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SYNTHESIS AND CHARACTERIZATION OF THE CUBIC FORM OF TANTALUM NITRIDE

Student: Project Supervisor:

Angel Alfonso Lopez Mats Johnsson

Department of Materials and Environmental chemistry (Stockholm University) 1

INDEX 1 Abstract ............................................................. Page 4 2 Nitrides


2.1 - Tantalum Nitride (TaN) ............................ Page 5 2.2 - Titanium nitride (TiN) .............................. Page 9 2.3 - Silicon nitride (Si3N4) .............................. Page 12

3 Carbides
3.1 - Tantalum Carbide (TaC) .......................... Page 17 3.2 Titanium Carbide (TiC) ............................ Page 19 3.3 - Tungsten Carbide (WC) ........................... Page 22

4 Solid Solutions ................................................ Page 26 5 Grinding Mill .................................................... Page 28 6 Spark Plasma Sintering (SPS) ....................... Page 31 7 Archimedes Principle . Page 34 8 X-Ray Diffraction . Page 36 9 Scanning Electron Microscopy (SEM) .. Page 43 10 Experimental procedure
10.1 Mixture preparation Page 48 10.2 - Powder mixing .. Page 50

10.3 - Spark Plasma Sintering (SPS) Page 51 10.4 - Powder X-Ray analysis Page 55 10.5 Theoretical Density calculation .. Page 55 10.6 Archimedes method Page 57

11 Results and discussion


11.1 SPS sintering results .. Page 59 11.2 SPS sintering discussion Page 62 11.3 - Powder X-Ray diffraction results . Page 63 11.4 - X-Ray results discussion . Page 81 11.5 - Density measurements results Page 82 11.6 - Density measurements discussion .. Page 85 11.7 - SEM images . Page 86 11.8 - SEM discussion .. Page 103

12 Conclusions . Page 105 13 Bibliography . Page 107

1- Abstract
The aim of this study is to optimize a method to turn the typical lattice of TaN at normal conditions (hexagonal) into its cubic counterpart using Spark Plasma Sintering (SPS). The effect of some parameters such as synthesis temperature and pressure on the cubic conversion is studied, as well as the role that plays the addition of some dopants (TaC, TiN) in low quantities. On the other hand, some physical parameters such as density and compactness were assessed for each of the samples, in an attempt to relate them to the presence of cubic and hexagonal lattice. To carry out the study, different characterization techniques such as XRay diffraction were used to determine the hexagonal and cubic present lattices, as well as density measurements. Some SEM images were also obtained providing information about the formation of the lattices, their physical properties and the grain sizes of the different samples.

2 - Nitrides
Nitrides are compounds consisting of Nitrogen and another element which is less electronegative than Nitrogen, in which N has a -3 valence in the bonding. Since they cover a large variety of compounds, their properties, applications and synthesis methods are different for each compound. Apart from the ordinary nitrides, there are other compounds formed with nitrogen ions such as pernitrides (N2-2) and azides (N3-)

Uses of Nitrides Nowadays, nitrides are most widely used for the following applications:

1) As abrasives ( Cubic Boron Nitride) 2) As lubricants ( Hexagonal Boron Nitride) 3) As refractory materials ( like Silicon Nitride ) 4) For the fabrication of cutting tools ( Silicon Nitride) 5) For metallic coatings ( Titanium Nitride ) 6) For hydrogen storage, because of their high reactivity with H2 (Lithium Nitride), creating the species LiNH2 when the hydrogen is stored

2.1 - Tantalum Nitride (TaN)

Properties
Tantalum Nitride (TaN) is an inorganic compound consisting of crystals whose tonality is within a range from brown to black and has a Co-Sn structure type. In fact, its colour is dependent on the lattice arrangement, which can be either hexagonal or cubic when the moles ratio is 1:1. Although naturally TaN presents itself in an hexagonal lattice, the cubic phase can also be formed when applied high pressures and temperatures to the synthesis process. TaN is also insoluble in water and possesses a high melting point (around 3360 C) as well as the fact that it is a refractory material capable of retaining its strength at high temperatures.

Some of its main physical properties are presented in the following table Molecular Weight (g/mol) Density for the Hexagonal form (g/cm3) Color Melting Point Appearance 195 13.7 Brown to Black 3360C Crystalline Solid

Synthesis
Various methods can be used to synthesize solid TaN

1) Chemical Vapor Deposition (CVD)

CVD is a set of chemical reactions that turn gaseous molecules (called precursors) into a solid material, creating either a powder mixture or a thin film on the surface of the substrate. When choosing the precursor different considerations must be taken into account, such as its bonds strength (which will affect the operating temperature and the purity of the product), its thermal stability and reactivity. For example, tantalum hydrides (TaH, TaH2) and tantalum halides (TaCl4, TaCl5) could be used as a precursor.

Energy can be applied as thermal energy (from furnaces and lamps) or as photovoltaic energy (from UV and laser) to the reactor. Apart from the solid, also gaseous products are formed, which means they must be treated carefully if hazardous. In the process, the precursor is densified by a thermically enhanced nitrating gas made up of oxygen, nitrogen and ammonia. A metal nitride layer is subsequently formed and densified thanks to the nitrating gas action, even though sometimes a metal layer must be deposited over the substrate prior to the gas exposure. To create semiconductor devices such as electrodes, by depositing dielectric layers between the tantalum nitride layers hence creating a stack.

Solidification process in CVD

2) Atomic layer deposition (ALD)

ALD is a technique to create thin films out of gas reactants by a chemical process. This process allows the creation of metal nitrides layers with ease. Mostly 2 different precursors are used. The reaction takes place between the precursors and the substrate surface (one precursor at a time) in a sequential way. It differs from CVD in the fact that ALD breaks the CVD into two half reactions, meaning that each precursor is used in a different half reaction. Since the precursor amount in each reaction cycle is set, the reaction is self-limiting which makes it easy to control and so is the film thickness, which can be as low as 0.1 per monolayer. The amount of precursor is controlled by means of a purged gas (nitrogen or argon) which removes the remaining gas from the former reaction stage.

The process consists of four major steps which are repeated subsequently 1) Application of the 1st precursor 2) Purge of the precursors and the gaseous products of the 1st stage 3) Application of the 2nd precursor 4) Purge of the precursors and the gaseous products of the 2nd stage The main advantage of ALD over CVD is its ease to control film thickness only by setting the number of cycles, and also that the mixture neednt to be homogeneous which simplifies the process because it allows larger contact area and higher reproducibility. The only drawback to this technique is its slowliness since only a layer is deposited at a time.

