Chapter 5

Nanotechnology in a Modern Economy

Abstract

Actual nanotechnology products are examined, both the upstream nanocomponents and the downstream consumer products. Current annual production is evaluated, both in terms of monetary value and tonnage. Company activity is assessed in terms of the numbers of patents assigned. Some problems with compiling statistics of nanotechnology output are considered. Future projections of market size are assessed.

Keywords

Incremental products; Consumer products; Nano-object production; Carbon nanomaterials; Fullerenes; Carbon nanotubes; Graphene; Noncarbon nanomaterials; Nanotechnology statistics; Market predictions; Company activity

This chapter addresses the questions: What types of nanotechnology are there (from a commercial perspective), and what is already commercialized? How big is the actual market? How big is the potential market? Detailed coverage of the actual technologies takes place in the six remaining chapters of this part. Here, the main purpose is to put the whole in perspective.

From a commercial perspective, nanotechnology comprises materials, devices, processes, and metrology. Nanomaterials—comprising nano-objects and nanostructured materials—and nanodevices are obviously made by nanoprocesses (nanofacture). Contemporary commercial nanostructured materials are usually made by incorporating nano-objects into a matrix—they are nanocomposites (although the purist might argue that they are not nanomaterials unless the positioning of the nano-objects within the matrix takes place with nanoscale precision). The process of incorporation may itself be a nanoprocess; more commonly it is simply mixing as a chemical engineering process. Many ancillary operations are involved, such as surface functionalization of the nano-objects, the process of dispersion itself, and formulation, which may involve adding additional substances to the composite to improve dispersion of the nano-objects and the stability of the dispersion. Optimizing these processes requires the ability to measure key attributes of the material, which is the realm of nanometrology. The makers of nanometrology instruments, especially ultramicroscopes (including the various forms of electron and scanning probe microscopies), have a market that is overall worth about the same as the nanomaterials themselves (about 4×109Image USD per annum).

A very important market for nanometrology instruments is the semiconductor processing industry (SPI). A very large scale integrated (VLSI) circuit is, in fact, a nanostructured material according to the established criteria. The output of the SPI is not, however, normally included within nanotechnology market size estimates, because it would completely dominate them.

Nanotechnology is usually considered to be an “upstream” or enabling technology. Carbon nano-objects such as fullerenes, carbon nanotubes and graphene platelets are often perceived as epitomizing nanotechnology. They are then incorporated into other, “downstream”, products. The same can be said about the SPI. VLSI circuits fabricated using “top–down” nanofacture are assembled into microprocessors (which rank as nanodevices), which are in turn nowadays ubiquitous.

To answer, then, our first question: “types” of nanotechnology closely correspond with the definitions already elaborated in Chapter 1. Figure 5.1 summarizes the current situation (cf. Section 1.4). The higher upstream (i.e., closer to the primary source) the nanotechnology, the more indirect the connexion between nanotechnology and the final product. The more indirect, the harder it is to introduce a radical technology, since much more needs to be overturned. Until now, nanotechnology has been most prominent as a substitutional indirect technology (e.g., the introduction of, successively, 65, 45, 32, 22, and 16 nm lithographies for making computer chips), and as an incremental quasidirect technology (carriers for active ingredients in cosmetics).

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Figure 5.1 Indirect, direct and conceptual branches of nanotechnology (from left to right; upstream to downstream from top to bottom), with examples (cf. Section 1.4).

5.1 Types of Nanotechnology Products

From the viewpoint of the industrialist, the question is whether the nanocomponent or process will simply substitute for an existing one at a larger scale, or whether the introduction of nanotechnology implies a radically new product. Radical novelty is epitomized by the carbon nano-objects—the fullerenes, nanotubes and graphene—since nanotubes can be made semiconducting or metallic, whereas fullerenes are insulating, electronic circuits made entirely with these materials [1], or entirely with graphene [2] are envisageable, although all-carbon electronics are still far from being commercial realities. At present, the commercially produced volumes of noncarbon materials exceed those of the nanoforms of carbon. Given the present intense interest in the global carbon cycle, it is worth noting the potential contribution of all-carbon nanotechnology to diminishing atmospheric carbon dioxide, widely seen as a major contributor to global warming.

The final destination of most nanoproducts is the consumer. The main exception is ultraprecision engineering. The market for ultraprecision machine tools is relatively small, amounting to a few tens of millions of dollars annually. The USA, the world leader, has just two companies in this business, each one selling a few dozen machines a year; the machines themselves cost hundreds of thousands to a million dollars apiece. A typical ultraprecision-engineered product is a large telescope mirror.

5.1.1 Products of Substitution

These represent the lowest level of innovation. The consumer may not even be aware of any change; the main advantage is to the producer (lower manufacturing costs through a simplified process or design), and possibly to the environment (a smaller burden, due to the use of a smaller quantity of raw materials, hence less weight to transport and less waste to ultimately be disposed of). In this case the anticipated market is the same as the present market; if there is an increasing or decreasing trend it may be considered to continue (e.g., exponential, linear or logarithmic or a combination of all three, i.e. logistic) in the same fashion.

If the innovation reduces production costs, the enhanced profitability may attract other manufacturers (assuming that the innovation is not protected by patent or secrecy), which would tend to depress the price in the long term.

