MM4010

Powder Metallurgy, Refractories and Ceramics

Self-propagating High-temperature Synthesis

Assignment Report

by

Vinay Ishwar Hegde

MM07B024

Department of Metallurgical and Materials Engineering

Indian Institute of Technology Madras

Chennai 600 036

7th September, 2010

Contents
1 Introduction 2

2 Discovery and Development 2

2.1 Discovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2 Subsequent Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

3 Process Characteristics 3
3.1 Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2 Processes Involved . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2.1 Combustion Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2.2 Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2.3 Combustion Front Propagation . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.4 Combustion Wave Subzones . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3 Fundamentals of SHS chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.3.1 Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.3.2 Chemical Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.3.3 Combustion Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.3.4 Physical Materials Science . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.4 Product Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.4.1 Morphology and Macroscopic Structure . . . . . . . . . . . . . . . . . . . 9
3.4.2 Product Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.4.3 Microstructure of Products . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.4.4 Class of products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4 Production Methods 9

5 SHS Research 10

6 Applications 11

7 Advantages 12

8 Related Issues 13

9 Conclusion 13

10 References 14

1
1 Introduction
Ceramic materials offer a unique combination of properties that makes them indispensable for
meeting the materials requirements for many high technology applications. But large-scale
production of ceramic bodies by conventional powder-consolidation methods is somewhat cum-
bersome because high temperature furnaces (1200o to 1800o C) and relatively long processing
times (several hours) are required. As a result, it is difficult to achieve and maintain high pro-
ductivity. Moreover, solid-state reactions of powder mixtures in high temperature furnaces are
often incomplete, allowing unreacted substances to act as impurities and leading to poor-quality
products. These shortcomings of conventional ceramic-production techniques triggered several
initiatives to develop better, more cost-effective production methods. These techniques included
Gas-phase Plating, synthesis in a Low Temperature Plasma and Shock-wave Compression, as
well as a new method called Self-propagating High-temperature Synthesis.
Self-propagating High-temperature Synthesis (SHS) means the synthesis of compounds in a
wave of chemical reaction (combustion) that propagates over a starting reactive mixture owing
to layer-by-layer heat transfer. This combustion-like process is ignited by point-heating of a
small part (usually the top) of the prepared sample. The heat is enough for initial burning of
surrounding material, which in turn, generates heat that burns the following part of the material,
and in this way a wave of exothermic reaction is generated that covers the rest of material as
an autowave.
It is sometimes referred to as ’Solid Flame Phenomenon’ (SF), simply ’Combustion Synthe-
sis’, ’High Temperature Chain Fusion’ or ’Spin Combustion’. It is officially registered as ’The
Phenomenon of Wave Localization of Autoretarding Solid-Phase Reactions’.

2 Discovery and Development

2.1 Discovery
The SHS method for producing ceramic materials was discovered in 1967 at the Macrokinetics
Lab of the Noginsk Scientific Center, a major subdivision of the Institute of Chemical Physics
in Chernogolovka. A.G. Merzhanov, head of this laboratory, is credited with the discovery of
SHS and has been most responsible for the promotion of this technology. I.P. Borovinskaya and
V.M. Shkiro have been the other principal researchers at this institute and also took part in the
discovery. Y.I. Maksimov of the Institute of Applied Mathematics and Mechanics, Tomsk State
University, has also contributed greatly to the research and development (R&D) of SHS.
The discovery of SHS was a spinoff of Soviet research that took place throughout the 1960s
regarding new models of combustion in condensed, solid-state systems, specifically during the
synthesis of copper and silver acetylenides that could be expected to burn with no gas evolution.

2.2 Subsequent Development

At first, SVS was considered by most of the Soviet scientific community to be merely a laboratory
curiosity. It was not until the early 1970s, after a large number of refractory compounds had
been synthesized, that the full potential of SHS and the impact that such a method could have
on the industrial production of ceramic materials were realized and investigation on a a variety
of carbides, nitrides, borides, and silicides of the transition metals began.