3) Magnetron Sputtering deposition technique.

This is a type of physical vapor deposition (PVD). In this technique material from a source (which is called target) is resputtered or reejected into the substrate where the thin films are created by means of a sputtering gas which provides the atoms of the target with the necessary energy. The sputtering gas has a wide energy distribution which goes up to 10eV. Some of the sputtering gas atoms can cause the atoms from the target to be ionized and head for the substrate and impact energetically to create the thin film. This effect is called resputtering and is the main effect which produces the film formation. The sputtering gas must be inert (Argon for example) so as not to react with the substrate. Its energy can be controlled by setting the pressure conditions of the sputtering gas. The closer the atomic weights of the sputtering gas and that of the substrate are, the better the momentum is transferred to the atoms on the substrate. Thats why neon is more likely to be used when spluttering light elements and krypton is usually used for heavier elements. There are a lot of parameters to take into account in this process which make it complex. However, its complexity also allows a high control over features such as film growth and microstructure if the parameters are well controlled. All its features make it suitable for fields such as electronics, (especially when depositing thin films of various materials to create integrated circuits) or coating.

The main advantage over other techniques is that it can even sputter high melting point substrates if the sputtering gas beam is energetic enough, the fact that the film composition is very close to the former substrate, and better adhesion of the films. Its main disadvantage is that the sputtered atoms cant be directed exactly to the substrate, which may lead to chamber contamination.

Magnetron Sputtering deposition technique.

Applications
Tantalum Nitride (TaN) has its main applications in the electronics field. Some of its most usual applications are listed below:

1) Barrier Layers

TaN is used in the electronics industry to create thin barriers which are placed between copper and silicon-based components such as interlevel dielectrics (ILDs) made of silicon dioxide, in integrated circuits. TaN based layers are effective when it comes to avoiding copper or silicon diffusion between the layers. This non-diffusive properties are kept even at high electric fields and voltages when TaN is used. This barrier also presents a good adhesion between the metallic copper layer and the silicon-based ILDs.

2) Resistors

A resistor is a device that produces a voltage between two electronic components. This voltage is directly proportional to electric current according to Ohms law.

Together with nickel-chrome, tantalum nitride is used to manufacture resistors for precission applications due to the reduction of thermal and electronic noise that this material provides in the shape of thin films, being the most widely used material for that purpose. Unlike its nickel-chrome counterparts, tantalum nitride films are resistant to humidity even at high application potentials. This occurs thanks to a tantalum oxide layer formed espontaneously on the surface which prevents it from corroding, process known as passivation.

2.2 - Titanium nitride (TiN)

Properties

Its a ceramic and hard material stable at room temperature (oxidizes at 800C) and reactive to strong acids. It also has good IR properties in the range of gold (Au) which give it a golden colour. Most commonly it presents the Na-Cl type crystal structure when the stechiometry is 1:1 that is a cubic lattice. Some other stechiometrys also present stable structures for titanium nitride.Its good properties make it suitable for applications such as coating or superinsulators among others. Some other of its properties are

Vickers hardness = 18-21 GPa Thermal conductivity = 19.1W/(m* C)Modulus of elasticity 251 GPa Modulus of elasticity = 251GPa Thermal expansion coefficient = 9.35*10-6 K-1 Superconducting transition temperature = 5.6 K

Synthesis
TiN films are usually synthesized by physical vapor deposition (PVD) techniques such as sputtering, electron beam heating or cathodic deposition as well as by chemical vapor deposition (CVD). Titanium reacts with highly energetic nytrogen in vacuum conditions to create titanium nitride. As explained, PVD is mostly used when TiN is combined with higher melting point materials like stainless steel or to create titanium alloys. TiN can also be obtained by packing powdered titanium by compression in a nitrogen atmosphere (nitrogen or ammonia) at high temperature (1200C) . The heat is provided by the exothermal reaction between titanium and nitrogen, having as a product a compact and hard material. TiN coatings can also be obtained by thermal spraying.

Applications

Electronics Thin films of TiN are used for semiconductors. Theyre used in coper based chips as a conductive barrier placed between the silicon parts and the metallic ones. Its role is to block copper diffusion and allow electrons to flow through at the same time, acting as a metal diffusion blocker. Its also used to improve transistor performances. In fact, when combined with gate dielectrics such as HfSiO posseses better performance than pure SiO2 providing them with a better threshold voltage and a lower leakage

Coatings TiN is used to avoid corrosion, specially on tools such as drills milling cutters and even improving their lifetime at least trice. Its also used to coat another metals such as chromium or nickel on plumbing and hardware applications. Since its not toxic, can also be applied to medical tools such as scalpels or orthopedic saw blades which provide the necessary cutting sharpness for medical operations. In fact, TiN can also be used to make up prothesis.It is also used for jewellery and decorative motifs because of its golden colour.

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As a constituent in steel making

Titanium is added intentionally to some steel alloys to form TiN within the steel alloy. Its produced at high temperatures in the form of micrometric cubic particles and has a low solubility in steel. The titanium helps to stabilise the steel by hindering possible corrosion, since titanium has a higher affinity for carbon, oxygen and nitrogen rather than chromium, thus producing stable carbides, oxides and nitrides in the steel formation process. All these species could have formed detrimental compounds if they had not reacted with titanium, which could lead to reduced mechanical properties. However, this kind of steels are prone to cracks formation after welding.

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2.3 - Silicon nitride (Si3N4)

Properties
Silicon Nitride is a hard ceramic material which is resistant over a broad range of temperatures. It also has a low thermal expansion coefficient, moderate thermal conductivity, a high elastic modullus and quite a high fracture toughness (unlike most ceramics). All these properties provide Si3N4 with the capabilities of supporting high loads succesfully and with excellent thermal shock resistance, which make it suitable for applications such as manufacturing devices which operate at high temperatures (turbines, car engines ..) as well as cutting tools and metal working. Silicon nitride films are also used in the electronics industry.

