- Email: [email protected]
In situ synthesis of TiC nano-reinforcements in aluminum matrix composites during mechanical alloying
Accepted Manuscript In situ synthesis of TiC nano-reinforcements in aluminum matrix composites during mechanical alloying Vladimir A. Popov, Manfred Burghammer, Martin Rosenthal, Anton Kotov PII:
S1359-8368(17)34341-X
DOI:
10.1016/j.compositesb.2018.02.023
Reference:
JCOMB 5548
To appear in:
Composites Part B
Received Date: 15 December 2017 Revised Date:
14 January 2018
Accepted Date: 22 February 2018
Please cite this article as: Popov VA, Burghammer M, Rosenthal M, Kotov A, In situ synthesis of TiC nano-reinforcements in aluminum matrix composites during mechanical alloying, Composites Part B (2018), doi: 10.1016/j.compositesb.2018.02.023. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
1
ACCEPTED MANUSCRIPT
In situ synthesis of TiC nano-reinforcements in aluminum matrix composites during mechanical alloying Vladimir A.Popov1*, Manfred Burghammer2, Martin Rosenthal2, Anton Kotov1 1
National University of Science and Technology “MISIS”, Leninsky prospect, 4, 119049
Moscow, Russia 2
ESRF, 71 avenue des Martyrs, 38000 Grenoble, France
*corresponding author e-mail address: [email protected]
Abstract In this paper the possibility of fabrication of titanium carbide reinforcing nanoparticles inside an aluminum matrix by in situ synthesis during mechanical alloying will be discussed. The application of nanodiamond particles as carbon precursor for synthesis allowed obtaining TiC particles in nanosized form due to the size of initial nanodiamond particle of 4-6 nm. The developed composites were investigated by scanning electron microscopy, X-ray diffractometry, and differential scanning calorimetry. Keywords: A: Metal-matrix composites (MMCs); Particle-reinforcement; B: Microstructures; D: Electron microscopy 1. Introduction The advancement of science and technology requires the development of new materials. On the one hand, modernized materials enhance the quality of various products and increase their service life, while on the other hand they create new technical solutions that are fundamentally different when compared to existing ones. Metal matrix composites [1-18] provide a new level of properties unattainable in conventional non-reinforced metals and alloys. However, composites with powder-like reinforcing particles still deserve considerable attention. Multiple studies have been dedicated recently to the development of nanocomposites. e.g., composites with nano-sized reinforcing particles. However, nano-powders in this application display a number of features,
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such as an increased surface area and high activity of the material, which results in a large amount of foreign matter and contamination on the surface of the nanoparticles. Contamination at the interface between the metal matrix and the reinforcing particle is one of the major reasons preventing a wider application in industry. This is explained by the fact that despite being an insignificant amount, these contaminations and inclusions considerably reduce the bonding strength between the composite components. In casting technologies, contaminations and inclusions on the surface of nanoparticles result in reduced dampening between the components which, at the very least, causes irregular distribution of reinforcing particles in the matrix, and more often leads to them being removed from the melt along with the slag. To reduce contamination at the interface between the metal matrix and the reinforcing particle, various methodologies have been developed. A promising approach is the in situ synthesis of nanoparticles in the matrix. In this case, the synthesized nanoparticles have no contact with air, and thus no contamination between the reinforcing particle and the metallic matrix is formed. Recently, titanium carbide has been generating increased interest due to its good mechanical characteristics. The literature includes reports on in-situ studies of the synthesis of titanium carbide reinforcing particles during the mechanical alloying process [11-13]. In the described processes, titanium and graphite (or soot) particles were used as precursors. The synthesis is often carried out when annealing granules after mechanical alloying. The hereby presented work is intended to study the in-situ synthesis of nanoparticles of titanium carbide in an aluminum matrix during mechanical alloying when using nanodiamond powders and titanium particles as precursors. The extremely small size of nanodiamond particles and their exceptional hardness are those characteristics of nanodiamonds (ND) that led to their choice for the experiment [19-29]. The exceptional hardness and the quantity of nanodiamonds