5.1.2 Incrementally Improved Products

Examples are tennis rackets reinforced with carbon nanotubes, making them stronger for the same weight. Very often this will make the product more expensive, so elasticity of demand is a significant factor. On the other hand, it is doubtful whether the laborious compilations of demand elasticity that have been made in the past are really useful. What degree of improvement ranks as incremental? It might not take very much for the product to be considered as essentially new. Furthermore, how is one to quantify quality? If a laptop computer originally weighing 2 kg can be made to weigh only 1.5 kg with the same information processing performance, different users will value the difference in different ways.

5.1.3 Radically New Products

These are goods that, in their qualitative nature, did not exist before. Of course, it is perhaps impossible for something to be totally new. Polaroid “instant” film (which could be developed and made visible seconds after taking a snapshot) was certainly a radical concept, but on the other hand it was still based on a silver halide emulsion and the mode of actually snapping the shot was the same, essentially, as with a Kodak box camera.

The future is in this case very difficult to predict, and an ad hoc model (Section 12.6.1) is probably needed if any serious attempt at planning is to be made.

5.1.4 Carbon-Based Nanomaterials

Fullerenes (sp2Image hybridization), carbon nanotubes (CNT, sp2Image hybridization) and graphene (sp2Image hybridization) are true children of the Nano Revolution: they did not exist as commercial commodities before. Although carbon black (sp2Image and sp3Image hybridization) and diamond-like carbon (sp3Image hybridization) thin films have some nanofeatures, they are not atomically engineered and, moreover, existed before the era of nanotechnology; we do not propose to recruit them retrospectively. Figure 5.2 shows the striking growth (as measured by the annual number of publications) of carbon nanotubes, with a hint of saturation and the concomitant rise of graphene. A further member of the family, carbyne (a true 1-dimensional chain of sp1Image hybridized carbon) would be barely visible, with only a handful of papers, but recently it has been successfully grown inside CNT [3].

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Figure 5.2 Annual numbers of publications dealing with carbon nanomaterials excluding carbyne. Reproduced from A.I. Terekhov, Developing nanoresearch in Russia: a bibliometric evaluation. Nanotechnol. Perceptions 7 (2011) 188–198 with permission of Collegium Basilea.

Industrial problems associated with large-scale fullerene manufacture have been solved [4]; to date, their applications remain niche, however. Far more interest is associated with carbon nanotubes (CNT) [5], and even more with graphene [6]. Some of the extraordinary properties of CNT include: a very high aspect ratio (their diameter can be less than 1 nm, but they can be many micrometres long), making them suitable for field emission applications and as conducting additives to polymer matrices with a very low percolation threshold; very high electron mobility; the highest current density of any known material, approximately 109 A cm−2 (cf. copper with 106 A cm−2, and aluminum 10 times less); ballistic electron transport; the highest Young's modulus of any known material (approximately 1 TPa along the axis); the highest thermal conductivity of any known material (approximately 4000 W m−1 K−1). Manufacturing problems seem to be on the way to being solved (note that some key applications use only very small quantities); the main issue today is purity: nanotubes grown from a hydrocarbon feedstock such as acetylene using chemical vapor deposition require a metal catalyst (usually iron or nickel), which can be troublesome to remove afterwards; preparations are nearly always contaminated with amorphous carbon. The electrical properties will be revisited in Chapter 7; Table 5.1 summarizes some of the mechanical properties of carbon materials.

Table 5.1

Some properties of bulk and nanoscale carbon materialsa

Property Unit Diamond Graphite CNT
Young's modulus N m−2 109 1010 1012
Thermal conductivity W m−1 K−1 2000 20 3000

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a The given values are only approximate, in order to enable a rough comparative idea of the material properties to be formed. Actual measured values still depend on many experimental details.

Because of their great strength, carbon nanotubes (CNT) are especially attractive nanocandidates for incorporation into a matrix for the purpose of mechanical reinforcement. Even more attractive than CNT are graphene fragments (nanoplatelets). The graphene is typically corrugated due to numerous defects introduced during preparation, which is excellent for locking the material into the polymer (whereas CNT surfaces are usually smooth and defect-free). Per unit mass, graphene anyway gives double the interfacial area compared with CNT (which are, essentially, rolled up graphene). An additional advantage is that small sheets are much better at intercepting cracks in the composite than small tubes. This kind of composite in effect overcomes the reverse Hall–Petch relationship that prevents grain size being usefully decreased down to the nanoscale in order to strengthen a material [7].

Their good field emission characteristics (including ultrahigh brightness and small energy dispersion) make carbon nanotubes outstandingly good electron sources for scanning electron microscopy—although the world market is very small in terms of mass. They are also useful in residual applications of vacuum tubes (e.g., high-power microwave amplifiers). There is obviously an enormous potential application as field emission displays, although parallel innovations are required here, including a convenient means of positioning the CNT. Furthermore, there is intense competition from organic light-emitting devices. The electronic properties (very high current densities) make CNT attractive for the vertical wires (VIAs) connecting layers of integrated circuits, although exactly how their fabrication will be integrated into existing semiconductor processing technology has not been worked out. They may also be used as gates in field effect transistors (recalling that they can be prepared as semiconductors or metals). This configuration can be used to construct sensors for substances, if the gate is modified such that it interacts with the substance to be sensed. An even simpler configuration is merely to measure the electrical resistance of a substance-sensitized nanotube.