Synthesis

There are three different routes to obtain Silicon Nitride (Si3N4)

1) By reaction between silicon and nitrogen at high temperatures (1300 1400C) 3 Si(s) + 2 N2(g) Si3N4(s)

2) By diimide synthesis: SiCl4 + 6 NH3 (g) Si (NH)2(s) + 4 NH4Cl(s) at 0 C 3 Si(NH)2(s) Si3N4(s) + N2(g) + 3 H2(g) at 1000 C

3) By carbothermal reduction in nitrogen atmosphere at 14001450 C: 3 SiO2(s) + 6 C(s) + 2 N2(g) Si3N4(s) + 6 CO(g)

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The simple nitridation of silicon was formerly the main large scale production method. However, silicates are also formed and contaminate the process. The diimide synthesis produces amorphous silicon nitride which needs further annealing with nitrogen at high temperatures to make it crystalline. The carbothermal reduction method and presents high cost and S3N4 purity performances Si3N4 films can be formed by chemical vapor deposition CVD,being one of its variants, Plasma enhanced chemical vapor deposition (PECVD) the most effective method.The process complies with the following reactions 3 SiH4(g) + 4 NH3(g) Si3N4(s) + 12 H2(g) 3 SiCl4(g) + 4 NH3(g) Si3N4(s) + 12 HCl(g) 3 SiCl2H2(g) + 4 NH3(g) Si3N4(s) + 6 HCl(g) + 6 H2(g)

If what is needed is to place films between semiconductor substrates (made of silicon), also Low pressure chemical vapour deposition (LPCVD) can be used. In this process, deposition parameters are important since if not controlled correctly, it could lead to stress appearance, due to the fact that Si2N4 and pure silicon dont have the same lattice parameters.

Applications
The main drawback when using Si3N4 is not its technical performance but rather its price. Since it has become cheaper, new horizons have opened to this promising material, being the most important

1) Car industry

One of the major applications of sintered silicon nitride is in automobile industry as a material for engine parts. Those include, in Diesel engines, glowplugs for faster start-up; precombustion chambers (swirl chambers) for lower emissions, faster start-up and lower noise; turbocharger for reduced engine lag and emissions.

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In spark-ignition engines, silicon nitride is used for rocker arm pads for lower wear, turbocharger for lower inertia and less engine lag, and in exhaust gas control valves for increased acceleration. As examples of production levels, there is an estimated more than 300,000 sintered silicon nitride turbochargers made annually.

2) Bearings

Different types of bearings Si3N4 bearings can be either pure or ceramic hybrids altogether with steel. The silicon nitrides good shock resistance makes it perfect for such an application. Since Silicon Nitride is harder than metal, when such a material is used for bearings the contact with the bearing track is radically reduced. This leads to lower friction (80% lower than when its metal counterpart is used), longer lifetime, higher operation temperature and to a reduction in corrosion.

3) High-temperature material Due to its excellent behaviour at high temperatures, shown by its resistance to high thermal shocks and thermal gradients, this material can play an important role when used in devices which operate at high temperatures such as rocket engines.

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4) Metal working

Silicon Nitride is perfect to play roles such as milling, grinding and piercing of metals. In fact, is used for cutting and abrasive tools because of its excellent thermal and mechanical performance. S3N4 can cut through cast iron and high steel at a speed 25 times higher than when conventional materials are used. In fact, Silicon Nitride has had a great importance to assemble well-finished metal products.

5) Electronics S3N4 is used in electronics as both an insulator and a chemical barrier for integrated circuits and to electrically isolate circuit parts. As a chemical barrier is better than SiO when blocking species such as water and sodium ions which can cause corrosion and instability. It can also be used as dielectric between polysilicon layers in capacitors.

3 - Carbides
A carbide is a binary compound made of carbon and a more electropositive element. Carbides can be classified into different groups, and their properties, synthesis and applications are dependent on the group to which they belong to. The simplest classification is:

1) Salt-Like carbides: They are compounds formed by carbon and the compounds from groups I,II A and III B (except Actinium).depending on the lattice arrangement, these carbides can be represented by the anions C4-, C34-,C222) Covalent carbides: These are silicon (SiC) and boron carbides (B4C). Both materials are hard and refractory, which makes them important industrially speaking.

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3) Insterstitial carbides: These group includes the transition metals from the groups IV, V and VI B (except chromium). They all are refractory and possess metallic properties. Some of them (Titanium carbide, tantalum carbide and tungsten carbide) are used to coat cutting tools.

4) Molecular carbides: These are metal complexes containing carbon. There are molecules with carbon fragments or most commonly clusters in a metal-centered body. One example of a molecular carbide is the compound Fe5C(CO)15

Fe5C(CO)15 molecular carbide .

Uses of Carbides

1) Abrasives and cutting tools ( Silicon carbide) 2) Steelmaking (Calcium Carbide) 3) Coatings on Iron and Steels ( Titanium Carbide) 4) High temperature applications (Tantalum Carbide) 5) Machine tools and military purposes (Tungsten Carbide)

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3.1 - Tantalum Carbide (TaC)

Properties
TaC is a hard and refractoryceramic material (with a hardness around 9 10 mohs). Its one of the hardest materials, and only diamond has a higher hardness.This makes its use suitable for cutting tools and for the manufacturing of ceramicmetallic materials among others. It appears to be a brownish powder and its crystal arrangement is cubic and equal to that of NaCl. In fact, is the stechiometrically binary compound (1:1) with the highest melting point, only excedeed by its counterpart TaC0.89, with a melting point of 4000C. Its also a flammable compound when its presented in the form of a dust, because it can form flammable gases.

Some other of its physical properties are exposed in the following table: Molecular weight Density Melting Point Boiling Point Appearance Solubility Crystal Structure Risks 192.96 g/mol 13.9 g/cm3 3880C 5500C Solid brownish powder Not soluble in water Cubic None

Synthesis
There are various routes to synthesize TaC:

1) By mixing tantalum pentoxide (Ta2O5) with tantalite [(Fe, Mn) (Ta,Nb)2O6] in the p resencepresence of carbon ( C ) and sodium carbonate (Na2CO3) at 1500C, leaving 6% of djdjdjdunreacted carbon.

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2) By means of a simple reaction among metallic magnesium (Mg), sodium carbonate (Na2CO3) and tantalum pentachloride (TaCl5) at 600C, thus obtaining good tantalum carbide with good thermal stability and oxidation resistance when used below 450C in an air environment.

3) By the reaction of metallic Tantalum powder (Ta) with carbon (C) at 2000C in a graphite furnace. This method leaves around 6% of unreacted carbon.

4) Carbidization of tantalum powder and tantalum oxides in the presence of carbon and a hydrogen stream at 1600C

Applications
1) Oxidation and thermal protection coating:

TaC layers can be deposited on materials such as carbon, refractory metals and alloys to protect them from thermal impacts and oxidation with a very good performance. The advantages of this carbide for this use are the possibility to coat the material at a low temperature (10% of the melting point of the carbide), the lack of porosity in the coating and its adaptation to difficult shapes and surfaces. TaC offers great protection in very corrosive and high temperature environments.

