Chapter 4

Nanopowders
Oleg D. Neikov, Frantsevich Institute for Problems of Materials Science (IPMS), Kiev, Ukraine

Currently, it is the convention to consider several which the creation of the materials on atomic or
kinds of nanomaterials. Under conditions, they can molecular level promises. He also showed that the
be denoted as consolidated objects, nanosemiconduc- necessity will arise to create an absolutely new class of
tors, nanoporous structures, numerous nanotubular operative and measuring apparatus for handling such
objects, nanopolymers, catalysts and supramolecular small, nanosize objects.
structures [1]. Here, however, we are concerned with The apparatus predicted by Feynman appeared
their use as powders. The general rule is that the only in 1980 (scanning tunnel and atomic power
size of the basic structural components (crystallites, microscopes and other devices). At the same time,
phases, pores, particles and molecular ensembles) considerable progress in computer techniques had
does not exceed 100 nm. been made, which allowed us to model the material
Such traditional materials as dispersion-strength- characteristics on the nanoscale. In this connection
ened alloys, the structure of which includes ultrafine- a new paradigm, based on submicron assembling,
and nanoparticles, occupying usually only some arose. In the traditional technological approach,
5–10 vol%, as well as wrought metals and alloys, in which is termed ‘top-down’, the fine and ultrafine
which assemblies and local non-oriented areas are objects are created (miniaturization) from large ones
small but the original coarse grain size remains, do (for example, by means of comminution). The second
not come into the category of nanomaterials. approach termed ‘bottom-out’, which is popularized
It is necessary to note several terminological pecu- in organic chemistry and chemistry of high-molecu-
liarities. The terms with ‘nano-’ prefix such as nan- lar compositions, is based on submicron erection of
otechnology, nanochemistry, nanoscience, etc. have the material with given composition and structure
a wide dissemination. In American literature [2], the followed by an increase in its size.
nanotechnology concept is accepted as the ability to Starting with the pioneer work of H. Gleiter and his
create and use the materials, devices and systems in colleagues [3–5], the interest in nanomaterials is
which structural elements have sizes ranging from growing steadily. The nanomaterials, because of their
1 to 100 nm. The nanoscience is science about low- unique properties, occupy key positions in state-of-
sized matters – that is an aggregate of knowledge the-art materials science. The nanotechnologies and
about properties of substances and effects on the nanomaterials information grows greatly – articles in
nanometer scale. journals (Nanotechnology, UK; Journal of Cluster Science
Nanoparticles are low-sized hard substances, including Nanostructured Materials, The Netherlands,
the geometrical size of which ranges from tenths to USA; Journal of Metastable and Nanocrystalline Materials,
100 nm. The nanopowders and nanoparticles con- Switzerland, Germany; Journal of Computational
cepts are in many respects overlapping. But, cer- and Theoretical Nanoscience, USA; Journal of Nanoparticle
tainly, it is necessary to bear in mind the possible Research, The Netherlands, USA; Journal of Nanoscience
separate nature of the former and the necessarily and Nanotechnology, USA; Materials Science of
aggregated state of the latter (the powder – that is an Nanostructures, Ukraine; Physics of Low-Dimensional
aggregate of the separate hard small particles rang- Structures, Switzerland; International Journal of
ing from 0.001 to1000 m). Nanoscience, Singapore; and Journal of Aerosol Science,
The fundamental importance of the low-sized objects USA), the proceedings of the numerous conferences
was underscored in 1959 by Nobel Prize Winner and annual symposia, patents and monographs.
Richard Feynman in a lecture (Feynman, R.P. ‘There is In this chapter, the main attention focuses on the
plenty of room at the bottom’. In Miniaturization. New production of ultrafine and nanopowders and their
York: Reinhold, 1961), which later became famous. application in the particulate condition and consoli-
Feynman told the audience about fantastic perspectives dated state.
 Nanopowders 81

Production Methods 3. formation of solid particles by condensing

or decomposing the gaseous chemical com-
Several methods are available for the production of pounds (nucleation and growth of a new
ultrafine powders used for manufacturing nanoma- condensed phase).
terials. Conventionally, they can be subdivided into
chemical and physical. Such subdivision is yet greatly In the case of physical condensation, the temper-
tentative. Thus, chemical reactions take a large part, ature of the vapor source is higher than that of the
for example by evaporation in reacting gas media, powder formation zone; in most cases of chemical
while many chemical methods are based on the phys- precipitation it is vice versa.
ical phenomena (such as low-temperature plasma, The following conditions are necessary for the
laser emission and others). The most typical methods condensation of metallic vapor and the formation
of obtaining ultrafine powders are the following: of a particulate phase: high supersaturation of the
vapor sufficient to trigger simultaneous and multiple
● evaporation and condensation in a vacuum or formation of nucleation centers, and the presence
inert gas of a neutral gas acting as a medium preventing the
● gas-phase method of reacting in a gaseous coagulation and growth of particles due to diffusion,
medium or evaporation in a vacuum and following physical
● high-energy disintegration (high-energy com- vapor deposition.
minution, detonation gun spray process and The presence of foreign inclusions, ions and chem-
electro-bursting) ically active compounds in the neutral gas promotes
● plasma spray process the nucleation. Forced or natural circulation of the
● mechano-chemical method gas ensures the transfer of the condensation heat
● electrochemical precipitation and of the particulate matter and contributes to a
● chemical precipitation from solution variety of modes of their growth.
● self-propagating high-temperature process Temperature (T) and pressure (p) are the principal
● thermal decomposition. thermodynamic characteristics of the process. The
evaporation and precipitation take place at T1 and p1
(zone evaporation), at T2 and p2 (zone precipitation),
One of the basic processes is inert gas condensa- respectively.
tion (IGC). With IGC, high-quality powders with low Under the equilibrium conditions, the phase rule is
chemical impurities from precursor materials and observed in each zone:
low amounts of oxides or nitrides from the produc-
tion process can be produced. Other processes, like G  N 2
flame reduction or plasma reduction, use the decom-
position and reduction of metal in a gas flame or where G,  and N stand for the number of compo-
plasma. The chemical vapor reaction (CVR) process nents, phases and degrees of freedom, respectively.
uses the reaction of metal chlorides and hydrogen in Homogeneous and heterogeneous nucleations
a hot wall reactor. A wet-chemical approach in which are distinguished. The former represents the volu-
the nanoparticles are produced by gelation, precipi- metrical condensation. Realizing the evaporation in
tation and hydrothermal treatment is used in the an inert gas over a deposition surface, it is possible
so-called sol–gel processes. Let us consider some of to provoke heterogeneous nucleation, for which the
these methods of producing ultrafine powder in more nucleation energy barrier is much lower in compari-
detail. son with the volumetrical condensation.
By changing the system of supersaturation (by
increasing or lowering of vapor pressure, varying,
Condensation Technique for example, the process temperature), it is possi-
The process of powder formation comprises three ble to adjust the critical nucleus size and obtain the
stages: required powder particle size.
Detailed information on the theoretical basis of
the gas-phase method and mechanism of powder
1. vaporization, either by evaporating the formation during vapor condensation can be found
metal or by its chemical interaction with the in Chapter 6.
components of a gas phase The inert gas condensation (IGC) is realized by
2. feeding the vapor into the zone of condensa- evaporating and condensing a suitable material in
tion (decomposition) a vacuum chamber filled with low pressure inert
82 Handbook of Non-Ferrous Metal Powders

