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Nanoengineering: Global Approaches to Health and Safety Issues

Nanoengineering: Global Approaches to Health and Safety Issues

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Nanoengineering: Global Approaches to Health and Safety Issues

1,458 pages
14 hours
May 26, 2015


Nanoengineering: Global Approaches to Health and Safety Issues provides a global vision on the impact of engineered nanomaterials both for the consumer/general public and in occupational settings. The book also presents a hint on what can be expected for the future from nanomaterials and their effects on our lives, both at home and at work. In addition, users will find valuable information on nanomaterials' irreplaceable value and their risks for health, safety, and environmental issues. Case studies illustrate key points and provide information on important processes.

  • Provides a global vision on the different aspects related to nanosafety and a synthesis of the information available
  • Gives all the information required for precision decision-making in a single book, offering both general public and occupational aspects
  • Contains separate chapters on each subject written by world-renowned contributors
  • Presents a complete vision of the problem, with perspectives on global approaches
  • Includes case studies that illustrate important processes
May 26, 2015

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Nanoengineering - Elsevier Science


Global Approaches to Health and Safety Issues


Patricia I. Dolez

CTT Group, St-Hyacinthe, QC, Canada

Table of Contents

Cover image

Title page


List of Contributors


Section 1. Introduction/General Points

Chapter 1.1. Nanomaterials Definitions, Classifications, and Applications

1. Definitions

2. Classifications of Nanomaterials

3. Properties of Nanomaterials

4. Fabrication Methods

5. Applications

6. Conclusions

7. Sources of Further Information

Chapter 1.2. Routes of Exposure to Nanoparticles: Hazard Tests Related to Portal Entries

1. Introduction

2. Possible Routes of Exposure to Nanoparticles—A Brief Review

3. Nano Risk Framework or Nanoparticle Risk Management—Development of Base Set Toxicity Tests as Related to Potential Routes of NP Exposures—As Related to Portals of Entry

4. Sources of Further Information

Chapter 1.3. Methods of Detection and Characterization

1. Introduction

2. Concepts of Airborne Particle Behavior

3. Concepts of Particle Morphology

4. Methods for Detection and Chemical Characterization of Particles Dispersed in the Air

5. Methods for Size Distribution Characterization of Particles Dispersed in the Air

6. Conclusion

Chapter 1.4. Nanotoxicology: Determining Nano-Bio Interactions and Evaluating Toxicity Using In vitro Models

1. Introduction

2. Summary of the Field

3. Making Nanotoxicology Experimental Design Relevant to Real-Life Exposure Scenarios

4. Promises and Risks

5. Current Status of Initiatives

6. Conclusions

Chapter 1.5. Fire and Explosion of Nanopowders

1. Introduction

2. Where Do Explosions Usually Occur?

3. What is an Explosion of Nanopowder?

4. Detonation/Deflagration: Explosion Regimes

5. Main Necessary Conditions Triggering Fires and Explosions

6. What is the Difference Between a Fire and an Explosion?

7. Classical Nanopowder Explosivity Laboratory Tests

8. Typical Safety Parameters for Microsized Combustible Powders and Their Trends with the Powder Particle Size: What Effects to Expect for Nanopowders?

9. Experimental Explosion Safety Parameters for a Few Nanopowders

10. Influence of the Particle Size on the MIE

11. Turbulence and Scaling Effects on Explosion Characteristics

12. Reliability of the Extrapolation Scaling Laws on Explosion Parameters

13. Relationship Between the Explosion Severity and the Flame Velocity

14. Intrinsic Limitations of Previously Described Experimental Methods

15. How to Secure Nanopowder Production Facilities?

16. Worldwide Initiatives

17. Future Trends

18. Conclusions

Section 2. Consumer/General Public

Chapter 2.1. Public’s Understanding, Perceptions, and Acceptance of Nanotechnology through the Lens of Consumer Products

1. Background/History of the Project on Emerging Nanotechnologies Consumer Products Inventory

2. Public Understanding of Nanotechnology in the US Has Not Changed

3. Methodology behind the CPI

4. Pitfalls of the Inventory

5. A Need for LCA of Nano-Enabled Consumer Products

6. Nanosilver—Excerpt from Release of Silver from Nanotechnology Consumer Products and Potential for Human Exposure

7. US Regulatory System

8. European Regulatory System

9. Public Engagement with Insufficient and Complicated Data

10. Looking Forward

Chapter 2.2. The Application of Nanotechnology to Drug Delivery in Medicine

1. Introduction

2. Types of Nanomaterials Used as Nanomedicines

3. How Nanomaterials Address Biological Problems in Medicine

4. Where We Stand: Current Clinically Used Nanomedicines

5. Promises/Risks: Existing and Potential Risks of Nanomedicines

6. Current Status, Future Direction, and Global Initiatives

7. What is Expected for the Future: Current Therapies in Clinical Trials, Future Nanomaterial Design for Improving Treatments

8. Sources of Further Information

Chapter 2.3. Life Cycle Assessment and Risk Assessment of Manufactured Nanomaterials

1. Introduction

2. Life Cycle Assessment of MNMS

3. Risk Assessment of MNMS

4. Concluding Remarks

5. Sources of Further Information

Chapter 2.4. Environmental Perspectives

1. Introduction

2. Use of ENMs that Could Improve Environmental Health

3. Effects of Incidental ENMs

4. Considerations for Environmental Risk and Hazard Assessment

5. Chapter Summary and Ways Forward

6. Sources of Further Information

Chapter 2.5. Risk Management and Surveillance of Nanomaterials for Public Health

1. Introduction

2. Knowledge Gaps for Nanomaterial Toxicity and Surveillance Systems

3. Regulatory Gaps for Nanomaterials and Surveillance Systems

4. Risk Management Approaches for Nanomaterials and Surveillance

5. Public Health Surveillance Tools and Databases

6. Overcoming Knowledge Gaps and Improving Public Health Surveillance

7. Conclusion

8. Sources of Further Information

Chapter 2.6. Nanoengineering: Ethical Issues and Social Governance

1. Introduction

2. Identifying Ethical Issues: A Cultural-, Social-, and Disciplinary-Context-Based Approach

3. Where We Stand: The Complexity of Identifying Ethical Issues in Nanoengineering

4. Public Communication: Promises and Risks

5. Current Status of World Initiatives

6. What Is Expected for the Future/What Should Be Done

Chapter 2.7. The EU Regulation of Nanomaterials: Smoother or Harder? The Precautionary Tool Chest as the Basis for Better Regulating Nanomaterials

