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# High-Energy Ball Milling: Mechanochemical Processing of Nanopowders

Автор: Elsevier Science

## Активность, связанная с книгой

Начать чтение- Издатель:
- Elsevier Science
- Издано:
- May 24, 2010
- ISBN:
- 9781845699444
- Формат:
- Книге

## Описание

Part one discusses the basic science of mechanochemistry with chapters on such topics as the mechanism and kinetics of mechanochemical processes, kinetic behaviour in mechanochemically-induced structural and chemical transformations and materials design through mechanochemical processing. Part two reviews mechanochemical treatment of different materials including synthesis of complex ceramic oxides, production of intermetallic compound powders, synthesis of organic compounds, synthesis of metallic-ceramic composite powders and activation of covalent bond-based materials. Part three covers mechanochemical processes in metal powder systems and other applications with coverage of topics such as plating and surface modification using ultrasonic vibrations, activated powders as precursors for spark plasma sintering, titanium dioxide photocatalyst synthesis by mechanochemical doping and synthesis of materials for lithium-ion batteries.

With its distinguished editor and international team of contributors, High energy ball milling: Mechanochemical processing of nanopowders is a standard reference for all those involved in the production of ceramic and metallic components using sintering and other powder metallurgy techniques to produce net shape components. Examines the latest techniques in mechanochemistry and how they can be applied to the synthesis and processing of various high-tech materials Discusses the basic science of mechanochemistry including kinetic behaviour, processes and mechanisms and materials design through mechanochemical processing Reviews mechanochemical treatment of different materials including synthesis of ceramic oxides, organic compounds and metallic-ceramic composite powders

## Активность, связанная с книгой

Начать чтение## Сведения о книге

# High-Energy Ball Milling: Mechanochemical Processing of Nanopowders

Автор: Elsevier Science

## Описание

Part one discusses the basic science of mechanochemistry with chapters on such topics as the mechanism and kinetics of mechanochemical processes, kinetic behaviour in mechanochemically-induced structural and chemical transformations and materials design through mechanochemical processing. Part two reviews mechanochemical treatment of different materials including synthesis of complex ceramic oxides, production of intermetallic compound powders, synthesis of organic compounds, synthesis of metallic-ceramic composite powders and activation of covalent bond-based materials. Part three covers mechanochemical processes in metal powder systems and other applications with coverage of topics such as plating and surface modification using ultrasonic vibrations, activated powders as precursors for spark plasma sintering, titanium dioxide photocatalyst synthesis by mechanochemical doping and synthesis of materials for lithium-ion batteries.

With its distinguished editor and international team of contributors, High energy ball milling: Mechanochemical processing of nanopowders is a standard reference for all those involved in the production of ceramic and metallic components using sintering and other powder metallurgy techniques to produce net shape components. Examines the latest techniques in mechanochemistry and how they can be applied to the synthesis and processing of various high-tech materials Discusses the basic science of mechanochemistry including kinetic behaviour, processes and mechanisms and materials design through mechanochemical processing Reviews mechanochemical treatment of different materials including synthesis of ceramic oxides, organic compounds and metallic-ceramic composite powders

- Издатель:
- Elsevier Science
- Издано:
- May 24, 2010
- ISBN:
- 9781845699444
- Формат:
- Книге

## Связано с High-Energy Ball Milling

## Отрывок книги

### High-Energy Ball Milling

Africa

**1 **

**Introduction to mechanochemical processing **

**Małgorzata Sopicka-lizer, Silesian University of Technology, Poland **

**Abstract: **

This chapter discusses the development of mechanochemical processing in various systems throughout its short history and shows the most impressive industrial application of the technique. A brief description of the complex action that takes place during powder mechanochemical processing is also included.

## Key words

**crystal disordering **

**mechanochemical **

**metastable equilibrium **

**process feature **

Mechanochemical processing (MCP) can be defined as ‘a powder processing technique involving deformation, fracturing and cold welding of the particles during repeated collisions with a ball during high-energy milling’. Using mechanical energy to grind down various materials dates back to the beginning of human history and the application of flints to make a fire can be seen as an example of a mechanochemical treatment of materials. However, throughout the centuries, mechanical milling only involved diminution of particles without changing their structure and/or properties.