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results in intensification of the mechanical alloying process, and their small size has a positive effect upon the size reduction of synthesized titanium carbide particles. 2. Materials, equipment, and methodologies The composites were fabricated by mechanical alloying [30-34]. In the studies, commercially available aluminum, titanium and detonation-synthesized nanodiamond powders were used as initial materials. A technical grade aluminum powder was applied to the matrix, with an initial particle size of 30-100 µm. As precursors for the synthesis of titanium carbide particles, technical grade titanium powders were used with a particle size of 100 µm, alongside detonationsynthesized nanodiamond powders manufactured by Kombinat Elektrohimpribor (FSUE). Primary nanodiamond particles are near-spherical in shape; in general, they are 4-6 nm in size. A distinctive feature of nanodiamonds, just like most nanopowders, is that they can combine into agglomerates reaching up to hundreds of micrometers in size. In terms of nanoparticle bonding strength, there are primary and secondary (and sometimes tertiary) agglomerates. The strongest are primary agglomerates. At the start of mechanical alloying, secondary agglomerates deagglomeration into primary nanoagglomerates of up to 100 nm. A substantial period of time is required for complete deagglomeration of the agglomerates. A Retsch PM400 planetary mill with four tightly closed grinding jars was used for mechanical alloying. Balls of 12 mm in diameter were used as the milling tool. The ratio of ball weight to the weight of the processed material was 10:1. The rotation velocity of the grinding jars around the common axis (rotation rate of the carrier) was 300 rpm. The drums were aircooled during operation. To prevent overheating, the planetary mill was stopped after every 10 minutes of operation for 5 minutes to cool-down. The processing time was deemed to be the time when the mill was operating, disregarding the cool-down intervals. The granules obtained after mechanical alloying were studied using a scanning electron microscope Helios NanoLab™ 600i DualBeam™ (FEI). Secondary electrons registration mode was used. For the studies, granules were cut by an ion beam to avoid surface contaminations
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influencing the analysis. The quantitative metallography (determination of reinforcing particle size) was performed using the AxioVision Release 4.5 software package. Thermal effects occurring when heating the samples were studied using a differential scanning calorimetry DSC 404 C Pegasus (NETZSCH, Germany). The measurements were conducted in platinum-rhodium crucibles with aluminum oxide inserts at a rate of 20 °C/min. During the measurement process, a dynamic inert atmosphere was maintained (argon, 50 ml/min). The XRD analysis was carried out on a Bruker D8 ADVANCE diffractometer and a DRON-3 diffractometer using CuKα-radiation in both cases. 3. Results and discussion For in situ synthesis of TiC particles in the metal matrix via mechanical alloying, it is necessary to use precursors: titanium and carbon particles. Titanium particles have tens and hundreds micrometers in size. Graphite and soot consist of particles with similar sizes. Reaction between titanium and carbon micro-particles leads to formation of TiC micro-particles, basically. Fig. 1 shows cross sections of several composite granules with TiC reinforcements produced from graphite and soot precursors.
a
b
Fig. 1. Cross sections of composite granules with TiC reinforcements produced from graphite (a) and soot (b) precursors (SEM images)
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It is possible to obtain reinforcing nano-particle inclusions from in-situ synthesis just based on mechanical alloying the use of nano-precursors. Nanodiamond powder as carbon precursor was applied for the investigation. The total mass of the mixture of initial materials for processing in a single grinding jar during mechanical alloying was 70g. The weight ratio of titanium to nanodiamonds in each sample corresponds to the ratio of their atomic weights. The following combinations of initial components were studied: 1) Al (10 g) + (Ti+ND) (60 g) 2) Al (20 g) + (Ti+ND) (50 g) 3) Al (30 g) + (Ti+ND) (40 g) 4) Al (35 g) + (Ti+ND) (35 g) 5) Al (40 g) + (Ti+ND) (30 g) 6) Al (50 g) + (Ti+ND) (20 g) During mechanical alloying of mixtures 1 and 2, i.e. “10 g Al + 60 g (Ti+ND)” and “20 g Al + 50 g (Ti + ND)”, respectively, the synthesis of titanium carbide particles was extremely intensive. Fig. 2a shows the X-ray pattern obtained for mixture 1. It can be seen that the titanium carbide synthesis was fully completed with no initial components left. The titanium carbide synthesis set in almost immediately after the start of the milling process, e.g., while the major part of the nanodiamond agglomerates have not yet been crushed. This results in a significant part of synthesized titanium carbide particles being around 1 µm in size (Fig. 2b). At the same time, the milling drums heated up significantly leading to damages in the sealing gaskets in some cases, causing disruption of the process.