1. The EU Policy Framework for Nanomaterials

2. The EU Legislative Framework for Nanomaterials: Recent Developments

3. Hard Regulation of Nanotechnologies: Conceptualizing Precaution with the Help of the Precautionary Toolbox?

4. Nanomaterials and Precaution: Lessons Learned

5. Sources for Further Information

Chapter 2.8. A Case Study: Nano-sized Titanium Dioxide in Sunscreens

1. Introduction

2. The Life Cycle of Nano-sized TiO2 as Sunscreen Ingredient

3. Characterization of Human Exposure to Nano-sized Sunscreen TiO2

4. Characterization of Health Effects of Nano-sized TiO2 in Sunscreens

5. Conclusion

Section 3. Occupational Settings

Chapter 3.1. Overview of Workplace Exposure to Nanomaterials

1. Introduction

2. Situations of Exposure

3. Exposure Study Methodologies

4. Exposure Study Tools and Strategies

5. Results on Workplace Exposure

6. New Strategies and Tools

7. Challenges

8. International Initiatives

9. Future Trends

10. Conclusions

11. sources of Further Information

Chapter 3.2. Addressing the Challenges to the Risk Assessment of Nanomaterials

1. Introduction

2. Current Practices for Risk Assessment in the EU

3. Challenges to Nanospecific Risk Assessment

4. Strategies for Improving the Risk Assessment of NMS

5. Discussion and Future Prospects for Nanospecific Risk Assessment and Risk Governance

6. sources of Further Information

Chapter 3.3. Exposure Measurement at Workplaces

1. Introduction

2. Exposure Assessment Strategy

3. Exposure Metrics

4. Instrument Classification

5. Stationary Equipment

6. Portable Equipment

7. Personal Equipment

8. Conclusions

9. Sources of Further Information

Chapter 3.4. Nanoengineering: A Toolbox of Standards for Health and Safety

1. Why Standards for Nanotechnologies Matter

2. ISO/TC229 and IEC/TC113

3. The Role of Standards in Regulations

4. The ISO and IEC Standards Process

5. ISO and IEC Standards for Nanotechnologies—Toolbox Specifics for Health and Safety

6. What Is Expected for the Future?

7. Sources for Further Information

Chapter 3.5. Risk Management and Good Practices Guidelines

1. Context

2. Risk Management

3. Design Stage

4. Risk Assessment

5. The Hierarchy of Controls for ENMS Exposures

6. Evaluation of Controls

7. Periodic Reevaluation Process

8. Managing the Safety of ENMS

9. Challenges for Risk Management: What is Expected for the Future?

10. Sources of Further Information

11. Conclusion

Chapter 3.6. Progress in Personal Protective Equipment for Nanomaterials

1. Introduction

2. Current State of Knowledge

3. Remaining Questions

4. Current Status of World Initiatives

5. Future Trends

6. Conclusions

7. Sources of Further Information

Chapter 3.7. Occupational Regulations

1. Introduction

2. Lessons Learned from the Past

3. The Worldwide Community

4. Global Efforts

5. Conclusion

Chapter 3.8. CNTs in Composites: A Case Study

1. Introduction

2. Case Studies

3. Issues Regarding Exposure Assessment During Handling of CNT Composites

4. Recommendations for Handling CNT Composites in the Workplace





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List of Contributors

Rickard Arvidsson,     Division of Environmental Systems Analysis, Department of Energy and Environment, Chalmers University of Technology, Gothenburg, Sweden

Christof Asbach,     Institut für Energie- und Umwelttechnik e.V. (IUTA), Air Quality & Filtration Department, Duisburg, North Rhine-Westphalia, Germany

Jacques Xavier Bouillard,     INERIS, Verneuil-en-Halatte, France

Jessica R. Child,     RTI International, Research Triangle Park, NC, USA

Maximilien Debia,     Department of Environmental and Occupational Health, School of Public Health, Université de Montréal, Montréal, Québec, Canada

Paul De Hert,     Law, Science, Technology & Society Studies (LSTS) Vrije Universiteit Brussel, Brussels, Belgium

Patricia I. Dolez,     CTT Group, St-Hyacinthe, QC, Canada

June Freeland,     Department of Safety Services and Occupational Health, University of Strathclyde, Glasgow, UK

Raphaël Gellert,     Law, Science, Technology & Society Studies (LSTS) Vrije Universiteit Brussel, Brussels, Belgium

François Gensdarmes,     Institut de Radioprotection et de Sûreté Nucléaire (IRSN), PSN-RES, SCA, Aerosol Physics and Metrology Laboratory, Gif-sur-Yvette, France

Marco Giardiello,     Department of Chemistry, University of Liverpool, Liverpool, UK

Brian Haydon,     CSA Group, Toronto, ON, Canada

Mathew Hull,     Woodrow Wilson International Center for Scholars, Washington, DC, USA

Jutta Jahnel,     Karlsruhe Institute of Technology, Institute for Technology Assessment and Systems Analysis (ITAS), Karlstrasse, Germany

Todd Kuiken,     Woodrow Wilson International Center for Scholars, Washington, DC, USA

Georges A. Legault,     Faculty of Law, Institut interdisciplinaire d'innovation technologique, Université de Sherbrooke, Sherbrooke, QC, Canada

Neill Liptrott,     Department of Molecular and Clinical, Pharmacology, University of Liverpool, Liverpool, UK

Eugenio Mantovani,     Law, Science, Technology & Society Studies (LSTS) Vrije Universiteit Brussel, Brussels, Belgium

Tom O. McDonald,     Department of Chemistry, University of Liverpool, Liverpool, UK

Sean McGinnis,     Woodrow Wilson International Center for Scholars, Washington, DC, USA

Heather V.A. McShane,     Department of Natural Resource Sciences, McGill University, Quebec, Canada

Darren Moss,     Department of Molecular and Clinical, Pharmacology, University of Liverpool, Liverpool, UK

Mariko Ono-Ogasawara,     Work Environment Research Group, Japan National Institute of Occupational Safety and Health, Tama-ku, Kawasaki, Kanagawa, Japan

Claude Ostiguy

Department of Environmental and Occupational Health, School of Public Health, Université de Montréal, Montréal, Québec, Canada

Institut de recherche Robert-Sauvé en santé et en sécurité du travail, Montréal, Québec, Canada

Andrew Owen,     Department of Molecular and Clinical, Pharmacology, University of Liverpool, Liverpool, UK

Johane Patenaude,     Faculty of Medicine and Health Sciences, Institut interdisciplinaire d'innovation technologique, Université de Sherbrooke, Sherbrooke, QC, Canada

S. Pavel,     Department of Dermatology, Charles University, Pilsen, Czech Republic

Marina E. Quadros,     Woodrow Wilson International Center for Scholars, Washington, DC, USA

Steve Rannard,     Department of Chemistry, University of Liverpool, Liverpool, UK

Christie M. Sayes,     RTI International, Research Triangle Park, NC, USA

Marco Siccardi,     Department of Molecular and Clinical, Pharmacology, University of Liverpool, Liverpool, UK

T. Smijs,     Centre for Optical Diagnostics and Therapy, Department of Radiotherapy, Erasmus Medical Centre, Rotterdam, The Netherlands

Geoffrey I. Sunahara,     Department of Natural Resource Sciences, McGill University, Quebec, Canada

Danielle Tapin,     Faculty of Medicine and Health Sciences, Institut interdisciplinaire d'innovation technologique, Université de Sherbrooke, Sherbrooke, QC, Canada

Michael G. Tyshenko,     Institute of Population Health, University of Ottawa, Ottawa, ON, Canada

David B. Warheit,     DuPont Haskell Laboratory, Newark, DE, USA


Nanotechnology has emerged as the forefront of science with its multidisciplinary and diverse scope of research and applications. Nanoengineering materials such as carbon nanotubes and fullerenes with their novel and extraordinary properties have captured a great deal of public interest and imagination over the past 20  years.

Dated back in 1986, Eric Drexler popularized an idea that the coming era of nanotechnology would radically change our world. The U.S. National Science and Technology Council in 2000 indicated that The effect of nanotechnology on the health, wealth, and lives of people could be at least as significant as the combined influences of microelectronics, medical imaging, computer-aided engineering, and man-made polymers developed in this century. However, some visionaries warned that with its omni power nanotechnology could pose a great risk and danger to humanity and the environment at large.