The effect of chemical reactions initiated by mechanical action was found at the end of 19th century when Carey Lea first reported that the halides of gold, silver, platinum and mercury decomposed to halogen and metal during fine grinding in a mortar (**Carrey Lea, 1893). His paper was published just after Ostwald introduced the term mechanochemistry in 1891. Heinicke’s much later definition (Heinicke, 1984) that ‘mechanochemistry is a branch of chemistry which is concerned with chemical and physicochemical transformation of substances in all states of aggregation produced by the effect of mechanical energy’ has been widely accepted. **

Since then the main applications of mechanochemical treatment of materials were found initially within the field of extractive metallurgy, where the process was used as a pretreatment step prior to leaching and extraction in order to increase the solubility of the minerals in question. The application of this rather simple technique to manufacturing advanced materials was driven by the industrial necessity to develop an alloy combining oxide-dispersion strengthening (ODS) with γ′-precipitation hardening in a nickel-base superalloy intended for gas turbine applications. Benjamin’s work in the late 1960s showed that mechanochemical alloying (MA) must be used when ordinary dispersion of oxide particles in liquid metal is not possible (**Benjamin, 1970). **

The majority of the further work on development and production of ODS superalloys for application in the aerospace industry was done in the INCO laboratories in the USA (**Ivanov and Suryanarayana, 2000). This is presently the major user of the MA process in the commercial production of nickel or iron-based high-temperature alloys which can be used at operating temperatures higher than 1300 °C in carburizing or sulphidizing environments (Benjamin, 1970). Another spectacular example of commercial application where mechanochemically alloyed powders of Mg and Fe were used as heaters of MRE (meal, ready-to-eat), comes from their intensive use during the Desert Storm Operation by the USA in 1996 (Ivanov and Suryanarayana, 2000). **

On the other side of the world, in the former USSR, intensive studies on the application of mechanochemical processes in mineral and waste large-scale processing resulted in several practical applications including treatment of tungsten-containing ore which was introduced at the Chirchik Plant or production of amalgam for children’s dentistry which was introduced at the Nikolsky Plant (**Boldyrev, 2002). Development of unique grinding equipment in a variety of scales broadened the range of practical applications and new types of materials are being researched all over the world. Since 2000, more than 1500 scientific papers in the field of mechanochem-istry have been published every year (Ivanov and Suryanarayana, 2000) and excellent reviews and monographs are available (Suryanarayana, 1999, 2004, 2008; Tkacova, 1989; Gutman, 1998; Arzt and Schultz, 1989; Barbadillo, 1993; Lai and Lu, 1998; Avvakumov, 1986). However, great developments in the technique itself and the accompanying milling devices have brought about new applications of MCP, broadening the range of the new materials and opening up new perspectives. There has been considerable interest in updating and summarizing existing knowledge of MCP. **

Mechanochemical processes use mechanical energy to activate chemical reactions and structural changes as well as particle size reduction. Under the action of cyclic loading, after breaking crystal bonds, MCP engages powder particles into a non-equilibrium state with a relaxation time of 10− 7 − 10− 3 s (**Meyer and Meier, 1968). Comparison with other far from equilibrium processes (Table 1.1; Froes et al., 1995) shows that departure from equilibrium in MCP is faster than in rapid solidification. In addition, some long-lived defects with a lifetime of 10− 3 − 10⁶ s can be generated because of the solid imperfections and even if relaxed, the residual disorder remains in the activated material (Meyer and Meier, 1968). **

**Table 1.1 **

**Departure from equilibrium achieved in various processes ( Froes et al., 1995) **

*N*a, Avogadro’s number.

⁎Assuming relaxation owing to kinetic effects.

The mechanism of particle failure changes with the particle size and the structure of the particles undergoing grinding. A change in the accumulated energy relaxation from fracture to plastic deformation results in a dramatic increase in the strain followed by an extreme dislocation flow. Accordingly, the elastic strain energy transforms into elastic energy in the lattice defects and into structural disordering or it can be relaxed by the fracture of brittle material or crystallographic lattice rearrangement in polymorphic transformation. If more than one component is under the action of ball/powder particles collisions, then relaxation occurs by mechanical alloying, decomposition or synthesis of a new chemical compound. Thus stress, deformation and fracture initiate changes in the solids while the type and capacity of the changes involved remain a function of material’s properties (lattice bonds and crystal structure, elastic modulus, particle surface properties) and stress conditions in a milling device (the magnitude and direction of acting forces, stress rate and frequency of loading). It appears that the increase in energy of the milled powder caused by the increased volume fraction of grain boundaries and lattice disordering raises the free energy above the level of the amorphous state.

