Market Report - Nanomaterials – the driving force

Market Report

Nanomaterials – the driving force

QinetiQ Nanomaterials Ltd, Y25 Bldg, Cody Technology Park, Ively Road, Farnborough, Hants GU14 0LX, UK, URL: www.nano.QinetiQ.com

Available online 9 December 2004.

The growth in activity surrounding nanomaterials continues unabated as more R&D funds are poured into nanotechnology and companies look to exploit the expanding range of novel properties that are being discovered. Advances in existing production techniques are improving the quality and yields, providing a clear prospect of commercially viable volume production. There is still a wide range of processes being used, and it is clear those that will be commercially successful will be those for which the materials have been developed at the same time as the application. Recent reports from a number of working groups have highlighted the need for increased examinati 22422p155w on of the health, environmental, and ethical aspects of nanotechnology, and this is an area that the industry will need to understand more fully and take appropriate action on if the benefits of nanomaterials are to be realized.

Article Outline

What are nanoparticles?

Why are they interesting?

How are nanoparticles made?

Wet chemical processes

Mechanical processes

Form-in-place processes

Gas-phase synthesis

Growth in commercial activity

The market for nanoparticles

Health, environmental, and ethical issues

The future for nanoparticles and the companies that make them

Conclusion

References

The nanotechnology bandwagon continues to roll. The number of individuals and groups active in this field continues to grow as funding, especially for government-supported work, continues to rise. It has been estimated that $8.6 billion will be spent worldwide on nanotechnology-related R&D in 2004, of which just over half ($4.6 billion) is from governmental bodies¹. A consequence of this is the accelerating number of publications and patents²coming out each year (Fig. 1).

https://www.sciencedirect.com/science?_ob=MiamiCaptionURL&_method=retrieve&_udi=B6X1J-4F07P23-W&_image=fig1&_ba=1&_coverDate=12%2F01%2F2004&_alid=258551991&_rdoc=1&_fmt=full&_orig=search&_cdi=7244&_qd=1&view=c&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=51ea0d77517a978eef0ac479f35a8910(62K)

Fig. 1. The growth in the number of patents and journal publications on nanotechnology³

An added incentive to researchers developing applications, especially budding entrepreneurs, is the talk of nanotechnology companies going public and the high share values associated with them, although this has taken a tumble in recent months. The drive behind nearly all this activity is the continued development of nanomaterials and the constant stream of new properties and capabilities that are being discovered. These innovations appear to make possible an ever-increasing number of applications for which nanomaterials can provide improved performance and the promise of competitive advantage and value creation. In many areas where the industries are mature, such as automotives, commodity plastics, and power generation, the slightest advantage over one's competitors can mean the difference between struggling to survive and a sustainable existence. The use of nanomaterials in these industries and others is increasingly being seen as one way of gaining this advantage in the marketplace.

However, nanotechnology is not new and, although the term was first coined in the 1960s, it can be argued that material scientists and chemists have been working in nanotechnology since their disciplines started. In fact, nanoparticles were used over 2000 years ago in Roman glass⁴, where clusters of Au nanoparticles were used to generate vivid colors, and more widely in ceramics and glass from the 10^th century⁵.

The real move toward the use of nanoparticles did not occur until the early 20^th century with the production of carbon black and, subsequently, fumed silica in the 1940s. The discovery of C₆₀ in 1985⁶ and carbon nanotubes in 1991⁷ gave a real stimulus to the development of nanomaterials and made scientists ready to explore more avidly the use of these materials. The advances in computing power and materials modeling, coupled with significant advances in characterization such as atomic force microscopy (AFM) and scanning tunneling microscopy (STM), and greater interest in synthesis routes, have provided the additional factors that have enabled nanomaterials to be designed for specific purposes. It is this ability to design and characterize materials at the nanoscale that distinguishes modern nanotechnology from previous activities in materials science and chemistry.

What are nanoparticles?

Although nanotechnology is widely talked about, there is little consensus about where the nano-domain begins. In fact, in the recent report⁸ by the Royal Society and the Royal Academy of Engineering in the UK, the definitions of nanoscience and nanotechnology avoided the use of dimensions at all:

• Nanoscience is the study of phenomena and manipulation of materials at atomic, molecular, and macromolecular scales, where properties differ significantly from those at a larger scale.

• Nanotechnologies are the design, characterization, production, and application of structures, devices, and systems by controlling shape and size on the nano scale.

