Acta mater. 49 (2001) 3991–4003 www.elsevier.


J. R. HARRIS1, J. A. D. WATTIS1† and J. V. WOOD2
Division of Theoretical Mechanics, School of Mathematical Sciences, University of Nottingham, University Park, Nottingham NG7 2RD, UK and 2School of Mechanical, Materials, Manufacturing Engineering and Management, University of Nottingham, University Park, Nottingham NG7 2RD, UK
( Received 10 November 2000; received in revised form 25 July 2001; accepted 25 July 2001 )

Abstract—Five potential models describing the particle size distribution of powder during the mechanical alloying process have been analysed. The models are based on Smoluchowski’s coagulation–fragmentation equations and use a range of size dependent aggregation and fragmentation rates. A technique has been developed to determine model parameters from the experimental average particle size. Size distributions predicted by these parameters compare well with the corresponding experimental results. The most successful models identify the most accurate size dependence. The numeric values of some aggregation and fragmentation rate parameters are qualitatively related to material properties of the initial powder charge.  2001 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved. Keywords: Mechanical alloying; Theory & modelling; Smoluchowski coagulation–fragmentation equations PACS: 81.05.-t; 81.20.Bv


Mechanical alloying (MA) is a particularly useful and versatile application of high-energy ball milling. The ball mills employed have a chamber containing an agitated media and powder charge. Powder is trapped during media collisions, causing severe plastic deformation. If two or more different powders are placed in the mill the particles will aggregate forming a coarse composite and subsequently fragment. Repetition of this process refines the composite structure until fine mixing is achieved and the two powders combine chemically by diffusion or reaction processes, creating an alloy in the solid state [1]. MA has become a popular manufacturing route for novel materials. The process was developed by Benjamin [1] to produce high quality oxide dispersion strengthened super-alloys. The continued aggregation and fragmentation of particles causes dispersoids to be intimately and evenly mixed in the powder, producing a homogeneous component after consolidation. INCO Alloys International use this technique to produce commercially successful superalloys based on Fe, Ni and Al [2, 3]. Other applications of MA include the formation of

† To whom all correspondence should be addressed. E-mail address: (J. A. D. Wattis)

super-saturated solid solutions, and mixtures of materials that are immiscible by other means. A high degree of plastic deformation is imparted to the powder, causing refinement of grain structure and amorphisation. The refined material is often suitable for modern super-plastic forming methods; Godfrey et al. have developed a Ti–6Al–4V alloy with boron additives suitable for this type of processing [4]. It is clear that the MA process is complex; attempts to model MA treat the problem in two parts, concentrating on the mechanics of the milling machinery and the changes induced in the powder charge to varying degrees. Models may be grouped into three categories, looking exclusively at mill design, exclusively at powder evolution or at some combination of the two. Models that analyse mill dynamics are able to predict distributions in the velocity, angle and frequency of collisions and describe the mechanical loading experienced by the powder charge. Watanabe et al. [5] and Dallimore and McCormick [6] have studied the dynamics of media motion in vibrator, tumbling and planetary mills. They use discrete element methods and variations on Kelvin’s dashpot-spring model to predict the path of balls in the mill. Rydin et al. [7] have filmed the motion of balls in an attritor and estimate the collision frequency and intensity using the dents formed on a small number of carefully placed lead balls. Davis et al. [8] have characterised the collisions in a SPEX mill using a combination of video analysis software and classical mechanics.