The very low percolation threshold of these extremely elongated objects (a few volume percent) enables the preparation of electrically conducting polymers with such a low volume fraction of CNT that the composite is visually unaffected by their presence. The main product of Hyperion (Chapter 16) is conducting paint suitable for the mass-production lines of the automotive industry. Other applications include antistatic coatings and electromagnetic screening films. Of great interest is the possibility of preparing transparent conducting films that could be used as the counterelectrode in displays. At present, tin-doped indium oxide (ITO) is the main material used for this purpose, but not only is it too brittle to be usable in flexible displays, but the world supply of indium is expected to be exhausted within a few years at present rates of consumption.

CNT can also be used as the charge storage material in supercapacitors. All the atoms of single-wall nanotubes are on the surface, hence they have the highest possible specific surface area (1.5×103 m2g1Image), suggesting a theoretical upper limit for energy density of 20 W h kg−1. Supercapacitors rated at 1000 F are commercially available. Nevertheless, carbon black, which is much cheaper, is almost as good, hence it is doubtful whether this application will be commercially viable.

The very small size of a single nanotube makes it an attractive electrode material in electrochemical applications, for which microelectrodes have already been shown to diminish transport-related overpotentials.

As far as composites are concerned, despite the extraordinarily high Young's modulus, mechanical performance has not been demonstrated to be superior to that already attainable with carbon fibers. The problem is how to disperse the CNT in the matrix.

The variable valence and the availability of electrons makes CNT attractive potential catalysts for certain reactions, for example in the petrochemical industry.

In many ways graphene, the newest carbon nanomaterial, is the most versatile of the three—fullerenes, nanotubes and graphene—and it is expected to overtake the others commercially. Although it only received its official name in 1986, graphene has a remarkably long history—its crystal structure by Debye and Scherrer in 1916, the band structure calculation (of graphite) by Wallace in 1947, the isolation and observation of freestanding graphene by Boehm et al. in 1962, and subsequently grown on many different transition metals and carbides. Graphene-based electronics were conceived at the start of the present century, with key achievements in transport and gatability and visions of large-scale integrated electronics based on ultrathin films of lithographically-patterned graphite. There has been good recent progress in tailoring the properties of graphene [8]; graphene-reinforced composites seems to be the area closest to technical maturity [9].

5.1.5 Noncarbon Nanomaterials

The main raw nanomaterials manufactured on a large scale are nanoparticles. The bulk of those typically included in market research reports are traditional particles, notably carbon black, synthetic amorphous silica, silver halide emulsion crystals, and pigments, which are in no sense engineered with atomic precision; some of them merely happen to fall within the accepted range of nano-objects [10]. These products are, in fact, typically quite polydisperse. Attempts to synthesize monodisperse populations on a rational basis have a considerable history [11]. Natural materials such as clays also provide a significant source of nanoparticles. Key parameters of nanoparticles are size (and size distribution), chemical composition, and shape (including porosity).

Composites

Nanoparticles have relatively few direct uses; mostly their applications are in composites (i.e., a mixture of component A added to a matrix of component B, the latter usually being the majority component)—a nanocomposite differs from a conventional composite only insofar as the additive is nanosized and better dispersed in the matrix. The purpose of adding materials to a polymer matrix is to enhance properties such as stiffness, heat resistance, fire resistance, electrical conductivity, gas permeability, and so forth; the aim of making any composite is to achieve an advantageous combination of properties. If the matrix is a metal, then we have a metal–matrix composite (MMC). A landmark was Toyota's demonstration that the incorporation of a few weight percent of a nanosized clay into a polyamide matrix greatly improved the thermal, mechanical, and gas permeability (barrier) properties of the polymer [12].

There is no general theory suggesting that the advantage scales inversely with additive size; whether a nanocomposite is commercially viable depends on all the parameters involved. There is such a huge variety of materials that it is perhaps futile to attempt a generalization. However, the very small size of individual nano-objects would make it feasible to incorporate a greater variety of materials within the matrix for a given additive weight percent. Very often ensuring wetting of the nanoparticle—the most commonly used shape hitherto, although this will change as fragments of graphene, which is a nanoplate, increases in importance—by the matrix presents a significant technological hurdle. Most successful composites require the additive to be completely wetted by the matrix. Wetting behavior can be predicted using the Young–Dupré approach [13]; if, however, the particle becomes very small, the surface tension will exhibit a curvature-dependent deviation from the bulk value appropriate for a planar particle–matrix interface.

The chief manufacturing routes for polymeric nanocomposites are blending preformed nano-objects with the molten matrix; dispersing preformed nano-objects in the monomer precursor to the matrix and polymerizing it; and synthesizing the nano-objects in situ within the matrix. In all cases the composite may advantageously be prepared as a concentrated masterbatch (especially if effectively dispersing the nano-objects in the matrix requires some special technology) that is then shipped to the converter who can readily blend it with pure matrix polymer (e.g., if all the materials are pelleted, it may suffice to simply mix the pellets in the feed hopper of the converter).