Nanomaterials cross the boundary between nanoscience and nanotechnology and link the two areas together, so these definitions are very appropriate. It is recognized that the size range that provides the greatest potential and, hence, the greatest interest is that below 100 nm; however, there are still many applications for which larger particles can provide properties of great interest. Therefore, for the purposes of this article, I have arbitrarily taken nanoparticles to be discrete particles that have a diameter of 250 nm or less.

Trying to convey what this means in terms of scale has led to some awe-inspiring statistics. For example, 2 g of 100 nm diameter spherical Al nanoparticles contains sufficient particles to give every human on the planet 300 000 particles each, while nanosilicates have an interfacial area that is equivalent to cramming a football field within a raindrop. Furthermore, nanomaterials cover a hugely diverse range of materials: polymers, metals, and ceramics.

Nanoparticles can come in a wide range of morphologies, from spheres, through flakes and platelets, to dendritic structures, tubes, and rods. Fig. 2 shows some examples of nanomaterials. The sophistication of the production processes for some materials has reached the level in the laboratory where complex three-dimensional structures such as springs, coils, and brushes have been made⁹ (Fig. 3).

https://www.sciencedirect.com/science?_ob=MiamiCaptionURL&_method=retrieve&_udi=B6X1J-4F07P23-W&_image=fig2&_ba=2&_coverDate=12%2F01%2F2004&_alid=258551991&_rdoc=1&_fmt=full&_orig=search&_cdi=7244&_qd=1&view=c&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=1de07e9a8be24137801f17baf9a87955(215K)

Fig. 2. Micrographs of different example nanomaterials: nanopowders of (a) Co; (b) copper oxide; (c) ZnO; and (d) Ag.

https://www.sciencedirect.com/science?_ob=MiamiCaptionURL&_method=retrieve&_udi=B6X1J-4F07P23-W&_image=fig3&_ba=3&_coverDate=12%2F01%2F2004&_alid=258551991&_rdoc=1&_fmt=full&_orig=search&_cdi=7244&_qd=1&view=c&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=612f73c8950cba67d26188e56d3d8f8c(111K)

Fig. 3. Nanostructures of ZnO synthesized under controlled conditions by thermal evaporation of solid powders⁹

Why are they interesting?

Just because materials can be made into very small particles does not immediately mean that they have any practical use. However, the fact that these materials can be made at this scale gives them the potential to have some very interesting properties (Table 1).

Table 1.

Characteristic lengths in solid-state science model¹⁰

Materials at the nanoscale between 1 nm and 250 nm lie between the quantum effects of atoms and molecules and the bulk properties of materials. It is in this ‘no-man's-land’ where many physical properties of materials are controlled by phenomena that have their critical dimensions at the nanoscale.

By being able to fabricate and control the structure of nanoparticles, the scientist and engineer can influence the resulting properties and, ultimately, design materials to give desired properties. The electronic properties that can be controlled at this scale are of great interest¹¹. The range of applications where the physical size of the particle can provide enhanced properties that are of benefit are extremely wide. Some of the applications that utilize these characteristics are discussed later in this article.

How are nanoparticles made?

Manufacturing nanoparticles can be achieved through a wide variety of different routes: some have been around for many years; others are far more recent. In essence, there are four generic routes to make nanoparticles: wet chemical, mechanical, form-in-place, and gas-phase synthesis. It is worth exploring each of these basic routes, as the resultant materials can have significantly different properties, depending on the route chosen to fabricate them, and some routes are more aligned with the fabrication of certain classes of materials.

Wet chemical processes

These include colloidal chemistry, hydrothermal methods, sol-gels, and other precipitation processes. Essentially, solutions of different ions are mixed in well-defined quantities and under controlled conditions of heat, temperature, and pressure to promote the formation of insoluble compounds, which precipitate out of solution. These precipitates are then collected through filtering and/or spray drying to produce a dry powder.

The advantages of these wet chemical processes are that a large variety of compounds can be fabricated, including inorganics, organics, and also some metals, in essentially cheap equipment and significant quantities. Another important factor is the ability to control particle size closely and to produce highly monodisperse materials. However, there are limitations with the range of compounds possible, bound water molecules can be a problem, and, especially for sol-gel processing, the yields can be quite low.

New processes that might overcome some of these problems are being developed, such as high-throughput microreactors¹². For bulk production, large quantities of starting materials may be required, which can be expensive. Having the nanoparticles well dispersed in a suspension, however, is an advantage if further surface treatment is required to encapsulate or functionalize their surface.