At the 2nd International Congress of Nanotechnology (ICNT) in 2005, I had the privilege of chairing the first Symposium on the Environmental Health and Safety Impact of Nanotechnology (nanoEHS). The conference was a tribute to Prof. Richard Smalley, a Nobel laureate for the discovery of fullerenes, who passed away at the age of 62 due to leukemia. Prof. Smalley left a remarkable legacy through his devotion to science even when it put his own health at risk with constant exposure to fullerenes in his laboratory without adequate protection.

Over the past 10  years, it has been a controversial topic to discuss nanoEHS. While a majority of researchers favored an increased funding for nanoEHS, some expressed concern that the study on the environmental and health and safety impact would impede the momentum of the research and commercial applications of nanotechnology.

Thanks to consensus among researchers that requested more funding for nanoEHS, the U. S. National Nanotechnology Initiative (NNI) research dedicated to nanoEHS grew substantially from $25  million in FY 2005 to an estimated $121.1  million requested for FY 2014. Between FY 2005 and FY 2014 the National Nanotechnology Initiative will have invested $750  million in research with the primary function of understanding EHS issues.

Since its founding in 2003, the International Association of Nanotechnology has recognized the important role of environmental, health and safety practices as a foundation for a safe and beneficial Nanotechnology. The novel physicochemical and biological properties that can make nanotechnology applications so exciting, also require extensive studies on any effects on product safety, effectiveness, or other attributes.

This book is a timely review on the global effort on the health and safety issues of nanoengineering materials, devices, and structures. The book brings together nanotechnology researchers from around the world to discuss a wide spectrum of topics under three major sections:

Section 1 starts with a general introduction on natural and engineered nanomaterials with various definitions, classifications, and synthesis routes and applications. Routes of exposure to nanomaterials throughout their entire life cycle are described, in addition to metrology and methods of detection and characterization from the perspective of industrial processes and hygiene evaluation.

As engineered nanomaterials have gained a strong foothold in a large number of consumer products, humans have been exposed to nanomaterials through intentional intake such as food and medicines, and unintentional such as inhalation of nanoparticles in workplace settings. As a result, it is important to assess the long-term exposure and to evaluate the toxicological and biological impact of nanomaterials and their safety. Nano-bio interactions and nanotoxicity in in vitro models is described and discussed.

As a case study, combustible nanopowders which have a high likelihood of explosion because of their high specific surface and their low threshold limits of ignition energy conditions are described. It is interesting to observe that the explosion severity of combustible nanopowders is governed by their primary particle size and their tendency to agglomerate/coagulate, which significantly differs from the behavior of micropowders.

Section 2 focuses on nanomedicine and consumer products. According to the Project on Emerging Nanotechnologies at the Woodrow Wilson International Center for Scholars, consumer products containing nanomaterials have grown from 54 in 2005 to well over 1500 products in 2013. This first-of-its-kind consumer products inventory is one of the most widely cited inventories of nanotechnology consumer products. However, it has been rightfully criticized due to its lack of scientific data, which should have been based on exposure, toxicity, and life cycle implications of nanomaterials.

The NNI framework for nanoEHS research strategy integrates several important concepts—risk assessment and product life cycle stages—into the basic and applied research to understand the EHS impacts of nanomaterials. In this book, life cycle assessment and risk assessment of manufactured nanomaterials, environmental perspectives, and risk management and surveillance of nanomaterials are discussed. Risk assessment takes into account the life cycle of nanomaterials, which once released into the environment may undergo transformation by environmental conditions such as temperature and salinity, and the presence of co-contaminants. These transformations may alter the form of the nanomaterials to which humans and ecosystems are exposed and which are transported through the environment.

The ethical issues of nanoengineering are a scientific quest for studying the long-term impact of nanomaterials on the economic development, the have and the have-not and societal implications.

The EU regulation of nanotechnology, which is based on the precautionary approach, serves as a starting point toward regulating nanomaterials in the industrial applications. A case study involving nano-sized titanium dioxide in sunscreens is highlighted as an example to frame the discussion on the impact of the environmental, health and safety of a new nanomaterial product in the marketplace.

Section 3 is devoted to occupational aspects with the potential workplace exposure to manufactured and nonmanufactured nanomaterials in the research laboratories and manufacturing industrial settings. While risk assessment is a primarily evidence-based process to evaluate public health and environmental issues of concern, it has become a dominant policy tool for informing regulatory and technological decisions and setting priorities for research and funding. However, risk assessment is not always universally accepted, as it depends on the sociocultural and regulatory contexts of the issues. As a result, a resource tool box and a set of good practices are presented as practical guidelines which include intrinsic safety, engineering controls, administrative procedures, and personal protective equipment (PPE).

Workforce training safety awareness among nanotechnology workers and good emergency plans are essential constituents of the prevention program. Even where engineering controls and safety systems of work are applied, some hazards might remain. In that context, PPE plays an important role in the risk management toolbox under the precautionary principle adopted by several H&S agencies worldwide.

While progress has been made in understanding biological responses to engineered nanomaterials, the full consequences of occupational exposure are unknown. To address this, national and international efforts have been made to provide guidance using both new and existing regulations to support research and development to limit and prevent worker exposure. Lastly, a case study involving carbon nanotubes compares different aspects covered by these section chapters, in particular their potential interaction with workers during their entire life cycle.

This book presents a review of the global effort in studying EHS, which is a complex and an unchartered territory. After all, one of the hallmarks of science is to study and explore the unknown. Exploring the unknown furthers our understanding of the wonders of materials science, enabling us to make the best use of nanoengineering products for the benefits of our society at large.

I congratulate the authors, editor, and publishers for their hard work in enlightening the readers with the latest development in global approaches to health and safety issues of nanotechnology.

Lloyd L. Tran,     International Association of Nanotechnology, Mountain View, California, USA

Section 1

Introduction/General Points


Chapter 1.1. Nanomaterials Definitions, Classifications, and Applications

Chapter 1.2. Routes of Exposure to Nanoparticles: Hazard Tests Related to Portal Entries

Chapter 1.3. Methods of Detection and Characterization

Chapter 1.4. Nanotoxicology: Determining Nano-Bio Interactions and Evaluating Toxicity Using In vitro Models

Chapter 1.5. Fire and Explosion of Nanopowders

Chapter 1.1

Nanomaterials Definitions, Classifications, and Applications

Patricia I. Dolez     CTT Group, St-Hyacinthe, QC, Canada


Even though the presence of nanotechnologies in man-made products can be traced back at least to the beginning of the Bronze Age, progress and discoveries made over the last 40 years have shed more light on the particularities of matter at the nanoscale level. They have also led to the more widespread use of nanotechnologies in a wide variety of commercial products, for example, in health, electronics, appliances, automobiles, and food. This chapter provides a general introduction on natural and anthropogenic nanomaterials. It starts with various definitions and classifications. Then, an overview of the particular properties of nanomaterials and the different synthesis methods is presented. This chapter ends with a description of some of their current and future applications.


Applications; Classifications; Definitions; Nanomaterials; Properties; Synthesis

1. Definitions

According to the International Organization for Standardization (ISO), the prefix nano refers to a size ranging approximately from 1 to 100  nm [1]. As a comparison, the diameter of a carbon atom is about 0.25  nm, and the distance between carbon atoms is 0.15  nm. Nanomaterials are thus larger than single atoms or even small groups of atoms. Nature's examples of nano-sized objects include DNA molecules, which have a diameter of 25  nm, viruses, with the smallest identified one, parvovirus, being 25  nm wide, and proteins that are typically 10  nm long.