Figure 4.1 Scheme of equipment to produce metallic nanop-

owders by the inert gas condensation process.

gas (e.g. 100 Pa helium) [6]. The evaporation of the

material is performed by electron beam, magnetron
sputtering laser, either in a resistance or induction
furnace. The vapor forms particles homogeneously
due to collisions with the cold inert gas. The parti-
cle fog condenses on cooled substrates (crystallizers)
that are inserted into the vacuum chamber.
Figure 4.1 shows the scheme of well-known
installation utilizing an induction furnace for the
metal evaporation. A nitrogen stream directs the zinc
vapor to the rotating crystallizer. The particles form a
flaky powder layer on the cooling crystallizer surface
that is removed continuously by a scraper. The oper-
ating conditions for producing zinc nanopowders
are as follows: the melt temperature in the induction Figure 4.2 Draft of two different variants of the inert gas
condensation process: (a) purely convective powder trans-
furnace ranges from 650 to 800°C, the pressure of port and thermophoretic deposition on cooled surfaces fol-
nitrogen from 3 to 20 kPa and the powder yield in lowed by mechanical stripping-out of the powder deposits;
the range from 10 to 15 kg/h. (b) nanoparticles are transported to the filter substrate by
Figure 4.2 shows the scheme of equipment used enforced gas flow. Powder removal is realized by means of
on the lab scale by Fraunhofer for the production of pressurized backflow pulses.
precious metal nanopowders with a rate of about 1
to 2 kg per day [7]. The particles are transported to
and deposited on cooled surfaces due to free thermal The excess inert gas volume thereby introduced into
convention (Figure 4.2(a)); by this scheme it is diffi- the system is pumped off within a few seconds. Thus
cult to achieve real control of the powder deposition the process basically runs at a constant background
process resulting, e.g. in a rather low output of usa- pressure.
ble powder material. A closed-loop gas flow design, as The main problem in the production and process-
outlined in Figure 4.2(b) has improved on the above ing of metallic nanopowders is their high reactivity,
concept and may operate at a higher level of gas explosibility because of very high specific area, and
pressure (ranging from 2 to 5 kPa). The condensed agglomeration of particles.
silver particles coagulate within the gas flow form- In the Gleiter’s installation, the ultrafine pow-
ing highly porous (spongy) aggregates that deposit der obtained in the atmosphere of the evacuated
as a fluffy layer on a filter substrate. By using back- inert gas is combined with vacuum compacting [3].
flow pressure pulses, the powder is easily removed. Condensed on the cooled rotating cylinder, surface
 Nanopowders 83

In high vacuum, molecular evaporation from an

open surface takes place at a rate that is determined
by the Langmuir formula [9]:

⎛ M ⎞1 /2
V  4.4  104  P0 ⎜⎜ ⎟⎟⎟
⎜⎝ T ⎠

where V is the material mass (g), evaporating from

1 cm2 in 1 s; P0 is the equilibrium pressure of mate-
rial vapor at a given temperature, Pa; M is the
material molecular mass; T is the evaporation tem-
perature, K. Experimental values of vapor pressures
and evaporation rates of the elements and inorganic
compounds are given in publications [10,11].
At the beginning of the 1960s, the EO Paton
Electric Welding Institute started systematic research
Figure 4.3 Scheme of Gleiter’s installation. (Source: Ref 3) and equipment development of electron beam evapo-
ration followed by physical vapor deposition in a vac-
uum (EBPVD) to produce thick films (1–2 mm) and
bulk condensates of inorganic materials with preset
structure and properties [12].
The electron beam evaporation of materials in a
vacuum differs from other methods in such condi-
tions, namely thermal and ion plasma, primarily by
its versatility, technological flexibility and cost effec-
tiveness. During collision of flying electrons with
the solid surface, their kinetic energy is consumed in
heating, secondary emission and in excitation of X-
ray radiation. The main part of the kinetic energy of
the electrons on their collision with a solid surface is
transformed into thermal energy in a thin subsurface
layer of 1–2 m thickness. At a voltage of 20–25 kV
and beam current several amperes, energy losses for
X-ray radiation excitation are about 0.1% of the total
power of the electron beam. X-ray radiation arising
in the above voltage range, has a low penetrability
and is completely absorbed by the chamber’s metal
Figure 4.4 Scheme of microlayered material deposition on walls, which are several millimeters thick. Energy
gas turbine blades. (Source: Ref 8) losses for excitation of secondary emission (really
true secondary emission and reflected electrons) are
about 15%. Here, in heating by an electron beam,
powder particles are taken away by a scraper and the heat source is located in the working chamber
collected in a press mold of the preliminary press- (see Figure 4.4), and provides the maximum com-
ing, under pressure up to 1 GPa (Figure 4.3), then plete transformation of the electric energy into ther-
the green compact is re-pressed at higher pressures mal energy.
(3–5 GPa). Modern electron guns of 50–100 kW power ena-
A novel technology for manufacture of semi-prod- ble evaporation of metallic materials at high enough
ucts directly from metal vapor, omitting the operation rates, approximately to 102 g/cm2s. The evapo-
of producing nanopowder, is promising (Figure 4.4) rators usually used contain a water cooled copper
[8]. The simultaneous evaporation of several materi- crucible, which collects the evaporated material in
als, mixing their vapor flows, followed by condensa- the form of an ingot (cast or compacted) with diam-
tion on a substrate and subsequent thermomechanical eter ranging from 25 to 70 mm. The level of the liq-
treatment allows the construction of materials with uid pool surface from which evaporation proceeds is
unique properties. kept constant in most cases, using the mechanism of
84 Handbook of Non-Ferrous Metal Powders

vertical displacement of the ingot. For evaporation in one source without any change of the initial com-
a vacuum of 104–106 torr, the spatial density of position of the compounds is possible only under the
the vapor flow above the evaporator follows the cosi- condition that dissociation products have practically
nusoidal law of distribution, according to which the the same volatility, i.e. a harmonized ‘congruent’
maximum density is observed in the direction nor- evaporation of the compounds is required. Refractory
mal to the evaporation surface (angle   0) [10]. At oxides (i.e. Al2O3, Y2O3, ZrO2 and MgO), carbides (i.e.
a vacuum down to 102 torr, the vapor flow is dissi- TiC, ZrC and NbC) and borides (i.e. TiB2 and ZrB2)
pated to produce a more uniform density distribution. can be evaporated from water cooled copper cruci-
For evaporation of a 70 mm diameter ingot, the bles using electron beam heating with practically no
rate of vapor flow condensation on a flat stationary change in the composition.
substrate located above the liquid pool surface at A number of compounds, for instance, WC,
300 mm distance, can be up to 30–50 m per minute SiC, TiN, AlN and ZrN cannot be deposited by direct
for metals and alloys and 15–20 m per minute for evaporation because they decompose on heating,
ceramics (i.e. oxides, carbides and borides). forming products with markedly different volatili-
Similar to alloys, pure metals are evaporated as ties. Such compounds can be produced in the form
individual atoms. For most alloys, however, the com- of condensates by component evaporation from two
position of the vapor phase above the liquid alloy is independent sources (i.e. WC and SiC) or using the
not equivalent to the average ingot alloy composi- so-called reactive evaporation, bleeding the appro-
tion. Alloy fractionation occurs, namely condensate priate gas into the working chamber and vapor flow
layers beside the condensation surface, and con- ionization [10].
tains maximum amounts of volatile components. Figure 4.5(a) and (b) shows the schematics of
Condensates of multicomponent metallic materials electron beam evaporation of material A from one
of a composition homogeneous across their thick- and A and B from two sources, and subsequent
ness are produced, using various evaporation tech- vapor flow condensation on flat surfaces. The con-
niques, including evaporation of individual alloy densation surfaces can also be cylindrical or have a
components from independent sources. more complex shape and can be stationary (Figure
Evaporation of compounds (e.g. oxides, car- 4.5(a)) or make certain movements in space, using
bides and borides, etc.) is, as a rule, accompanied an appropriate feed mechanism for motion transfer
by change of the initial molecules. Many refractory (Figure 4.5(b)). The schematic (Figure 4.5(b)) cor-
compounds are characterized by dissociation of ini- responds to the technological process of deposition
tial molecules with the formation of gaseous prod- of a two component material AB, for instance WC or
ucts, for instance: O, Al, AlO3 and Al2O form during SiC, on a flat surface in the form of a circle rotating
Al2O3 evaporation. Results of analysis of thermal about a vertical axis. Substrate rotation is required
dissociation of compounds are generalized [10,13]. to produce a uniform composition across the
Producing condensates by direct evaporation from condensate thickness.