1359-6454/01/$20.00  2001 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved. PII: S 1 3 5 9 - 6 4 5 4 ( 0 1 ) 0 0 3 0 2 - 0

in particular the concept of a milling “intensity” (collision frequency and velocity).: MECHANICAL ALLOYING At the opposite extreme. of size 2. Cr..s. Al. Aikin and Courtney have studied particle size effects and mixing by developing large scale models that are similar to our models [12–14]. fixed volume. 24]. Applying the model to any particular system requires appropriate relations between particle size and likelihood or rate of aggregation or fragmentation to be specified. 22] as well as MA and milling [23. We have used a range of experimental data taken from literature to examine a variety of metals covering a range of hardnesses (Cu. br. The most complex of these is the mechanistic approach described by Maurice and Courtney [10]. Observed changes in powder properties are related to critical milling parameters. polymerisation [21. given the range of particle sizes present in the mill. some models only predict changes in powder properties. reducing complexity by retaining only the most important features. Borner and Eckert [17] examine grain refine¨ ment. The model is commonly applied to particulate systems experiencing aggregation and fragmentation events such as aerosol formation [20]. 2. some with SiC additions). the next largest particle. These models typically assess the effect of an average collision on an element of powder and extrapolate the results to predict changes in the powder charge. Five combinations of relations are proposed and investigated to see which gives the most accurate results under a variety of milling scenarios taken from the literature. Khina and Froes [9] review many models developed before 1996. The matched parameters are used to calculate particle size distributions that are compared with the experimental measurements to find the most realistic model. moving the highly diffusive pipe to another location. When two particles of sizes r and s aggregate the original particles are lost from the mill and a new particle of size (r + s) is created. relating each assumption to the ball milling process. [18] have found that the formation of an amorphous material requires a sufficiently high peak in the milling intensity. Using Cr to represent a particle of size r. fractional sizes are not allowed. Process modelling—a brief derivation of the Smoluchowski equations Each powder particle is modelled as a cluster of discrete units. Five models are proposed. In his model. The dislocations move when the powder is impacted. The parameters are determined from experimental data describing the change in the total number of particles in the mill (or equivalently. Cr Cs→Cr ar. Gaffet et al. (2) . 8] to create computer programs capable of predicting several mechanical properties of the milled powder [11]. relating aggregation and fragmentation rates to particle size in different ways. The fragmentation process provides a reverse reaction at a rate br. Our models concentrate on the particle size distribution of the powder charge. generic model due to Smoluchowski [19]. They imply that subsequent reductions in the intensity do not reverse the reaction. an aggregation rate parameter and a fragmentation rate parameter. (1) where ar. MODELLING Our techniques employ a well established. solute material diffuses into the solvent along dislocation “pipes”. A different approach is adopted by Badmos and Bhadeshia who present a thermodynamic model that describes the formation of atomic mixtures (solid solutions) as a consequence of intense mechanical mixing [16]. without addressing the mechanisms by which changes occur. Mg. The process applies to every possible combination of sizes r and s. Each model uses two parameters. Whilst these models describe mechanical properties of the powder and composite formation they do not predict chemical changes.s is the aggregation rate for particles of size r and s. They apply standard empirical relationships and results from Hertzian collision theory to determine the effect of collisions on the powder charge.3992 HARRIS et al.s s . etc. When the model is used to analyse experimental data the size scale must be fixed: the volume of the unit element is chosen so that a particle of size 1 is smaller than the smallest measured particle size. When aggregation occurs two particles amalgamate to form a new larger particle.s Cr s →Cr Cs . using a bare minimum of information about the milling machinery. the average particle size). the process may be represented in the notation of chemical reactions by. Particle shape is not predicted by the model. Their description has been coupled with studies of milling dynamics [7. Each unit has the same. contains two units. a fragmentation event breaks a particle into two fragments that are not necessarily of equal size. 2. They suggest that milling intensity controls the number of grain boundaries formed during powder deformation while the milling temperature will affect the number of boundaries lost through recrystallisation and recovery processes. Schwarz [15] has developed a model that explains the formation of super-saturated solid solutions.1. A derivation is presented in the following section. The size distribution of particles changes as a consequence of aggregation and fragmentation events. The smallest powder particle in our model is composed of a single unit. The third type of model takes a broad view of both machine dynamics and powder evolution.