The use of nanotechnology is far from being new. For example, it was used around 2600 BC in dyes to impart color to fibers and fabrics [2]. Another example can be found in Middle Age churches, where stained glass artisans utilized nanoscopic scale (or nanoscale) gold and silver particles to impart ruby red and deep yellow color to window panels [3]. Another example is the Damascus steel produced by the twelfth to the eighteenth century Middle Eastern metalsmiths, which includes cementite nanowires inside carbon nanotubes [4]. At that time, they had no way to observe the nanostructures they created. More recently, carbon black has been employed since 1910 to reinforce tires, without knowing that it was the interaction between rubber and the nanoscale carbon black particles that imparted the tires with increased hardness, strength, abrasion, and tear resistance [5].

The first scientist to raise attention on nanotechnologies, even if the word was not coined yet, was Richard Feynman. In a talk he gave in 1959 at the annual meeting of the American Physical Society entitled There's plenty of room at the bottom—An invitation to enter a new field of physics, he challenged his fellow physicists to write the entire 24 volumes of the Encyclopedia Britannica on the head of a pin [6]. He also offered a $1000 price to the first person who would build a 1/64-cubic inch working electrical motor. It must be mentioned that this price was claimed not long afterward by a student, William McLellan, who constructed such a motor using the conventional, watch-making design [7].

The word nanotechnology was used for the first time in 1974 by Norio Taniguchi in reference to machining and finishing dimensional tolerances for semiconductor processes [8]. It is derived from the Greek word for dwarf and means a billionth of a unit. However, it was only after the development of the scanning tunneling microscope in 1981 by IBM researchers Gerd Binning and Heinrich Rohrer [9] that progress really kicked off; it was now possible to observe matter at the nanoscale. They were awarded a Nobel Prize in physics in 1986 for this discovery, which takes advantage of the quantum phenomenon exhibited by conductor and semiconductor materials at the nanoscale. Then, fullerenes were discovered in 1985 by Harold Kroto, Robert Curl, and Richard Smalley [10], who won a Nobel Prize in chemistry in 1996 for this achievement. The first controlled growth of carbon nanotubes is attributed to Sumio Lijima and his colleagues in 1991 [11].

Since that time, the use of nanoscale materials and structures in commercial products has largely increased. The worldwide market for nano-enabled products was valued at US$22.9  billion in 2013 [12]. It is expected to reach US$64.2  billion by 2019, with a compound annual growth rate of 19.8% between 2014 and 2019. The last update in 2013 of the Nanotechnology Consumer Products Inventory of the Woodrow Wilson International Center for Scholars has identified 1628 commercial nanoproducts, including 440 on the European market [13]. As knowledge about the potential dangers of nanomaterials as well as the need for standardization in this new field have increased too, efforts have been devoted to defining the terminology used, even if differences exist between countries. For example, according to ISO, nanomaterials are defined as materials with any external dimension in the nanoscale or having an internal structure or surface structure in the nanoscale [14], the nanoscale referring to a size ranging approximately from 1 to 100  nm [1]. On the other hand, the European Commission's recommendation on the definition of nanomaterial released in 2011 is a natural, incidental or manufactured material containing particles, in an unbound state or as an aggregate or as an agglomerate and where, for 50% or more of the particles in the number size distribution, one or more external dimensions is in the size range 1–100  nm [15]. They provide for exceptions for specific cases when concerns exist for environment, health, safety, or competitiveness, in which case the concentration threshold is reduced below 50%, and for fullerenes, graphene flakes and single wall carbon nanotubes with one or more external dimensions below 1  nm, which are considered nanomaterials regardless of concentration. Canada has also established its own working definition of nanomaterials, which are any manufactured substance or product and any component material, ingredient, device, or structure […] if it is at or within the nanoscale in at least one external dimension, or has internal or surface structure at the nanoscale, or it is smaller or larger than the nanoscale in all dimensions and exhibits one or more nanoscale properties/phenomena [16]. This last definition allows considering materials that are larger or smaller than the nanoscale range if they exhibit the properties or phenomena that are characteristic of the nanoscale dimension.

2. Classifications of Nanomaterials

Whatever the exact definition they are given, nanomaterials can be classified according to their source, their dimensions, and their constitutive materials. A classification has also been established according to their potential toxicity level [17].

2.1. Classification of Nanomaterials According to Origin

First, nanomaterials can be differentiated according to their origin: natural or anthropogenic. This last category can be divided into incidental and engineered nanomaterials, depending on whether their formation is intentional or not. Nanoparticles that have a natural and incidental origin are generally referred to as ultrafine particles. Natural sources of inorganic nanomaterials include, for example, erupting volcanoes, breaking sea waves, forest fires, sand storms, as well as soils [18]. For example, certain forms of clay are constituted of 1-nm-thick by 70- to 150-nm-wide stacked nanoplates. Some nanomaterials are also naturally found in living organisms, for example, biogenic magnetite, a ferromagnetic crystalline structure associated with magnetoreception in some animals, ferritin, an iron storage protein, and calcium hydroxyapatite, the hard nanocrystalline constituent of bones [19]. Fullerenes have even been recently discovered in space [20].

Nanomaterials can also be found as unintentional by-products of human activity. This includes, for example, internal combustion engines, power plants, incinerators, jet engines, metal fumes (smelting, welding, etc.), polymer fumes, heated surfaces, food transformation processes (baking, frying, broiling, grilling, etc.), and electric motors [21]. If the exposure resulting from motor vehicle emissions started to be documented at the end of the 1990s [22], only recently was the large prevalence of nanoparticle release by kitchen appliances [23] and laser printers [24] evidenced. The presence of potentially toxic nanoparticles in cigarette smoke was also lately demonstrated [25]. In terms of occupational exposure, arc welding and aluminum smelting have been shown to generate large amounts of airborne nanoparticles [26]. Conditions favoring the emission of incidental nanomaterials include the presence of vaporizable materials, a sufficiently high temperature to support vapor generation, and processes involving rapid cooling and a large temperature gradient [27].

Finally, nanomaterials are now manufactured using a large diversity of chemical constituents, for example, metals, semiconductors, metal oxides, carbon, and polymers. They are designed for specific functionalities and can be surface treated or coated. They come in a large variety of forms: spheres, wires, fibers, needles, rods, tubes, shells, rings, plates, coatings, etc., as well as in more exotic flower-like designs. Compared to natural and incidental nanomaterials, manufactured nanomaterials are characterized by their controlled dimension, shape, and composition [21].

2.2. Classification of Nanomaterials According to Dimensionality

A second categorization of nanomaterials is based on their dimensionality (Figure 1) [28]. Nanomaterials with all external dimensions at the nanoscale, that is, between 1 and 100  nm, may be classified as zero-dimensional (0D). This includes quantum dots, which are semiconductor nanocrystals with dimensions <10  nm that act as a potential well and are used in electronics to confine electrons and holes [29]. The 0D nanomaterials comprise also various types of nanoparticles: full spheres like anatase titanium dioxide; dendrimers that are highly symmetrical, branched macromolecules; hollow spheres made, for example, of carbon (fullerenes), sodium–tungsten or gold; cubes constituted of palladium; rings of zinc oxide; star-shaped crystal structures of vanadium oxide; and various more complicated flower- or tree-like structures obtained, for example, with silicon carbide, magnesium oxide, or molybdenum disulfide. The 0D nanomaterials can be used individually, for example, as a cell marker [30], in solution as an emulsifier [31] or within a solid matrix as a reinforcement filler [32].

