own, such as substituted phenols and quaternary ammonium salts, were tested using the soil burial test and found to have sufficient antifungal properties. However, these agents had issues such as incompatibility with the wax finish, leaching, or discoloration due to instability in light. Unlike some of the other compounds tested, the application of organomercury compounds to fabrics could be performed in a single-bath process, which was desirable for quicker turnover of product during expanded procurement periods. However, the level of mercury-containing fungicide incorporated had to be increased from 0.5% to 1.0% due to persistent failure of the soil burial test (>10% loss of tensile strength after 14  days). Even at 1.0%, these compounds were not providing adequate performance, but due to shortages in 1944 of more active inhibitors, the organomercury compound formulation was approved for application at 1.0% with the soil burial performance requirement waived. In 1945, the Office of the Surgeon General issued a ruling on the toxicity of fungicides that instructed the level of fungicides be cut in half. This further impacted their effectiveness, and the use of the organomercury class of inhibitors was permanently discontinued at the end of the war once sufficient quantities of better inhibitors were more widely available [4].

Figure 2.1  Common small molecule antimicrobial/antifungal treatments used by the US Army from 1940s to 1980s.

Other metals that were tested included zinc, silver, and cadmium compounds. Most zinc compounds were found to be half as effective as copper equivalents, or were highly susceptible to caustic acid, suggesting the treatment would not be durable. Silver compounds were very efficient, but also quite costly at that time. Cadmium compounds were costly and not as effective as zinc, so they were quickly rejected. Although toxicity would not begin to be adequately addressed until 1945, reports of employees contracting contact dermatitis from handling fabrics with high levels (>1.5%) of a fungicide helped to substantiate maximum loading levels of 2% set by the Office of the Surgeon General. This limit disqualified many compounds from further study based on their low activity at these levels [4].

The use of fungicides was not limited to the exterior tent walls. Copper naphthenate, for example, was not sufficiently compatible with tent finishes, but was used extensively in rope and webbing [5,6]. An ammoniacal copper compound was tested in fabric for sterilizing water bags, and recommended for adoption [7]. Cu-8, which had issues with color changes, was recommended for use in fabrics with a dark color, such as for Red Cross markers [8]. Floor cloth for surgical shelters had G-4 incorporated into them to prevent fungal growth [9]. Although many of these advancements in treatments and processes occurred toward the end of WWII, the knowledge gained from these studies would be invaluable in the wars to come.

3.2. Research Advancements in Textile Treatments (1945–74)

Up until the 1950s, much of the research and development work for Army materiel (e.g., textiles, plastics, food, etc. and their durability in different environments) was spread over multiple installations across the United States. It was recognized that a centralized approach would be more efficient and decrease overlapping and duplicate efforts. Therefore, in 1954, the Quartermaster Research and Development Center opened in Natick, Massachusetts, bringing together scientists and engineers from numerous disciplines to tackle problems associated with the improvement of items for Soldier use [10]. One of the high priority problems continued to be degradation due to microorganisms. After WWII, the US Army realized that even the more effective treatments used from 1942 to 1945 provided inadequate prevention against fungal degradation in their current form. The estimated loss through mildewing of tentage alone during WWII was $40,000 per day (dollars as of 1954), as illustrated in Fig. 2.2. This estimate did not take into account other materiel losses and demonstrated the importance of a concerted effort under centralized management to prevent degradation due to microorganisms. In 1950, the US Army assigned research and development cognizance in the field of mycology to the Office of the Quartermaster General [10]. With the establishment of the Quartermaster Research and Development Center, yearly summary updates were generated on the status of research and development programs in this critical area.