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 By 1976, at least 30 different organizations were engaged in SHS R&D. The major efforts
were still being conducted at the Institute of Chemical Physics, Chernogolovka, as well as
at the Institute of Applied Mathematics and Mechanics, Tomsk State University. Research
programs were becoming more analytical and less empirical in nature. The mechanisms of heat
transfer, chemical reactions, and product formation and kinetics of SHS processes were some
of the topics under study. The development of compounds having optimum property values
(maximum hardness, for example) were of practical interest. More than 200 different compounds
had been synthesized by the late 1970s, and catalogues for binary refractories, non-stoichiometric
compounds, weakly exothermic systems were available.

3 Process Characteristics
3.1 Classification
In SHS, there is a direct interaction of two chemical elements, one of which, the fuel (usually a
metal), is in the condensed state, while the other, the oxidizing agent (non-metal), is either in a
condensed or in a gaseous state. Depending on the aggregated state of the oxidizing agent, the
processes can be classified as:

• Solid fuel - solid oxidizing agent (sol + sol)

Initial reagents are pressed together.

• Solid fuel - gaseous oxidizing agent (sol + gas)

Powders are covered with liquids or suspensions.

• Solid fuel - liquid oxidizing agent (sol + liq)

Porous samples pressed from a powder of the fuel and placed in a medium of the gaseous
oxidizing agent.

SHS can also be carried out in gas suspensions, layered systems and (gas + gas) systems but
they are not as prevalent as the ones mentioned above.
The starting sample morphology must favour chemical reaction at high temperatures and the
materials should possess high crystal lattice binding energies. Elements, individual compounds
and their mixtures can be used as reagents while inert compounds as fillers or diluents. Mineral
raw materials and industrial waste can also be used as starting reagents.
According to analysis of elementary routes of chemical reactions performed by Borovinskaya,
all SHS reactions can be classied into the following ve groups:

1. Reactions involving no intermediates:

Ti + C →
− TiC
N2
Zr −−→ ZrN

2. Reactions involving one intermediate product:

Ta + C →− 0.5Ta2 C + 0.5C → − TaC
Nb + B →− 0.5NbB2 + 0.5Nb → − NbB

3. Reactions involving several intermediates:

N2
2Ti + C −−→ TiC + TiN →− Ti2 CN
Synthesis of YBa2 Cu3 O7−x

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 4. Branching reactions:
H2
Ti + C −−→ 1. TiC + H2
H2
Ti + C −−→ 2. TiH2 + C →− TiC + H2

5. Independent thermally coupled reactions (chemical oven):

Ti + C →
− TiC
W+C→ − WC

3.2 Processes Involved

3.2.1 Combustion Modes

For SHS systems, the most popular are the following modes of combustion:

1. Gasless combustion
Powder mixtures with little or no gas evolution.

2. Infiltration-assisted combustion
Solid-gas systems with a reactive gas.

3. Multiphase combustion in multicomponent systems

The SHS process usually involves three stages: Initiation, Front Propagation and Product Cool-
ing. They are considered in further detail below.

3.2.2 Initiation

The reaction is normally initiated from the sample surface with a heat flux (heated wire, electric
spark, laser beam, etc.). After initiation, the reaction proceeds in the mode of self-propagation.
The duration of heating is markedly shorter than the time of reaction (combustion). In some
cases (mostly low-caloric reactions), reaction may be initiated by bulk heating in a furnace and
carried out in the mode of thermal explosion.

(a) Diagram of the SHS process (b) Cryogenic reactor for producing ceramic materi-
als

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3.2.3 Combustion Front Propagation

The characteristics and patterns of wave propagation are useful in understanding the macroki-
netics and chemistry of SHS. The combustion wave front can propagate broadly in two ways:

1. Steady propagation
This is the simplest case of propagation where the velocity of combustion front (all the
wave points) propagation is independent of time and/or coordinates. This is considered
to be preferable for material synthesis.

2. Unsteady propagation
When the steadiness of the wave front propagation is disturbed, it may undergo:

(a) Planar auto-oscillations in the front velocity.

(b) Localization of reaction in one or several hot spots that move along a spiral trajectory.
(c) Chaotic motion of numerous hot spots.