cannot be solved analytically. (4) not allow a cluster Cr to aggregate with a cluster of size greater than N r. so a factor 1/2 is included to give the required contributions. Any particle larger than r can fragment to give an r-sized particle and the necessary remainder particle of size s. due to each process is calculated and the four results are summed. ar. where there are no smaller particles.s depend only on the sizes of . The rate at which r-particles are lost by aggregation with s-particles is then written ar. r = 1.N where N is the total number of equations retained. Summing over all values of s gives the total gain in r-particles due to fragmentation. is conserved. All possible values of s must be considered. (6) + Cq for q r 1.s and br.scr s 1 ). Combining all four sums gives the Smoluchowski coagulation–fragmentation equations.…. s 1 (ar 1 s. Finally. br. It has been rigorously proved [25] that the total volume or mass in the system is conserved for many physically relevant choices of ar. so the total loss of r-particles by aggregation is given by ar. However. 1.s r s s c c br s s.scrcs br. We use the mass conserving truncation to model the closed mill system. The law of mass action is applied to aggregation and fragmentation events in the mill. The system is then solved for cr(t).2.scrcs.s is the aggregation rate of r. Some conditions under which this proof cannot be applied are discussed later. The model assumes that aggregation and fragmentation rates. (iii) If an r-particle fragments in any way it will be lost from the system.scr+s. 1. This allows all possible cluster aggregations. but does not conserve mass as particles of size N are formed and lost from the system. The error incurred by either truncation will reduce as N increases. where br. In the notation of equations (1) and (2) we write this (br q.s is the rate at which r + s particles fracture to fragments of size r and s. To calculate the change in concentration of r-sized particles requires the separate treatment of each of the four processes in Fig. (ii) Conversely. If the top limit of the second sum is N r then the total volume (mass) of particles in the system. dcr dt 1 2s r 1 trated on the left of Fig. although such clusters are present in the system. which can be written as Cr q + Cq → Cr. is obtained by omitting the first sum. We make use of both numerical simulations and asymptotic methods.: MECHANICAL ALLOYING 3993 These two processes control the system of particles. (3) The gain in r-particles due to fragmentation of particles of size r + s occurs at a rate br. if a larger particle of size r + s fragments. cr(t) = [Cr].2. 1.s. (5) and the loss of r-particles by fragmentation as 1 2s r 1 br 1 s. this does r=1 s . In general. If N is too small the effect of the reduced aggregation will be evident. Interactions between r sized particles and those of other sizes.s r s s c c. These two processes are illus- ar q.s r c) (7) (ar. Four aggregation and fragmentation events affect particles of size r as follows: (i) If an r-particle aggregates with another particle of any size s then the number of r-particles will be reduced [equation (1)]. it may produce an r-sized fragment and an ssized fragment as in equation (2).scrcs where ar. so approximation techniques must be used. (iv) there is a possibility that two smaller particles will aggregate to form a particle of size r. Two methods of truncation should be considered. The change in concentration of r-particles. 1. resulting in a model capable of predicting the concentration of clusters of each size present at any one time. equation (7).q ) as Cr → Cr q Similar analysis gives the gain in r-particles due to aggregation of smaller pieces as 1 2s r 1 ar 1 s.s r c.HARRIS et al. Relating aggregation and fragmentation rates to particle size Fig. the infinite system.q These summations count each combination of smaller particles twice.s and br. The alternative truncation uses N in place of N r as the upper limit of the sum in equation (3). Numerical methods require the system to be truncated by replacing the infinite upper limit of the second sum with a finite limit. rN = N rcr.and sparticles. 2.scr s 1 The special case r = 1. These processes are shown on the right in Fig.