The first of these summary updates provided context for the research and development being pursued. In addition to the problem of cost, the treatments used during WWII caused textile fabrics and rope to become stiff and brittle, especially at low temperatures. The compounds imparted an objectionable odor to some materials, and some treatments had a detrimental effect on feel, water repellency, or tensile strength. Copper-containing compounds became the gold standard in the late 1940s, replacing most other treatments used during WWII, and simplifying the procurement process, as they could be applied to many different textile materials, such as on thread (Fig. 2.3). However, copper is a critical resource during wartime, and therefore other alternatives were sought to replace it. In addition, with no suitable treatment for application on wearing apparel due to toxicity concerns, there was still a substantial amount of research and development to be done. Finally, the report identified the following characteristics for the ideal textile preservative: high resistance to weathering, compatibility with dyes, water-repellent and fire-resistant treatments used on fabrics, ease of application, color, odor, stability to leaching, minimum or no deteriorating effects on the treated fabrics, and toxicity clearance for prolonged intimate skin contact [10].

Figure 2.2  Widespread fungal growth on tents (left) and a close-up of fungal growth on a tent showing visible degradation (right). Image taken from Office of the Quarter Master General, Prevention of Microbiological Deterioration of Army Materiel, First Annual Report, Natick, MA, 1955, pp. 1–26 (ADD751118).

Figure 2.3  Results from a test for fungal growth on (left) untreated and (right) treated thread. Image taken from Office of the Quarter Master General, Prevention of Microbiological Deterioration of Army Materiel, First Annual Report, Natick, MA, 1955, pp. 1–26 (ADD751118).

An early success story in combating fungal growth on wearable Army materiel was with combat boots. In Korea, there were catastrophic losses of boots to microbial degradation. An untreated pair of combat boots worn in the field would last 10  days before being rendered unserviceable by mold. An estimated 500,000 pairs of boots were consumed in a 2-month period because of this accelerated deterioration. The gold standard of treatment continued to be copper-based compounds, however they were not compatible with the rubber sole and were cost prohibitive, especially during wartime. In the late 1940s paranitrophenol (PNP) was found to be compatible with shoe polish and effective at concentrations as low as 0.3% on leather, as shown in Fig. 2.4. By 1955, PNP was the standard fungicide for all military footwear [10].

Figure 2.4  Untreated combat boot (left) and treated combat boot with PNP (right). Image taken from Office of the Quarter Master General, Prevention of Microbiological Deterioration of Army Materiel, First Annual Report, Natick, MA, 1955, pp. 1–26 (ADD751118).

Subsequent reports provided updates on tests undertaken in different facilities that simulate tropical environments, including Panama, New Orleans (Southern Regional Research Laboratory—USDA), and Fort Belvoir, Virginia (Engineer Research and Development Laboratories). These locations provided an opportunity to test treated materials as they would be used and handled by Soldiers, up to years at a time, as well as study the effects of weathering and sunlight. The early results from each location showed that the copper-containing compounds remained the most effective at preventing degradation. Over the next decade, the government performed thorough screenings of over 13,000 existing compounds for treatment against microbial agents [11]. The Prevention of Deterioration Center (PDC), run by the National Research Council, compiled these results into the Handbook of Fungicides, which summarized descriptions of potential antimicrobial compounds and their targets [12]. Rather than synthesizing new classes of compounds to test, scientists used this database as a guide to modify known compounds for increased activity and improved formulation stability and compatibility [13]. This period also showed a rise in the study of synthetic polymers for military applications, including polyurethanes, polystyrenes, polyvinyls, polyamides, and acrylics. While many of these polymers themselves were found to be resistant to biodegradation, stabilizers/additives in the material formulations made them susceptible. Microorganisms could use them as a sugar source or the metabolic by-products could impact the structural integrity of the fabric. In many cases these by-products are acidic, which can degrade the substrate, and could result in a product that the microorganism can recognize as a food source, accelerating the deterioration [14–16].