Figure 4.5 Material evaporation process following by condensation: (a) from one source; (b) from two sources. (Source: Ref 12)
 Nanopowders 85

It should be noted that such a technological proc- This process is in principle shown in Figure 4.6.
ess could be easily transformed during production of By precise selection of process parameters, including
multilayer condensates of A/B type by placing a par- concentrations, temperatures, negative logarithm of
tition between the sources (marked by a dotted line in hydrogen-ion activity (pH) value, and time, it is pos-
Figure 4.4). At a constant rate of evaporation of sub- sible to control and adjust properties such as particle
stances A and B, the substrate rotation rate will be a size, apparent density, specific surface, and overall
simple and reliable process parameter for adjustment morphology to customers’ requirements.
of the thicknesses of alternate layers. Laboratory and Nano-sized copper powder produced by the wet
production units, developed by the EO Paton Institute chemical precipitation process on a lab-scale is
have three or four independent evaporators (water shown in Figure 4.7.
cooled crucibles) and corresponding electron beam The wet chemical precipitation process can be con-
guns for evaporation of three to four materials by a trolled in such a way as to adjust properties like par-
preset program [12]. ticle size and it is also able to produce agglomerated
However, with regard to simplicity and cost effec- as well as non-agglomerated powders (Figure 4.8).
tiveness of the deposition process, the technology
variants of evaporation from one source of mixtures
of dissimilar materials, prepared in the form of spe-
cial tablets or composite ingots, are particularly
interesting.

Chemical Precipitation from Solution

Ultrafine copper powders find wide application for
microelectronic components, multilayer ceramic
capacitors (MLCCs) and -metal injection molding
(-MIM).
-MIM is an advanced method of metal injection
molding, using sub-m-sized metal powders and very
fine molds to produce extremely small three-dimen-
sional structures with very high resolution, sharp
edges and outstanding aspect ratios, while the cheap
and well established method of injection molding is
applied.
Based on microelectronic components design cri-
teria, the sub-m particle size of metal powders used
is one key component, as e.g. the internal electrodes Figure 4.6 Process flow sheet for the wet chemical production
in MLCCs are only about 1–2 m in thickness. Theses of copper powder.
layers are manufactured by screen printing of metal
paste, a technique widely used in electronic compo-
nents manufacture [14].
Therefore, products like ceramic capacitors and also
-MIM parts need to use sub-m-sized metal powders
to assure the requirements defined by their dimen-
sional design. It is consequently essential to character-
ize the particle size not only by means of distribution
in general, but also to find a method to character-
ize the biggest particles present in such powders: for
example ceramic capacitor manufacturing normally
defines values of d100  1.5 m or even d100  1.0 m.
Industrial consumption of sub-m powders in
quantities of tonnes/month, as well as the cost
aspect, emphasizes that the wet chemical process of
powder production by precipitation from solution is Figure 4.7 Transmission electron micrograph of nanosized
able to fulfill these requirements in a competitive and copper powder, produced by wet chemical precipitation
economical way. process in lab-scale. (Source: Ref 14)
86 Handbook of Non-Ferrous Metal Powders

Figure 4.8 Copper powders of different particle size and morphology produced by wet chemical precipitation from copper
salt solution: (a) agglomerated powder grade, (b) non-agglomerated powder grade. (Source: Ref 14)

The latter are best suited for metal pastes used for
screen printing deposition of thin layers.
It is well known that, for a given cobalt content,
the hardness of WC–Co cemented carbides can be
increased by decreasing the WC mean particle size.
The classical ways of production of WC, described
in Chapter 21, allow the production a WC particle
size ranging from 0.5 to 20 m. During the produc-
tion of ultrafine powders – 0.3–1 m – starting for
instance with WO3, the formation of W18O49, should
be skipped over, and the two main reduction steps
WO3 → WO2, and WO2 → W should take place in
the lowest possible humidity environment [15]. The
formation of ultrafine powders is favored by:
Figure 4.9 SEM micrograph of polyol cobalt powder.
● decreasing the amount of tungsten oxide in (Source: Ref 15)
the boats
● increasing the hydrogen flow rate
● decreasing the passing through rate of the %
boats
● decreasing the reduction temperature – below 40
1400°C
Frequency distribution

● having a smooth temperature gradient in the

furnace 30
● using hydrogen with the lowest dew point
● using a two-step reduction process. 20

In the production of ultrafine and nanometric

powders, the carburization temperature must be kept 10
in the range of 750–1000°C. For such powder pro-
duction, special ultrafine cobalt powders are needed,
since the conventional ones, ranging from 1 to 3 m, 0.5 1 μm
are too coarse.
Figure 4.10 Polyol powder particle sizes distribution.
A new process has been developed for the produc- (Source: Ref 15)
tion of cobalt powder based on the reduction at 210°C
of cobaltous hydroxide by a mixture of ethylene-
and de-ethylene-glycol [16]. This powder named Replacement of the conventional ‘hydrogen
‘polyol cobalt’ is characterized by spherical shape, nar- reduced cobalt’ by ‘polyol cobalt’ greatly improves
row particle size distribution and non-agglomerated the microstructure of the sintered product and
particles (Figures 4.9 and 4.10). allows a decrease of the milling (mixing) time by
 Nanopowders 87

half, a decrease in the sintering temperature from 50

to 75°C, and even the avoidance of HIP of low cobalt
content grades.
The nanostructured WC-Co cermets starting from
water soluble precursor compounds have the advan-
tage that the cobalt can be mixed homogeneously
with tungsten at the molecular level, Co to W can be
varied over a large range, and additional constitu-
ents (Ti, Ta) or grain growth inhibitors (Cr, V) can be
introduced homogeneously at the same time.
It is a three step process:

1. preparation and mixing of the starting

reactants
● cobalt tris-ethylenediamine tungstate,
obtained by reaction between an aque-
ous solution of CoCl2 and a solution of Figure 4.11 Spray conversion process for production of
H2WO4 in ethylene diamine [17,18] tungsten carbide-cobalt nanopowders.
● ammonium metatungstate or ammonium
paratungstate (APT)  cobalt salt am-
monia (aqueous solution, pH  7) precipitat- is a versatile technology which can be applied
ing: (NH4)8(H2Co2W11O40) · H2O[19–21], to a variety of metal–metal systems (e.g. W–Cu)
[15,16].
● APT  cobalt salt  Cr(Cl O4) and VCl3
The nitrogen drying gas that is used in spray dry-
(grain growth inhibitors) [22] ing is heated to 75–100°C, depending on the mill-
2. fixed bed- or spray-drying (600–700°C) ing liquid used. The solids content of the slurry
of the resulting precursor to a chemically varies from 75 to 80%. Pressures for single-fluid noz-
homogeneous mixture of oxides zle atomization range from 590 to 1500 kPa.
3. classical or fluid-bed thermochemical con- Nanotech (Korea) manufactures WC–Co nanopow-
version (700–1000°C, H2, CH4, CO  CO2) ders by a novel process named the spray conversion
of the dried mixture into the desired nano- method [23]. This process consists of synthesizing
scale (20–50 nm WC powder) composite a liquid solution, spray drying, hydrogen reduction
WC–Co powder. and carburization for the purpose of the refinement
and homogeneous distribution of WC particles and
Nano-sized platinum particles are very active and cobalt binder (Figure 4.11).
commercially important as catalysts. One method of The commercially produced WC-10 wt% Co
production of platinum powder with a size of about nanopowder manufactured by Nanotech using a
30 nm is the reduction of chloroplatinic acid with patented liquid spray conversion process followed by
sodium borohydride. The reduction process can be hydrogen reduction and carburization [24] is shown
written: in Figure 4.12.
In order to produce ultrafine and nanometric pow-
ders, the carburization temperature must be kept in
H2 PtCl6  NaBH4  3H2O
Pt(s)  H3BO3  5HCl the range of 750–1000°C.
 NaCl  2H2(g)

An organic protective agent such as poly (vinylpyr- Plasmachemical Synthesis

rolidone) is commonly added to prevent coagulation Synthesis realized at temperatures of 6000–8000 K
of these ultrafine platinum particles. allows high supersaturation level, high reaction and
condensation process rates. The arc plasmatrons, as
Spray Conversion Method well as high- and plasma-microwave generators, are
used. The former is more efficient, however, the lat-
With the advent of closed-cycle systems, production ter ensures the production of fine and pure powders.
of cemented carbides by spray drying increased con- The diagram of such an installation is shown in
siderably in the 1980s. Spray conversion processing Figure 4.13 [25].
88 Handbook of Non-Ferrous Metal Powders

Figure 4.12 SEM micrograph (at different magnifications) of Nanotech (Korea) commercially manufactured WC-10 wt%Co
nanopowder produced by spray draying of liquid sources, subsequent hydrogen reduction and carburization.

Figure 4.13 Flowchart of plasmachemical synthesis

installation. Figure 4.14 Schematic drawing of the lab laser pyrolysis
reactor for nickel nanopowders production.

As the initial product, metal chlorides, metal pow-

ders and silicon- and metallo-organic compounds are This process makes possible the production of
used. Plasma microwave generators and plasmachem- nickel particles by laser-driven decomposition of a
ical powders of nitrides, metal oxides and other com- nickel precursor, such as nickel carbonyl (NiCO).
pounds are manufactured. Here, an infrared laser rapidly heats a dilute mixture
The plasmachemical technique provides for a pro- of nickel carbonyl and a photo-sensitizer in a carrier
duction of refractory metal ultrafine powders (W, Mo, gas, to decompose the precursor and initiate particle
Ni), compounds (TiN, AlN, Al2O3, SiC, Si2N4, Ti(C, N) nucleation. The photosensitizer is selected from the
and others), and composite material types such as group consisting of sulfur hexafluoride, ethylene, sili-
Si3N4  SiC and TiB2  TiN and others. Due to the con tetrafluoride, and ammonia. Nickel carbonyl was
features of plasmachemical synthesis (non-isothermal generated in situ from activated nickel powder and
process, coagulation of particles, and others), the par- carbon monoxide at room temperature. During the
ticle size distribution range is, in most cases, rather synthesis process, laser heating allows for rapid cool-
wide. ing of the freshly nucleated particles by mixing with
Laser pyrolysis has been developed for the produc- unheated gas. By varying the precursor flow rate,
tion of nickel nanopowders [26, 27]. A schematic laser energy and unheated gas flow rate to change
drawing of the lab laser pyrolysis reactor is shown in the residence time, precursor concentration and
Figure 4.14. reaction temperature, the average particle size can
 Nanopowders 89

be controlled over a range of primary diameters from The plasma arc discharge process is used for syn-
5 to 50 m. Figure 4.15 illustrates the nickel nano- thesis of ultrafine zirconium based alloy powder [28].
particle average sizes versus the carbon monoxide Such powders are of particular interest in hydrogen
flow rate. Figure 4.16 shows the TEM image and storage and gas absorption application.
selected area electron diffraction pattern of nickel par- Figure 4.17 shows the flowchart of the plasma
ticles produced with ethylene as photosensitizer. With arc process. This installation mainly consists of
ethylene, in comparison with the other above photo-
sensitizers, a much larger amount is needed, but
there is no risk of nickel fluoride formation and there
may be some beneficial effect on the particle mor-
phology as well.
Such powders are of growing interest in the
development of nanostructured magnetic materials,
motivated by the potential of these materials in a
broad range of applications including data storage,
biomedicine and telecommunications.

Figure 4.16 TEM image and selected area electron diffrac-

tion pattern of nickel particles produced with ethylene as
Figure 4.15 Nickel nanoparticle average sizes versus carbon photosensitizer. (Source: Ref 26)
monoxide flow rate.

Fume chamber

Ar

Electrode

Gas valve
H2
Specimen
Copper plate

Ar
  
O2

Electric
power
supply
Figure 4.17 Flowchart of plasma arc process
for synthesis of ultrafine zirconium-based
alloy powder. (Source: Ref 28)
90 Handbook of Non-Ferrous Metal Powders

the vacuum chamber, tungsten cathode, copper The chemical composition of the synthesized
anode, gas flow system and electric power supply. powder strongly depends on the volume content of
Zr57V36Fe7 bulk alloy was used as a raw material. hydrogen in the synthesis atmosphere. The chemical
The vacuum chamber was evacuated down to 105 composition of the synthesized powder approaches
torr and then backfilled with the hydrogen/argon that of the raw material with increasing hydrogen –
mixture gas to 300–550 torr. The arc plasma was up to 50% hydrogen atmosphere. The synthesized
then initiated between the tungsten cathode and the powder has an average particle size of 50 nm.
bulk alloy on the copper anode using an arc current By means of the plasma technique, nanoscale
140 A and an arc voltage of 21–25 V. The mixture metal oxide powders are produced on a commercial
ratio of the hydrogen to argon was changed from scale [29]. A high resolution TEM image of cerium
4 to 6 to equal volumes. oxide is shown in Figure 4.18. Particle size distribu-
tion of this powder is illustrated in Figure 4.19.