An adjunct to these processes are those involving biological materials that provide a template into which inorganic materials can be grown. Since biological materials, such as porphyrin¹³ and ferritins¹⁴, are highly reproducible, the resulting nanomaterials can be made to an extremely specific size with a high degree of accuracy. However, the range of sizes may be limited by the availability and structure of suitable template materials. These are being used to manufacture materials such as magnetic materials for use in high-density storage devices.

Mechanical processes

These include grinding, milling, and mechanical alloying techniques. Provided that one can produce a coarse powder as a feedstock, these processes utilize the age-old technique of physically pounding coarse powders into finer and finer ones, similar to flour mills. Today, the most common processes are either planetary or rotating ball mills. The advantages of these techniques are that they are simple, require low-cost equipment and, provided that a coarse feedstock powder can be made, the powder can be processed. However, there can be difficulties such as agglomeration of the powders, broad particle size distributions, contamination from the process equipment itself, and often difficulty in getting to the very fine particle sizes with viable yields. It is commonly used for inorganics and metals, but not organic materials.

Form-in-place processes

These include lithography, vacuum deposition processes such as physical vapor deposition (PVD) and chemical vapor deposition (CVD), and spray coatings. These processes are more geared to the production of nanostructured layers and coatings, but can be used to fabricate nanoparticles by scraping the deposits from the collector. However, they tend to be quite inefficient and are generally not used for the fabrication of dry powders, although some companies are beginning to exploit these processes. A number of universities and companies are developing variations on these processes, such as the electrostatic spray assisted vapor deposition process¹⁵.

Gas-phase synthesis

These include flame pyrolysis, electro-explosion, laser ablation, high-temperature evaporation, and plasma synthesis techniques.

Flame pyrolysis has been used for many years in the fabrication of simple materials such as carbon black and fumed silica, and is being used in the fabrication of many more compounds. Laser ablation is capable of making almost any nanomaterial, since it utilizes a mix of physical erosion and evaporation. However, the production rates are extremely slow and most suited to research uses. Both RF and DC plasmas are being used successfully to make a wide range of materials. The heat source is very clean and controllable and the temperatures in the plasmas can reach in excess of 9000ฐC, which means that even highly refractory materials can be processed. However, this also means that the technique is unsuitable for processing organic materials.

The production of fullerenes and carbon nanotubes is a specific subset of gas-phase synthesis techniques. Many variations have been explored and patented in the years since they were discovered¹⁶. All the techniques essentially involve the controlled growth of a nanotube on a catalyst particle through the cracking of carbon-rich gases such as methane. It is possible to make low-purity nanotubes using electric discharge techniques, but this results in wide variations in materials within a batch. Most techniques are increasingly focused on the production of either single- or multi-walled nanotubes, with significant efforts going into increasing the purity and yields. There are currently no large-scale production facilities in operation, but a number of companies in the USA, Japan, and Europe are planning to install significant production capacity.

As can be seen, there are a multitude of different methods employed to manufacture nanoparticles and carbon nanotubes. All are being used, some commercially, and each has its merits and drawbacks. However, it is clear that most of the methods will be utilized in commercial production at some stage since, although the materials are nominally the same, the characteristics of the materials produced by each process are not always equivalent and can have different properties. The manufacturing routes that become commercially successful, therefore, will predominantly be those for which the materials have been developed at the same time as the application.

Growth in commercial activity

Adding particulate materials to other matrix materials has been a common technique for changing the properties of materials since the human race first developed synthetic materials. However, the additives first used were usually larger than the nanoscale.

The first industrial production of nanomaterials occurred early in the 20^th century with the production of carbon black and subsequently, in the 1940s, fumed silica. These materials are still produced and used in vast quantities, and some well-known companies such as Degussa and Cabot owe their origins to these materials. However, it was not until the latter half of the 20^th century that the scientific understanding of materials incorporating ultrafine particulates really developed and it was realized that significant improvements to material properties could be achieved by using them.

During the 1960s, 1970s, and early 1980s there was a gradual expansion as large multinational companies established subsidiaries. The real burst in the commercialization of nanoparticle production has occurred over the last ten years or so. One of the main drivers for this has been the extraordinary growth in the electronics and optoelectonics industries. As the technologies have developed and functionality has increased, the drive has been to produce smaller and smaller products requiring smaller components. This has meant that designers are demanding more from the materials used to construct the devices, which has led to a search for ways to produce major improvements in performance and the move to nanoscale materials.