A unique feature of a mechanochemically activated mixture of powders is formation of numerous reaction couples which increase with decreasing particle size and regenerate through repeated particle fracture and welding events. What is even more important, the reaction product phase does not separate the reactants as happens in ordinary chemical reactors since continuous product phase removal takes place during ball/powder particles collisions. Lack of a diffusion barrier in the reacting couples as well as formation of various defects acting as the fast diffusion paths overcomes the problem of the diffusion as the rate-controlling process. Consequently, the reaction can proceed with acceptable kinetics without the necessity of raising the reaction temperature. Therefore, several solid phase chemical reactions or alloying reactions occur at ambient temperature during MCP or they could easily proceed for the duration of the subsequent thermal treatment if necessary.

In a summary of MCP’s features, the application of this technique to the manufacture of advanced materials provides an opportunity to make products with unique characteristics, which may be difficult to produce in any other way. These products have the following benefits:

• exceptionally high reactivity of the resultant crystalline powder particles, besides substantial size reduction, because of their higher free energy accumulated in the defective crystal lattice and increased grain boundary volume;

• significant decrease in crystalline grains at the nanometer level or transformation to an amorphous structure as a result of growing crystal cell disordering when the mechanochemical treatment is lengthened;

• extension of solid solubility over the range of the equilibrium owing to the formation of a metastable equilibrium between the terminal solid solution and an amorphous phase;

• formation of micro(nano)-structured dense composite particles with a homogeneous distribution of (nano)dispresoids if the various elastic properties of the mechanically activated particles are employed;

• nucleation of various composites and complex oxides at ambient temperature by formation of hetero-bridging bonds as a result of intimate mixing under controlled shear stressing in the dry solid process and short range atomic transfer across the boundaries of solids, which no other method, like photo-, magneto- or plasma chemical processes, could achieve;

• synthesis at room temperature of a variety of equilibrium solid compounds without transition phases and/or without the need to use solvents because numerous reaction couples are formed and there is continuous removal of diffusion barriers.

This book presents the application of MCP to a variety of systems and the latest advances, challenges and future trends are described. Each chapter has been written by an internationally well-established and experienced researcher. The book starts by dealing with kinetics problems that arise during the action of MCP; generalized equations are constructed followed by the presentation of experimental research on kinetics in the chosen systems. Then the effects of mechanochemical treatment in a variety of systems and special application of the activated novel materials are covered. Finally, the drawbacks of the method (contamination, production cost) are discussed.

**References **

Arzt E., Schultz L., eds. New Materials by Mechanical Alloying Techniques. Oberursel, Germany: DGM Informationgesellschaft, 1989.

Avvakumov, E.G. *Mechanical Methods of Activation of Chemical Processes*. Novosibirsk: Nauka; 1986.

De Barbadillo J.J., Froes F.H., Schwarz R., eds. Mechanical Alloying for Structural Applications. Materials Park, OH: ASM International, 1993.

Benjamin, J.S. Dispersion strengthened super alloys by mechanical alloying. *Metall Trans V*. 1970; 1(10):2943–2951.

Boldyrev, V.V. A historic view on the development of mechanochemistry in Siberia. *Chem Sust Develop*. 2002; 10:3–10.

Carrey Lea, M. On endothermic reactions effected by mechanical force: Part I. *Am J Sci III*. 1893; xlvi:241.

Froes, F.H., Suryanarayana, C., Russel, K.C., Ward-Close, C.M., Proceedings of the *International Conference on Novel Techniques*Singh, J., Copley, S.M., eds. Synthetics and Processing of Advanced Materials. TMS, Warrendale PA, 1995:1.

Gutman, E. *Mechanochemistry of Materials*. Cambridge, UK: Cambridge International Science Publishers; 1998.

Heinicke, G. *Tribochemistry*. Berlin: Academy Verlag; 1984.

Ivanov, E., Suryanarayana, C. Materials and process design through mechanochemical routes. *J Mater Synth Process*. 2000; 8(3–4):235–244.