Coatings

Many properties of materials essentially only concern their surfaces; if so, it is much more cost-effective to apply an expensive material as a thin film coating the bulk object in order to achieve the desirable interfacial attribute(s) (e.g., a low coefficient of friction). Furthermore, desirable bulk properties are not compromised. Alternatively, the surface can be modified using a technique such as ion implantation [14].

5.1.6 Consumer Products

The Project on Emerging Nanotechnologies at the Woodrow Wilson Center created a list of consumer products containing nanotechnology that continued to be curated until March 2011, when it listed 1317 products [15]. Some of these are given in the next three tables, 5.2, 5.3, and 5.4. These data provide a useful snapshot of the commercial market as it was in 2011. The project was essentially continued as the crowdsourced Consumer Products Inventory (http://www.nanotechproject.org/cpi/) [16]. Other, more specialized, inventories include the EU's inventory of nanomaterials in cosmetics, which was due to be published in 2014 but has only just been released (on 15 June 2017), although it is dated 31 December 2016. Perhaps the further delay was due to the need to translate it into the numerous official languages of the EU before its official release. It was based on submissions made by “responsible persons” to the “Cosmetics Products Notification Portal”. It is perhaps typical of official EU documents that they appear with great delay and are of extremely poor quality. This “Catalogue of nanomaterials used in cosmetic products placed on the EU market” is only 15 pages long and mostly consists of a four-column table with the headings “Name”, “Category of cosmetics”, “Exposure” (i.e., dermal, oral, etc.), and whether “Rinse off”, “Leave on”, or both. There is no verifiable indication whether the listed material is in the nanoscale. A less informative document could scarcely be imagined. It concludes with “less than 1% of cosmetic products notified in the CPNP [sic] were identified as containing nanomaterials.” There is no indication whether this is a percentage of the total quantity or of the number of distinguishable products.

Table 5.2

Numbers of consumer products in different categories (status in January 2009) [15]
Category Number %
Health and fitness 502 58
Home and garden 91 10
Food 80 9
Electronics 56 6
Automotive 43 5
Appliances 31 4
Other 70 8
Total 873 100

Table 5.3

Numbers of consumer products in the “Health and Fitness” category (status in January 2009) [15]
Subcategory Number %
Personal care 153
Cosmetics 126
Clothing 115
Sporting goods 82
Filtration 40
Sunscreen 33
Total 100

Table 5.4

Numbers of consumer products categorized according to the elements declared as constituting the nanocomponent (status in January 2009) [15]
Element Number %
Silver 235
Carbon 71
Titanium 38
Silicon 31
Zinc 29
Gold 16
Total 100

Regarding Table 5.2, it is not always clear what the exact criteria for inclusion are, especially for products that could fit in multiple categories. For example, would a household appliance be included under “Appliances” or under “Home and garden”? Most appliances include some electronics, one imagines. And does an automobile (which may contain some on-board information processors with nanoscale features in their chips) count as a single product? Spray paint containing nanoparticles for use by owners to repair minor scratches presumably ranks as an automotive product, but does each available color count as a separate product? Furthermore, the compilers of the data have not themselves verified whether the manufacturers claims are correct. Moreover, one has no indication of the volumes sold: cellphones probably outranked all other members of its category, for example.

It is perhaps surprising that there are already so many food products at least containing, if not based on, nanotechnology—these, incidentally, might well have been included in the “Health and fitness” category. The list is anyway dominated by health and fitness products, which are further broken down in Table 5.3. Presumably medical products not available uncontrolled to consumers (e.g., prescription drug delivery nanomaterials) are not included in the list at all—or else none are currently available.

Finally, it is interesting to look at which elements dominate nanotechnology applications (Table 5.4). Presumably these are mostly in the form of nanoparticles. Carbon presumably means fullerenes. Silicon, titanium and zinc are presumably nanoparticles of their oxides. Since the database is of consumer products, presumably silicon-based integrated circuits are not included.

The consumer market is of course extremely fickle. The epithet “nano” is sometimes used as a marketing ploy, even if the product contains no nanomaterials at all [17]. Furthermore, it is evolving with amazing rapidity. A camera in 1960 contained no electronics, but now contains probably 80% or more, much of which is in, or heading towards, the nanoscale. A similar trend has occurred regarding personal calculators, the functional equivalent of which would have been a slide rule or a mechanical device in 1960. The personal computer did not even exist then. A motor-car typically contained about 10% (in value) of electronics in 1960; this figure is now between 30% and 50% and much of it is already, or fast becoming, nano.

A crucial point regarding consumer market volume is the renewal cycle. Whereas in other markets technical considerations dominate—for example, in many European cities the underground railway trains and trams might be of the order of 50 years old and still in good working order—psychosocial factors dominate the decision whether to replace a consumer product. It seems remarkable that those who have a mobile phone (i.e., the majority of the population) typically acquire a new one every 6 months (many are anyway lost or stolen). Other consumer electronics items such as a personal computer, video recorder or television receiver might be renewed every 1–2 years. Even a motor-car is likely to be changed at least every 5 years, despite the many technological advances that ensure that it is still in perfect working order at that age.

Here, deeper issues are raised. Without the frenetic pace of renewal, the hugely expensive infrastructure (e.g., semiconductor processing plants) supporting present technology could not be sustained, and though rapid “planned obsolescence” seems wasteful, without it innovation might grind to a halt, with possibly deleterious consequences for mankind's general ability to meet future challenges (including those associated with global warming).