namely r and s. Both contributions must be present in an accurate model. Our first model is the simplest of all. After a certain time. which describes the material’s overall or averaged tendency to weld or fracture. ar. In model 2 the aggregation rate is proportional to the sum of the sizes of particles or equivalently the size of the agglomerate formed. These contributions are averaged over time and incorporated in the model through aggregation and fragmentation rate parameters. Many factors which influence the likelihood of particles to aggregate or fragment are not size-dependent. tg. We consider a rate that depends linearly on the size of the particle before fragmentation. finding the parameters for these models is a difficult task. employing the combinations of aggregation and fragmentation rates in Table 1. In order for a particle to aggregate or fragment it must be involved in a collision between milling media. we define a to be the constant of proportionality. where N is a large number.s b b b(r + s) b(r + s) b br. though it should be noted that this would introduce considerable complexity into the model. In model 5 the rate depends on the product of the sizes of the particles before combination. and is independent of the sizes of fragments produced. a and b.s = a and br. These terms are used to refer to the size independent part of the aggregation and fragmentation rates. having no size dependence. i. Such models may apply to experiments where significant amounts of powder are lost due to adhesion to the milling equipment. Five models have been selected for study. The aggregation and fragmentation rates are constant. This model is similar to that employed by Aikin and Courtney [14] and has been shown to provide a good first approximation to the observed behaviour. and reflects the average fracture characteristics of the material. It is possible to show that a particle’s likelihood of experiencing collision is proportional to its size. Table 1. whereas in model 5 they range from a to N2a. to form a single macroscopic entity. with many more parameters to be determined. We assume all these effects to be of secondary importance to the size-distribution of powder. the rates and rate parameters are synonymous.s = b. reflecting the material’s propensity to weld.: MECHANICAL ALLOYING the particles involved. but this is not the case in our other models that use size dependent rates. but introduce size-dependent fragmentation rates as well. where an “infinitely large” particle forms. This reflects the tendency of the material to weld. Our study of these five models aims to determine which size-dependence is most appropriate for each mill and type of material milled.. These rates assume that a large particle experiencing collision is just as likely to fragment as a small particle experiencing the same collision. a and b is a constant parameter to be determined Model 1 2 3 4 5 a a(r + s) a(r + s) a(rs) a(rs) ar.s Models 2 and 5 generalise model 1. then in model 2 rates vary from 2a to 2Na. Models 3 and 4 also use these size-dependent aggregation rates.s = ars represents a very strong aggregation effect. In this simple size independent case. This shows a more pronounced size dependence: consider a system of sizes r = 1. using aggregation rates that are size-dependent while maintaining a size-independent fragmentation rate. Previous mathematical analysis [26] has shown that the rate ar.s = b(r + s) (in models 3 and 4). Particles will experience collisions at different frequencies depending on their size and this variation must be reflected in both aggregation or fragmentation rates. The values of a and b are determined from experimental data using a . A more refined model could consider time-dependent aggregation and fragmentation rates. or coalesce. a. also milling causes the contents of the mill to warm up with a consequent higher aggregation rate later on in the process than at the start. for example powder hardness and milling intensity. Given that a particle of a certain size is involved in a collision.e. The divergence is interpreted as the limit of a process in which larger clusters collide forming even larger clusters at an accelerating rate.N.. In each case. For example work-hardening will cause the material to become more brittle. This proportionality is incorporated in the aggregation rate ar. so that fragmentation rates would be slightly larger towards the end of the experiment than at the start. We define the constant of proportionality. In reality these parameters will vary throughout the milling. In this case the constant of proportionality is defined to be b. In a similar way. the chances of it aggregating or fragmenting will also be size-dependent. and refer to it as the aggregation rate parameter. Aggregation and fragmentation rate parameters used in the various models. Our aggregation and fragmentation rates are thus taken as averages over the duration of the milling process. Again. In the absence of any fragmentation process this effect is so strong that the model will lose powder through a process called gelation. In order to be consistent with later definitions we refer to the constants of proportionality a and b as the aggregation rate parameter and the fragmentation rate parameter respectively.3994 HARRIS et al. The other aggregation and fragmentation rates do not increase as quickly with size. as they incorporate a component which reduces the likelihood of an impacted particle aggregating or fragmenting as the particle’s size increases. However.s = a(rs) (in models 4 and 5) and the fragmentation rate br. the strong aggregation leads to a divergence in the system. the presence of surface impurities may make the aggregation rates lower at the start of milling.