However, frequently, the non-uniformity of combustion does not affect the product quality.

It should be noted that in case of strong heat losses (small sample diameter, low adiabatic
temperature), wave propagation is not sustained altogether (as the process works on positive
feedback).
The energy from internal heat sources, i.e., heat of exothermic reactions, furnishes 50-98%
of the total energy needed for the synthesis. In this respect SHS is placed between the processes
in explosives and the processes utilising exothermic reactions in more conventional ceramic
technologies.
A Combustion Thermogram gives evolution of temperature at a given point of charge during
SHS. A simple thermogram has an irregular-bell shape. More complicated thermograms exhibit
breakpoints, inflexions, and isothermic plateaus. In case of unsteady combustion, thermograms
may exhibit temperature oscillations within an ascending portion of the curve.

3.2.4 Combustion Wave Subzones

The combustion wave represents an expanded zone comprising a set of subzones. Each subzone
is characterized by processes occurring in it. A typical SHS wave consists of the following zones:

1. Preflame zone
It is characterized by a high thermal gradient and intense heat exchange takes place though
main chemical reactions do not occur. Phase transformations and side reactions can take
place.

2. Main heat release zone

The main combustion reactions occur. According to the modern combustion theory, the
velocity of combustion front propagation is determined by the heat release and heat transfer
in the main heat release and preame subzones correspondingly. If the heat losses from the
main heat release subzone are signicant, combustion might be quenched.

3. Afterburning zone
If the reaction occurring is not complete, the area of afterburning (where the processes do

5
 not affect the wave propagation) can be distinguished after the main heat release subzone.
It is also sometimes called the zone of complete reaction.

4. Structure formation zone

A number of processes (crystallization, recrystallization, product condensation, phase
transformation and others) take place in this subzone. They do not affect the combustion
wave velocity but strongly inuence the structure of the product. The product starts to
cool down in this subzone.

5. Cooling down zone

The product cooling is complete and the final products are obtained. It is also sometimes
referred to as the final product zone.

These are the zones observed in case of non-equillibrium adiabatic conditions (as is mostly the
case).

(c) Non-equilibrium adiabatic structure of synthesis wave (d) Equilibrium adiabatic structure of synthesis wave

If the rate of wave propagation is low or if the process occurs at relatively low temperatures,
the SHS process can be considered to be in equilibrium. Under these conditions, the postprocess
zones merge with the zone of heat release, forming a single transformation zone called the ’zone
of synthesis’. Synthesis, during which chemical bonds form, and structurization, during which
the formation of the product phase takes place, occur simultaneously.
Owing to the specicity of SHS, its products may be expected to appear in their non-
equilibrium (quenched) state. The state of the products (equilibrium or non-equlibrium) can
tsf
be predicted by analyzing the ratio S = tthr where tsf and tthr are the characteristic times for
structure formation in the reaction product and for thermal relaxation of sample, respectively.
When S << 1, the sample cools down slowly so that the product has enough time for crystalliza-
tion and, hence, appears in its equilibrium state. When S >> 1, a product can be expected to
appear in its non-equilibrium (quenched) state. In this case, we can talk about auto-annealing
and auto-quenching, respectively. For intermediate values of S, the product structure may turn
out to be rather complicated: the product may have an equilibrium chemical composition but
a non-equilibrium phase composition.
The main parameter of the SHS process is the maximum combustion temperature Tm , which
affects the combustion front velocity and the structure of the product. Tm can be controlled by
introduction of an inert diluent into the charge (decreasing Tm ) or by preliminary warming-up
of the charge (increasing Tm ).
Typical values for SHS process are as tabulated below:

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 Burning velocity 0.1 - 20 cm/s
Combustion temperature 2200 - 4100 K
Heating rate 103 - 106 K/s
Igniting fluence 10 - 200 cal/(cm2 · s)
Induction time for ignition 0.2 - 1.2 s
Ignition temperature 800 - 1200 K
Thickness of synthesis zone 0.1 - 5.0 mm

3.3 Fundamentals of SHS chemistry

SHS is a science-intensive process. Its comprehension requires erudition in thermodynamics,
chemical kinetics, general and structural macrokinetics, materials science, and other allied fields
of knowledge.