One-dimensional (1D) nanomaterials have two external dimensions at the nanoscale, the third one being usually at the microscale. This includes nanofibers, nanotubes, nanowires, and nanorods. Nanofibers have been produced with inorganic materials, for example, carbon, titanium dioxide, silicon dioxide, zirconium dioxide, aluminum oxide, titanium nitride, or platinum, and a large variety of polymers including nylon, polyurethane, polyolefins, polyethylene terephthalate, polycarbonate, polyvinyl alcohol, polylactic acid, polystyrene, polyamide, etc. They can be formed as a web for filtration applications or spun into a yarn [33]. Nanotubes display a peculiar hollow cylindrical crystalline shape with atoms organized as pentagons, hexagons, and/or heptagons [34]. Carbon nanotubes are the best known, but nanotubes can also be produced with boron nitride, molybdenum, tungsten or copper sulfides, and various halides like nickel chloride, cadmium chloride, and cadmium iodine. Nanowires have the largest aspect ratio of 1D nanomaterials with a length to width ratio ≥1000 [35]. This allows them to confine electrons laterally, which is of large interest for electronics applications. Nanowires can be made with semiconductor compounds like silicon, indium phosphide, gallium nitride; metals such as nickel, lead, gold, silver, and cobalt; and electrical insulators like silicon dioxide and titanium dioxide. Finally, nanorods are situated at the boundary between 0D and 1D nanomaterials with an aspect ratio generally situated between 3 and 20 [36]. Some nanorods have the capability to change their reflectivity when their orientation is modified with an electric field. They may also generate heat upon absorption of infrared radiation.

Figure 1  Dimensionality-based classification of nanomaterials.

With only one external dimension at the nanoscale, 2D nanomaterials comprise thin films, nanocoatings, and nanoplates. Thin films consist of ceramic or metal coatings that can be as thin as a few atomic layers [37]. They are mostly used in physics and electronics, for example, to manufacture electronic components with insulating or conductive surface properties or to change the optical reflectivity of surfaces. Various materials can also be used to produce nanocoatings, including polymers and composites [38]. The objective in that case will be to improve the hardness, the resistance to abrasion or corrosion, or provide an insulating layer, for example. The last category of 2D nanomaterials is composed of nanoplates, which can be of natural origin like smectic clay, or manufactured like graphene, silver, gold, bismuth selenide, or bismuth telluride nanoplates. The thickness of nanoplates is generally a few nanometers, and their width and length are 70–150  nm for nanoclay [39] and up to 600  nm for graphene nanoribbons [40]. Nanoplates can be used as components in electronics and as a reinforcement filler for composites to improve their mechanical, and thermal and diffusion barrier properties, for example.

The last dimensional category of nanomaterials, 3D nanomaterials, display internal nanoscale features but no external dimension at the nanoscale. This includes nanocomposites and nanostructured materials. Nanocomposites are multiphase solid materials with at least one of the phases with at least one nanoscale external dimension [41]. The term nanocomposite is generally used to describe nanofillers dispersed in a bulk matrix. These nanofillers can be selected among 0D, 1D, or 2D nanomaterials. Matrices may be polymers, ceramics, or metals. The final material can be 1D, 2D, or 3D, that is, a fiber, a film, or a volume. An example of a natural nanocomposite is bones, with calcium hydroxyapatite nanocrystals dispersed in a collagen matrix. The difference between nanocomposite and composite materials is related to the very large surface to volume ratio of the nanofillers; the nanofiller/matrix interface appears as a fully fledged third phase with properties differing from that of the matrix. Polymer–matrix nanocomposites have found numerous applications as structural materials, with increased strength and modulus, and as packaging materials, with an increased barrier performance. Finally, nanostructured materials include nanoporous structures, for example, aerogels with an extremely low thermal conductivity [42], coatings with nanoprotrusions displaying superhydrophobic properties [43], block copolymers [44], and nanostructured metals and alloys used, for instance, as shape-memory materials.

2.3. Classification of Nanomaterials According to Chemical Composition

Another possible categorization of nanomaterials is based on the chemical nature of the constituents [45]. Examples of metal and metal alloy nanomaterials include silver used in medical diagnostic, antibacterial, conductive, and optical applications [46]; copper employed as a catalyst, electrical and thermal conductor, sintering and lubricant additive, and antibacterial agent [47]; gold applied for drug delivery, medical testing, cancer detection, electronics, heat dissipation, specialized alloys, and fuel cells [48]; iron exploited for its chemical reactivity in ground contamination treatment, for its bactericide characteristics in water treatment, and for its superparamagnetic properties in drug delivery, data recording and magnetic detection [49]; platinum and palladium utilized as catalytic converters [50,51]; aluminum, magnesium, titanium, aluminum–magnesium alloys, and titanium–aluminum alloys used in aerospace and high-temperature applications thanks to their high strength and low weight [52]; and iron–silicon–boron alloy employed in electronics for its exceptional magnetic properties [53].

A second chemical category of nanomaterials is constituted of metal oxides. Titanium dioxide has found applications as a transparent ultraviolet (UV) filter for cosmetics, chemical catalyst for cleaning products and wall paint, antibacterial agent for filtration devices, and in solar cells, for example [54]. Zinc oxide has some interesting UV, catalytic, and antibacterial properties, too; it is also used as an antistatic agent [55]. Nanosilica is exploited for its high chemical reactivity, excellent thermomechanical reinforcement of polymers, optical absorption, photoluminescence, and as a hollow carrier for drug delivery [56]. Nanoalumina is employed in abrasion-resistant coatings; as chemical catalyst; and as mechanical, thermally conductive, and optical reinforcement [57]. Depending on their type, iron oxides may be used for biomedical and electronic applications thanks to their excellent magnetic properties, for water purification, and as pigments, flocculants, and ion exchangers, for example [58]. Cerium oxide is applied as a chemical–mechanical polishing agent for silicon wafers, as a vehicle exhaust catalyst, in fuel cells, and as a UV absorber in lacquers and coatings for wood [59].

Semiconductors constitute another category of nanomaterials. At the nanoscale, the optical and electronic properties of semiconductors are governed by quantum mechanics [60]. Nanosilicon is used in photovoltaics, rechargeable batteries, solar cells, electronics, solid-state lighting, and biological applications. Thanks to its low thermal conductivity and high optical absorbance at the nanoscale, silicon–germanium has thermoelectric and photovoltaic applications. Gallium nitride is employed to make flexible and water-resistant light-emitting diodes (LEDs), transistors for electric cars as well as photonic and optoelectronic devices. Gallium arsenide is used as a photodetector, in solar cells, and in optomechanics. Indium gallium nitride can be formed as nanorings for LEDs, nanoflowers for optoelectronics, and nanocolumns for photovoltaic applications.

Another category of nanomaterials includes silicates, carbonates, and nitrides. One of the most used nanosilicate is clay, a magnesium aluminum silicate [39]. It can take the shape of nanoplates in the case of Montmorillonite, for example, or nanotubes with Halloysite. Nanoclay is used as a filler in composites to improve their mechanical performance, barrier properties, resistance to heat and flame, and electrical conductivity. It may be functionalized with organic groups to improve its dispersion and adhesion with organic matrices. Another interesting silicate is zeolite with applications as a catalyst, molecular sieve for hydrocarbons, and germ for the fabrication of separation membranes [61]. In the case of calcium carbonate, if its role at the microscale as a filler for composites is mostly aimed at cost reduction, when at the nanoscale, it can improve their resistance to impact, environmental aging and creep, their barrier properties, surface finish, thermal conductivity, dimensional stability, and modulus, as well as lower contraction during processing [62]. For their part, silicon nitride nanoparticles increase the resistance of composites to crack propagation and help with radar and infrared (IR) camouflage.