s.e. and is easily matched to the equivalent quantity derived from the experimental data. and Aikin and Courtney [13]. 3. representing the averaged tendency of particles to weld or fracture. The second scaling assumes an arbitrary constant thickness for all particle sizes. Our first scaling assumes the disc’s thickness. It is then possible to convert back to sieved size measure using the same scaling. [28]. APPLICATION OF MODEL TO EXPERIMENTAL DATA depends on k. [27]. k = constant).: MECHANICAL ALLOYING 3995 matching technique. leaving unspecified the absolute size of particles in our model. Converting sieved sizing to a particle volume measure requires knowledge of the powder particles’ shape. Neither approximation will accurately describe the latter stages of some long milling experiments where equiaxed particles develop. The resulting differential equations are solved. This is referred to as the “thinning disc approximation”. the volume of particles with diameter D will depend on k. increases. Such an expression contains the parameters a and b. so that T = k. It follows that M1/M0 gives an average particlesize measure. 3. 1 (8) M0(t) representing the number of particles per unit volume of mill. These parameters should be determined so that the prediction of the model matches the experimental data as closely as possible. 2. Our methods assume the particles have a disc shape as shown in Fig. To achieve this we calculate an analytic expression for the total number of particles in the mill at any time. 0 2 (9) which is a Ricatti equation with solution 2 p1 a 1 K1p2e(p2 K1e(p2 p1)t M0(t) p1)t (10) where p1 b √b2 4 b √b2 4 4abM1 . and Aikin and Courtney mill different materials under identical conditions.HARRIS et al. aM0(0) 2p2 4abM1 . and M1 = r representing the fraction of mill volume occupied by particles. 31]. a and b. The calculations that follow assume that particles are divided equally by number amongst the model cluster sizes within each sieve classification. Lu et al. using the following method. The aggregation and fragmentation rates determined for these experiments are compared to material properties in Section 4. Particle size conversion Published data commonly measures the particle size distribution of milled powder by sieving. to a particle of size D.2. can be calculated from equation (7) by substituting for ar. Thus a non-dimensionalisation is built into our conversion from experimental data to model variables. Papers by Huard et al. Moshksar and Zebarjad [29]. a constant quantity. according to T = k/√D. The experiments use different milling equipment and powdered materials (detailed later) but our technique can be applied to all the milling situations. Geometry used to model a powder particle.p2 2p1 aM0(0) . as described by Benjamin and Volin [30]. D. When using these approximations. However. for model 1 we have dM0 dt 1 [aM2 b(M1 M0)].1. decreases as the diameter. whose size Mp(t) r rpcr. In both cases the particle geometry does not vary over time (i.2 have been matched to experimental data taken from publications by Huard et al. so the influence of each factor does not need to be found explicitly. a value for k does not need to be found because we assign a number of volume elements. The evolution of the cluster distribution function predicted by the model depends on two rate parameters. M0(t).s and br. then summing from r = 1 to r = [26. for model 2 we obtain . T. Moments of the cluster distribution function are defined by The parameters in the five models proposed in Section 2. 2. to see if any correlation can be found. Such information is not universally available. The published mass percentages per sieve must also be converted to a size distribution across the full range of sizes used in the model. Similarly. Aggregation and fragmentation rates The conversion procedure outlined above converts experimental data into the form of a cluster distribution function as predicted by our model. The concentration of particles in the model. Sieve data must be processed to obtain particle volume measures suitable for our model. 3. and K1 Fig.