Lai, M.O., Lu, L., Mechanical Alloying. *Kluwer Academic*. Boston, Massachusetts, 1998.

Meyer, K., Meier, W. Kristal Technik. 1968; 3(399)

Suryanarayana, c. *Non-equilibrium Processing of Materials, volume 2*. Oxford: Pergamon Materials Series; 1999.

Suryanarayana, C. *Mechanical Alloying and Milling*. New York: Marcel Dekker; 2004.

Suryanarayana, C. Recent developments in mechanical alloying. *Rev Adv Mater Sci*. 2008; 18:203–211.

Tkacova, K.Mechanical Activation of Minerals. Amsterdam: Elsevier, 1989.

**Part I **

Basic science of mechanochemistry

**2 **

**Mechanism and kinetics of mechanochemical processes **

**F.K.h. Urakaev, InstitutSSe of Geology and Mineralogy SB RAS, Russia **

**Abstract: **

Parameters of the impact interaction between the milling tools and the material to be treated have been calculated for a series of mechanochemical reactors (comminuting devices, ball mills) using models based on non-linear elastoplastic theory for collision of solids. Possible mechanisms in the formation of nanocrystal particles and of chemical reactions taking place during crystallization have been studied. Generalized equations have been deduced for the kinetics rate constants of mechanochemical reactions and for the mechanical activation of substances in ball mills. Various examples of the application of the generalized kinetic equation to the calculations of *ab initio *rate constants of specific mechanochemical processes in ball mills are presented. The obtained theoretical values have been compared with experimental results.

## Key words

**mechanochemistry **

**ball mills **

**mechanical activation **

**mechanochemical reactions **

**kinetics **

**theory **

**numerical modelling **

**2.1 Introduction **

The popularity and rapid development of investigations into mechanochemistry and mechanical activation (MA) (**Urakaev and Boldyrev, 1999a,b,c, 2000a,b; Suryanarayana, 2001; Takacs, 2002; Koch, 2003; Miani and Maurigh, 2004; Butyagin and Streletskii, 2005; Kajdas, 2005; Butyagin, 2006; Urakaev and Shevchenko, 2007; Korchagin and Lyakhov, 2008; Urakaev, 2007, 2008, 2009) render actual character to the problem of the creation of models to describe the performance of devices used as mecha- nochemical reactors to predict the results of mechanical treatment of solids and to evaluate numerically the kinetics of mechanochemical processes (MP). **

In this context it is helpful to discuss the approaches to this problem recently proposed by **Vasil’ev and Lomaeva (2003) and Butyagin (2003). In these works, the authors considered the athermic diffusion and deformation mechanisms of formation of cementite (Fe3C) upon the MA of an iron and carbon powder mixture. Note that the role of local heating caused by the impact–friction interactions of milling tools with particles of a treated material in the course of MA was completely ignored. This contradicts not only classical works, for example, by the Bowden-Tabor school (Bowden and Persson, 1961; Bowden and Tabor, 1974, 1986; Vick et al., 2000; Vick and Furey, 2001, 2003), but also all the practice of human history, which has aimed either to decrease heating of materials when they are treated mechanically or to use released heat, including primitive ways of making fire. The modelling of MP associated with arising short pressure or temperature pulses or the so-called t–P–T conditions (Urakaev and Boldyrev, 2000a) is built upon a rigorous thermodynamic basis. In my opinion, this basis can be complemented by invoking diffusion and deformation processes, but under no circumstances can be replaced by them. **

In the present work, on the basis of the models constructed for the interaction of milling tools with the substance under treatment, *t*–*P*–*T *conditions for different MP in ball mills are calculated. **Urakaev and Boldyrev (2000b) show that the time factor ( t) of the momentum of mechanical action upon the substance, along with traditional pressure and temperature characteristics, is especially important and the determining factor in the specific character of MP providing their difference from thermochemical and other methods used to perform solid state reactions. Known t–P–T conditions at the impact–friction point of contact of the particles to be treated allow traditional thermodynamic and physicochemical approaches to be used to consider the mechanism and to calculate the kinetics of MP in ball mills. **