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a
b
Fig. 2. X-ray diffraction pattern (a) and granule cross section (b – SEM image) of composite “10 g Al + 60 g (Ti+ND)”
Mixture 3 of initial materials is identified to be the most promising: Al (30 g) + (Ti+ND) (40 g), which is Al – 30g, Ti - 31.98g; nanodiamonds - 8.02g (the following approximate composition is obtained: 43%wt.Al + 57%wt.TiC). The diffraction pattern of mixture 3 is shown in Fig. 3a. In this case, the nanodiamond agglomerates are crushed before the synthesis process sets in. Basically, only the non-agglomerated nanodiamond particles 4-6 nm in size reacted with titanium during in-situ synthesis of TiC during mechanical alloying. Theoretical evaluation shows that the size of a titanium carbide nanoparticle obtained from a single nanodiamond particle is smaller than 10 nm. Fig. 3b shows SEM micrograph of a cross-section of composite granules of this composition. The cross-section is made by the help of ion beam cutting, which guarantees the absence of impurities during the manufacturing process. It can be seen that the titanium carbide particles obtained are of nanosize and are evenly distributed through the matrix with no defects along the phase boundary. Determining average grain size and computing the particle size distribution histogram (Fig. 3c) shows that the average size of a reinforcing particle is 31 nm. Some increase in the average size of the real titanium carbide nanoparticles when
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compared to the theoretically calculated value is explained by the fact that some nanodiamond nanoagglomerates undergo the synthesis reaction before they have been completely crushed.
a
b
c Fig. 3. Results of study of composite “30 g Al + 40 g (Ti+ND)”: (a) X-ray diffraction pattern; (b) SEM image of cross section of granule; (c) TiC particle size distribution histogram
The study has shown that applying nanodiamonds results in intensified mechanical alloying, which leads to the synthesis of titanium carbide, forming nanoparticles in the aluminum matrix. If the amount of aluminum in the mixture exceeds the optimal composition the synthesis process is slowed down. With a 35:35 ratio between the aluminum weight and the total weight of titanium and nanodiamonds, no formation of clear crystalline phases are observed after 6 hours of treatment (Fig. 4)., apart from the onset of titanium aluminides forming. In this case some of
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the titanium is removed from the TiC synthesis which is undesirable. For an Al: (Ti+ND) ratio of 50:20, no titanium carbide synthesis is observed, and only titanium aluminides are formed.
Fig. 4. X-ray diffraction pattern from composite “35 g Al + 35 g (Ti+ND)”
The evaluation of X-ray diffraction patterns (Fig. 3a) showed that the size of titanium carbide crystallites is 18 nm, but as already indicated, the average size of a reinforcing particle was 31 nm. This means that not all titanium carbide nanoparticles are monocrystalline, and some of them must be crushed into smaller crystallites. Differential scanning calorimetry (DSC) was applied to determine the temperature stability of the developed composites being important to verify the general applicability of such composite materials. Fig. 5 shows the DSC curves obtained for mixture 3.