High-energy Comminution
The lower limit of particle size of powders produced
by high pressure gas or water atomization is between
1 and 5 m. Examples are trademark product FLQT5
of aluminum atomized powder with medium diame-
ter 2 1 m or trademark of silver atomized powder
with average diameter 1.2 m [30].
Vibratory, attrition, jet, planetary and large-
diameter tumbler mills may be classified as high-
energy mills.
The agglomerated particles of nano-sized WO2 and
W to WC powder, generated by direct carburization,
were crushed by a jet mill [31]. This ensured disin-
tegration of the agglomerated particles and led to a
decrease of the average particle size of powders, sepa-
rated in a bag filter, from 72 to 61 nm and increased
specific surface area from 5.28 to 6.28 m2/g.
Commercial jet mills are available from NETZSCH-
Feinmahltechnik Company. A fluidized bed jet mill
CGS 16, which is able to realize the finest jet milling
Figure 4.18 Transition electron microscopy image of cerium
oxide powder particles. (Source: Ref 29) in the existing CGS series, is shown in Figure 4.20.

20 100
90
Frequency distribution (%/nm)

80
Cumulative distribution

15
70
60
10 50
40
30
5
20
10
0 0
0 10 20 30 40 50 60 70 80 90 100
Particle size (nm)
Figure 4.19 Cerium oxide nanopowder particle size distribution. (Source: Ref 29)
 Nanopowders 91

The product to be milled is fed through a double flap by the fines outlet and are separated sequentially in
valve and inlet into the milling chamber above the a cyclone and filter. The CGS 16 mills hard materi-
milling nozzles (Figure 4.21). The material is formed als down to median particle size d50  0.8 m with
in the bottom of the milling chamber on a fluid- powder yield of 4.5 kg/h.
ized bed by the gas stream from the milling nozzles. For nanotechnologies, NETZSCH-Feinmahltechnik
Particles from the fluidized bed are drawn into the offers a commercial attritor LMZ Type (Figure 4.22)
gas stream and accelerated with increasing velocity [32]. The circulation mill LMZ 60 is used for pigment
towards the center of the chamber. The milling gas, production, including titanium dioxide, the most
laden with ground particles, rises centrally to the clas- effective white pigment. Its particle sizes are below
sifier wheel, which is driven by a controlled variable 1 m with a throughput above 5000 kg/h.
speed motor. Coarse particles are rejected by the clas- To produce composition materials of the TiN–AlN
sifier wheel and return directly to the fluidized bed. system, the initial raw materials consist of titanium
Fine particles together with worked-out gas leave hydride and aluminum powder with specific surface
1.5 and 2.1 m2/g, respectively and are treated in a
planetary mill where mechanical activation acceler-
ates the nitriding process which takes place in liquid

Figure 4.20 Model CGS 16 fluidized bed jet mill. Courtesy of Figure 4.22 Type LMZ wet attritor. Courtesy of NETZSCH-
NETZSCH-Feinmahltechnik Company. Feinmahltechnik Company.

Motor
Classifier
wheel
Inlet

Fines
outlet

Milling chamber Milling

chamber

Milling
nozzles

Nozzle
Figure 4.21 Draft of a fluidized bed jet mill.
92 Handbook of Non-Ferrous Metal Powders

nitrogen [33]. The processing was fulfilled with 1440 mixed together to give a 93W–4.9Ni–2.1Fe composi-
promptness per minute in liquid nitrogen. The pro- tion using a turbular mixer. The mixture was milled
portions of the ingredients corresponds to the equi- in an ultrasonic bath for 50 and 100 h. After dry-
librium for the reaction: ing at 80°C, the powder was sieved. Mean particle
size of samples after 50 and 100 h was measured as
3TiH2  Al  2N2  3TiN  Al N  3H2 500 and 400 nm, respectively. Particle size distribu-
tion of the 100 h sample is narrower and the mean
The specific surface of the product amounts to 2.8, size of agglomerates is smaller. The mixture was then
4.39, 6.16 and 9.49 m2/g as a result of milling for reduced at 800°C in hydrogen atmosphere for 1 h.
10, 30, 40 and 60 minutes, respectively. The average Explosive evaporation of metal followed by con-
particle size was 160 nm. The mechanical activation densation of the vapor is another technique for pro-
accelerates the nitriding process. ducing fine particles. It is possible to obtain, in one
Some bulk alloys are easily crushed to fine pow- installation, between 50 and 200 kg/h powders with
der in a hydrogen atmosphere. The Nb–Ti alloys are particle size ranging from 50 to 100 nm using power
examples of this kind [34]. These alloys were hydro- inputs 25–50 kWh/kg [37]. The explosive metal
genated by a gas–solid thermal reaction system: they evaporation occurs by passing through a relatively
were placed in a furnace containing high-purity thin wire of current impulses of 104–106 A/mm2.
hydrogen gas and annealed at 1200°C for 3 hours, Depending on the atmosphere, the particles may be
followed by furnace cooling to room temperature. metallic (in neutral atmospheres) or oxide or nitride.
The hydrogenated Nb–Ti alloys are brittle and friable Required particle sizes and powder yield are con-
in comparison with the original alloys. The hydro- trolled by the discharge circuit parameters and wire
genated Nb94Ti6 powders milled in a planetary ball diameter. The particle shape is mainly spheroidal.
mill with tungsten-carbide balls in air for 60 minutes
at room temperature have an average particle size of
2.3 m, while by milling at a temperature lower than
203 K, the average particle size is less than 1 m with Powder Processing Methods
better uniformity.
Porous compact structures of pure niobium and The powder processing methods such as classifica-
niobium alloys such as Nb–Ti and Nb–N are widely tion, blending, thermal treatment and compaction
used as a metal substrate for electrolytic capacitors, are complicated with nanodispersed metallic sys-
which realize a large electrical capacity in a surface tems due to their high surface activities and, in many
layer of niobium pentoxide. Here, the porous com- cases, new approaches are required. While the influ-
pacts are generally produced from powders and one ence of the free surface and interfacial energies in the
of the ways to improve the performance is to employ micrometer scale is limited to the well known powder
powders having finer particle size under 1 m and metallurgy phenomena of driving forces for sinter-
higher impurity so as to increase the relative surface ing, wetting behavior, and grain growth – on moving
area of porous compacts with solid niobium pentox- to the nanometer scale, even characteristics that gen-
ide layers. erally are considered to be constant will change. So
Ultrasonic milling was used for obtaining of tung- the melting temperature may be lowered by hundreds
sten heavy alloy [35]. This process uses ultrasonic of degrees, the lattice parameter decreases while
cavitation, which leads to the violent collapse of mac- the vapor pressure over the solid surface strongly
roscopic bubbles, producing extremely high energy increases if the particle size is as small as 10 nm [38].
densities [36]. This energy source can be used to With the decreasing particle size, the proportion of
produce nanopowders free of impurities. The design atoms located in surfaces or interfaces increases and
of the interface structure of tungsten heavy alloys the surface and grain boundary diffusion with coeffi-
such as 93W–4.9Ni–2.1Fe is essential for property cients 103 to 104 times higher than those of volume
improvement. In particular, it is necessary to reduce diffusion [39] become dominant in thermally acti-
particle sizes, to homogenize the powder mixture, vated processes. Important factors for the proper-
and to maintain purity, in order to reinforce interface ties of nanostructured materials are the interactions
strength. Previously, mechanical alloying in an attri- between lattice defects and interfaces or surfaces as
tor was used, but this resulted in deterioration of the well as dimensional electric and magnetic effects.
properties of the powder as a result of the pick-up of Fundamentals on this matter are given in [40, 41].
impurities. Without arrangements specified during pow-
In an ultrasonic milling process [35] with WO3, der production, strong agglomeration of powder
NiO and Fe2O3 as source materials, powders were particles can take place owing to surface diffusion.
 Nanopowders 93