Ball milling is characterized by a relative velocity **W **of the action of milling tools at the conjunction of particles under treatment (**Fig. 2.1). For example, this case is realized in ball planetary mills (Fig. 2.2) characterized by the kinematic coefficient κ = ω/ω1 which is the ratio of the angular velocity of mill vial rotation ω1 to the angular velocity of the carrier rotation ω (scalar |ω| = 2πω, where ω is the frequency of the mill rotation); another characteristic of these mills is geometric, Γ = D/D1 which is the ratio of the distance D between the rotation axes to the radius D1 of the mill vial; Equation [2.1] follows (Urakaev, 2004, 2009): **

**2.1 **Modern vibratory (including SPEX 8000) and planetary (AGO-2) mills and schemes for temperature, intensity measurement and calculations used for planetary (**Chattopadhyay et al., 2001; Pustov et al., 2001; Mio et al., 2002) and vibratory (Delogu et al., 2000) **

**2.2 **Scheme for calculation of a planetary ball mill (AGO-2).

**[2.1] **

where cos φ = −(1 + κ)/Γ determines the condition of a ball leaving the wall and where *W*n and *W*t are the normal and tangential components of the relative velocity, respectively.

Now we shall characterize in brief the major direction of fundamental investigations into the theory of impact on solids. The most widely known is the elementary Newton’s theory of collisions based on the introduction of the collision coefficient at impact (**Goldsmith, 1960). The wave theory of impact was first developed by Saint-Venant, Bernoulli, Poisson and Navier (Poisson, 1817; Kilchevsky, 1976; Kubenko, 1999). However, the methods they used resulted in very slow convergence of the rows. A diametrically opposite theory was worked out by Hertz (1895). He assumed that the development of the impact process involves only small regions inside the bodies adjacent to the contact surface while other parts are not deformed during collision and move as absolutely rigid bodies. As a result, the problem of the collision of two elastic bodies was reduced to the problem of the collision of two material points, an elastic element being present between them (a spring or springs, Fig. 2.3). In the case of non-central collision of two elastic bodies, Routh’s ‘ξ-hypothesis’ was accepted (Routh, 1897; Maw et al., 1976; Keller, 1986; Stronge, 1990; Stoimenov, 1992). Accordingly, the connection between the tangential (It) and normal (In) momentums during the impact is formulated similarly to the Coulomb law of friction (Painlevé, 1895) It ≤ ξln, where ξ is the dynamic friction coefficient (Fig. 2.4). The inequality sign is related to the cases when It is so small that slipping does not take place. If slipping occurs, the equality sign should be accepted. **

**2.3 **Kinematics and dynamics of impact–friction contact of two elastic bodies (or particles) *i *and *j, *selected arbitrarily from the lined layer, in the region π*r*²δ of impact action produced by a ball, see also **Fig. 2.4b and Fig. 2.5. **

**2.4 **Game in billiards, (a) illustrates Hertz theory and Routh’s ‘ξ-hypothesis’ (**Coriolis, 1835; Delassus and Peres, 1923; Peres, 1923, 1924; Horák, 1948; Johnson, 1985; Persson, 2000; Popov et al., 2002, Schmitz et al., 2003; Ismail and Stronge, 2008) application to calculation of ball milling. (b) Impact–friction contact of lined (1, 2) or unlined (2, see Fig. 2.5) balls. **

The essence of our approach to calculations in ball milling is best illustrated by the game of billiards. For example, to hit a ball into the right top billiard pocket under the Hertz theory it is necessary to strike the ball exactly at its centre (**Fig. 2.4a). Clearly, the possibility of getting the balls into the correct position and of having a player with the ability to hit the ball directly at its centre is rare. Therefore in ball mills, as in billiards, noncentral interactions prevail as shown by the direction of the ball in the top middle billiard pocket. In this case the normal interactions of balls are described by Hertz theory and the tangents are described by the Routh ξ-hypothesis. When the interactions are equal friction comes into force and the time taken by the frictional interaction is identical to the time taken by the normal interaction of the balls in Hertz theory. The same is true for impacts of a ball with a billiard table wall. **

Moving on to mechanochemistry, it is sufficient to cover balls and billiard table walls with a treated material (**Fig. 2.4b) according to the known property of self-lining of a surface by milling tools. The accuracy of the calculations of the parameters of collision by this procedure will depend on how precisely we manage to measure the altered elastic properties of self-lined balls and walls. **