2) Cutting tools When TaC is used to manufacture cutting tools it provides very good mechanical properties such as high hardness, low tool deformation even at high temperatures, good wear resistance and low brittleness. All of these properties are paramount when cutting at high speeds. In fact, tantalum carbide coated tools cut three times faster than high-speed steels. Tantalum carbide is often used with a mixture of other carbides to obtain the necessary mechanical properties. Its specially used to manufacture high-speed machine tool bits, mining equipment, cutting tools and teeth for construction.

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3) Cermet material (metallic-ceramic) composites This composite can be created with the ceramic material Tantalum Carbide. The main reason is to combine its properties with those of metals, such as malleability. For this application the most interesting properties provided by TaN are its resistance to high temperatures and its good wear resistance.

4) Tantalum carbide/graphite composite material This hybride is one of the hardest materials ever manufactured by man, and has a meltng point of 3738C. This material combines the best properties of each material, being the best properties of one of the material the worst of the other, thus neutralising them. In other words, carbon has very good ablation and thermal shock resistance, but erodes easily. Tantalum carbide resists erosion perfectly, but its ablation and thermal shock resistance is poor. In the output composite materials, all of these properties have been improved when compared to the former materials. This improvement opens a new horizon of applications where excellent thermal and mechanical properties are required, such as bearings, turbines or rocket nozzles.

3.2 Titanium Carbide (TiC)

Properties
Titanium carbide is a refractory ceramic material, with a hardness around 9.5 in the Mohs scale. Its a crystalline black powder with a cubic centered structure like NaCl. This material is resistant to wear and corrosion, and preserves its hardness at high temperatures. Its not flammable in the solid state, although grinded dust can be flammable and also cause skin and eyes irritation. Its also a chemically stable compound which only dissolves in acids or alkalis. All this properties make it useful for applications such as cermets assembly, cutting tools and alloying.

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Some of its properties are listed below:

Molecular weight Density Melting Point Boiling Point Appearance Solubility Crystal Structure Risks

59.9 g/mol 4.93 g/cm3 3160 C 4820 C Black powder Not soluble in water Cubic Can cause irritation

Synthesis
Different methods can be used to synthesise TiC, among which the following were remarked:

1) Self-propagating High-temperature Synthesis (SHS) This synthesis takes place inside of a reactor and can be easily reproduced industrially. In this process, titanium powder (Ti), carbon black (C), and an inert diluent such as titanium carbide (TiC) form the starting mixture. The TiC diluent plays an important role: it reduces the combustion rate, decreases the necessary synthesis temperature around 200K and enables the obtention of TiC in a powder form. Different gases are formed during the synthesis due to the impurities present in the starting powders, such as TiO2 layers that may have been formed, which need to be purged to avoid product contamination.

2) Mechanochemical process By means of mechanical grinding, the reaction between black carbon and titanium in powder form can take place at ambient temperature. This process is relatively cheap and fast, and provides ultrafine powder that is perfect to manufacture cutting tools due to its improved fracture toughness.

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3) Chemical Vapor Deposition (CVD) In this synthesis, the used precursors are TiCl4 gaseous molecules. These solidify to form solid TiC thin films over a quartz substrate after the reaction with toluene (the carbon source) takes place. The depositing temperature must be set over 900C and nickel must be present to play an important role as a catalyst. Otherwise, only amorphous carbon would be deposited. The reaction to obtain TiC is the following:

7 TiCl 4

C 6 H 5 CH 3

Ni ( cat .), T

900 C

7 TiC

8 HCl

10Cl 2

Applications

1) Tool bits and cutting tools Titanium carbide is widely used for cutting tools and tool bits because of its good mechanical properties. When it is added to hard metals it provides excellent wear resistance and hardness (since it is one of the hardest carbides) and oxidation stability, being usually combined with a mixture of other carbides to improve the mechanical properties. Titanium carbide is used for cutting tools such as grooves, cutting teeth and milling slots. This material is also used for surgery tools as coating.

2) Titanium carbide nickel-cobalt Cermets (ceramic-metallic composite) These cermets can be prepared with a wide range of metals (nickel, cobalt, chromium, molybdenum, stainless steel ). Their main characteristic is their high toughness and hardness although theyre dependent on the material base. And so then, nickel based cermets with titanium carbide are thermally and abrasive wear resistant, making them suitable for engineering applications such as turbine blades and electrical brushes. Chromium-Titanium carbide cermets possess high temperature erosion resistance, which makes them suitable for metal coating.

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3) Coatings By coating different metals such as steel and iron with Titanium Carbide their wear and corrosion resistances are improved, as well as their hardness. It also acts as a heat barrier which allows titanium carbide to be used for applications in which the thermal shock is important such as aerospacial components, ball bearings, compressor blades and metal cutting tools coatings. Its high hardness also makes it suitable for scratch-proof coating applications such as clinical dentistry and watches.

3.3 - Tungsten Carbide (WC) Properties


Tungsten carbide is an inorganic compound made up of Tungsten (W) and Carbon (C) in a molar ratio 1:1. It has got the appearance of a grey powder which is usually pressurized into different shapes for industrial purposes. WC has very high strength as shown by its high stiffness (three times stiffer than steel) and hardness. Only few compounds among (SiC or diamond among others) can polish it. Its impact resistance performance is good even at low temperatures and also possesses high thermal and electrical conductivities. Its hardness is maintained up to 760C and has got a low coefficient of friction. This material is also more corrosion resistant than noble metals and more wear resistant than steel as well as resistant to heat and oxidation. At high temperatures it decomposes to tungsten (W) and carbon (C) and is oxidized over 600C. The most normal crystal structure is the hexagonal (-WC) although at high temperatures a cubic structure can be formed (-WC)

Some of the WC properties are the following: Molecular weight Density Melting Point Boiling Point Appearance Solubility Crystal Structure Risks 195.9 g/mol 15.8 g/cm3 2870C 6000C Grey Solid Insoluble in water Hexagonal Can cause irritation, inhalation may cause lung damage (fibrosis) 22

Synthesis

Tungsten carbide can be prepared in many different ways.