Table 4.1 The relative density data of Ni and Si3N4 from various particle size
powders pressed at 1 GPa

Particle sizes (m) Conventional pressing Hydrostatic pressing

Ni Si3N4 Ni Si3N4

50 0.82 … 0.86 …
5 0.73 … 0.77 …
1.1 … 0.64 … 0.69
0.05 0.58 0.54 0.68 0.60
0.015–0.017 0.49 0.47 0.61 0.50

The powder keeps a high specific surface area, but are: nanocomposites, coatings, catalysts, magnetic
particles cannot be separated. To prevent agglomera- recording materials, electrically conductive inks and
tion, particles may be introduced into a liquid before pastes, power engineering, chemical industry, bio-
they come into contact. The interactions between technologies and environmental control [1,2].
powder particles and the environment can also be
minimized by coating procedures included in the
powder production process [42]. Vapor Deposition in a Vacuum
Densification by compaction is difficult as for duc-
tile metals when the particles become very small Today, the prevailing methods to produce nanopow-
and their hardness increases. At particles sizes of ders in a controlled way are gas-phase processes and
50–100 nm, dislocation mechanisms are still active to sol–gel techniques.
enable plastic deformation. Smaller particles are dis- Due to the high reactivity of nanopowders, the
location free and the image forces counteract disloca- main problem of pickup of oxides or nitrides dur-
tions to penetrate into particles [42]. Higher densities ing processing or storage needs to be prevented. As
are achieved at elevated temperatures during com- nanopowders are used or processed in suspension,
paction [43]. The relative density data of Ni and Si2N4 agglomeration is also a quality issue because of
powders of various particle size pressed at 1 GPa are the need of deagglomeration of the powders. Both
given in Table 4.1 [44]. They illustrate the aforesaid: parameters, the pickup of gaseous impurities and
the ductile nickel powders and brittle silicon nitride agglomeration, increase with decreasing particle
powders in the ultrafine state are pressed equally. size. Therefore, for nanopowders, the development of
Higher densities are achieved at elevated tempera- technologies that combine production and processing
ture during compaction [40]. The biggest problem, is essential. Just such a principle was used in Gleiter’s
however, is connected with grain growth if dense lab installation [3] and is used in recent commercial
and nanostructured materials have to be obtained units [24,29,46–49]. While the IGC process equip-
by free sintering. Grain growth in the nanostructure ment was in the beginning used only in fundamental
can be reduced at least to a certain extent by mul- studies [3,7], tonnage quantities of nanopowders are
tiphase alloy design and pressure sintering at lower now being produced [47–50].
temperatures. For example, sintering of titanium The general view of the UE-204 installation of the
nitride powders with initial average particle size EO Paton Electric Welding Institute International
60 nm at temperature ranges from 500 to 800°C and center for electron beam technologies is presented
pressing pressure 7.7 GPa gives compacts with low in Figure 4.23. Its work chamber amounts to one
porosity (below 3–5%), while by conventional sinter- cubic meter in size and is provided with four inde-
ing without high pressure, the porosity ranges from pendent evaporators and six beam guns, each 60 kW
10 to 12% [45]. in capacity. The vapor yield in such installation
amounts to 10 kg/h.
Figure 4.4 shows the scheme of the installation in
the process of microlaminate coating forming on the
Applications rotating blade of a gas turbine. Electron beam guns
located in the gun chambers isolated from the work-
At present, there are a number of application fields of ing chamber perform the evaporation of the initial
nanopowders and numerous potential applications in ingot materials. The two upper guns heat the substrate
advanced engineering and technology. Some of these to the required temperature. The partition prevents
94 Handbook of Non-Ferrous Metal Powders

mixing of the vapor flows formed in the left and right evaporation of the NiCrAl alloy, chromium is the first
parts of the working chamber and the substrate rota- to evaporate and it forms a chromium rich layer (55
tion provides the formation of a microlaminate con- wt% Cr) 4–5 m thick on the bed coat surface. Then,
densate [51]. as the insert evaporates, NiAl intermetallic with
Typical distribution of the main elements in 5%Cr forms approximately 10 m thick. The second
the coating cross-section, produced by successive bond coat consists of two layers: first, a chromium
evaporation of CrAlY alloy ingot and of the above rich layer and then an NiAl intermetallic layer.
composite ingot is shown in Figure 4.24 [52]. In the Figure 4.25 gives typical data of ultimate strength
(a) and microhardness (b) of two phase Fe–Cu, C–Cu
and Mo–Cu condensates, produced by deposition
from two independent sources at substrate tempera-
tures of 600, 850 and 950°C.

Figure 4.23 Installation UE-204 of the EO Paton Electric

Welding Institute International center for electron beam
technologies used for electron beam evaporation and fol-
lowing physical vapor deposition in a vacuum and the man-
ufacture of various materials and components. Courtesy of Figure 4.24 Element distributions across the coating thick-
Professor BA Movchan. ness produced by evaporation of CrAlY alloy. (Source: Ref 52)

1000 4.0
3 3
900
3.5
800
2 3.0
700
σB (MPa)

Hμ (GPa)

600 2.5
1 2
500 2.0
400 1
1.5
300
1.0
200

100 0.5
0 20 40 60 80 100 0 20 40 60 80 100
(a) Cu (vol%) (b) Cu (vol%)
Figure 4.25 Ultimate strength and microhardness of two phase (1) Fe–Cu, (2) Cr–Cu and (3) Mo–Cu condensates depending
on copper volume concentration. (Source: Ref 12)
 Nanopowders 95

Because the structural coatings have a greater The powder particles have a spherical shape, control-
thickness as compared with normal protective coat- led size distribution in the range 100 nm 50 nm,
ings, they can perform the function of the bearing and high surface area to volume ratio ranging from
members. The bimetal structures in which the sec- 25 to 30 m2/g. The residual metal content is 65%.
ond layer is produced by the EBPVD method is the QinetiQ Nanomaterials Ltd [49] is developing the
simplest example of structural coatings. Some expe- process to cover a range of metals including copper,
rience is available on the application of structural nickel, tungsten and silver.
coatings for producing channeled components. First, An assessment of the worldwide value of physi-
precise casting or machining is used to make semi- cal vapor deposition (PVD) industry development
products with open channels. Then the channels (published in July 2005) [53] showed that the value
are filled with a salt mask and structural coatings of worldwide shipments of PVD equipment was esti-
are deposited on the surface of the masked chan- mated to be $5.2 billion by 2005 and was forecast
nels. Next the aforenamed component is heated to a to rise at an average annual growth rate (AAGR) of
temperature above the condensation one. Salt filler
evaporates to empty the channels. Figure 4.26 shows
the blade and vane blanks with channels, produced
by precise casting, before (on the left) and after (on
the right) deposition of the about 0.7 mm structural
coating.
Figure 4.27 shows examples of a disk and billets
produced by EBPVD process [12].
At present, the following examples of existing and
currently developed practical applications of vapor
phase technologies are given [12]:

● protective and structural coatings on gas turbine

blades for various purposes
● solid oxide fuel cells
● superhard coatings on tools for material
processing
● catalysts in the form of graded coatings on an
appropriate surface (e.g. wire and strip, etc)
● materials and coatings with special physical
properties (e.g. optical, electric, magnetic, etc)
● biomaterials and biocoatings.