The synthesis of the wave theory and Hertz theory is usually performed in two directions. One of them (**Goldsmith, 1960; Harris and Piersol, 1961; Panovko, 1977; Brach, 1989; Zegzhda, 1997) implies the expedient fulfillment of the boundary conditions at the edge of colliding bodies. The second (Timoshenko, 1955; Brennan, 1957–58; Horák and Pacáková, 1961; Panovko, 1985) is based on the combination of the theory of transverse vibrations of a rod (a body) and Hertz’s theory of contact interaction. This is a modern approach (approaches) involving Hertz’s theory and wave theory, but like the theory presented by Timoshenko (1955), is only connected with the studies performed by Saint-Venant (Kilchevsky, 1976). **

It is curious that the experimental confirmation of these theories is only found in the cases of rather small relative velocities of collision (*W *≤ 10 m s− 1, billiards) or rather high ones (*W *≥ 1 km s− 1, shells), when the energy released is sufficient to change the aggregate state of colliding bodies. In this case, the problem is reduced to the solution of hydrodynamic equations of movement for a plastically deformed solid (liquid) in another liquid. Classical Newton’s theory does not take account of the physical properties of colliding bodies. Because of this, its application in the calculations of comminuting devices (mechanochemical reactors) gives the desired results only in the calculation of the kinematics and dynamics of the movement of particles under treatment in comminuting devices in combination with Hertz’s theory. On the other hand, the application of modern concepts of collisions in calculations for ball mills seems not to be feasible practically owing to the complexity of the mechanochemical processes occurring in them. This is possible only in the framework of non-linear elastic or elastoplastic Hertz’s theory with minimum (hypothetical) application of wave theory. The impact of balls with each other and of balls with a wall have been studied in detail and within 10% of the difference between the experimental measurements and the calculated data can be coordinated with Hertz’s theory if the relative velocity ** W of **collision does not exceed 10 m s− 1. Relative velocities of interaction of milling tools in ball mills are approximately 10 m s− 1 also, therefore the Hertz–Routh theory is the best available for modeling MP. Therefore, its main statements and the results which will be used to construct the model and to calculate the comminuting devices are listed below.

**2.2 General issues **

Let us consider the collision of two solids, *i *and *j *(**Fig. 2.3), without any connection to ball mills. In the framework of classical non-linear elastic Hertz theory, the connection between the impact force fij and the total deformation εij = εi + εj of the colliding bodies is accepted: fij = Bεij³/². The coefficient B depends on the properties of materials of which the bodies are made and on the surface curvatures of the bodies Lk = 1/Rk, where Rk is the curvature radius at the contact point. The deviations in the calculations according to this theory increase with an increase in the relative normal velocity Wn of collisions, owing to the appearance of plastic deformations. More precise values (up to Wn = 30 m s− 1) are obtained using the semi-empirical non-linear elastoplastic model (Batuev et al., 1969) in which it is accepted that f ij= bεijn where b and n are constants determined experimentally. The results of calculations performed according to the non-linear elastic theory which is true up to Wn = 10 m s− 1 are presented. The final results of calculations of the most important parameters have been presented in the most convenient form by Dinnik (1952) and Urakaev (2004) as follows: **

• time *tij *of interaction of the two solids

**[2.2] **

• maximum force *fij *of the interaction

**[2.3] **

• maximum stress σ*ij *in the center of the contact area

**[2.4a] **

• mean mechanical stress < σ*ij*> at the contact point

**[2.4b] **

• maximum radius *rij *of the contact area,

**[2.5a] **

• maximum surface *sij *of the contact area,

**[2.5b] **

• maximum total deformation ε*ij *of the bodies,

**[2.6a] **

and from **Equation [2.6a] **

**[2.6b] **

Here ρ*i*and ρ*j *are the densities, θ*i*= 4(1 − v*i*²)/*Ei *and θ*j *= 4(1 − v*j²*)/*Ej *are the values of compliance coefficients, v*i *and v*j *are the Poisson coefficients, *Ei *and *Ej *are the values of Young’s modules for the solids *i *and j.

**2.3 Calculation of ***t*–*P*–*T *conditions at point of contact of milling tools and treated particles

*t*–

*P*–

*T*conditions at point of contact of milling tools and treated particles

When building up a calculation model of ball mills, the following facts were used (**Urakaev and Boldyrev, 1999a, 2000a; Urakaev, 2004). **

1. One ball (*N *= 1; hypothetical choice) is present in the mill vial to comminute the material (the procedure for other numbers of balls *N *> 1 will be described below).