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a
b
Fig. 5. Results of DSC studies of composite “30 g Al + 40 g (Ti+ND)”: (a) initial heating and cooldown: (b) repeated heating of the same sample and cooldown
The “as milled“ composite granules were subject to 2 subsequent heating and cooling cycles from 300 C to 900 C using a heating/cooling rate of 20 °C/min in order to appreciate the impact of the thermal and mechanical history on the thermal stability of the composites. The DSC curve obtained during the initial heating clearly shows three major peaks: two peaks when heated and one peak when cooled down. During heating, the first endothermic peak at 630-670°С is caused by the aluminum matrix melting. To explain the second peak (also endothermic) the following hypotheses can be suggested. Since the X-ray phase analysis (Fig. 3a) showed only two crystalline phases (aluminum and titanium carbide) this suggests that during mechanical alloying, an unstable amorphous phase occurs in the Al-Ti-C system, which is a precursor for double titanium carbides and aluminides. Since this phase is amorphous, it will be hardly detected by X-ray analysis. When heated this phase disintegrates into aluminum, titanium carbide, titanium aluminide Al3Ti and double carbides Ti3AlC2, Ti2AlC. This process sets in at about 750 °C marked by a minor exothermic peak. The released aluminum melts, which causes the second endothermic peak to occur. peak
occurs corresponding to the aluminum melt
crystallization. During the second heating, the peak caused by the aluminum matrix melting at 630-670°С is significantly increased when compared to the first heating, which supports the
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suggestion that aluminum is liberated during the initial heating (in the second peak temperature interval). No chemical interaction between the aluminum matrix and titanium carbide was found. The composite’s primary components are aluminum and titanium carbide. This means that this composite can be applied in casting technologies without any concern that undesirable chemical reactions may occur. This application is possible both as master alloy and an individual material. 4. Conclusion The presented work shows that in-situ synthesis of titanium carbide nanoparticles in the aluminum matrix during mechanical alloying is possible when nanodiamonds are used as a precursor. The following composition of initial materials is identified as the most promising: Al (30 g) + (Ti+ND) (40 g), which is Al – 30g, Ti - 31.98g; nanodiamonds - 8.02g (the following approximate composition is obtained: 43%wt.Al + 57%wt.TiC). In this case, the synthesis of titanium carbide nanoparticles is complete and the average size of particles obtained is around 30 nm. Differential scanning calorimetry showed that the composite developed is stable within a wide range of temperatures, which permits its application in casting technologies. Acknowledgements The research leading to these results has received funding from the Ministry of Education and Science of Russian Federation under the project number 14.587.21.0030 (identifier RFMEFI58716X0030). The authors are grateful to A.S.Prosviryakov, B.R.Senatulin, M.Y.Presniakov and E.V.Shelekhov for assistance in investigations.
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Figure Captions
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Fig. 1. Cross sections of composite granules with TiC reinforcements produced from graphite (a) and soot (b) precursors Fig. 2. X-ray diffraction pattern (a) and granule cross section of composite “10 g Al + 60 g (Ti+ND)” Fig. 3. Results of study of composite “30 g Al + 40 g (Ti+ND)”: (a) X-ray diffraction pattern; (b) SEM image of cross section of granule; (c) TiC particle size distribution histogram Fig. 4. X-ray diffraction pattern from composite “35 g Al + 35 g (Ti+ND)” Fig. 5. Results of DSC studies of composite “30 g Al + 40 g (Ti+ND)”: (a) initial heating and cooldown: (b) repeated heating of the same sample and cooldown
S1359-8368(17)34341-X
DOI:
10.1016/j.compositesb.2018.02.023
Reference:
JCOMB 5548
To appear in:
Composites Part B
Received Date: 15 December 2017 Revised Date:
14 January 2018
Accepted Date: 22 February 2018
Please cite this article as: Popov VA, Burghammer M, Rosenthal M, Kotov A, In situ synthesis of TiC nano-reinforcements in aluminum matrix composites during mechanical alloying, Composites Part B (2018), doi: 10.1016/j.compositesb.2018.02.023. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
1
ACCEPTED MANUSCRIPT
In situ synthesis of TiC nano-reinforcements in aluminum matrix composites during mechanical alloying Vladimir A.Popov1*, Manfred Burghammer2, Martin Rosenthal2, Anton Kotov1 1
National University of Science and Technology “MISIS”, Leninsky prospect, 4, 119049
Moscow, Russia 2
ESRF, 71 avenue des Martyrs, 38000 Grenoble, France
*corresponding author e-mail address: [email protected]
Abstract In this paper the possibility of fabrication of titanium carbide reinforcing nanoparticles inside an aluminum matrix by in situ synthesis during mechanical alloying will be discussed. The application of nanodiamond particles as carbon precursor for synthesis allowed obtaining TiC particles in nanosized form due to the size of initial nanodiamond particle of 4-6 nm. The developed composites were investigated by scanning electron microscopy, X-ray diffractometry, and differential scanning calorimetry. Keywords: A: Metal-matrix composites (MMCs); Particle-reinforcement; B: Microstructures; D: Electron microscopy 1. Introduction The advancement of science and technology requires the development of new materials. On the one hand, modernized materials enhance the quality of various products and increase their service life, while on the other hand they create new technical solutions that are fundamentally different when compared to existing ones. Metal matrix composites [1-18] provide a new level of properties unattainable in conventional non-reinforced metals and alloys. However, composites with powder-like reinforcing particles still deserve considerable attention. Multiple studies have been dedicated recently to the development of nanocomposites. e.g., composites with nano-sized reinforcing particles. However, nano-powders in this application display a number of features,