In all, there are over 1500 companies involved in nanotechnology R&D worldwide¹. It is not easy to extract from the data which companies are nanomaterials focused but, where the data^{17, 18, 19, 20, 21, 22 and 23} is available, one can see this rapid growth charted in Fig. 4, which shows that the number of companies doubled in the 1990s.

https://www.sciencedirect.com/science?_ob=MiamiCaptionURL&_method=retrieve&_udi=B6X1J-4F07P23-W&_image=fig4&_ba=4&_coverDate=12%2F01%2F2004&_alid=258551991&_rdoc=1&_fmt=full&_orig=search&_cdi=7244&_qd=1&view=c&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=e75f5299f3698bf5d96c39b37b91e4c9(116K)

Fig. 4. Growth in number of nanomaterials companies^{17, 18 and 19}

The vast majority of this growth has come through the establishment of small start-up companies spun out of universities, government laboratories, or set up by entrepreneurs based on government-funded research. Currently, it is estimated that over half of all nanomaterial companies fall into this category. To a certain extent, this phenomenon has been fueled by the growth in venture capital as a source of funding^{1 and 24}, particularly in the USA where a significant proportion of these companies are situated. However, the increasing number of Chinese companies promoting themselves in the West indicates that this is not a US/European phenomena. There are also indications that some of the early entrants are finding it tough to survive when the major commercialization of products can be many years away, since there have been a few company amalgamations in the last year^{25 and 26}.

Although accurate data are difficult to obtain, there are probably in excess of 320 companies producing nanomaterials in various forms around the world today, of which about 200 are nanoparticle producers. The split between types of material is shown in Table 2.

Table 2.

The primary material product types and primary market focuses of nanomaterials companies^{17, 18 and 19}

However, not all these companies sell the nanomaterials they make and many are geared up to generate and license intellectual property around the use of these nanomaterials. In addition to these companies, there are others making nanomaterials for use in their own products. The strongest indication that the market for nanomaterials is set to grow significantly is the fact that many major industrial materials-based companies are investing heavily in either their own production capability or buying into existing companies^{27 and 29}.

The market for nanoparticles

The question that arises is, what are the markets for nanomaterials that have made this field so attractive and led to the rapid growth in the number of companies?

To a certain extent the markets already exist. There are a large number of applications where the possibilities of re-engineering existing materials down to the nanoscale can enable new performance and hence improved products. Examples include cermet cutting tools, where smaller particle sizes translate into improved performance and lifetime; lapping and polishing compounds, where track dimensions on chips are approaching 90 nm so the polishing media need to be significantly less than this to keep defects small compared to the track dimensions; and magnetic recording media, where higher-density storage is driven by finer particle and grain sizes with the trend towards terabyte storage capacities. This type of evolutionary progression into nanoscale materials will continue as the benefits are realized. However, the growth in interest cannot be totally explained by this evolutionary development and, as more research is directed towards investigating nanoscale materials, the ability to make a step-change in performance is being found all the time.

Table 3 Estimated global production rates for various nanomaterials and devices, based on international chemical journals and reviews (2003–2004) and market research (2001). Rates are intended for guidance only, as validated numbers are commercially confidential⁸

This is opening up totally new applications and the possibility of making products that have been hypothesized about for many years, such as targeted drug delivery, new optoelectronic devices, and smaller, more efficient energy devices. Carbon nanotubes are proving to have some unusual properties¹⁶, such as being able to convert light into electric current³⁰, which could enable an enormous range of new applications. This is prompting some companies to gear up to produce significant quantities of these materials, of the order of hundreds of tonnes per year³¹.
This wealth of potential applications has given rise to some widely differing estimates of the overall size of the nanotechnology market and of the subsidiary nanomaterials market. Nanotechnology as a whole is estimated to have a market of $11 trillion by 2010, with nanomaterials growing from $490 million today to $900 million in 2005 and $11 billion in 2010^{19, 32 and 33}. However, the impact of nanomaterials will extend way beyond the immediate value of the materials themselves. One estimate has been made that nanostructured materials and processes could have an impact of over $340 billion by 2010³⁴.
Looking at the major markets for functional nanomaterials today, the largest by volume are automotive catalysts, chemical-mechanical planarization (CMP), magnetic recording media, and sunscreens with 11 500 tonnes, 9 400 tonnes, 3 100 tonnes, and 1 500 tonnes, respectively¹⁷. However, the value of the market is dependent on the materials used and the actual use so, although catalysts have a much larger volume than sunscreens, their values are very similar. The extreme end of the spectrum is biodetection and labeling materials, where a small amount goes a long way and, although only a few kilos are sold, the price per kilo is many orders of magnitude greater than, for example, CMP materials.
There is a myriad of applications using nanoparticles either on the market or under development. Table 4 identifies some of the key applications.