Carbon nano-objects represent one of the best known categories of nanomaterials. They include graphene, carbon nanotubes, carbon nanofibers, fullerenes, and carbon black. Graphene is made of one-atom-thick carbon atom sheets [63]. Its industrial manufacturing process is still in development, but several potential applications have already been identified: electrodes for solar cells and organic LEDs; reinforcement for polymer–matrix composites; electronic components with a higher electron speed than with silicon; hydrogen storage for fuel cells; electron storage for supercapacitors; gas separation membranes, sensors, etc. Carbon nanotubes are graphene sheets wound into a cylinder and self-aligned under Van der Waals force [64]. Current applications include reinforcement for composites, tips for atomic force microscopes, and scaffolds for bone growth. Carbon nanofibers are also formed with wrapped graphene sheets but without the perfect arrangement of nanotubes [65]. They are used in field electron emission sources, as scanning electron microscope tips, and as composite reinforcement, for example. In the case of fullerenes, the graphene sheets are folded into a sphere or an ellipsoid [66]. Their applications include antiaging cosmetics, contrasting agents for medical imaging, catalysts for water purification and methane conversion, electronics, photovoltaics, and reinforcement for composites. Finally, carbon black has been added to polymers and elastomers for >100  years as a mechanical reinforcement, UV absorber, heat and electricity conductor, and antistatic agent [67]. It is made of amorphous carbon particles produced by the incomplete combustion of heavy oil products.

Polymers are the last category of nanomaterials. At the nanoscale, their optical, mechanical, thermal, electrical, and magnetic properties differ from the bulk [68]. All three types of polymers, that is, thermoplastics, thermosets, and elastomers, can be used to make nano-objects including nanospheres, nanofibers, and nanoporous membranes. Their applications comprise reinforcement for structural composite parts, filtration membranes, barrier membranes, membranes for fuel cells, fire-resistant and antibacterial textiles, optical components, and flexible electrical elements. Micelles are also a special type of nanostructured materials made of copolymers with alternating hydrophobic and hydrophilic blocks [69]. They can be used as chemical sensors, filtration membranes, drug carriers, support for tissue regeneration, and artificial muscles, for example. Finally, cellulose is a natural pseudopolymer composed of nanofibrils or nanocrystals [70]. With their low cost, low density, very high mechanical resistance, ease of functionalization, electrical conduction, biodegradability, low abrasion during processing, gas impermeability for the crystalline part, they may be used as mechanical, thermal, and barrier reinforcement for composites and in flexible displays.

In terms of produced quantities of these different types of nanomaterials, information is still difficult to obtain. Some data are starting to become available as a result of the now mandatory declaration of produced and imported manufactured nanomaterials in France (according to the European definition of a nanomaterial) [71]. Among the 500,000  tons of produced and imported manufactured nanomaterials declared in 2014, carbon black and silicon dioxide come ahead with >100,000  tons each. Calcium carbonate and titanium dioxide are reported at 10,000–100,000  tons/year each. Declarations for aluminum oxide, aluminum oxide hydroxide (boehmite), cerium dioxide–zirconium dioxide mix, polyvinyl chloride, and silicic acid magnesium salt totalize between 1000 and 10,000  tons/year each. Kaolin is listed at 100–1000  tons, zinc oxide and cerium dioxide at 10–100  tons, carbon nanotubes at 1–10  tons, and silver at 0.1–1  kg. Large quantities of various types of pigments were also declared. Discrepancies in the relative importance of the different nanomaterials may be noted, for example, with the 2013 update of Nanotechnology Consumer Products Inventory in which 51% of the listed products contain nanosilver [13]. Differences exist also with a study published in 2011, which reports that nanoclay is one of the three nanomaterials used in most significant quantities in Denmark [72].

2.4. Classification of Nanomaterials According to Potential Toxicity

The potential risk for health related to nanomaterials was first evidenced in the 1990 [73]. Pioneering work had previously revealed the association between acute respiratory problems and zinc smelting and fumed silica, but without attributing the effects to the size of the particles. Since that time, efforts have been dedicated to getting a better knowledge about the potential toxicity of nanomaterials (Chapter 1.4). Even if gaps still exist, workplace exposure limits have been proposed by several groups in different countries [17]. For that purpose, nanoparticles have been grouped into categories corresponding to their potential toxicity level.

The first category corresponds to fiber-like nanoparticles. This includes rigid, biopersistent carbon nanotubes, fiber-like metal oxides, and carbon nanotubes without asbestos-like effects [17]. The first two categories of nanomaterials have the lowest proposed exposure limits (10⁴–10⁵ fibers/m³ or 0.007–0.03  mg/m³ depending on the group) while the proposed value for carbon nanotubes without asbestos-like effects is 4  ×  10⁷ fibers/m³.

The second category regroups biopersistent granular nanoparticles with a density <6000  kg/m³ [17]. It includes titanium dioxide, silica, zinc oxide, aluminum oxide, nanoclay, carbon black, fullerenes, dendrimers, and polystyrene. The proposed exposure limits range between 2 and 4  ×  10⁷ particles/m³, between 0.066 and 0.1  ×  WEL (work exposure limit) of the corresponding coarse material, and between 0.3 and 3.5  mg/m³. In the case of biopersistent granular nanoparticles with a density >6000  kg/m³ like gold, silver, cobalt, lanthanum, lead, iron, iron oxide, cerium oxide, antimony oxide, and tin oxide, the proposed exposure limits are 2  ×  10⁷ particles/m³, 0.066  ×  WEL of the corresponding coarse material, and 0.03 Australian inhalable or 0.1 Australian respirable WEL. A value of 0.3  mg/m³ has been proposed for insoluble nanoparticles for which no WEL is available.

Another category corresponds to CMAR (Carcinogenic, Mutagenic, Asthmagenic, Reproductive toxin) nanoparticles, that is, with carcinogenic, mutagenic, asthmagenic, or reproductive toxin-proven effects in their larger size form [17]. It comprises nickel, cadmium-containing quantum dots, chromium VI, beryllium, arsenic, and zinc chromate. Proposed exposure limits are 2–4  ×  10⁷ particles/m³, 0.1  ×  WEL of the corresponding coarse material, and 0.3 and 3.5  mg/m³. A value of 0.003  mg/m³ has been proposed for insoluble nanoparticles for which no WEL is available.

Finally, in the case of liquid and soluble nanoparticles like fat, hydrocarbons, siloxane, and sodium chloride, it has been proposed to use the same WEL as for the coarse material or half its value [17]. For soluble nanoparticles for which no WEL is available, the proposed value is 1.5  mg/m³.

3. Properties of Nanomaterials

Since the first application of nanomaterials as pigments, some of their other unique properties were progressively uncovered as well as the reasons for such exceptional characteristics. These can be attributed to their very small size and very large surface area [74]. Indeed, when an object dimension is smaller than the characteristic length of carriers like electrons and photons so that they become confined, the laws of quantum mechanics apply: energy levels are discretized and waves reveal their corpuscular nature. In addition, at the nanoscale, the surface to volume ratio of objects is very high, and their behavior becomes controlled by surface properties, which are close to that of free atoms, rather than by volume properties. In particular, the effects of gravity and inertia become negligible compared to that of Van der Waals and electromagnetic forces. The consequences of the nanoscale size and surface effects can be observed on the optical, electrical, mechanical, chemical, physicochemical, thermal, and magnetic properties of nanomaterials, for example.