1) Reaction of tungsten metal and carbon at high temperatures:

W ( s)

C ( s)

1400 2000 C

WC (s)

2) A fluid bed process which entails the reaction of tungsten metal or blue tungsten oxide with carbon oxides and hydrogen at high temperatures in a patented fluid bed

W ( s)

CO / CO2 ( g )

H 2 (g)

900 1200 C

WC (s)

H 2O

3) By Chemical vapour deposition (CVD) WC can be synthesized in two different reactions:

3.1) Tungsten hexachloride reacts with methane in the presence of a reducing agent (H2)

WCl 6 (s)

CH 4

H 2 (g)

670 C

WC (s)

6HCl

3.2) Tungsten hexafluoride reacts with methanol in the presence of H2

WF6 (s)

CH 3OH

H 2 (g)

350 C

WC (s)

6HF

H 2O

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Applications
Tungsten Carbide is used in a wide range of applications. Those most important are described below

1) Machine tools Tungsten carbide is used in machinery parts, cutting tools, drills and abrasives. When manufacturing these tools, the used tungsten carbide has been bound specially with cobalt, which is known as cemented carbide and belongs to the group of cermet materials (ceramic metal matrices). For example, WC is used to manufacture both huge and tiny drills with a wide range of applications. Tungsten Carbide is the hardest material besides diamond and the second most efficient when it comes to cutting. In fact, a tungsten-copper-steel alloy is used to bind millimetric diamond pieces that would not be of further industrial use as a grinding tool, thus increasing the diamond lifetime twice. When applied to rotatory cutting tools, it cuts five times faster and also has a much longer lifetime than a steel-made one. Tungsten Carbide tools can also be used at higher temperatures and produce better finish to products than their steel counterparts. WC drills hold a great significance when exploiting earth resources such as gas and petroleum because of its great hardness, which allows piercing deep layers of soil made up of different materials.

Generally speaking, tungsten Carbide cutting tools are important when operating on hard materials such as steel or large material quantities, where most of the tools would wear out. This wearing out resistance is what makes it suitable for applications such as bearings and machinery parts.

2) Cemented Carbide synthesis Cemented carbide is a cermet material (a composite made of a ceramic and a metal) obtained by binding the ceramic material (WC) with a metallic compound, mostly with cobalt (Co) and sometimes with nickel (Ni).

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This material combines the hardness and temperature resistance of the tungsten carbide with the malleability of the metal which allows stress application without breaking. In other words, the metal addition reduces brittleness. This composite can be easily synthesized and also provides magnificent properties. During the sintering, tungsten carbide is soluble in cobalt at high temperatures, and the used cobalt-based liquid precursor also spreads out properly throughout tungsten carbide. This leads to a dense and pore free product cermet which possesses high hardness, toughness and strength at the same time.

3) Military

Both its high density and hardness make it a perfect material (especially when uranium is not available) for military machines parts, piercing ammunition and projectiles due to its high penetration power. In fact, tungsten carbide is especially used in the cores of ammunition made up of two different parts in which the two of them come off on impact. WC is also widely used in the nuclear weapons industry due to its capability to reflect neutrons, which allows nuclear chain reactions.

4) Sports

The tungsten carbide hardness allows its use in poles which are meant to hit hard surfaces and poles used in trekking and skiing simulation in hard surfaces. This carbide allows the traction and duration that such poles need. This material is even used in tires studs to provide a better adherence on ice, being its performance better than that of steel studs.

5) Jewellery Tungsten carbides remarkable properties make it perfect for jewellery. This material provides jewellery with contrast and bright mirror-like finishes with an hematite-like colour, apart from improving the jewels resistance to marks and scratches. However, due to its high hardness they can barely be removed. In fact, only specialised tools can cut through it without jeopardizing the hands wellbeing.

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4 - Solid Solutions

Introduction
A solid solution is a mixture of two solid compounds that form a single crystalline solid. There are various methods to produce solid solutions. Therefore, they can be formed by melting two different solids, mixing them and cooling down the mixture or by dissolving both solutes in a common solvent and letting it dry up. Vapor deposition over a substrate also leads to solid solutions in the shape of a thin film.

Solid solutions are most likely to be produced when the solutes are close to each other in the periodic table (especially for metals). In fact, solids and liquids behave alike in solubility. That is, depending on their chemical properties and crystalline structure, they have different degrees of mutual solubility which determine the positions of the mixed atoms in the final crystal.

Types of solutions

These type of solutions can be formed either by a substitutional mechanism (in which the atoms of one species replace some from the other) or interstitial (in which the atoms occupy free gaps in the solvent lattice). The solubility of the species is dependent on their concentrations in the mixture and in the solids nature. Different properties of both compounds regarding chemical composition and crystal lattice must be taken into account to determine whether a solid solution will be formed, some of which are listed below.

1) Both must have similar radii with less than 15% difference. 2) Their valency must be alike 3) The electronegativities of the compounds must be close 4) Their lattice arrangement must be similar.

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When the solid solution conditions are not met, the solid solution is reversed and two separate phases make their appearance. This process is called exsolution.

Examples
Some examples of such solutions are minerals created naturally at high temperatures and pressures like the solid solution composed of two olivines, fayalite (Fe2SiO4) and forsterite (Mg2SiO4). Both species form mutual solid solutions with a wide range of different iron and magnesium concentration which provides the mixture with slightly different physical properties than that of the starting materials. Therefore, solid solutions can provide if used with the proper concentrations better properties than that of the former materials which leads to potential commercial and industrial applications such as metal alloying. Most of the alloys such as brass (Co-Zn) are considered solid solutions formed by a substitutional mechanism, whereas in steel carbon is interstitially forming a solid solution in an iron matrix.

Solid solutions are also a great asset in the semiconductors industry because they allow the selection of intermediate electrical properties between those of the former materials which make them suitable for optical and electronical applications. An example is the band gap of the solid solution formed by InAs and GaAs which can be set somewhere between the values for InAs (0.36eV) and GaAs (1.4eV). 27

5 - Grinding Mill
A grinding mill is a mechanical device that breaks the fed solid into smaller particles, thus reducing the particle size of the solid which was introduced. In the mill, the machines mechanical forces try to surpass those of the internal bonds of the matter itself, in order to eliminate such bonds. After this, the grain size and their shapes are totally modified, as well as their arrangement. The grinding purpose may be to extract valuable constituents in different ore materials or to prepare the raw materials for an industrial process, such as grinding coal for furnaces or clay for pottery. In engineering, it helps to increase the surface area of a solid and also to create products with the desired grain size.Various kinds of grinding mills can be found. In the very beginning they were operated by manual rotation (like mortars), animal force, and the action of wind and water. Later on electrical ones were introduced. The main types of grinding mills are listed below according to their operation principle:

Ball mill
It consists of a tilt or horizontal cylinder which rotates around its horizontal axis, filled up with balls, either metallic or made of stone. By impact, friction and abrasion these balls grind the fed solid material to a certain degree of grain size. These ball mills are used in industry (for example to manufacture cement) in a large scale. There can be also found little versions used in research laboratories which are used to grind sample material in order to ensure the quality of the sample.