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such as an increased surface area and high activity of the material, which results in a large amount of foreign matter and contamination on the surface of the nanoparticles. Contamination at the interface between the metal matrix and the reinforcing particle is one of the major reasons preventing a wider application in industry. This is explained by the fact that despite being an insignificant amount, these contaminations and inclusions considerably reduce the bonding strength between the composite components. In casting technologies, contaminations and inclusions on the surface of nanoparticles result in reduced dampening between the components which, at the very least, causes irregular distribution of reinforcing particles in the matrix, and more often leads to them being removed from the melt along with the slag. To reduce contamination at the interface between the metal matrix and the reinforcing particle, various methodologies have been developed. A promising approach is the in situ synthesis of nanoparticles in the matrix. In this case, the synthesized nanoparticles have no contact with air, and thus no contamination between the reinforcing particle and the metallic matrix is formed. Recently, titanium carbide has been generating increased interest due to its good mechanical characteristics. The literature includes reports on in-situ studies of the synthesis of titanium carbide reinforcing particles during the mechanical alloying process [11-13]. In the described processes, titanium and graphite (or soot) particles were used as precursors. The synthesis is often carried out when annealing granules after mechanical alloying. The hereby presented work is intended to study the in-situ synthesis of nanoparticles of titanium carbide in an aluminum matrix during mechanical alloying when using nanodiamond powders and titanium particles as precursors. The extremely small size of nanodiamond particles and their exceptional hardness are those characteristics of nanodiamonds (ND) that led to their choice for the experiment [19-29]. The exceptional hardness and the quantity of nanodiamonds
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results in intensification of the mechanical alloying process, and their small size has a positive effect upon the size reduction of synthesized titanium carbide particles. 2. Materials, equipment, and methodologies The composites were fabricated by mechanical alloying [30-34]. In the studies, commercially available aluminum, titanium and detonation-synthesized nanodiamond powders were used as initial materials. A technical grade aluminum powder was applied to the matrix, with an initial particle size of 30-100 µm. As precursors for the synthesis of titanium carbide particles, technical grade titanium powders were used with a particle size of 100 µm, alongside detonationsynthesized nanodiamond powders manufactured by Kombinat Elektrohimpribor (FSUE). Primary nanodiamond particles are near-spherical in shape; in general, they are 4-6 nm in size. A distinctive feature of nanodiamonds, just like most nanopowders, is that they can combine into agglomerates reaching up to hundreds of micrometers in size. In terms of nanoparticle bonding strength, there are primary and secondary (and sometimes tertiary) agglomerates. The strongest are primary agglomerates. At the start of mechanical alloying, secondary agglomerates deagglomeration into primary nanoagglomerates of up to 100 nm. A substantial period of time is required for complete deagglomeration of the agglomerates. A Retsch PM400 planetary mill with four tightly closed grinding jars was used for mechanical alloying. Balls of 12 mm in diameter were used as the milling tool. The ratio of ball weight to the weight of the processed material was 10:1. The rotation velocity of the grinding jars around the common axis (rotation rate of the carrier) was 300 rpm. The drums were aircooled during operation. To prevent overheating, the planetary mill was stopped after every 10 minutes of operation for 5 minutes to cool-down. The processing time was deemed to be the time when the mill was operating, disregarding the cool-down intervals. The granules obtained after mechanical alloying were studied using a scanning electron microscope Helios NanoLab™ 600i DualBeam™ (FEI). Secondary electrons registration mode was used. For the studies, granules were cut by an ion beam to avoid surface contaminations
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influencing the analysis. The quantitative metallography (determination of reinforcing particle size) was performed using the AxioVision Release 4.5 software package. Thermal effects occurring when heating the samples were studied using a differential scanning calorimetry DSC 404 C Pegasus (NETZSCH, Germany). The measurements were conducted in platinum-rhodium crucibles with aluminum oxide inserts at a rate of 20 °C/min. During the measurement process, a dynamic inert atmosphere was maintained (argon, 50 ml/min). The XRD analysis was carried out on a Bruker D8 ADVANCE diffractometer and a DRON-3 diffractometer using CuKα-radiation in both cases. 3. Results and discussion For in situ synthesis of TiC particles in the metal matrix via mechanical alloying, it is necessary to use precursors: titanium and carbon particles. Titanium particles have tens and hundreds micrometers in size. Graphite and soot consist of particles with similar sizes. Reaction between titanium and carbon micro-particles leads to formation of TiC micro-particles, basically. Fig. 1 shows cross sections of several composite granules with TiC reinforcements produced from graphite and soot precursors.