In addition to novel polymers, synthetic resin coatings on textiles and chemical modification of natural materials were explored as alternatives to incorporating biocidal molecules into the fiber [17]. These approaches aimed to prevent enzymatic degradation in very different ways: physically blocking the susceptible groups with an inherently resistant material, or chemically altering the cellulose, rendering the material unrecognizable to the enzyme. Studies conducted using the coating approach noted that while most synthetics were not actively degraded by fungi, they often supported surface growth and could be degraded if the microbe produced acid from metabolic processes [18]. Photochemical (actinic) degradation and delamination from the substrate were also potential issues with this approach, mainly due to chemical breakdown or physical disruption from normal wear and tear or laundering. One of the most promising types of synthetic resin coatings were made from a methylolmelamine precursor. Melamine resins received attention due to their ability to chemically bind to cellulose, changing its structure, and had the added benefit of providing a more durable coating than noncovalent treatments. Methylolmelamine resin treatments exhibited protection for over a year in tropical climate testing and exhibited less actinic degradation than other treatments as well. However, the melamine coating affected mechanical properties of the textile and therefore was not pursued further [14]. Chemical modification of the cellulose, as opposed to a resin coating, had little effect on the feel (hand) of the material and circumvented any delamination concerns. Conversion of hydroxyl groups on cotton was investigated through acetylation, cyanoethylation, carboxymethylation, and by the addition of other small molecules. Small molecules exhibited a high rate of substitution due to their ability to penetrate and react within the fiber rather than remaining on the surface. This technique was field tested on cotton duck in the mid-1950s and demonstrated strong resistance to fungal degradation and began being tested for use in materiel such as sandbags [10,17].

Cotton sandbags have been used in bunkers since at least the 18th century and, if untreated, have a notoriously short field life. Studies on the chemical modification of cotton by acetylation or cyanoethylation resulted in sandbags that endured upward of 5  years of exposure without any appreciable degradation. However, this approach doubled the cost of the sandbag and was deemed uneconomical [10]. As the Korean War came to a close, so did the need for long-life sandbags, and this work was abandoned until the problem reemerged in Vietnam in the 1960s. At the beginning of the Vietnam War, sandbags were treated with copper naphthenate or Cu-8, but copper naphthenate was subject to leaching and actinic damage and Cu-8, while effective, was cost prohibitive. When treated, they had a field life of 6  months, which resulted in a requirement of over 100,000 replacements every month [19]. Synthetic polymers were affordable and inherently inert, making them ideal candidates for sandbag materials. Poly(vinyl chloride), cellulose triacetate, polyethylene, acrylics, and polypropylene were investigated. The US Army Engineering Research and Development labs collaborated with industrial partners to develop polypropylene sandbags. These were expected to have a service life of at least 18  months [19]. Production testing was performed in 1966, and in 1967 the first polypropylene sandbags were sent to Vietnam. However, they were found to be susceptible to sunlight; bags used in the top layer of bunkers and on rooftops were severely deteriorated after 7  months of exposure (Fig. 2.5). Fortunately other polymer formulations were being pursued in parallel. Acrylic bags performed very well in testing; they were less slippery than the polypropylene bags and were still intact after 30  months of exposure in the Canal Zone, Arizona, and Virginia [21]. These began arriving in Vietnam in late Fall 1968 and had an immediate economic impact. In 1968, 327  million sandbags were delivered, whereas in 1969 this number was reduced to 146  million due to the longer lifetime of the polypropylene bags. A cost benefit analysis was performed in 1970, which concluded that if the new bags lasted 24  months rather than the 6  months exhibited by copper naphthenate–treated cotton sandbags, an estimated $41.3  million in annual savings would be achieved [21].

Figure 2.5  Testing of sandbags for biological and actinic degradation. Untreated cotton sandbag showing significant degradation (left). Polypropylene sandbag showing significant actinic degradation (right). Images from U.S. Army Natick Laboratories, Minutes of Conference on Prevention of Microbial Deterioration of Army Materiel, No. 16, Natick, MA, 1968, pp. 24–31, 110–129 (AD0835564).