Laboratory ball mill 28

Rod mill
Theyre also usually referred to as slitting mills. In this type of mills a rotating vessel helps to create the necessary mechanical friction between steel rods and the solid particles. Its rods are usually made of iron or some other metal.

Laboratory Rod Mill

SAG mill
SAG or Semi-Autogenous Grinding are comprised by mills that use for grinding a mixture of both steel balls and big rocks. Its ball charge ranges from 6 to 15%. In this mill, both the balls and the rocks are thrown down at the solid and this action causes the break down into smaleer pieces of the solid samples by impact and compression while the drum is rotating. These drums are usually large in diameter and short in length. There are lifts installed on the inside to lift the solid particles up and around the mill, after which it falls off the plates boosting particle movement throughout the mill. Some of its industrial applications are the grinding of precious metals such as gold, platinum and silver among others.

29

Principle of SAG Mill operation

SAG Mill

Autogenous mill
In this system large rocks are thrown down thus breaking down the solid particles by impact and compression. In fact, it is very similar to the SAG system, apart from the fact that it does not use metal balls. It can be used when contamination by metals is to be avoided.

High pressure grinding rolls mill


The solid meant to be grinded is put between two rollers located very close to each other. These rolls rotate in opposite directions thus crushing the solid material.In fact, while it is spinning, the solid fits into a tiny gap in between, and it reaches pressures so high that are capable of breaking it down into finer particles, even fracturing the material at the grain size level.

Operation diagram of a high pressure grinding rolls mill

30

6 - Spark Plasma Sintering (SPS) Definition


SPS (Spark Plasma Sintering) is a sintering process that can assemble compact samples from ceramics and metal powders at a different range of temperatures and pressures. The technique is especially interesting due to its capability of doing so at low temperatures. It is yet to be discovered which are the mechanisms taking place in the densification and grain growth processes as no direct observations of a plasma have been made. In this process uniaxial pressure is applied while heating. In order to heat, a pulsed direct current goes through the electrically conducting plates and sometimes also through the sample, unlike other heating systems. This means that the sample is heated from both the inside and the outside.

SPS Sample Holder

Mechanism
When operating, the SPS applies pulsed direct current. When the voltage is applied to the powdered material the energy is transferred and dispersed homogenously all over the powder, thus presenting highly energy efficient sintering conditions. This method focuses the energy on the intergranular bondings which leads to synthesis improvements when compared to other methods such as hot-press sintering. As explained, because of the spark discharges between the particles of the material, localized and high temperatures are achieved. This leads to both vaporization and melting of the powder which causes plastic transformations of the material.

31

In the end, a dense tablet of over 99% compactness is obtained. As a matter of fact, since only the surface of the particles is heated a better control over the grain growth is held, and a rapid and precise sintering is possible.

SPS instrumentation

Features

What makes this process special is the fact that fast heating rates in short periods of time can be used to produce quite dense samples. There are three main factors which contribute to this purpose:

1) The mechanical pressure: It helps the powder to diffuse therefore avoiding porosity

2) The heat transfer: The equipment presents incredible heat transfer efficiency from the plates to the sample. In fact, the plates act as a heat source themselves.

3) The use of direct current: The presence of an electrical field generates spark discharges and plasma appearance within the powder. This helps to dispose of adsorbed substances such as CO2 and H2O in the first place. Afterwards, both the lack of contaminants and the spark discharges boost material diffusion all over the sample increasing its density.

32

However, since this is a rapid densification process the grain growth is difficult to control, and that is the reason why the conditions must be set appropriately. In fact, conditions like holding time, applied pressure, heating rate and initial and final temperature influence the grain growth and the mechanical properties of the sample such as brittleness and fracture toughness.

Laboratory SPS sintering equipment

Main Advantages
The advantages offered by SPS over other sintering methods are: Tight control over temperature, pressure and cooling down. Fast and uniform synthesis Obtention of highly dense tablets with low porosity Efficient method, which leads to low costs. Easy to operate. Elimination of present contamination Low grain growth Low effect of the sintering on the material microstructure.

Besides, it also allows the attachment of some accessories such as automation systems and robotic interfaces.

33

7 - Archimedes Principle

This principle allows the volume determination of an object when it is immersed in a liquid media. Therefore it can be used to determine densities.

Such as shown by the density formula, the density is the relation between a mass and the volume it occupies ( = m/V). The mass can be easily weighed by a set of scales, whereas the volume determination cannot be performed accurately most of the times, especially when the objects to be measured present irregular shapes. It is in such cases when the Archimedes principle becomes useful.

The volume of an object or a liquid can be easily calculated applying the principle of buoyancy force, which simply states that an object in a liquid is subjected to forces from all directions, caused by hydrostatic pressure. However, the value of the vertical forces caused by the liquid, which point towards both directions (up and down) do not usually cancel each other out. The reason is that the gravitational force of the water must also be taken into account in the vertical axis, being directly proportional to the depth at which the object is located in water.

Vertical forces caused by hydrostatic pressure in an immersed object

34

In fact, the resulting force (Buoyancy force) in the vertical axis (F2 F1) is proportional to the gravitational force applied by the mass of liquid displaced to the object as follows:

FB

Vl

or

FB

Vo

Where:

Vl = Volume of liquid displaced by the object. Vo = Volume of the immersed object.

Eventually, since the volume of the object is the same as that of displaced water (Vl ) the value of the objects volume can be easily worked out from the former formula. Once both values (weight and volume) are known the density value can be easily assessed.

35

8 - X-Ray Diffraction Introduction


In this technique, X rays interact with matter thus preceding interferences (which can either be positive or negative). The interaction of different wavelength rays are plotted and later used for analysis. The software measures all the atom positions in the crystal. Once the cell parameters are known its possible to determine the matter structure and the corresponding angles.

X-ray diffractometry are physical techniques used for the identification of substances, and for other types of analysis, principally for crystalline materials in the solid state. In these techniques, a monochromatic beam of X-rays is directed onto a polycrystalline (powder) specimen, producing a diffraction pattern that is recorded on film or with a diffractometer. This X-ray pattern is a fundamental and unique property resulting from the atomic arrangement of the diffracting substance. Different substances have different atomic arrangements or crystal structures, and hence no two chemically distinct substances give identical diffraction patterns. Identification may be made by comparing the pattern of the unknown substance with patterns of known substances. . In modern age, X-ray diffractography is undoubtedly one of the largely used techniques because the experimental measurement is relatively short in time and allows finding out the compounds and phases present in an unknown sample and also all sort of data regarding its structure and even the processes the phases have gone through in the past. It must be taken into account that even though in powder diffraction the material is not forming a simple crystal in its own right, the analysis is still possible since this powder is still capable of diffraction thanks to the degree of crystallinity it possesses.