a
b
Fig. 1. Cross sections of composite granules with TiC reinforcements produced from graphite (a) and soot (b) precursors (SEM images)
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It is possible to obtain reinforcing nano-particle inclusions from in-situ synthesis just based on mechanical alloying the use of nano-precursors. Nanodiamond powder as carbon precursor was applied for the investigation. The total mass of the mixture of initial materials for processing in a single grinding jar during mechanical alloying was 70g. The weight ratio of titanium to nanodiamonds in each sample corresponds to the ratio of their atomic weights. The following combinations of initial components were studied: 1) Al (10 g) + (Ti+ND) (60 g) 2) Al (20 g) + (Ti+ND) (50 g) 3) Al (30 g) + (Ti+ND) (40 g) 4) Al (35 g) + (Ti+ND) (35 g) 5) Al (40 g) + (Ti+ND) (30 g) 6) Al (50 g) + (Ti+ND) (20 g) During mechanical alloying of mixtures 1 and 2, i.e. “10 g Al + 60 g (Ti+ND)” and “20 g Al + 50 g (Ti + ND)”, respectively, the synthesis of titanium carbide particles was extremely intensive. Fig. 2a shows the X-ray pattern obtained for mixture 1. It can be seen that the titanium carbide synthesis was fully completed with no initial components left. The titanium carbide synthesis set in almost immediately after the start of the milling process, e.g., while the major part of the nanodiamond agglomerates have not yet been crushed. This results in a significant part of synthesized titanium carbide particles being around 1 µm in size (Fig. 2b). At the same time, the milling drums heated up significantly leading to damages in the sealing gaskets in some cases, causing disruption of the process.
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a
b
Fig. 2. X-ray diffraction pattern (a) and granule cross section (b – SEM image) of composite “10 g Al + 60 g (Ti+ND)”
Mixture 3 of initial materials is identified to be the most promising: Al (30 g) + (Ti+ND) (40 g), which is Al – 30g, Ti - 31.98g; nanodiamonds - 8.02g (the following approximate composition is obtained: 43%wt.Al + 57%wt.TiC). The diffraction pattern of mixture 3 is shown in Fig. 3a. In this case, the nanodiamond agglomerates are crushed before the synthesis process sets in. Basically, only the non-agglomerated nanodiamond particles 4-6 nm in size reacted with titanium during in-situ synthesis of TiC during mechanical alloying. Theoretical evaluation shows that the size of a titanium carbide nanoparticle obtained from a single nanodiamond particle is smaller than 10 nm. Fig. 3b shows SEM micrograph of a cross-section of composite granules of this composition. The cross-section is made by the help of ion beam cutting, which guarantees the absence of impurities during the manufacturing process. It can be seen that the titanium carbide particles obtained are of nanosize and are evenly distributed through the matrix with no defects along the phase boundary. Determining average grain size and computing the particle size distribution histogram (Fig. 3c) shows that the average size of a reinforcing particle is 31 nm. Some increase in the average size of the real titanium carbide nanoparticles when
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compared to the theoretically calculated value is explained by the fact that some nanodiamond nanoagglomerates undergo the synthesis reaction before they have been completely crushed.
a
b
c Fig. 3. Results of study of composite “30 g Al + 40 g (Ti+ND)”: (a) X-ray diffraction pattern; (b) SEM image of cross section of granule; (c) TiC particle size distribution histogram
The study has shown that applying nanodiamonds results in intensified mechanical alloying, which leads to the synthesis of titanium carbide, forming nanoparticles in the aluminum matrix. If the amount of aluminum in the mixture exceeds the optimal composition the synthesis process is slowed down. With a 35:35 ratio between the aluminum weight and the total weight of titanium and nanodiamonds, no formation of clear crystalline phases are observed after 6 hours of treatment (Fig. 4)., apart from the onset of titanium aluminides forming. In this case some of
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the titanium is removed from the TiC synthesis which is undesirable. For an Al: (Ti+ND) ratio of 50:20, no titanium carbide synthesis is observed, and only titanium aluminides are formed.