3.3. Environmental Impacts and Regulatory Challenges (1964–90)

There was a shift in research and development focus starting in the late 1960s, away from new treatment development and toward defining and improving test methods for antimicrobials on military materiel. The Army Environmental Handbook was developed to outline environmental factors such as temperature, humidity, flora, fauna, terrain, vibrations, radiation, etc. and where certain conditions can be found around the world [20]. The Panama testing facility is comprised of several test sites with differing conditions: forested, open, wet, arid, marine, and fresh water. Efforts were begun to monitor chemistry of the atmosphere for levels of compounds such as nitrous oxide, sulfoxide, carbon dioxide, and ammonia to elucidate atmospheric effects on materials [14]. This information was compiled into The Environmental Data Base Program for Regional Studies in the Humid Tropics as a resource for researchers to fully understand their testing requirements, to choose an appropriate site that would match the microenvironment of the deployed area [19]. The need to better understand environmental effects on durability as early in the materiel development process as possible led to advances in in vitro testing as well. Lab scale chambers were developed to better control every aspect of the environment and used to assess materiel durability [14,22]. Devices were designed to simulate leaching and sunlight in a controlled manner and led to changes in the protocol for the soil burial test. It became common practice to perform a soil burial alone, soil burial following simulated leaching, and soil burial after exposure to artificial sunlight or weathering for any treated item [15]. These new testing procedures allowed scientists and engineers to isolate the causes of degradation and make appropriate design changes.

There were also many studies done to develop accelerated testing that would be indicative of field tests, such as increasing flow rates in the leaching chamber, augmenting light intensity in UV testing, and temperature and water cycling. Light exposure could be altered based on the light source, the wavelength, or the use of mirrors [23,24]. Artificial test instruments called weather-ometers were developed and could be programmed to perform light/dark, temperature, and water/humidity cycles [24]. While this offered a high level of control and helped to evaluate material durability, the environment experiences much more variation than could be simulated at the time, thus they could not be precisely correlated to field tests. Typical preliminary testing was 100  h of light exposure in a weather-ometer and extensive testing was considered to be over 500  h [25]. Outdoor accelerated testing was more successful in creating a direct correlation. This was accomplished through exposure at a desert site using mirrors to focus sunlight and periodic water treatments. Chemical changes caused by degradation normally observed after 8–10  years of outdoor exposure were seen after 1  year under accelerated conditions [24,26]. Accelerated tests were not developed to replace full-scale field testing, but rather were used as design guides throughout product development to quickly determine if an item should be pursued or abandoned to get effective technologies to the Soldier.

The view of microorganisms as a scourge on the US Army was also changing during this time frame. Whereas the prevention of biological degradation of materiel had been a top focus through the 1960s, researchers at the Natick Labs and other Department of Defense installations began to investigate ways to promote degradation in a controlled manner [27]. Funding started to be directed toward projects that co-opted bacteria and fungi for practical uses such as treating pollutants, and there was a desire for materials and solvents that could also be processed microbially when their use was exhausted [15]. Concurrent with these shifts in US Army research and development vision was a growing national concern for environmental impact and workplace safety. A variety of laws were passed to provide greater protections for employees and the environment, including: the Toxic Substance Control Act, the National Consumer Health Information and Health Promotion Act, the Research Conservation and Recovery Act, and the Federal Insecticide, Fungicide, and Rodenticide Act. The regulations imposed by these laws brought into question the safety of many of the chemicals used to treat Army materiel [26].

A prime example of this difficulty arose from the treatment of Army combat boots. The military had been treating boots with PNP for over 20  years, but due to the strengthening of regulations in 1972 this compound needed to be reregistered with the Environmental Protection Agency (EPA). Scientists were cautioned that, Every fungicide in use will be reviewed by EPA. We should be prepared either not to use the fungicide during an interim period or to be prepared for a big time lag while toxicity and other data are acquired [26]. The reregistering process required data that proved the material and its components did not have adverse effects on the environment or on humans. Unfortunately much of the previously recorded data could not be used due to concerns over conflicts of interest. The EPA required health and environmental impact reports such as: oral and dermal LD50, dermal and eye irritation, mutagenicity, teratogenicity, and fish and wildlife toxicity, for acute and chronic exposures [28]. The EPA also required verification of the safety of items and the validity of the data proving that safety. Due to the necessity of long-term data (2–3  years), the EPA granted an exemption for the use of PNP with the stipulation that the registration process would be started, toxicity studies would be performed, and an alternative would be pursued [22].