36

Lattice geometry
The atoms in crystalline substances are arranged in a symmetrical three-dimensional pattern: some atomic arrangement is repeated by the symmetry of the crystal along straight lines throughout the crystal. The smallest group of atoms which has the symmetry of the entire pattern is called the unit cell. The traces of the various lattice planes (normal to the drawing) are indicated by heavy lines. To identify the planes, one must count the number of planes crossed from one lattice point to the next along a, then repeat the procedure along b and c are known as the Miller indices of that set of planes, and assignment of indices to each line is called indexing. The spacings d between the planes are related to the Miller indices and the unit cell dimensions.

In crystals of the cubic system (such as cubic TaN), the crystallographic axes are normal to each other and have the same length, a = b = c; and spacing d is given by Braggs law:

37

Braggs law:

2 d Sin

Where is the wavelength of the incident X-Rays. The angle between the two spacing is . 2 is the angle between impact and detection line.

Thus the conditions for x-ray reflection are very restrictive because these is only one angle at which the X-rays of a given wavelength are reflected by a particular set of atomic planes of spacing d.

Characteristics of powder patterns


Many materials are not available in the form of large single crystals, and moreover it is impractical to obtain all the X-ray reflections from single crystals for identification purposes.

If the sample does not already exist in polycrystalline form, it may be pulverized. When a fine grained powder consisting of thousands of small, randomly oriented crystallites is exposed to the X-ray beam, all the possible reflections from the various sets of atomic planes can occur simultaneously. Pieces of information can be derived from the experimental pattern:

(1) The 2 value from which the d-spacing can be calculated; (2) The absolute intensity, from which relative intensities can be calculated; (3) The peak width; (4) The form of the background.

The complexity of the pattern is determined primarily by the symmetry of the substance rather than by its chemical composition.

38

If the crystallites do not have a completely random orientation, the line shapes and relative intensities will change accordingly. Comparison of the random and oriented X-ray patterns shows the degree of orientation in the sample. Since the two types of patterns are so different, the method is ideally suited to distinguish between crystalline and amorphous substances and to determine the degree of crystallinity of substances between the two extremes.

There are also many smaller changes in the X-ray pattern which may reveal important information. In substitutional solid solutions, for example, atoms of different elements may substitute for one another and occupy the same relative positions as in the pure metals. The substitutions of solute atoms occur on the same lattice sites occupied by the solvent atoms, but are randomly distributed. If the atoms are of different size, the average unit cell size will change accordingly. In simple cases, it is possible to determine the chemical composition of intermediate members by measuring the unit cell dimensions because there is often a nearly linear relationship between the two. In interstitial solid solutions, atoms are added to the empty spaces in the structure and there are little, if any, changes in the dimensions.

Diffraction databases
There are a number of databases available for X-ray diffraction work. The majority of these databases are designed and maintained for the single-crystal community rather than for the powder community. However, some Powder Diffraction File (PDF) are calculated from single crystal data of the type contained in the other databases.

The Powder Diffraction Files (PDF) are collections of single-phase x-ray powder diffraction patterns in the form of tables of the interplanar spacings (d) and relative intensities characteristic of the compound. These databases have proven their usefulness in a wide range of applications because every crystalline material gives, at least in principle, a unique x-ray diffraction pattern, study of diffraction patterns from unknown phases offers a powerful means of qualitative identification by comparing an X-ray pattern from the material to be analyzed with a file of single phase reference patterns.

39

The ability to recognize a reference pattern in an unknown material strongly depends on the quality of the ds and Is in both the reference material and the unknown sample. One of the major problems in the identification of materials by comparison of an experimental pattern with reference patterns is the variability in the quality of the data. As the quality of both reference and experimental patterns improves, the problem of pattern recognition becomes easier.

Instrumentation
There are many types of powder diffractometer available ranging from simple laboratory instruments to versatile and complex instruments using a synchrotron source. Completely automated equipment for X-ray analysis is available. Most laboratory instruments consist of a high-voltage generator which provides stabilized voltage for the X-ray tube, so that the X-ray source intensity varies by less than 1%. X-rays are produced using a molybdenum source. Electronic circuits use an X-ray detector to convert the diffracted X-ray photons to measurable voltage pulses, and to record the diffraction data. The number of elements useful for X-ray tube targets is limited to a few, of which tungsten is the most commonly used. During the tests, either the X-ray tube or the detector move, depending on the settings, thus covering all the 2 range

X-ray diffractometer

40

Optical Instrumentation in a X-Ray diffractometer

Signal Instrumentation in a X-Ray diffractometer

41

The Rietveld Refinement


This analysis technique is used to analyze the presence of different phases in powder X-Ray diffractograms. In fact, powder diffraction is used for the analysis of the great majority of materials since they cannot be synthesized in the form of big crystals. However, one of its main drawbacks is the overlapping of data, which makes difficult a proper determination of the materials structure. These difficulties can be overcome by using the Rietveld refinement, which indeed separates the overlapping data, therefore making it possible to determine the structure accurately. Its accuracy relies on the fact that it analyses the overall diffractogram as a whole, and takes into account the height, widths and positions of the reflections by means of a least squares approach. This approach tries to reproduce the data profile mathematically and as approximately as possible. Ever since the application of this technique to analyze powder diffraction huge improvements like never before have been made in the reliability of the so commonly overlapped data. This method is so trustworthy that nowadays structures can be determined almost as well by powder diffraction as they are in its single crystal counterpart. Some other of its applications are the determination of different components in mixturesl, also known as phase analysis and therefore find some industrial uses in fields such as the oil or cement industry.

Figure showing a Rietveld calculated profile (in blue), its divergence with the diffractogram data (black line) and the determined structure (red lattice)

42

9 - Scanning Electron Microscopy (SEM)

Definition
The Scanning Electron Microscope technique is an instrument that allows the study of organic and inorganic materials, providing morphological information. Its used to observe surfaces and analyze their relief, texture, grain sizes, grain shapes and chemical composition (EDS) from biological and mineral simples. That is why it is a technique with a wide range of applications in different fields concerning science and technology. It allows the carrying out of qualitative and quantitative analysis by using the Energy Dispersive X-ray Spectroscopy (EDS) technique. Results regarding the atomic mass percentage and percentages from the different elements present in the sample are obtained.

Theoretical basis
In SEM, the image appears when the electrons beam goes down through the column until the sample. A scanning generator is responsible for the beam movement. When the electrons come into contact with the sample, some signals are emitted, which are then picked up by their corresponding detectors (each signal has its own detectors). The detector turns the received signal into an electronic one. Afterwards the latter is sent out to a Cathode Ray Tube (CRT), which allows either the formation of the image or the chemical analysis.