5.2 The Nanotechnology Market

5.2.1 Nanotechnology Statistics

A huge number of statistics about nanotechnology are floating around the world. Websites, electronic newsletters and reports of commercial research are the main secondary sources. Hullman compiled a summary of some of the secondary sources to create a tertiary report [18], which well highlights the two main (related) problems: the huge variation among numerical estimates for most quantities (“indicators”), and the difficulty of defining categories. The main reason for the huge variation appears to be the wide variety of definitions of the indicators that are employed. The more easily accessible secondary sources (e.g., electronic newsletters) rarely, if ever, carefully define how they arrive at the quantities given. Reports that are supposed to be based on primary research might be more reliable, but this cannot be established without scrutinizing them in detail, and since they are rather expensive (typically costing several thousand US dollars) few people or organizations acquire a number of different ones and critically compare them. The best solution is probably to undertake the primary research oneself. The nanotechnology industry is still small enough to make this feasible at a cost reasonable compared with that of acquiring the commercial reports, and with a considerable gain in reliability.

One of the most glaring ambiguities regarding market size is whether the quoted value refers solely to the sale price of the raw (nano) ingredient or to the sale price of the final product incorporating that ingredient. The latter price might be one or more orders of magnitude greater than the former. For example, the world semiconductor market is presently considered to be worth about 40×109Image USD annually, whereas the world computer market is worth about 400×109Image USD annually. Since many nanomaterials are upstream additives in the production process, this consideration is very pertinent when assessing the size of the nanotechnology industry. If the final finished product is a true system, in which every part relies on every other part, then it is anyway not meaningful to separate out the values of the discrete ingredients, although it can of course be done in a narrow accounting sense. Nevertheless, if one were to omit one ingredient, the value of the final product would not simply be lessened by the cost of that ingredient.

Adding to the confusion surrounding the so-called quantitative indicators is the fact that two of the most widely used terms in the commercial predictions, “billion” and “trillion”, have parallel definitions differing respectively by three and six orders of magnitude from one another. Although the geographical origin of the number and its context usually allow one to decide what is meant, it is regrettable that this ambiguity has been allowed to persist. Usage in the UK is currently the most confusing because although located in Europe, it shares the same language as the USA. The definitions are summarized in Table 5.5. To avoid confusion, in this book we shall wherever possible write out the numbers explicitly.

Table 5.5

Definitions of commonly used words for large numbers

Word used in: S.I. terminology
Quantity Europea USA Prefix Symbol
106 million million mega M
109 milliardb,c billionc giga G
1012 billiond trilliond tera T
1015 e e peta P
1018 trillion exa E

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a The same word, with the same meaning, is used in English, French and German.

b Contemporary Italian uses “bilione” and aligns its meaning with that of the USA.

c N.W. Pirie has made the sensible suggestion of using “gillion” for 109, aligning its initial with the S.I. symbol.

d Analogous reasoningc suggests that the word for 1012 should begin with “t”. “Trillion” is, however, inappropriate because “tri” signifies 3, hence its meaning of a million cubed. Consistency demands that we create the word “tillion” for 1012.

e Logically,d the word should be “pillion”.

5.2.2 The Market in 2006

Figure 1 of the Hullman report [18] shows the predicted evolution of the world nanotechnology market (presumably defined as sales). Predictions for the year 2010 ranged from about $1011 to over $1.4×1012Image—in other words, roughly the same as the entire present manufacturing turnover in the USA ($1.1 ×1012Image in 2007, one (US) trillion in round numbers; the Taylor Report [19] predicted a global nanotechnology market exceeding $2 ×1012Image around 2012).

As mentioned, a major ambiguity is whether the entire value of a consumer product containing upstream nanotechnology is counted towards the market value; often the nanotechnology only constitutes a small part of the total. Another major ambiguity (see Figure 2 of the Hullman report) is the possibility of double counting. Frequently, the nanotechnology market is divided into different sectors without a clear indication of the criteria for belonging to each division. For example, much of nanobiotechnology is concerned with medical devices, and the devices themselves may contain nanomaterials, yet these are all given separate categories; most aerospace applications involve materials, yet these are two separate categories.

Yet another problem is that it is rarely clear to what extent “old” nanotechnology is included. The world market forecast for nanotechnology given in Figure 1 of the Hullman report starts from zero in the year 2001 (but other data given in the same report suggests that in 1999 the world market was already of the order of $1012!). This report is, in fact, unusual insofar as nanotools or nanobiotechnology are given as the dominant sectors (e.g., Figure 3 of the Hullman report) whereas elsewhere it is generally accepted that the overwhelming part of the nanomarket is at present constituted from nanomaterials, with nanodevices and nanotools occupying an almost negligible part [20]. A more reasonable estimate is that the background level of nanomaterials valid at least up to about 2005 is a global turnover of $5×109Image per annum. This is relatively minor—for comparison, the annual sales of Procter & Gamble in 2007 were $75×109Image. The nanomaterials market is dominated by nanoparticles, which includes (i) a very large volume of carbon black (2006 revenue was approximately $1.25×109Image), chiefly used as a reinforcing additive for the rubber used to make the tyres for motor vehicles; (ii) silver halides used in the photographic industry to sensitize the emulsions with which photographic film is coated (a sector that has sharply declined); and (iii) titanium dioxide used as a white pigment in paint—in other words, “old” nanotechnology (which should therefore not be considered as nanotechnology at all—according to the definitions in Chapter 1).