3.3.1 Thermodynamics

The synthetic potential of SHS can be evaluated by using the following three approaches:

1. Empirical
It is based on intimate knowledge of chemistry as well as on experience in the eld of SHS
practice.

2. Thermodynamic
The thermodynamic approach requires calculation and analysis of the adiabatic combus-
tion temperature Tad and the equilibrium composition of the products at this temperature.
There are two methods for thermodynamic analysis of combustion:

(a) Simplified
The adiabatic combustion temperature Tad is calculated under the assumption that
the product composition is known or given.
For example, Tad can be calculated as:

Qe
Tad = To +
c̄
where
n
X
Qe = Q − Liph
i=0

is the effective heat release in the reaction, and

Z Tad
c̄ = (Tad − To )(−1) C(T )dT
To

diamt is the mean heat capacity of the product in the considered temperature range.
(b) Complete
The complete method of thermodynamic analysis allows calculation, not only of the
adiabatic combustion temperature Tad , but also of the equilibrium composition of
the products at this temperature. This method is especially important for multicom-
ponent systems when the product composition can hardly be predicted.

7
 It should be noted that that the simplied approach to SHS in sophisticated systems may
lead to a wrong decision concerning the optimal composition of the charge.

3. Macrokinetic
The kinetics of heat release in the combustion wave and heat losses are taken into con-
sideration, which allows one to determine whether SHS can occur in the given medium or
not. However, it can hardly be used in practice because of the absence of the kinetic and
thermophysical data for high temperatures.

(e) Temperature profile for the combustion wave, (f) Temperature profile for the combustion wave,
Nb+2B system 5Ti+3Si system

3.3.2 Chemical Kinetics

The kinetics of chemical reactions in SHS systems provides information about the rate of heat
release at high temperatures. The latter is normally assessed from the dependence of the burn-
ing velocity on combustion temperature as well as from the thermograms of combustion or
electrothermal explosion. For reactions of metal with gases, similar data can be assessed from
electrothermographic measurements.

3.3.3 Combustion Theory

Wave propagation and wave structure are readily described in terms of the combustion the-
ory. The latter is based on joint analysis of the equations of heat conduction with non-linear
heat sources (heat release in chemical reaction) and chemical kinetics (ideal solid-flame combus-
tion). Calculations may also take into account the processes of melting and capillary spreading
(solid-flame combustion with a melting interlayer), infiltration of a gaseous reagent (infiltration
combustion), and various other heat transfer processes (like heterogeneous combustion).
For example, simple mathematical analysis of front propagation can be considered using the
equation:
∂T
Cρ = ∇ · (λ∇T ) + QρKo e−E/RT Φ(n)
∂t
where Φ(n) is a functional taking into account the state of the initial reagents and the other
terms have their usual meanings.

3.3.4 Physical Materials Science

The methods of classical materials science are also applied in characterizing SHS products. The
effect of cooling rate on equilibrium (nonequilibrium) in SHS products is investigated. For off-

8
stoichiometric products, the extent of ordering and formation of hyperstructures are investigated
by neutron diffraction. Mathematical modeling of SHS is also performed with regard to the
constitution diagram.

3.4 Product Properties

3.4.1 Morphology and Macroscopic Structure

Solid SHS products may appear in the form of powders, particle conglomerates, foams, cakes,
ingots, films, whiskers, fibers, and crystals. The batch weight depends on charging and the
type of process. In case of premixed green mixtures, the macrostructure of product is normally
uniform. For the solid-gas systems, the product composition may be expected to vary over
the sample cross section. In some cases, the product macrostructure is intentionally made
nonuniform, e.g., multilayer and functionally graded materials.

3.4.2 Product Composition

The chemical and phase composition of combustion product depends on green composition,
extent of conversion, and cooling conditions. Product contamination depends not only on the
purity of starting reagents but also on the extent of self-purification during combustion. Prod-
ucts synthesized under optimized conditions exhibit low content of unreacted components and
contaminants.