1. 2 (13) aM2(0) . The functions M0(t) are programmed into Gnuplot [32] which has a fitting facility used to determine values of a and b that fit the experimental data. Al in a horizontal ball mill Moshksar and Zebarjad [29] have milled pure aluminium in a horizontal ball mill and studied how various mill parameters affect the powder evolution. [28]. b/2)t (19) ) (12) for 1 e t tmax 2aM0(0)/b Model 3 gives dM0 dt 1 [2aM1M0 b(M2 M1)]. Similar methods are applied to model 4. The lines of best fit found using the constant thickness disc scaling of particle size are shown in and dM2 dt aM2 2 b [M M4]. b. using measures of particle number (average size). [27] and Aikin and Courtney [13]. 6 4 (14) dM0 dt 1 [aM2 b(M1 M0)]. Huard et al. The equation for M4 will contain terms with higher order moments. and the model discarded. M2 is unknown. Size distributions are predicted and compared with those measured experimentally. 1 2 (17) The outlined procedure has been used to match the models to experimental data from Lu et al. 3ar bM2(0) (16) The accuracy of the solution falls dramatically as t approaches tmax. indicating that the model is not well suited to the data in question. (22) b [3(1 e 6a art art ) (15) M2(0) 2art e (e r )]. The consequences of inaccuracies are discussed later.3996 HARRIS et al. They publish detailed results of a sieve analysis of the powder. 2 (11) giving an approximate M2 M2(0)/(1 aM2(0)t) and M0(t) M0(0) 1 2 1 ar t b(rt 2 2 aM2(0)t)). 1 log(1 a solution with solution M0(t) bM1 (1 e (aM1 2aM1 b M0(0)e (aM1 b/2)t. giving a first order solution for systems with weak fragmentation: M2(t) M2(0)exp(2atM1(0)) and hence M0(t) M0(0)e apt ) M0(0)e bt/2 . but determined by dM2 dt 2aM2M1 b [M M2]. again unknown. The parameters a and b are found as outlined above. We apply asymptotic methods to equations (13) and (14) assuming b to be a small parameter. RESULTS The approximation is not valid if the leading order term is smaller than the first correction term. Moshksar and Zebarjad [29]. so the solution is valid for a finite time t tmax 1 6arM0(0) log . (20) Finally. 1 2 (21) being solved by M0(t) bM1 aM2 1 (1 e b bt/2 This equation involves terms in M4. so some other method of solution must be found. model 5 can be solved exactly. where dM0 dt 1 [aM2 b(M2 M1)]. The values are then used to calculate particle size distributions that are compared with experimental results at all available intermediate times to see if the model has made successful predictions. and values of a and b are determined using the fitting procedure. It is not uncommon for this procedure to generate negative values for the fragmentation rate. 4. which includes the second moment M2. suitable for use with our models. In each case the experimental data is converted to volume size measure.: MECHANICAL ALLOYING dM0 dt 1 [2aM1M0 b(M1 M0)]. Such unphysical results are neglected. 6 2 (18) . 4.

Experimental. Model 3 provides a close match at early times but since our approximation for M0(t). Models 1 and 2 show a good fit. the fit routine assumes that the derived solution is accurate. However. 3. fitted and calculated particle totals for aluminium converted using the constant disc thickness approximation for particle shape. Model 5 does not match the data well at all. Gelation has adversely affected model 5. 3(c).5wt%Cu/15wt%SiC in a horizontal ball mill. Fig. the behaviour of the system is not representative of the underlying theory because of these restricted aggregation conditions. as shown in Fig. they publish results after 1. 3. The asymptotic solution for model 3 is not valid after 4 h. causing large discrepancies between the average size in the model and in the experiment.HARRIS et al. 4.2. equation (15). They mill a powder mixture with nominal composition Al–4. Al–Cu–SiC in a horizontal ball mill Lu et al. This data set highlights potential weaknesses in the fitting techniques rather than demonstrating which size dependent rates give solutions that are more accurate. 10. and fits it through all the data points. . The corresponding size distributions are presented in terms of mass fractions on each experimental sieve as shown in Fig. All the results are presented using the experimental time scale. but models 3 and 5 do not fit the data so well. No model matches the data exceptionally closely. Since there is no explicit time dependence in our model. The fit curves used to establish values of a and b together with corresponding values calculated from the numerics are shown in Fig. 5. 5. After time tg the truncated system of equations used to generate the numeric solution will artificially restrict the aggregation process. the fragmentation rate for model 4 was negative. 4. The constant disc thickness scaling has been used to convert particle sizes. the size distribution of powder milled for 1 h has been used as an initial condition. 15 and 20 h of milling. fails at large t the resulting values for a and b give poor results at later times.: MECHANICAL ALLOYING 3997 Fig. Although the average particle sizes match quite closely. [28] have made a dispersion strengthened composite by MA. The initial size distributions of their powders are not published. instead.