Furthermore, one almost never sees any uncertainties associated with these estimates. They must often be of the same order of magnitude as the estimates. For example, Figure 12 of the Hullman report shows the distribution of company sizes (measured by turnover) in different countries; in the USA and the UK the overwhelming majority of companies do not reveal their sizes.

Another criticism is that in many cases a per capita comparison would be more relevant than an absolute one; for example, Figure 14 of the Hullman report compares the numbers of institutions active in nanotechnology for European countries—at first glance the graph simply seems to follow the populations of the countries. Even when normalized by population, though, the distribution of institute sizes might vary widely from country to country.

Given these deficiencies, we can only repeat what was already stated above—the best recommendation we can give in this book is that if a company wishes to forecast the market in its particular niche, it had better attempt it by itself—the results are likely to be more reliable than those taken from elsewhere, and the assumptions used in compiling the data can be clearly stated and, hence, will be transparent and accessible to the users of the information.

5.2.3 The Market in 2013

In 2003, total global demand for nanoscale materials, tools and devices was estimated at $58×109Image and forecast to grow at an average annual growth rate (AAGR) of around 30%. Five years ago, the global market value for all of nanotechnology was expected to increase to nearly $27×109Image in 2015 [21]. The largest segment of the market, namely nanomaterials, was expected to have reached nearly $20×109Image by the end of that year; the second-largest segment, nanotools, a value of about $7×109Image; and the smallest segment, nanodevices, was projected to reach about $230 million in 2015. Note that in 2007 the largest end-user markets for nanotechnology were environmental remediation (56% of the total market), electronics (1%) and energy (14%). Electronics, biomedical, and consumer applications had much higher projected growth rates than other applications over the following 5 years (30%, 56% and 46%, respectively.) In contrast, energy applications were projected to grow at a CAGR [22] of only 12.5% and environmental applications were predicted to decline by an average of 1.5% per annum. The global market for nanotechnology-enabled products was forecast to reach $2.4×1012Image by 2015. It was predicted that by 2016 the global market for nanomedicine should have reached about $130×109Image, of which anticancer products were expected to comprise about 35% and products for diagnosing disorders of the central nervous system about 23%.

Hence, comparing nanotechnology at that time to other key emerging technologies, the global nanotechnology market is roughly comparable in size to the biotechnology sector, but far smaller than the $3.6×1012Image (2012 estimate) global informatics market. However, the nanotechnology market is believed to be growing more than twice as fast as either of the other two.

As stressed in Section 5.2.1, numbers of this nature are necessarily somewhat approximate, not least because of the lack of uniformity regarding the criteria for inclusion; that is, the answer to the question, what is nanotechnology (cf. Chapter 1)? The global personal computer market was expected to yield revenues (from the microprocessors used in the devices) of about $40×109Image in 2013; in line with Moore's law continuing its march, most of this market could reasonably be included in the nanotechnology sector on the basis of current device feature sizes.

Nanoscale metal oxide nanoparticles are already very widely used. Typical applications include sunscreens (titanium oxide and zinc oxide), abrasion-resistant coatings, barrier coatings (especially coatings resistant to gas diffusion), antimicrobial coatings, and fuel combustion catalysts. Applications of fullerenes, carbon nanotubes, and graphene, which are “true” nanotechnology products, still constitute essentially niche markets. In 2008 the fastest-growing nanomaterials segments were nanotubes (with an amazing projected AAGR of 170–180% over the following five years) and nanocomposites (about 75% AAGR). These predictions were somewhat upset by the growing prominence of graphene, which is displacing carbon nanotubes in many applications, including composites [6].

The nanomaterials segment, which, as already mentioned, includes several long-established markets (“old” nanotechnology) such as carbon black (used as reinforcing filler for rubber, especially in automotive applications such as tires), synthetic amorphous silica (used as a polymer filler, in toothpaste, and as an anticoagulant in comestible powders), catalytic converter materials, and silver nanoparticles used in photographic films and papers (this sector is now greatly diminished), until fairly recently accounted for almost all (i.e., in excess of 95%) of global nanotechnology sales. By 2008, however, the nanomaterials share of the market had shrunk to around 75% of total sales, and further decline is occurring as nanotools and nanodevices establish a major presence in the market.

5.2.4 Tonnages in 2013

it might be thought that tonnages are expected to be more reliable indicators of market volume then price. Piccinno et al. have assembled some data for the materials most widely produced in the nanoscale (Table 5.6) [23]. The wide uncertainties of each estimate are indicative of the problems in assessing production. The data was obtained by asking companies either producing or consuming nano-objects to estimate regional or worldwide production. Notwithstanding the higher median tonnage of silica, titanium dioxide is probably the most-produced material in the nanoscale, given the difficulty in precisely defining nanosilica. For comparison, annual world production of carbon black is about 12 million tonnes, but annual production of all forms of titanium dioxide is about 1.7 million tonnes in the USA alone [24].