3.4.3 Microstructure of Products

SHS products normally have a polycrystalline structure with a grain size of 1-5 mm. SHS may
also yield nanophase, amorphous or coarse-grained products. The grain size depends on the
cooling rate and kinetics of crystallization and recrystllization. The porosity of products ranges
between zero (compact materials) and 90-95% (foam materials).

3.4.4 Class of products

SHS is known to yield the following classes of compounds:

• oxygen-free refractory compounds, oxides, intermetallides, chalcogenides, phosphides and

hydrides

• reduced elements (B, Ti, Mo, Ta and others)

• inorganic composites (ceramics, cermets, mineraloceramics, composite materials)

• organic compounds (piperazine malonate, quinhydrone, ferrozerone (o-carboxybenzoylferrozene))

• polymers (prepared by frontal polymerization)

4 Production Methods
SHS production has much in common with: preprocessing of raw materials/ synthesis/ product
processing. Instead of furnaces and plasmotrons, SHS is performed in reactors. Six technological
types (TTs) of SHS are identified:

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 (g) Initiation, Front Propagation and Product Formation (h) Malonic acid, halogenation

TT-1 Chemical synthesis

Preparation of cakes and grinding them to powders.

TT-2 SHS Sintering

Sintering of preformed pellets.

TT-3 Forced SHS Compaction

Consolidation of still hot combustion products by external influence.

TT-4 SHS Metallurgy

Processing of high-temperature melts/ melted products of highly caloric reactions.

TT-5 SHS Welding

SHS reaction in a gap between two items that are to be joined.

TT-6 SHS with a Gaseous Mass-Transporting Agent

Deposition of thin coatings onto the surface of items placed into a green mixture.

5 SHS Research
Three levels of experimental diagnostics exist, with respect to SHS processes:

Level I Phenomenology
Detecting a wave propagation mode (steady, pulsating, spinning) and measuring the fol-
lowing readily measurable parameters:

- burning velocity and combustion temperature [for steady combustion]

- mean burning velocity and pulsation frequency [for unsteady combustion]
- mean burning velocity and hot spot velocity [for spinning combustion]
- chemical and phase composition of end products

The experimental techniques that are used include motions pictures and video recording,
thermometry, pyrometry, chemical analysis, XRD and metallography.

Level II Zone structure of the combustion wave

The experimental techniques that are used include thermography and time-resolved pyrom-
etry. The obtained temperature profiles shed light on the mechanism of physicochemical
transformations in and the structure of the combustion wave.

10
Level III Dynamics of phase transformations behind the combustion front
The experimental techniques used include time-resolved x-ray diffraction [TRXRD] and
quenching to arrest the wave propagation.

The objective, finally, is to be able to take control of parameters like burning velocity, combus-
tion temperature, extent of conversion, composition and structure. This is generally achieved
by varying the green parameters (charge composition, particle size, density, charge volume,
initial temperature, type and amount of additives and fillers) and the combustion conditions
(composition and pressure of ambient gases, external influences) among other parameters.

(i) Morphological changes during synthesis of nanomaterials

6 Applications
SHS products find their application in mechanical engineering, metallurgy, chemical industry,
electrical and electronic engineering, aerospace industry, building industry among others. A few
of the interesting applications are listed below:

1. SHS materials with shape memory property are used in surgery and implants.

2. In space experiments and microgravity experiments.

3. To manufacture ceramic-lined steel pipes for transportation of ores and coal.

4. To prepare crystalline, agglomerate (polycrystalline), and composite powders which result

in products with exceptional hardness.

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 5. To produce cast materials and tungsten-free hard alloys.

6. To manufacture functionally graded materials, nano-sized powders and compact nano-

grained materials.

7. In deposition of thin films on materials.

8. To join ceramics to ceramics, ceramics to metals and metals to metals.

9. In the production of abrasives, high temperature heating elements and electrodes, solid
lubricants, semiconductor materials, and polishing pastes.