Military labs began screening compounds for a more environmentally friendly leather antifungal treatment. Of those evaluated, Diiodomethyl-p-tolylsulfone (DIMPTS) and isothiazol-3-one showed the most promise [28]. The DIMPTS treatment showed no growth for 8  weeks in a tropical chamber even after leaching but did not perform as well after outdoor weathering [22]. The isothiazol-3-one exhibited no growth after 12  weeks in the tropical chamber and maintained its activity after leaching and weathering, even at low concentrations [28,29]. However, these treatments were much more expensive than PNP, so reregistration of PNP was continued in conjunction with the search for alternatives. Although these chemicals had previously been registered for use in tanning, the differences between the processes for tanning versus the antifungal treatment were significant enough to warrant an additional set of toxicity studies, which were a significant expense that manufacturers were unwilling to cover [28]. At the same time, preliminary results from short-term and long-term tests on PNP, carried out by the Army Environmental Hygiene Agency (AEHA) and the National Cancer Institute (NCI), respectively, indicated low toxicity; thus it was decided to pursue conditional registration. The test of alternatives was put on hold, and in 1981 conditional registration of PNP was granted, followed shortly thereafter by full approval [25,30].

The increased EPA regulations not only affected the treatment compounds, but also the way in which they were formulated. Cu-8 had been applied with organic solvents, but in response to increased restrictions, industry developed aqueous Cu-8 emulsions [29]. However, these were typically very acidic and necessitated agitation to remain in suspension [25,31]. These new formulations were tested on textiles but resulted in uneven coatings that did not provide adequate water repellency [31]. In 1983 the Army began testing synthetic/cotton blends treated with both solvent-based and aqueous-based G-4 and Cu-8 for tents. These were compared in 8  week soil burial studies with leaching and weathering. The Cu-8 aqueous performed much better than G-4 and was chosen for further testing. While Cu-8 aqueous was performing well in lab scale tests, industrially produced textiles were failing due to inconsistent coatings [32]. As of 1984 no industrial water-based Cu-8 treatment was able to pass military specifications. To alleviate this, it was decided to retreat tents in the field. Although this solved the fungal problem, it introduced an environmental problem: Reports started coming in of Cu-8 contaminating the soil and ground water near the retreated tents. The Cu-8 was not binding as well to the fabric under aqueous conditions as it had in a solvent application, causing leaching of the antifungal compound. Cu-8 fell out of favor and studies were started to find a replacement for antifungal treatments on shelter fabrics, which largely focused on testing commercially available products as US Army research and development funding shifted to other priorities. Due to a number of factors, including stringent testing parameters, the shift away from natural fabrics, and a change in combat theater focus, only a couple of commercially available treatments showed sufficient antimicrobial activity on par with Cu-8 to be approved for use on cotton-based Army materiel [33,34].

4. Recent US Army Textile Research Focus

4.1. Deemphasis on Natural Biological Degradation

By the mid-1980s, the US textile industry was replacing cotton (and other natural fibers) in many commercial items with synthetics, leaving fewer suppliers available to make Army materiel using these materials at scale. Numerous studies had shown the advantages of using synthetic polymers and composites in tropic environments, even replacing metal in combat boots to prevent rust (Fig. 2.6). The late 1980s saw a change in combat theater, away from temperate and jungle to arid and desert environmental zones, as the US military engaged in the Middle East. This change in environment highlighted different problems to address and caused the research focus to shift toward preventing physical degradation due to issues such as ultraviolet radiation and sand abrasion. This can be seen in hindsight as a crucial turning point in the use of natural fabrics for nonwearable Army materiel—in addition to the fact that cotton required antifungal compounds that could accelerate the effects of actinic degradation, advancements in processing of synthetics led to the creation of high strength fibers that could withstand the abrasive conditions of the desert. Once it was shown that these materials easily passed the required testing protocols without any additional treatments, natural fabrics were systematically replaced with synthetics throughout the US Army.

Figure 2.6  Level of degradation of (left) speed lacing loops, (center) metal eyelets, and (right) nylon-coated eyelets after 2   weeks in a simulated tropical environment. Image taken from B.J. Wiley, 31st Conference on Microbiological Deterioration of Military Materiel, Final Report, TR-82/027, Natick, MA, 1983, pp. 116–123 (ADD436951).