Table 4.

A selection of current and future applications using nanoparticles.

Considerable effort is being put into developing advanced defence applications for nanomaterials, which are unlikely to reach deployment for quite a few years to come, but which could have a large impact on commercial applications^{35, 36 and 37}. The scope and number of applications^{38, 39, 40, 41, 42 and 43} for nanoparticles continues to grow and companies are finding more and more uses for these materials.

Health, environmental, and ethical issues

Over the last couple of years, the potential impact of introducing nanotechnologies and nanomaterials into the market has received a greater profile. This has generated much debate, both in the scientific world and the general media.

The result of this increased interest has been the establishment of a number of working groups to look into the health, environmental, and ethical issues surrounding nanotechnology^{44, 45 and 46}. Even the insurance industry has examined the potential impact on its business⁴⁷.

One of the major concerns of these studies is the potential health and environmental risks associated with nanomaterials. Currently there is little information available concerning the risks, but there are data on nanoparticles produced by combustion and smoking. It is also recognized that there are already vast numbers of nanoparticles already present in the air. As the Royal Society report⁸ observes, “Small size alone is not the critical factor in the toxicity of nanoparticles; the overall number and thus the total surface area (essentially the dose) are also important.” This lack of information requires correction, both while the quantities of materials produced are small and to answer the question of whether nanomaterials are different to other forms of the same material purely through their small size. In addition to recommending further research into the toxicological aspects of nanomaterials, the report also recommends that chemicals in the form of nanoparticles or nanotubes are treated as new substances and assigned a new Chemical Abstract Service (CAS) Registry number. This could have a major impact on the development and adoption of new nanomaterials, so the implications need to be considered seriously by the nanomaterials industry.

The future for nanoparticles and the companies that make them

The use of nanoparticles is set to escalate and the market has the potential to increase dramatically over the next ten years, as more uses for these materials are developed and commercialized.

A major impact will be in the medical and pharmaceutical markets as new treatments using nanoparticles obtain licenses for use. But there are many other applications where the time to market is considerably less than the pharmaceutical market, particularly in consumer goods. However, there are still many challenges for nanomaterials companies to overcome before the potential is fully realized. These include:

• How to produce materials in volume commercially at viable prices – many current techniques cannot scale up sufficiently to produce the cost reductions required to target volume markets;

• How to supply the materials in a form suitable for inclusion in manufacturing processes – understanding the surface chemistry and how particlescan be dispersed in a wide variety of media will be key to the adoption of many materials;

• Consistency and reliability in volume production – tolerances on size and composition can be achieved reliably for simple compounds such as binary oxides and for more complex materials in small batch production, but doing this for the complex materials in volume manufacturing is not so easy;

• Characterization – it is possible to characterize materials to a great extent. However, many of the techniques are appropriate for the research lab but not for the production environment. Rapid, bulk, and preferably on-line techniques are required to monitor properties such as particle size distribution;

• The need to focus in a very broad market – the ability to pick out the applications that will come to market early will determine the survival of many nanomaterials companies in the short term as they start to build revenues and try to survive while products are developed and production capability is installed;

• How to add and retain value – this will be key to the longer-term viability of companies as volumes increase and pressure to reduce prices and hence margins increases. The approach adopted by many is of securing intellectual property to provide a longer-term income stream;

• Health, safety, and environment – the profile of nanotechnology has increased in recent years with a focus on the potential long-term effects of nanotechnology and, more immediately, nanomaterials on people and the environment^{8, 44, 45, 46, 47, 48, 49, 50 and 51}. As with any high-profile technology, questions will be asked, but some nanomaterials have been with us for many years without causing concern. However, it is very important to the success of this industry that any concerns are addressed. The key aspect is: are there any detrimental effects over and above those already identified purely from the fact that these materials are in the nano form? It is also highly unlikely that nanomaterials will be used without being incorporated into some other media, such as a composite or liquid. Research is underway into the effects of nanomaterials, and it is difficult to draw any firm conclusions to date, but there is evidence that there may be positive benefits from these types of material both for humans and the environment^{50 and 52}.

Conclusion

Nanoparticles and nanomaterials continue to attract a great deal of attention because of their potential impact on an incredibly wide range of industries and markets. Consequently, the technology is evolving rapidly and will develop faster over the coming years. The challenge for nanomaterials companies to see this potential come to fruition will be to provide the materials in volume to meet market demands, with the desired quality, in an economic and safe manner.

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