best fit and calculated particle number curves relating to a 20 vol% addition of SiC are shown in Fig. with additions of 10. 6. Experimental and model curves are all in reasonable agreement.3998 HARRIS et al. Huard et al. so model 5 will be neglected. with 90% of them smaller than 6 µm. 20 and 30 volume percent SiC particulates. In our models. but model 3 fits the data sets best. [27] have milled three Mg powders. The size of the calculated data increases a little too quickly implying that the aggregation rate is too high and/or the fragmentation rate is too low. The SiC particulates mix into the Mg matrix very early in the milling experiment so the errors introduced by this assumption are minimal. values of a and b are presented in Table 2. Corresponding particle size distributions are not presented here.3.: MECHANICAL ALLOYING Fig. [27] use a low energy horizontal ball mill similar to that used by Lu et al. 4. Huard et al. We have found that these approximations work well and our models can be applied to Huard’s data giving good results. The asymptotic approximation for M0 has failed earlier with the 30 volume percent data because the fragmentation rate. so the observed vari- . 4. Consequently. Mass distributions of aluminium calculated using the constant disc thickness approximation for particle shape. Data for all three compositions have been analysed. b. the material is assumed to be homo- geneously mixed at the start of the experiment. the calculated curve follows the experiment quite closely so inaccuracies are only expected after 15 h. The Mg powder had a mean diameter of 60 µm while the SiC particulates were 2 µm on average. do not alter their milling conditions. Figure 5(c) shows the effect of gelation on model 5 at very early times. is higher. Experimental. Mg with SiC particulate in low energy ball mill Huard et al. However. with model 2 providing a consistently good match. The accuracy of a and b values obtained for model 3 is restricted by the asymptotic solution. Since model 3 fits the data most closely. small errors are incurred in this data set at later times.

Huard et al. Table 2 shows a gradual decrease in the aggregation rate parameter.: MECHANICAL ALLOYING 3999 Fig. This is particularly true for the 30 vol% mixture. which will be almost saturated with SiC particles and will contain a semi-contiguous network of SiC additions bound by small isolated pockets of metallic material. The obtained values are of the correct order. and making the particles more brittle.HARRIS et al. Accurate values for a and b may be obtained before gelation occurs. fitted and calculated particle totals for Al–4. reducing ductility. Experimental. The cold welding process relies on clean metal–metal contact between powder particles. The numerical calculations for model 5 are inaccurate because gelation affects are not correctly incorporated. hardening the powder. but these values are not suitable for post gelation calculations. giving one explanation for the higher fragmentation rate parameter.5wt% Cu/15wt% SiC converted using the constant thickness disc approximation of particle shape. with SiC content may be attributed to these two mechanisms. are due to differences in the milled material. It is interesting to note that the gelation times found for model 5 are very close to those measured experimentally. high particulate additions will pin dislocations. a powder output ratio that indicates the amount of powder cold welded to the components of the mill. 5. Subsequent fragmentation of agglomerates will be easier and more frequent. and fragmentation rate parameter. The concentration of SiC particulates caught between compressed metallic particles will be greater for the higher addition mixtures reducing their tendency to weld or aggregate. ations in aggregation rate parameter. b. and develop- . Agglomerates are more likely to form in the higher addition mixtures rather than strong coldwelded particles. a. measure one particularly interesting quantity. Also. The sharp increase in the fragmentation rate parameter. b. a with increasing SiC content.