4.2. Uniforms and Soldier Health

Although fungal degradation drove much of the degradation prevention research through the 1990s, the maintenance of Soldier health was also vital to troop strength in the field. Earlier studies showed the debilitating effects of skin infections on combat troop strength; severe fungal infections affected as much as 70% of military personnel in hot humid environments [36]. Isolated efforts were made to alleviate this major issue, including changing the composition of socks from cotton to nylon, and providing quick-drying sneakers along with regulation combat boots to help prevent foot rot [37]. However, laundering was considered a sufficient way to deal with microbial loading on uniforms, though it was recognized that Soldiers may not always have ready access to laundering facilities in the field. Personal hygiene and its impact on Soldier effectiveness gained more research interest through the 1990s. Everyday activities and supplies, such as showering regimens and the soap being used, were scrutinized for effectiveness in preventing infection and disease in different environments and varying levels of activity [38]. The advent of commercially available antimicrobial treated clothing in the mid-1990s led to their incorporation into next-to-skin military textiles in the 2000s, to combat skin rashes and irritation, fungal infections, and odor (Table 2.1). However, in a number of cases the use of antimicrobial treatments has been removed from fielded textile items, due to questions of safety and efficacy.

Table 2.1

Examples of Fielded Clothing Items and the Types of Antimicrobial Technologies They Possess

The skin is the first line of defense against many invading species and has a complex system of both biological and physical mechanisms to prevent infection. The ecosystem of the skin, which includes a mixture of bacteria, fungi, and viruses, varies in composition and amounts in different parts of the body. These organisms assist in defense mechanisms for the epidermal barrier by producing antimicrobial peptides and creating competition for limited nutrients. In addition, innate physical defenses, including continual shedding of skin cells and a lower pH (acidic), create an environment unfavorable to nonnative, potentially pathogenic organisms [39]. Numerous factors contribute to variation and shifts in the skin's microbiome and can be classified into three broad categories: environmental (e.g., ambient temperature, humidity, and light exposure), genetic (e.g., gender and skin type), and behavioral (e.g., use of medications, occupational stress, and hygiene) [40,41]. These factors are especially important for Soldiers, as they are routinely exposed to these stressors in unfamiliar environments, such as during field training or a deployment. The changes in skin microbiome may disrupt normal immune defense mechanisms and may lead to an inability to protect the deeper tissue layers from abnormal and pathogenic organisms. Antimicrobial treatments that have broad activity against microorganisms on next-to-skin textiles (such as in Table 2.1) could have an adverse effect on the skin microbiome, potentially crippling a part of the innate defense mechanism against infection.

A few studies on these antimicrobial agents have concluded that they do not exhibit any toxicity issues, although nontoxicity effects (irritation, sensitization) on the skin have been reported for silane quaternary ammonium compounds (QACs) and triclosan [42,43]. In general, civilian clothing treated with antimicrobial compounds have been safe to wear; however, these items have been designed for normal use, in which it is assumed that laundering and shower facilities are readily available. For the Soldier, the deployed setting may necessitate several days to weeks without proper hygienic facilities. The extended exposure to antimicrobial textiles (AMTs) raises questions regarding their safety, including: (1) unwanted shifts in the skin microflora, adversely affecting skin health, (2) induction of resistant microorganisms, and (3) outgrowth of pathogenic microorganisms.

There are limited data on the impacts of prolonged skin exposure to AMTs. One study showed that silver-coated AMT swatches steadily reduced the skin microflora during a 9  h exposure. After removal of the swatch, the level of microflora reduction was maintained for an additional 9  h, followed by full recovery after 36  h [43]. A second prolonged wear study tracked skin microflora numbers for 4  weeks on subjects who wore specially constructed T-shirts (placebo-controlled right side and a silver-treated left side) for a minimum of 8  h/day, but did not engage in physical activity and wore a new T-shirt each week. There was no evidence of significant changes in the microflora levels during the study or the week during the period even though the treated fabric exhibited antimicrobial functionality in standard laboratory testing [44]. While there is close contact of treated fabric with