Table 5.6

Annual worldwide production quantities of nano-objects [23]

Material 25th percentile Median 75th percentile
SiO2 55 5500 55,000
TiO2 550 3000 5500
ZnO 55 550 550
CNT 55 300 550
Ag 5.5 55 550
AlOx 55 55 5500
CeOx 5.5 55 550
FeOx 5.5 55 5500
Fullerenes 0.6 0.6 5.5
Quantum dots 0.6 0.6 5.5
Total 100

Image

Piccinno et al. also obtained estimates of the nanoproduct end-uses (Table 5.7) [23]. Note that, for consistency, the values given here are consolidated and adjusted from Piccinno et al.'s values. Crude as they are, these data seem to represent the best available estimates.

Table 5.7

Annual worldwide production quantities of nano-objects [23]
Material Product group % of total use
SiO2 n.r.a
TiO2 Cosmetics 70–80
Coatings <40
Polymers <20
Cement 1
ZnO Cosmetics 70
Coatings 30
CNT Polymers 20–70
Batteries 50
Ag Coatings 10–30
Textiles 30–50
Electronics 10–20
Cosmetics 20
Medicine 20
Antimicrobial coatings 80–100
AlOx n.r.a
CeOx Polishingb 45–80
Fuel combustion catalyst 1–50
Coatings 5–10
FeOx n.r.a
Fullerenes R&D 80
Quantum dots Light conversion 90
R&D—imaging 10

a No response.

5.2.5 The Market in 2017

The global nanomaterials market is presently estimated to be worth about 410×109Image USD. The biggest share is taken by nanoparticles (30%), followed by nanotubes (25%), nanoclays (20%), and nanofibers and nanowires (each 10%). “Nanoparticles” includes all dendrimers and nanoclays. In terms of sectors of end use, the biggest is electronics (30%), followed by healthcare (22%), transport (8%), aerospace and defense (6%), construction (5%), water filtration (3%), consumer goods (1%), and numerous smaller sectors. In terms of regional output, we have North America (40%), boosted by the large electronics industry there, followed by Europe (35%) and the Asia–Pacific region (APAC) on about 25%; the rest of the world takes less than 10%. The global nanodevices market is reckoned to be about a third of the size of the nanomaterials market.

5.2.6 Company Activity

Table 5.8 shows the top 20 institutions in the world, ranked according to the number of granted US patents classifiable as nanotechnology. Most are commercial corporations; the University of California is a multicampus academic institution with about 250,000 students. Most of the top 20 are electronics companies; only a few focus on materials. One is a cosmetics company; none are pharmaceutical companies.

Table 5.8

The top 20 nanopatenters 1991–2012

Company Domicile Turnover/$Ma No patentsb
IBM USA 81,700 1119
Micron Technology USA 16,200 762
Samsung S. Korea 77,400 681
Univ. of Calif. USA 589
Hewlett Packard USA 103,000 557
Xerox USA 18,000 538
Hon Hai Precision Ind. Taiwan 136,000 508
Intel USA 55,900c 501
General Electric USA 116,000 433
3M USA 30,300 376
MIT USA 313
ITRI Taiwan 311
Eastman Kodak USA 1800 293
Du Pont USA 25,100 267
AMD USA 4000 247
Toshiba Japan 56,700 211
Motorola USA 5700 194
L'Oréal France 26,700 188
PPG USA 15,300 178
NEC Japand 24,500 175
Total 100

Image

a For 2015, from company annual reports.

b From the US Patent & Trademark Office (USPTO) [25].

c For 2014.

d Financial year runs from April to March, as in the UK.

Figure 5.3 shows the exponential-looking growth in the total number of nanotechnology patents. Up to 1992, only 277 patents classifiable as nanotechnology has been granted by the USPTO.

Image
Figure 5.3 Annual numbers of US patents granted in the field of nanotechnology. Data from the US Patent & Trademark Office (USPTO).

5.2.7 Future Projections

Most estimates of the current growth rate of the nanotechnology market converge on around 20% CAGR over the next decade. The most optimistic projections suggest that the total worldwide annual nanotechnology market will exceed 40×109Image USD by the end of the decade. Interestingly, there is not much expectation of change of the distributions of production and end-use (Section 5.2.5).

Projections naturally depend on a great many imponderables, including the general level of economic activity and economic growth. One highly debatable matter is the influence of government spending. Opinions range from unfavorable (i.e., government spending is a narcotic that hinders rather than facilitates technical progress), to favorable (i.e., it is makes an indispensable contribution to national competitiveness). We return to this theme in Chapters 12 and 13.

A significant imponderable is parallel technical developments. For example, the realization of printed electronics is heavily dependent on the availability of various kinds of nanoinks formulated with nano-objects. But if development of the non-nano aspects of the technology is delayed, there would be correspondingly diminished demand for the nano-objects.

It is clear that the range of applications for nanomaterials is growing rapidly. Whereas until recently nanomaterials have tended to be associated with niche consumer segments such as bouncier tennis balls, a new trend of serious large-scale applications is emerging, such as tires and other rubber products, other automotive components, advanced pigments, and synthetic bone. This last-named is a biomedical application, in which there is intense interest, but at the same time the challenges are greater than originally envisaged, and products have been very slow to gain approval from the regulatory authorities.