The unique optical properties of nanomaterials were the first to be exploited by our ancestors who used them as dyes for textiles as well as pigments for stained glass windows, glassware, and wall painting [75]. When at the nanoscale, matter may change color; for example, gold nanospheres turn blue or red depending on their diameter and wall thickness. Opaque substances such as titanium dioxide, zinc oxide, and copper may also become transparent. Phenomena involved in these effects are surface plasmon resonance, that is, a coherent excitation of free electrons by light, and electron confinement, resulting from the nano-object dimensions being smaller than the electron coherence length and the light wavelength. Applications taking advantage of these unique properties include nanowire and nanotube electrodes for lightweight and flexible displays; nanoparticle targeting and contrast agents for medical imaging; low cost, more efficient solar cells with low temperature manufacturing processes and reduced light reflection; and cosmetics with transparent UV absorbers like titanium dioxide and zinc oxide nanoparticles.

In the case of metals and semiconductors, electrical properties at the nanoscale are dictated by the fact that the object dimensions are smaller than the electron free mean path [45]. Collisions with the nano-object surface increase the material resistivity. In addition, the confinement of the energy levels can make metals like bismuth become semiconductors, and semiconductors like silicon become insulators. This offers large opportunities for smaller, lightweight, flexible, and energy-efficient electronic components, integrated circuits and electronic devices. When two conductors are positioned on each side of a nanoscale insulator, their electron wave functions may superimpose leading to tunnel conduction. This phenomenon is the basis of the scanning tunneling microscope and can be used for manufacturing high-efficiency magnetoresistive random access memory (MRAM). Replacing the two conducting materials with superconductors leads to the main constituent of the SQUID (superconducting quantum interference device) high-performance magnetic field detector as well as to one of the most efficient photon detectors [76]. Carbon nanotubes and wire-shaped nanomaterials also display a very interesting electrical property called ballistic conduction [77]. Resistivity due to scattering is reduced to a negligible level, which allows carrying very high currents without burning the conductor. Due to electron confinement, the nanowire resistivity does not change with its length. In addition, the electrical properties can be adjusted by controlling the nanotube geometry. Applications include electrical connections for metals, electronic connections for semiconductors, and flat screen for nanotubes.

With regard to mechanical properties, nanomaterials and nanostructured materials show a reduced modulus due to more slippage at grain boundaries because of smaller size grains [78]. Their strength, hardness, and abrasion resistance increase because dislocations are blocked at the more numerous grain boundaries. The very high strength of carbon nanotubes, filamentary crystalline whiskers, and nanocrystalline materials is caused by the fact that they contain no dislocations. Nanomaterials generally show a reduction in ductility and tenacity because their large grain boundary surface area restricts dislocation movement. The exceptions are ceramic materials that may become ductile at the nanoscale and be formed at lower temperatures. Applications include, for example, metallurgical processes following the traces of Damascus steel metalsmiths, cables and textiles made of nanofiber and nanotube yarns, and wear-resistant ceramic coatings for machinery parts, motors, aeronautics, and biomaterials. In the case of nanocomposites, strength generally increases also as well as creep resistance because of the impact of the nanofiller–matrix interface area [79]. However, modulus increases too, and deformation at break decreases, which may be an issue for some applications. Another concern with nanocomposites is that not much is known yet about fracture mechanics. A challenge with polymer–matrix nanocomposites is to obtain a good dispersion of the nanofillers and a good adhesion with the matrix. Mechanical applications of nanocomposites include sport equipment, household items, windmill blades, and construction materials like concrete and asphalt. Another item of interest regarding the mechanical performance of nanomaterials is related to nanoelectromechanical systems (NEMS). They are miniature mechanical structures with sensor and/or actuator functions [80]. NEMS provide extremely high sensitivity mass sensors with a much lower power consumption than their microscale microelectromechanical system (MEMS) counterparts. However, the range of application of these systems is limited by the impact of surface mechanisms like friction and surface tension.

The large chemical reactivity of nanomaterials is attributed to their large surface area as well as to the presence of more edges, angles, and crystal defects. As an illustration, a 1-cm³ cube has a surface area of 6  cm² and 12 edges. The same volume of matter split into 1-nm³ cubes has a surface area of 60,000,000  cm² and 12.10²¹ edges. This larger chemical reactivity makes nanomaterials ideal candidates for application as catalysts [81]. For instance, a large reduction in cost can be obtained by using nanoscale alternatives of the traditional expensive catalyst metals like platinum. It is also possible to employ nanoscale versions of less expensive materials like metal oxides. An additional benefit of nanoscale catalysts is that they form stable suspensions and have a much wider range of operating temperatures. Another type of application taking advantage of the large chemical reactivity of nanomaterials is sensors [82]. For example, carbon nanotubes and metal nanoparticles can detect various gas and solvent molecules as a result of a modification in their electrical conductivity or light absorption spectrum. In addition, the use of nanomaterials allows the miniaturization of these sensing devices. Nanomaterials can also be applied as antibacterial agents [83]. For example, silver nanocrystals create structural changes in cell walls and protein nucleus membranes, and prevent the replication of microorganisms. Several metal oxides such as titanium dioxide, zinc oxide, magnesium oxide, and copper oxide also have a decontaminating action against toxic gases like saran, mustard, and pesticides. In the case of titanium dioxide, the reaction proceeds through photocatalytic oxidation. The large surface area of nanomaterials promotes also their use as a support for functionalization. Another category of chemical applications of nanomaterials is related to their barrier properties. Nanoporous membranes can be used for water filtration by nanofiltration or inverse osmosis, decontamination of polluted waters with zero-valent iron coated membranes, and air filtration with nonwovens [84]. On the other hand, nanoparticles dispersed in composite membranes increase their barrier performance against gases and aerosols thanks to the tortuous path effect [85]. For example, large aspect ratio nanoparticles like nanoclay are largely used in the food packaging industry to reduce carbon dioxide leakage out of carbonated beverage bottles, and control oxygen and moisture flow through fresh food packaging.

Nanomaterials also display some interesting physicochemical properties, namely, superhydrophobicity. Indeed, nanoscale surface features allow one to obtain a contact angle >150° that prevents water from sticking to the surface, leading to the so-called lotus effect [86]. Two criteria must be validated to achieve the Cassie state: the contact force must be higher than gravity and the nanostructures must be tall enough to prevent water from touching their bases. In addition, the hydrophobicity can be made stable with a hierarchical structure, that is, with nanostructures decorating microstructures. Applications of nanomaterials with superhydrophobic properties include textiles with stain-resistant, rapid drying, easy decontamination, and more hydrodynamic performance; fog-free and self-cleaning glasses, windows and screens; easy to clean and decontaminate walls, floors, and counters; and more hydrodynamic and fuel efficient boats.

The thermal properties of nanomaterials involve a reduction of the characteristic temperatures, including melting, glass transition, degradation, evaporation, and sintering temperatures, which results from the larger number of free-like surface atoms [87]. In addition, an insulating layer can be created using aerogels made of silica, alumina, or polymer nanoporous materials. Some nanomaterials also display a fire-resistant performance [88]. This includes inherent fire-resistant materials such as zinc oxide, aluminum trihydrate, and magnesium hydroxide nanoparticles. They convey their fire-protective characteristic to the matrix polymer they are dispersed in. Nanoparticles also prevent the violent formation of bubbles during combustion and limit the diffusion of gases including oxygen thanks to the tortuous path effect. Finally, some nanomaterials like clay nanoparticles and carbon nanotubes favor the formation of a protective carbonaceous residual layer upon combustion. Applications taking advantage of the thermal and fire-resistant properties of nanomaterials comprise fire-protective clothing, interiors of air and ground transportation vehicles, and thermoelectric systems where a combination of maximal electrical conductivity and minimum thermal conductivity is needed.