10. They have also been used in the production of N and P fertilizers.

Other potential uses are the direct reduction of Fe from ferrous ores and the smelting of high
alloy, high temperature metals, and possibly casting refractories.

7 Advantages
SHS, as a process, and SHS materials enjoy a great number of advantages. A few of them are
listed below:

1. It is cost-effective.
This is normally associated with (1) utilization of reaction heat instead of electric power,
(2) high combustion temperature and burning velocity, (3) simplicity of facilities, and (4)
high quality of products.

2. It is often a material-saving process.

The high temperature developed during combustion results in almost complete transfor-
mation of the initial substances into the final product. Unreacted elements represent only
0.01 to 0.2 wt% of the product.

3. It is also be used for net-shape production of finished machine parts.

4. The rates of synthesis and therefore production are generally extremely high.

5. There exist possibilities of synthesizing metastable compounds and phases.

6. It can be carried out by using relatively simple facilities or even in open air, thus eliminating
the need for high temperature furnaces and complex processing equipment.

7. A good practical result can be obtained without having any detailed information about
the process.

8. The process parameters can be roughly estimated by performing thermodynamic calcula-

tions.

9. SHS-derived powders result in higher density and more homogeneous microstructure on

sintering or hot-pressing, than conventional powders.

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 10. Contamination normally does not occur.
In fact, the high temperature of combustion provides a ”self-purification” feature by evapo-
rating those impurities that are volatile and by removing oxide films on the metal particles
by a reduction process. High purity is therefore another inherent advantage.

11. Absence of the scale effect

Unlike other typical chemical processes, on going from the laboratory scale to industrial-
scale production, the quality of SHS products tends to increase.

12. An important task in the synthetic chemistry of SHS is the direct synthesis of materials
with a desired structure, thus avoiding preliminary preparation of powders.

13. To date, almost any compound can be prepared by SHS upon proper variation of the
charge composition and process conditions.

8 Related Issues
The process is under constant research and development and faces a few issues:

1. Limited range of inexpensive and accessible reagents that react with a sufficient heat
release.

2. The quality control requires a profound knowledge of the structural macrokinetics, a novel
area of research, which considers the positive and negative nonlinear feedback between the
rates of chemical reactions, structural transformations, and heat/mass transfer processes.

3. Performing accurate, predictive thermodynamic calculations is not easy.

4. Searching for suitable systems to produce the required products is a challenge.

9 Conclusion
Thus SHS is a highly cost-effective method for producing a variety of ceramic materials. Some
materials exhibit exceptional properties as a direct result of the uniqueness of the SHS process.
This materials technology has demonstrated its potential for industrial-scale production of re-
fractory compounds, and in most cases, is replacing conventional ceramic-production processes,
which consume large quantities of energy.

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10 References
The journal references used for the assignment are listed below:

1. Self-Propagating High Temperature Synthesis - A Soviet Method for Producing Ceramic Ma-
terials
Joey F. Crider [U.S. Army Foreign Science and Technology Center]

2. The chemistry of self-propagating high-temperature synthesis

Alexander G. Merzhanov, [J. Mater. Chem., 2004, 14, 17791786]

3. Self-propagating high-temperature synthesis of nanomaterials

A E Sytschev, [A G Merzhanov, Russian Chemical Reviews 73 (2) 147 - 159 (2004)]

4. Self-Propagating High-Temperature Synthesis: First Space Experiments

A. G. Merzhanov, A. S. Rogachev, and A. E. Sychev, [Doklady Physical Chemistry, Vol.
362, Nos. 13, 1998, pp. 299303]

5. The self-propagating high-temperature synthesis of sinterable powders

R. Pampuch, [JOURNAL DE PHYSIQUE IV, Colloque C7, supplement au Journal de
Physique 111, Volume 3, novembre 1993]

Other sources of information include:

1. http://en.wikipedia.org/wiki/Self-propagating high-temperature synthesis

2. The web resources of Institute of Structural Macrokinetics and Materials Science:

http://www.ism.ac.ru/handbook/shsf.htm

3. http://www.scientific.net/KEM.217

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