2. The velocity **W **of the impact action of balls, with radius R, upon the treated material is determined by a set of dimensional and dimension-less parameters describing the rotation (vibration) frequencies ωk and the linear dimensions of the mill *D*m so that |**W**| = *W*(*N*, ωk, *D*m) and *D*m >> *R*, for example, see **Equation [2.1]. **

3. At the initial time interval of treatment, a quasi-equilibrium size distribution of the particles to be ground is achieved which is described by the mean radii *Ri *(*i *= 1,2, . . ., *j *is the number of components of the material to be treated). For example (**Schneider, 1968), in case i = 1 in the treatment of model materials (sodium chloride or quartz): R1(NaCl) = 16 × 10− 5 cm and R1(SiO2) = 3 × 10− 5 cm. **

4. A phenomenon involving self-lining (a layer of compact powder will be formed on the surface of milling tools) occurs (**Kobayashi, 1995; Belyaev et al., 1998; Revesz and Takacs, 2007; Takacs and Torosyan, 2007), the thickness of the lining layer being 8 (Fig. 2.4b and Fig. 2.5). In this case, Ri << δ∼δ* << R. This material can be characterized by its eigen mechanical properties (E, v and others; see Anderson, 1965). **

**2.5 **Impact of milling tools on the layer of particles lining the near-wall being treated in a ball mill: (a) lined (1) or unlined (2*’*) ball with lining the inner wall; (b) lined (1) or unlined (2*’*) ball with the lined ball (2). The diagram also shows the friction (*ft*, ξ) contact of lined or non-lined balls with the layer of treated material lining the wall.

5. A ‘hindered’ impact action of the ball load on the particles of the material to be treated is performed either during a collision of an unlined or a lined ball with the near-wall lined layer of particles, or during the collision of lined balls with each other. The parameters of these collisions are described by Hertz’s theory.

6. The impact of the interaction of the particles being treated occurs as a result of stress wave propagation, in the region πr²δ of the impact of the balls (**Fig. 2.5) which is determined by the conditions listed in (5). The parameters of these collisions are also described by Hertz’s theory. Only the first pass of the stress wave is taken into account (Fig. 2.6). This is connected with the fact (Love, 1927) that approximately equal velocities of compression wave propagation in the ball v = [E(2 − 5v + 3v²)/ρ(2 − 5v + 2v²)]⁰⁵ ≈ (E/ρ)⁰.⁵ and in the layers of particles being treated determine their periods of vibration (differing by approximately ∼ R/δ, ∼ R/Ri and ∼ δ/Ri times). It is evident that under this assumption the times of impact interaction according to point 5 above (see Fig. 2.4b and Fig. 2.5) will be much longer than the time of impact interaction of particles being treated (Fig. 2.3, Fig. 2.6 and Fig. 2.7). **

**2.6 **Stress wave propagation in the region π*r*²δ of impact of the milling tools (between the balls and between a ball and the wall).

**2.7 **Impact–friction contact of two particles 1 and 2 (in calculating the kinetics of MP). *V *and *V** (= *sd**) are volumes of particles near the contact area, *s *is the contact area and *d *is the thickness.

Conditions 3 and 4 are sufficient for calculations to be correct, but are not obligatory in principle. In the most general case, it is possible to choose the material surrounding the ball so that it will not be lined by the substance to be treated. Then, if we use the Equations **[2.2]−[2.6], which describe the impact of the interaction of a ball with the layer of particles lining the inner wall (Fig. 2.5), it should be remembered that from the condition described in point 2 above, Li = 1/Ri >> 1/Dm = Lj = L, the inner wall layer can be treated in practical calculations of the collision with a ball with a density ρ = ρi., compliance θ = θi; and radius R = 1/Li as a plane with curvature Lj = L = 0 and compliance θ = θj = θ. Using Equations [2.2]–[2.6] for the impact interaction of lined balls with a plane inner wall layer of the treated material, in accordance with point 4 above, one should accept the following values of the radius, density and compliance of the lined (*) balls: R* = 1/ Li ≈ R, ρ* = ρi ≈ ρ and θ* = θj = θ. For the impact of lined balls with each other, one should accept Li = Lj = L* = 1/R* ≈ 1/R, ρi = ρj = ρ* ≈ ρ and θi = θj = θ⁎ ≈ θ in Equations [2.2]–[2.6]. **