The last category of unique behavior displayed by nanomaterials is related to their magnetic properties. For example, transition metals and their alloys display superparamagnetism when at the nanoscale, that is, large magnetization under an applied magnetic field without remnant magnetization [89]. This characteristic is very interesting for biomedical applications when nanomaterials can be used as contrasting agents, separation agents, and drug carriers with a limited risk of thrombosis. Applications of superparamagnetic nanomaterials can also be found in electronics, for example, as liquid gaskets in hard drives, heat carriers in speakers, high sensitivity sensors, and in data recording systems. Nanocomposite permanent magnets can be produced by coupling ferromagnetic and superparamagnetic phases. Magnetic interactions with other particles may also lead to interesting applications for nanomaterials, for example, for water decontamination of arsenic and carbon tetrachloride with rust nanoparticles [90]. Finally, magnetostriction, that is, deformation under an applied magnetic field, is also observed in some nanomaterials [91]. It has applications as driving element for microactuators, resonators with magnetically adjustable frequency, and stress-controlled inductance.

4. Fabrication Methods

Engineered nanomaterials are generally produced by a top-down or a bottom-up process (Figure 2) [92]: According to the top-down approach, larger scale, bulk matter is reduced to nanoscale objects by mechanical, chemical, or physical methods. With the bottom-up strategy, atomic or molecular components are assembled through chemical reactions or physical processes to produce nanoscale structures. Scientists are also exploring the concept of mechanosynthetic chemistry or molecular manufacturing that could allow atoms to self-assemble into nanoscale structures through what is called the bottom-to-bottom approach [7]. The bottom-up process is currently the most common synthesis route for industrial production of nanomaterials [93].

Nanoparticles can be produced using top-down, bottom-up, and bottom-to-bottom approaches [7]. Top-down approaches include crushing and grinding of bulk materials. Liquid nitrogen is used for soft materials. This technique has the advantages of being easy to implement, cheap, and universal. However, the produced particles are polydispersed, their size is generally >800  nm, and they contain a large number of defects. A new top-down technique is based on the electroerosion of granulated metals into nanopowder produced by high voltage electric discharges. The bottom-up process consists of nucleation and growth of atoms from a stable dispersion into nanoparticles by changing external parameters to favor the bulk phase. At first, fluctuations in the metastable phase lead to the appearance of small quantities of the new phase, which may eventually reach the nucleus critical size. At that point, growth proceeds to lower the system free energy. This method generally allows the production of nanoparticles with a well-controlled size distribution. The bottom-to-bottom approach involves moving each atom one by one to its predefined position using, for example, a scanning tunneling microscope. This method is still limited to some well-equipped research laboratories.

Figure 2  Schematic representation of top-down, bottom-up, and bottom-to-bottom approaches for the fabrication of nanomaterials.

Nanofibers and other 1D nanomaterials may also be produced by nucleation and growth [7]. The nucleation can be homogeneous for materials like polyaniline that naturally grows as needles. For others like carbon nanotubes, heterogeneous nucleation takes place by vapor condensation at the solid/gas interface of a little cluster of catalyst material, for example, iron–nickel alloy in the case of carbon nanotubes. Growth proceeds perpendicularly to the catalyst surface. Another strategy is based on the use of nanoporous molds. Uniform nanopores are produced by laser drilling or autoassembly. A thin layer of matter can be deposited on the surface of the pores, leading to the formation of nanotubes, or the pores can be entirely filled to produce nanowires. The mold is finally dissolved. Nanofibers can also be produced by electrospinning of viscoelastic liquids [94]. This method is often used with polymers. An electrical field is applied to a drop of liquid, which becomes instable, leading to the ejection of filaments. According to the capillary version of this technique, a charged liquid is fed into a capillary set at a high voltage. The ejected filament is attracted by a collector electrode. The capillary method is controlled by the applied voltage and leads to low output rates for nanofibers. An increase in nanofiber production rate can be obtained with the charge injection method. A nonconducting liquid is charged by being forced at a high pressure between two high voltage electrodes. It is then attracted by the third collector electrode. Electrospun nanofibers can be produced from a solution or a melt system. The polymer can be dissolved in a solvent for the electrospinning process. After spinning, the solvent is evaporated. Thermoplastic polymers may also be melted for spinning and then cooled down. Because of the high viscosity of polymers, fibers produced using melt spinning are not in the nanoscale range. Solutions to circumvent this problem are the use of a heated chamber or hot air blowing for capillary electrospinning, and of a very high mechanical pressure for charge injection electrospinning.

Nanocoatings may be produced by physical or chemical vapor deposition, liquid processes, or chemical grafting. Physical vapor deposition techniques include direct current (DC) sputtering, molecular beam epitaxy (MBE), and atomic layer epitaxy [7]. DC sputtering consists of condensing on a substrate atoms ejected from a negatively charged target acting as a source. This process can be used for metals as well as for ceramics if a reactive species such as oxygen or nitrogen is introduced in the chamber. The coating produced is generally thicker than 100  nm. A much more precisely controlled deposition is obtained through MBE. Source materials in evaporation cells are used to send molecular jets toward a heated substrate so that epitaxial growth takes place. This process, which is conducted at a very low pressure to limit scattering and prevent contamination, allows one to produce very thin coatings of a few square centimeters at a rate of one atomic monolayer per second. In atomic layer epitaxy, atomic monolayers of different materials are deposited alternatively on the substrate. Chemical vapor deposition is simpler to implement than physical vapor deposition and allows a better control of the stoichiometry [95]. The substrate is exposed to one or more gas-phase precursor, which chemically reacts or decomposes on the substrate surface to create the coating. It is thus possible to handle 3D structures and produce very thin coatings. The technique is very versatile both in terms of nanocoating material and structure, and type of substrate. The disadvantages of this technique include exposure of the substrate to high temperatures, production of toxic secondary products, and the high cost of the reactive chemicals. Liquid deposition processes comprise Langmuir–Blodgett films and self-assembled monolayers [7]. They proceed by emersion of a solid substrate from a liquid at the surface of which lie the molecules of interest. These molecules hold one hydrophilic and one hydrophobic group in the case of Langmuir–Blodgett films and are subsequently immobilized by polymerization. For self-assembled monolayers, one extremity of the molecules has a strong affinity for the substrate material and will establish chemical or hydrogen bonding with it. The other extremity is slightly solvated by the liquid so that the molecule only unfolds while out of the liquid. The last method developed to produce nanocoatings is chemical grafting [96]. Molecules are chemically bonded to a macromolecule and form lateral groups of a different nature or configuration, called brushes. This technique, which applies to polymers, is easy to implement and allows one to produce very stable chemical patterns with a wide variety of polymers.

The type of process used to produce nanocomposite materials depends on whether the matrix is organic or inorganic. In the case of polymer–matrix nanocomposites, they include in situ polymerization, nanofillers/matrix blending, and nanofiller in situ synthesis [97]. In situ polymerization was the first method developed. The monomer is used as a medium for nanofiller dispersion. Polymerization may be initiated by heat, radiation, or diffusion of an initiator grafted or fixed on the nanofiller prior to mixing with the monomer. This technique is quite complex to implement. The most frequently used technique consists of dispersing the nanofillers in the polymer matrix. This can be done by melt intercalation with the application of high shear stress in the

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