Because of their high reactivity, ultrafine powders

are provided with a passivating surface layer to aid
handling and incorporation into the final product Figure 4.26 Channel blade and vane with channels, pro-
[49]. The commercial ultrafine aluminum powder is duced by precision casting, before (left) and after (right) dep-
passivated with an oxide layer less than 5 nm thick. osition of the about 0.7 mm structural coating.

Figure 4.27 (a) 220 mm diameter and 15 mm thickness disk, composed of 10 000 alternating TiAl/Ti microlayers; (b) 300 
80  16 mm strips of Cu–Cr–Nb alloy.
96 Handbook of Non-Ferrous Metal Powders

10.1%, and reach $8.4 billion by 2010. The value of [15,54,55]. Along with this, the preparation of a
materials deposited was estimated to be $1.1 billion by homogeneous microstructure and the reduction of
2005 and was expected to rise at an AAGR of 11.1% size of crack initiating defects in parallel with the
to $1.8 billion by 2010. According to this forecast, the carbide grain size are important [53]. Commercial
microelectronics industry, encompassing semiconduc- cemented carbide powders with particle sizes below
tors, components and flat panel displays, remains the 200 nm are available (Table 4.2).
largest market segment with data storage representing The greatest challenge is grain coarsening during
the fastest growing sector. sintering. The reduction of the sintering temperature
Non-consolidated nanopowders find wide applica- appears to be the important factor. Two ways appear
tion due to their special catalytic, optical, biological, to be possible to reduce grain coarsening:
electrical and magnetic properties. A broad spectrum
of metal oxide nanopowders is produced for various ● adjustment of a favorable initial state for sin-
purposes [48], including antimicrobial (wood preser- tering with a homogeneous distribution of the
vation, marine antifouling, textile fibers, thermoplas- cobalt phase and homogeneous packing of the
tics and permanent coatings), catalysts (environmental carbide particles in order to avoid local densi-
catalysts and fuel cells), performance coatings (abra- fication during sintering connected with the
sion-resistant coatings), personal care, polishing (glass formation of large pores [53]; extensive densi-
polishing and semiconductor polishing). fication during solid state sintering
● densification at low temperatures using
pressure assisted sintering (hot pressing, HIP
Cemented Carbides or SPS).
The discovery that a reduction of the carbide particle
size results in considerable improvement in hardness Several processes are under development for the
and wear, as well as strength, makes further grain production of nanostructured cemented carbides, like
refinement down to real nanostructures interesting the Nanodyne Process [55–58], mechanochemical

Table 4.2 Commercial cemented carbide and cobalt powders

Property Unit Trade grade

NC6 NC8 NC9 NC10 NC12 NACO-UF

Nominal composition:
Cobalt wt% 6 8 9 10 12 99.85 min
Tungsten wt% 85–94 85–94 85–94 85–94 85–94 …
carbide  dopant
Total carbon wt% 5.85–5.95 5.75–5.85 5.72–5.82 5.65–5.75 5.55–5.65 0.05 max
Impurities max:
Aluminum ppm 20 20 20 20 20 …
Calcium ppm 10 10 10 10 10 40
Copper ppm 40 40 40 40 40 …
Iron ppm 5 5 5 5 5 50
Magnesium ppm 4 4 4 4 4 20
Manganese ppm 4 4 4 4 4 50
Molybdenum ppm 10 10 10 10 10 …
Nickel ppm 80 80 80 80 80 80
Lead ppm 2 2 2 2 2 20
Potassium ppm 1 1 1 1 1 …
Silicon ppm … … … … … 50
Sodium ppm 7 7 7 7 7 …
Sulfur ppm 40 40 40 40 40 50
Oxygen wt% … … … … … 0.5
Zinc ppm … … … … … 5
Particle sizes m 0.2 0.2 0.2 0.2 0.2 2–4a
Apparent density g/cm3
1.95
1.80
1.70
1.65
1.50 0.5–0.9
a
Median diameter of lognormal distribution of particle sizes. Source: Ref 24
 Nanopowders 97

synthesis [59], gas phase carburization [54], or high

energy milling.
Thus, mechano-chemical synthesis is accomplished
in the following way [60]. Mixtures of elemental pow-
ders (tungsten, graphite and cobalt with particle size
smaller than 75 m) are milled under argon in a plan-
etary ball mill. The particle size decreases to 16 nm
after 20 h and to 11 nm after 100 h of milling. The
integrated mechanical and thermal activation proc-
ess [61] consist of high energy milling of a mixture
WO3  CaO  graphite. The milled powder is subse-
quently subjected to reduction and carburization at
1000°C in argon.
High-purity nanosized WC–Co powders with a
mean WC particle size of 60 nm and a cobalt con-
tent of 11 wt% can be prepared from CoWO4 by a
two-step process: hydrogen-plasma reduction giving
W–Co powders around 40 nm in a very short time
(103 s); carburization at low temperature (550–
950°C) in CO  H2 atmosphere [62].
The problem of grain growth preventing sinter-
ing of ultrafine and nanometric WC–Co powders has Figure 4.28 Selection of nanometric WC-Co solid carbide
often been solved in recent decades by adding grain end mills, drills and rods. (Source: Ref 24)
growth inhibitors (mainly VC, Cr3C2 and TaC).
A new class of solid solution grain growth inhibi-
tor alloys, which are solid solutions of VC and Cr3C2 to 1000, can be produced by a chemical vapor trans-
in a Co-rich matrix, has been developed [63]. These port process carried out in a continuous flow reactor,
alloys form multicomponent liquids at tempera- using a support metal catalyst – a carrier tungsten
tures as low as 1200°C, so that the inhibitor carbide carbide coated with a metal catalyst (Co/P) – a volatile
phase can be dispersed in the Co-rich liquid phase at species source (tungsten oxide), and a carbon source
a lower temperature than is common. Thus ultrafine (carbon black). Iodine acts as the transport reagent.
and nanometric grades can be sintered to full density The powder thus obtained (WC nanorods  Co) is
at 1250°C, resulting in a finer microstructure with mixed with paraffin wax or stearate-based lubricants,
high magnetic coercivity; this leads to higher hard- formed by extrusion (which facilitates the directional
ness and toughness. arrangement of the tungsten carbide nanorods), and
The ultrafine- and nanometric-grained tungsten hot pressed in a hydrogen  ammonia atmosphere.
carbide-cobalt cemented carbides exceed the clas- As a result of the nanorods’ parallel orientation,
sical fine-grained WC–Co in hardness at identical the contact area between the rods is considerably
toughness, by displaying a 2 to 6 times higher wear decreased while, in the radial direction, the charac-
resistance. They are finding increasing application, teristics of this fiber-reinforced material is strength-
about 35% of the total cemented carbide production, ened [64].
in wear parts, round tools, end mills, drills (Figure
4.28), helical cutters, chipless forming tools, circu-
lar shearing and cutting blades for paper and plas- Gradient Materials
tics, dental tools and microdrills for the electronic Since the late 1960s, hundreds of patents and papers
industry. For instance, in this last application, a have been published on PVD and CVD coating of the
WC (0.4 m)6 wt% Co grade, with a hardness of surface of cutting inserts by a variety of functionally
HV30  2050 (94 HRA) is used to produce drills with different materials [15]. This shows the considerable
a particularly sharp cutting edge, working at a rotat- success of the coated cutting tools. But, nearly simulta-
ing speed of 40 000 revolutions/min. neously, many attempts have been made to create and
develop cemented carbides with a combination of dif-
ferent layers which complement the properties of each
Fiber-reinforced Material other, for instance by reciprocal co-sintering, common
Tungsten carbide nanorods, with diameters between gradual pressing, sputtering or electrophoretic deposi-
2 and 40 nm and a length to diameter ratio of 10 tion of different compositions [65].
98 Handbook of Non-Ferrous Metal Powders