Matches to the copper data using the thinning disc approximation of particle size are shown in Fig. b for Mg with different additions of SiC.3895×10 1. and fragmentation rate parameter. The values have been found using model 3 with the thinning disc approximation of particle size vol%SiC 10 20 30 3.4. model 2 provides the best match. Table 2. The chromium experiment is more difficult to model because the average size of the powder oscillates about a mean value (Fig. fitted and calculated particle totals for Mg with 20vol% SiC converted using thinning disc approximation of particle shape.8059×10 9 7 4 ment of more accurate matching techniques may allow model 5 to predict the loss of material stuck to the mill. 4. Variation in aggregation rate parameter.2343×10 2. 7(c)]. 7. 6.0720×10 a 3 3 3 b 3.0852×10 5. but may be able to predict the size distribution after 1 h of milling.9673×10 1. Models for . If all the matches are considered. However. For copper. Figure 8 shows the corresponding size distributions. niobium and chromium powders in a vertical attritor. This is probably because the average size in model 3 is closer to that measured experimentally for early times [Fig. a. before tg is reached. The media collisions in this type of mill have higher energies than those in the horizontal mills used in the other experiments. model 3 will not predict the experimental size distribution measured after 16 h of milling. but calculations at further times are numerically inaccurate because of the truncation used. Analysis of data published by Aikin and Courtney Aikin and Courtney have milled copper.: MECHANICAL ALLOYING Fig. The matches shown are similar to those for niobium. Model 5 matches the results for 1 h well. model 3 provides a better match to the data collected up to 8 h of milling. Model 5 will not give a good match because of gelation affects. Experimental. 9).4000 HARRIS et al.

Experimental. The rate parameters suggest that chromium mills two orders of magnitude faster than the other two powders. 5. chromium is a fairly brittle material at room temperature.s = a(r + s). Results for copper and niobium reflect the expected trends. so changes in the rate parameters a and b are caused by differences in the powder material. fitted and calculated particle totals for copper converted using thinning disc approximation of particle shape. Aikin and Courtney have used identical milling conditions for the three powders. The three powders are very different in nature. and may be expected to fragment readily and niobium will fall somewhere between the two extremes. The values of aggregation and fragmentation rate parameters used with model 2 are listed in Table 3. Copper is milled more quickly than niobium. An . which our model cannot take account of. Where suitable rates for model 3 have been not found. but are a great improvement on trial and error techniques or measurements based on mixing as used by Aikin and Courtney [14]. Copper is soft and would be expected to aggregate readily. CONCLUSION Applicability of the models to mechanical alloying has been demonstrated. These techniques do not always work with model 3. and matches are better than expected given the number of effects omitted by the models. with aggregation and fragmentation occurring more frequently. The size evolution of chromium is significantly different to that of copper and niobium. having aggregation and fragmentation rate parameters of similar order. and should not be considered as accurate as those for niobium and copper.HARRIS et al. 7. The parameter matching techniques are not perfect. Both models 2 and 3 use the aggregation rate ar. possibly due to the BCC structure of chromium making it brittle and giving it a significantly greater increase in work-hardening. but the model gives consistently good results if accurate parameter values can be obtained. model 2 fits the data best.: MECHANICAL ALLOYING 4001 Fig. this data do not show a large variation in particle size distribution over time.

Table 3. 9. The rate used in models 2 and 3 increases more slowly with size.: MECHANICAL ALLOYING Fig. Models 4 and 5 have not been successful because they predict that some proportion of the material will form infinitely large particles early in the process. the result is ar.4427×10 a 3 3 1 b 5.1878×10 2 1. These models may describe the collection of material on the milling machinery. 8. as described by .9882×100 Fig. Variation in aggregation rate parameter.9689×10 1.s = a(rs).1427×10 2 8. suggesting that smaller particles will aggregate more readily than larger ones when involved in a collision.4002 HARRIS et al. The values have been found using model 2 with the thinning disc approximation of particle size Material Copper Niobium Chromium 4. Experimental particle totals from Aikin and Courtney’s chromium experiment [14] plotted along side fitted and calculated particle totals from model 2 using the thinning disc approximation of particle shape. Mass distributions for copper using thinning disc approximation of particle shape. a.5095×10 1. and fragmentation rate parameter. earlier discussion established that larger particles are more likely to experience the effects of collision than smaller ones and if this dependency is included in the aggregation rate. b for different materials.

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