It is often not clear exactly what is included as nanotechnology and what is not. Sometimes what is included within nanotechnology is in effect merely a relabeled traditional product [26].

Very often these near-nano products enhance the attributes of the materials to which they are added to close to the theoretical limit, in which case the almost inevitably higher expense associated with substituting them by real nanomaterials would not result in any significantly increased added value, and hence there is no driver to make their substitution.

Predictions for the healthcare market are considered separately in Section 6.10.

References

[1] D-M. Sun, et al., All-carbon thin-film transistors as a step towards flexible and transparent electronics, Adv. Electron. Mater. 2016;2, 1600229.

[2] J. Liang, et al., Toward all-carbon electronics: fabrication of graphene-based flexible electronic circuits and memory cards using maskless laser direct writing, ACS Appl. Mater. Interfaces 2010;2:3310–3317.

[3] L. Shi, et al., Confined linear carbon chains as a route to bulk carbyne, Nature Mater. 2016;15:634–639.

[4] M. Arikawa, Fullerenes—an attractive nano carbon material and its production technology, Nanotechnol. Percept. 2006;2:114–121.

[5] B.O. Boscovic, Carbon nanotubes and nanofibres, Nanotechnol. Percept. 2007;3:141–158.

[6] X. Huang, et al., Graphene-based composites, Chem. Soc. Rev. 2012;41:666–686.

[7] G.J. Fan, et al., A model for the inverse Hall–Petch relation of nanocrystalline materials, Mater. Sci. Eng. A 2005;409:243–248.

[8] A. Dey, et al., Plasma engineering of graphene, Appl. Phys. Rev. 2016;3, 021301.

[9] A. Nieto, et al., Graphene reinforced metal and ceramic matrix composites: a review, Int. Mater. Rev. 2017;62:241–302.

[10] This remark does not do justice to the extraordinary sophistication of a fabricated photographic emulsion crystal, achieved over more than a century of intensive research. For a historical overview, see R.J. Hercock, G.A. Jones, Silver by the Ton. London: McGraw-Hill; 1977.

[11] J.J. Ramsden, The photolysis of small silver halide particles, Proc. R. Soc. Lond. A 1984;392:427–444.

[12] A much older composite is paint, which consists of a pigment (quite possibly made of nanoparticles) dispersed in a matrix of varnish. Paint combines the opacity of the pigment with the film-forming capability of the varnish. Another mineral–polymer composite is the material from which many natural seashells are constructed: platelets of aragonite dispersed in a protein matrix, In this case, however, the “matrix” only constitutes a few percent of the volume of the composite.

[13] For an introduction, see M.G. Cacace, E.M. Landau, J.J. Ramsden, The Hofmeister series: salt and solvent effects on interfacial phenomena, Q. Rev. Biophys. 1997;30:241–278.

[14] See Fraunhofer Gesellschaft, Produktionstechnik zur Erzeugung funktionaler Oberflächen. Status und Perpecktiven. Braunschweig; 2008; J.J. Ramsden, et al., The design and manufacture of biomedical surfaces, CIRP Ann. 2007;56(2):687–711.

[15] Project on Emerging Nanotechnologies: Consumer Products Inventory. Washington, D.C.: Woodrow Wilson International Center for Scholars (the project began in March 2006).

[16] M.E. Vance, et al., Nanotechnology in the real world: redeveloping the nanomaterial consumer products inventory, Beilstein J. Nanotechnol. 2015;6:1769–1780.

[17] See, e.g. D.M. Berube, The magic of nano, Nanotechnol. Percept. 2006;2:249–255 Another example is the Tata Nano, which is simply a small petrol-engined car, albeit one of advanced design and conception.

[18] A. Hullman, The Economic Development of Nanotechnology—An Indicators-Based Analysis. Brussels: European Commission, Directorate-General for Research, Nano Science and Technology Unit; 2006.

[19] New Dimensions for Manufacturing: A UK Strategy for Nanotechnology (report of the Advisory Group on Nanotechnology Applications, chaired by John Taylor). London, 2002.

[20] The Hullman report merely compiles secondary sources, without any criticism or even highlighting discrepancies.

[21] This prediction and the following numbers were issued by the Economic Research Unit of the INSCX exchange (inscx.com) on 2 August 2012.

[22] Compound annual growth rate (CAGR) is the geometric mean growth rate over a period of several years, calculated according to the formula, CAGR=(ending value/starting value)1/number of years1Image.

[23] F. Piccinno, et al., Industrial production quantities and uses of ten engineered nanomaterials in Europe and the world, J. Nanopart. Res. 2012;14:1109.

[24] C.O. Robichaud, et al., Estimates of upper bounds and trends in nano-TiO2 production as a basis for exposure assessment, Environ. Sci. Technol. 2009;43:4227–4233.

[25] H. Chen, et al., Global nanotechnology development from 1991 to 2012: patents, scientific publications, and effect of NSF funding, J. Nanopart. Res. 2013;15:1951–1971.

[26] E.g. J. Harris, D. Ure, Exploring whether ‘nano-’ is always necessary, Nanotechnol. Percept. 2006;2:173–187.

Further Reading

[27] P. McKeown, et al., Ultraprecision machine tools—design principles and developments, Nanotechnol. Percept. 2008;4:5–14.

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