Nanopowder-polymer Composites multilayer magnetic/non-magnetic films like Fe/Cr,

Co/Cu, etc, have proved to be very useful for efficient
Metallic filling powders in polymers play an impor- recording of information [68]. Various makeups of
tant role in the realization of electrical conductive nanostructure Co–Cu films obtained by electrolytic
adhesives, radio frequency shielding polymers, or precipitation were studied [69–71].
magnetic polymeric layers. In most cases, the use of Multilayer films of Nb/Fe and Nb/Gd systems con-
high-aspect ratio fibers and flake is advantageous. sisting of ferromagnetic and superconducting layers
The PVD process may be used for nanopowder are also considered as a promising area for electronics
polymer composites [12]. Coming back to the process and measurement technology.
sequence in Figure 4.5, it should be noted that if one
of the evaporated metals A or B is to be replaced by
a polymer, a variant of the nanopowder polymer will Semiconductors
be obtained.
A reduction of the relative amount of metal pow- In the case of semiconductors, the conversion to
der in an electrical conductive adhesive or polymer nanostructures is accompanied by shift of lumi-
is possible by using porous nanoscale powders. With nescence spectra in the short-wave area, increase
this reduction of filler volume, adhesives with a bet- of energy gap width, and other phenomena, and
ter thermo-cycling behavior can be produced for finds interesting and important applications [2].
applications in microelectronics [66]. Monocrystalline CdSe particles in polymeric matrices
are considered as light diodes and optical switches
for the laser systems, as well as sensors in biological
Thin Film Technique applications.
The semiconductor nanoparticles are synthesized
The manufacture of films of a variety of makeup in
by colloidal methods, hydrolysis treatment, gas phase
a non-porous state is possible in a wide range of par-
technique (included phase evaporation), etc.
ticle sizes, beginning at 1–2 nm and higher. Physical
Application of heterogeneous structures with mul-
vapor deposition (PVD) methods, as well as chemi-
tilayers as AlGaAs/GaAs in semiconductor lasers has
cal vapor deposition (CVD), and also electrodeposi-
allowed a considerable decrease in the threshold cur-
tion, ion deposition, and others are used. Excitation
rents, uses more short radiation waves, and improved
of the voltaic arc in a nitrogen or carbon-bearing
other field-performance factors in fast optical fiber
atmosphere is one of the most widespread ion depo-
information transfer systems. The conversion to nano-
sition technology variants; metallic cathodes are
structures with quantum wires and dots leads to still
used as metal ion sources. The electric arc evapora-
more considerable effects (further decrease of the
tion is a highly productive process but is compan-
threshold current, increase temperature stability and
ioned by formation of a dripping metal phase. The
others) important for lasers, optical modulators, detec-
magnetron variant of ion-plasma deposition, in
tors and emitters, working in the far-infrared region.
which a target (cathode) is atomized by means of
The semiconductor nanostructures are very promising
gas discharge ion-plasma bombardment, is free from
for solar energy conversion systems. Thus the advance
the above imperfection. The transversal magneto-
in the creation of heterogeneous structures with quan-
static field localizes the plasma at the atomized target
tum wires and dots will make possible improvements to
surface and increases the atomization efficiency. By
the performance of present day and future techniques.
magnetron deposition, the substrate temperatures
are moderate (below 100–200°C), that widens the
opportunities of nanograin and amorphous thin Miniaturized Systems
films. But spraying yields are some times less than by
the electric arc evaporation. Miniaturization of advanced techniques defines the
Nanograin films represent a diamagnetic (as cop- specifications of components used to design and
per) or paramagnetic (as rhenium) matrix with nan- produce, for example, highly integrated printed cir-
oparticle inclusions of ferromagnetic metal (cobalt, cuit boards (PCB) for PCs and cell phones. All these
iron and nickel) [45,67]. The devices for information advanced PCBs each use hundreds of capacitors –
recording (recording heads, magnetic carriers, disks, so-called MLCCs (multilayer ceramic capacitor) contain
etc) are an important field of application of the mag- components with ultrafine metal powders. A modern
netic nanomaterials. Lightness reproducibility, sta- cell phone for example, contains about 300–500
bility in storage, high recording density and low cost MLCCs and perfected electronics used in modern cars
are only some of the demands of these systems. The consume about 5000 MLCCs per car. To keep the units
giant magnetic resistance (GMR) manifestations in small in size, these capacitors are all typically not more
 Nanopowders 99

than 1.2 mm in thickness, although they have a quite 11. Nesmiyanov, A.N., Vapour Pressure of Chemical
complicated internal laminate structure consisting Elements. AN USSR Publishing House, Moscow,
of several hundreds of layers; most advanced MLCCs 1961.
already have even more than 1000 layers. 12. Movchan, B.A., Inorganic materials and coatings
Though the internal structure of these compo- produced by EBPED. Surface Engineering, 2006,
nents is really complicated and miniaturized, MLCCs 22(1):35–46.
have become a cheap mass product: e.g. in 2000 13. Kulikov, I.S., Thermal Dissociation of Compounds.
about 581 billion MLCCs were consumed at an aver- Metallurgia Publishing House, Moscow, 1969 (in
age price level of only US$ 0.0107 per capacitor [72]. Russian).
Another application requiring the use of ultrafine 14. Huenert, R., Ultrafine copper powder. In Proceedings
metal powders is -MIM, an advanced kind of metal of 2002 Powder Metallurgy World Congress,
injection molding (MIM) able to produce m-sized Princeton, MPIF Publishers, New Jersey, 2002, Vol.
three-dimensional structures with high resolution as 10, pp. 1–11.
a low cost mass product. 15. Pastor, H., Developments in tungsten carbide-
A lot of work is going on in the field of microelectro- cobalt cemented carbides. In International Powder
mechanical and nano-electromechanical (less than Metallurgy Directory & Yearbook, 12th edn,
100 nm) systems that find application in supermini- 2006/2007, pp 99–108.
ature sensors, electric motors, transformers, valves, 16. Pastor, H. et al., New spherical mono-dispersed and
shutters, etc. Currently, there are already pilot models non-agglomerated cobalt powder. In Proceedings of
of microelectric motors with rotor size about 1 mm and Int. Conf. on Advanced in Hard Materials Production.
rotor speed up to 40 000 revolutions per minute. EPMA, Shrewsbury, 1992, pp. 6-1–6-11.
17. US Patent 5,338,330 (Aug. 16, 1994), July 24,
1991.
References 18. US Patent 5,352,269 (Oct. 4, 1994) July 9, 1991.
1. Andrievski, R.A., Nanomaterials: conceptions and 19. Intern. Pat. WO 96 / 03239 (Feb. 8, 1996), Swed.
up-to-date problems. Russian Chemical Journal, Appl. July 21, 1994.
2002, XLVI(5):50–56. 20. Intern. Pat. WO 96 / 14952 (May 23, 1996),
2. Nanotechnology research directions: IWGN Swed. Appl. Nov. 16, 1994.
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