Fig. 4. X-ray diffraction pattern from composite “35 g Al + 35 g (Ti+ND)”
The evaluation of X-ray diffraction patterns (Fig. 3a) showed that the size of titanium carbide crystallites is 18 nm, but as already indicated, the average size of a reinforcing particle was 31 nm. This means that not all titanium carbide nanoparticles are monocrystalline, and some of them must be crushed into smaller crystallites. Differential scanning calorimetry (DSC) was applied to determine the temperature stability of the developed composites being important to verify the general applicability of such composite materials. Fig. 5 shows the DSC curves obtained for mixture 3.
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a
b
Fig. 5. Results of DSC studies of composite “30 g Al + 40 g (Ti+ND)”: (a) initial heating and cooldown: (b) repeated heating of the same sample and cooldown
The “as milled“ composite granules were subject to 2 subsequent heating and cooling cycles from 300 C to 900 C using a heating/cooling rate of 20 °C/min in order to appreciate the impact of the thermal and mechanical history on the thermal stability of the composites. The DSC curve obtained during the initial heating clearly shows three major peaks: two peaks when heated and one peak when cooled down. During heating, the first endothermic peak at 630-670°С is caused by the aluminum matrix melting. To explain the second peak (also endothermic) the following hypotheses can be suggested. Since the X-ray phase analysis (Fig. 3a) showed only two crystalline phases (aluminum and titanium carbide) this suggests that during mechanical alloying, an unstable amorphous phase occurs in the Al-Ti-C system, which is a precursor for double titanium carbides and aluminides. Since this phase is amorphous, it will be hardly detected by X-ray analysis. When heated this phase disintegrates into aluminum, titanium carbide, titanium aluminide Al3Ti and double carbides Ti3AlC2, Ti2AlC. This process sets in at about 750 °C marked by a minor exothermic peak. The released aluminum melts, which causes the second endothermic peak to occur. peak
occurs corresponding to the aluminum melt
crystallization. During the second heating, the peak caused by the aluminum matrix melting at 630-670°С is significantly increased when compared to the first heating, which supports the
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suggestion that aluminum is liberated during the initial heating (in the second peak temperature interval). No chemical interaction between the aluminum matrix and titanium carbide was found. The composite’s primary components are aluminum and titanium carbide. This means that this composite can be applied in casting technologies without any concern that undesirable chemical reactions may occur. This application is possible both as master alloy and an individual material. 4. Conclusion The presented work shows that in-situ synthesis of titanium carbide nanoparticles in the aluminum matrix during mechanical alloying is possible when nanodiamonds are used as a precursor. The following composition of initial materials is identified as the most promising: Al (30 g) + (Ti+ND) (40 g), which is Al – 30g, Ti - 31.98g; nanodiamonds - 8.02g (the following approximate composition is obtained: 43%wt.Al + 57%wt.TiC). In this case, the synthesis of titanium carbide nanoparticles is complete and the average size of particles obtained is around 30 nm. Differential scanning calorimetry showed that the composite developed is stable within a wide range of temperatures, which permits its application in casting technologies. Acknowledgements The research leading to these results has received funding from the Ministry of Education and Science of Russian Federation under the project number 14.587.21.0030 (identifier RFMEFI58716X0030). The authors are grateful to A.S.Prosviryakov, B.R.Senatulin, M.Y.Presniakov and E.V.Shelekhov for assistance in investigations.
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Fig. 1. Cross sections of composite granules with TiC reinforcements produced from graphite (a) and soot (b) precursors Fig. 2. X-ray diffraction pattern (a) and granule cross section of composite “10 g Al + 60 g (Ti+ND)” Fig. 3. Results of study of composite “30 g Al + 40 g (Ti+ND)”: (a) X-ray diffraction pattern; (b) SEM image of cross section of granule; (c) TiC particle size distribution histogram Fig. 4. X-ray diffraction pattern from composite “35 g Al + 35 g (Ti+ND)” Fig. 5. Results of DSC studies of composite “30 g Al + 40 g (Ti+ND)”: (a) initial heating and cooldown: (b) repeated heating of the same sample and cooldown