The resulting equations are presented in **Tables 2.1 and 2.2 where it is recommended that θ (Anderson, 1965) be described using the arithmetic means of compliances θ i of the particles of different components of the treated mixture that make up the layer for compliance of the lined near-wall layers. For example, for a single-component substance, θ = θ1, for a two- component mixture, θ ≈ (θ1 + θ2)/2, and so on. **

**Table 2.1 **

**Calculating expressions. Numerical values for the treatment of an equimolar mixture of calcite and quartz in a KhK 871 mill (ω = 11 s− 1, Wn= W= 9.2 m s− 1, balls from WCo8 alloy are given in parentheses). An asterisk (*) corresponds to the lined ball loada **

∆*T*(*x*, *t*) = 1.0 ξ12*W*(c1c2λ1λ2ρ1ρ2)− 0.25(θ + θ)− 2(θ1 + θ2)[ρ(ρ1*L*2³ + ρ2*L*1³)/ρ1ρ2(*L*1 + *L*2)³]⁰.⁵ × {*t*⁰.⁵*iErfc*[*x*/*2*(a1a2)⁰.²⁵*t*⁰.⁵ ] − (*t*− t*12*)⁰.⁵*iErfc*[*x*/*2*(a1a2)⁰.²⁵(*t *- t12)⁰⁵]}; ∆T(*x *= 0; *t *= t12) = 1300 K; ∆T(*x*= 0.5ε12; *t*= t12) = 1100 K.

aWhen studying the kinetics of reactions in mixtures of solids, we did not observe the lining of the balls made of WCo8 alloy. So, numerical values for different ∆*T*(*x*, *t*) sections are presented for the collisions of the unlined ball with the near-wall layer:

**Table 2.2 **

**Calculating expressions. Numerical values for the treatment of a model single-component material (sodium chloride) in a El 2 × 150 mill (ω = 10 s− 1, Wn = W = 8.4 m s− 1, steel balls are given in parentheses). An asterisk (*) corresponds to the lined ball loada **

ΔT(*x*, *t*) ≈ 0.96 ξ1*W*ρ⁰.⁵(*c*1λ1ρ1)− 0.5(θ + θ1)− 2θ1{*t*⁰.⁵*iErfc*[*x*/2(*a*1*t*)⁰.⁵] − (*t *− t1)⁰.⁵*iErfc*[*x*/2(*a*1(*t *− t12)⁰.⁵]}.

At the rise of ΔT: *T*m − *T*0 = ΔTm = ΔT(*x *= 0; *t *= tm) = ΔT(*x *= *x*m; *t *= t1); *t*m ≈ 2.5 × 10− 9 s; *iErfc*[*x*m/2(*a*1*t*)⁰.⁵] = 0.5642(tm/t1)⁰.⁵ and *x*m ≈ 8.7 × 10− 6 cm.

At the drop of ΔT: ΔTm = ΔT(*x *= 0; *t *= tm′); tm′ = (t1 + tm)²/4tm ≈ 1.0 × 10− 8 s.

ΔT(*x *= 0; *t *= t1) ≈ 1220 K; ΔT(*x *= 0.5ε1; *t *= t1) ≈ 1050 K; Δ*t*m = tm′ − tm ≈ 8.0 × 10− 9 s.

aIn the experiment on the treatment of NaCl particles, balls are lined only insignificantly, so the numerical values for different sections of temperature pulses are presented for the impact interaction of an unlined ball with the fl at near-wall layer (*T*0 = 375 K):

Both during collision in milling tools (**W**) and under impulse pressure or stress wave propagation (< σ > = *P*) at the conjunction of particles under treatment in the ball mills, the impact velocity **W **or force **f***ij *that acts at the point of contact between the milling tools and the particles can be resolved into normal (*W*n, *f*n) and tangential (*W*t, *f*t) constituents (**Figs 2.3–2.5). As a result, during a characteristic time interval τ* of the action of the momentum, deformation of milling tools occurs with a shift which leads to an increase in temperature T at the point of contact (Fig. 2.4b and Fig. 2.5). For example, during impact–friction contact of the unlined ball with the lined layer wall (Fig. 2.5), the following expressions were **

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