Interaction Incident Beam SEM sample


When the beam comes into contact with the sample, interactions between the electrons and the sample atoms take place. From this interaction signals such as secondary electrons, retrodispersed electrons, Auger electrons and X-rays are obtained, each of which is captured by a different detector. For example, the secondary electrons detector detects signals at low voltages (50eV) because those signals are emitted due to ionizations caused by inelastic interactions.

43

Scanning Electron Microscope Signals

Main characteristics
The SEMs main characteristics are its high resolution (~100 ), its great fields depth which provides 3D images and the samples preparation simplicity. This equipment also allows images obtention in a wide range of operation pressures (from vacuum to high pressure conditions). Good images can also be obtained at low potentials, which sometimes can spare sample pretreatments.

SEMs Instrumentation
. A Scanning Electron Microscope consists of different parts: An optical-electronical unit, which generates the electrons beam. A sample holder, with different movement degrees. A signal detection unit with an attached amplification system. An images display system A cathode Ray Tube (CRT) A vacuum system, a refrigeration system and an electrical power system, similar to those of MET A photographic, magnetic and video recording system An image processing system (optional) Different types of detectors depending on what to detect (secondary electrons, backscattered electrons, X-Rays, Auger electrons, transmitted Electrodes and light cathodoluminescence) 44

Applications
The Scanning Electron Microscope allows the main following applications:

1. Observation at a high magnification rate The image resolution is much more higher than that of its optical counterpart, since electrons ( with lower wavelength) rather than light are used.

2. Fractographic studies: Due to its great field depth, fracture surfaces can be observed at high magnifications. .

3. Chemical analyses of small areas, such as intermetallic phases, precipitates, pollutant particles

4. Morphological and analytical surface characterization of a wide range of materials

5. Diffusion, segregation, quality analysis and irregularity studies processes.

Energy Dispersive X-ray Spectroscopy (EDS).


In EDS the microanalysis is carried out by measuring the energy, intensities and signals distribution obtained from X-ray signals generated by the electrons beam. This allows to find out the materials chemical composition from areas down to 1mm2. Nevertheless, to carry out the analysis, the signals intensities must be compared with that of a pattern, which requires the samples surface to be flat and well polished. In the EDS analyzer different analyses are carried out, which are later on plotted in histograms and graphs that show the chemical elements distribution in the sample. The EDS spectrum is obtained by using a software which collects photons per minute emitted by the sample and classifies them according to energy. In the spectrum Energy in KeV (X axis) versus intensity (Y axis) is plotted. Then the software automatically identifies and analyzes the elements both quantitatively and qualitatively from the peaks of the histogram.

45

Energy Dispersive X-Ray spectrogram

Comparison between SEM and Optical microscope

The optical and the electronic microscope are almost identical. Both allow to magnify details invisible to the naked eye. The main difference is the illumination source. Therefore, the Optical Microscope uses a light beam whose wavelength is within the visible range, whereas the SEM emits an electrons beam of very short wavelength which allows a higher resolution to be obtained. The main advantages that the electronic microscope has over its optical counterpart are:

Higher field depth: The field depth is the capability of focusing on two different points at a different height. This allows the analysis of fracture surfaces at high magnification, which cant be done using optical microscopy.

Higher image resolution: The resolution boundary in an optical microscope is located around a wavelength of 2000 because of the visible light nature.

46

In the electronic microscope the electrons possess a wavelength lower than 0.5 , which makes it possible to reach magnifications up to 800.000x. However, due to instrumental parameters, it only reaches up to 75.000x.

Energy Dispersive X-ray Spectroscopy (EDS): Unlike the optical microscope, the electronical microscope has also an EDS detector which allows to carry out chemical analyses of the sample both qualitatively and quantitatively.

Scanning Electron Microscope

Optical Microscope

47

10 Experimental procedure

10.1 Mixture preparation

In order to transform the hexagonal form of TaN and also to stabilize the cubic form, solid mixtures with little amounts of similar compounds that already show a cubic form lattice (known as solid solutions) must be carried out.

According to this, two different types of mixtures were prepared by mixing TaN (hexagonal) with little amounts of TaC (cubic) or TiN (cubic).

1) TaN + TaC 2) TaN + TiN

TaCxN1-x Ta1-x TixN

These mixtures were prepared by using different molar rates of the compounds (x = 0.05, x = 0.03). The necessary amounts that needed to be weighted are the following:

A) Mixture of TaCxN1-x with molar ratio x = 0.05: If 30g of TaN are needed in the mixture, so as to have enough powder for preparing different samples:

The moles in 30g TaN:

30 g 194.95 g / mol

0.154 mol of TaN

If this amount entails 95% in moles of the sample (1-x), the remaining 5% is due to the presence of TaC. This quantity is:

0.154 mol * 0,05 0.95

8.1*10

mol of TaC

48

The weight in 8.1 *10-3 mol TaC:


Pm (TaC ) 192.95 g mol

8.1 * 10 3 mol * 192.95

g mol

1.564 g of TaC

B) Mixture of Ta1-x TixN with molar ratio x = 0.05 If 30g of TaN are needed in the mixture, so as to have enough powder for preparing different samples:

The moles in 30g TaN:

30 g 194.95 g / mol

0.154 mol of TaN

If this amount entails 95% of all moles in the sample (1-x), the remaining 5% is due to the presence of TiN. This quantity is:

0.154 mol * 0.05 0.95

8.1*10

mol of TiN

The weight in 0.154 mol TiN:

Pm (TaC )

61.867

g mol

8.1 * 10 3 mol * 61.867

g mol

0.501 g of TiN

49

10.2- Powder mixing

Once known which amount to take from each of the compounds, the mixtures can be prepared. One example of prepared mixtures is that corresponding to Ta1-xTixN with x = 0.05, prepared by weighing the following amounts:

m (TaN) = 30,0074 g m (TiN) = 0,5018 g

Afterwards, the mixture was dispersed in 2-Propanol (addition of 75g) and stirred up in a grinding mill during 30min. at a speed of 300 rpm. To help the mixing of the compounds, balls made up of ZrO2 were added during the grinding process. Once this is over, the suspension was dried in an oven at a temperature of around 80C overnight. The ZrO2 balls must also be cleaned up in the mill in water and dried before used again.

Lab weighing scales

Lab oven used to dry the solid solution

50

10.3 - Spark Plasma Sintering (SPS)

This process was run to turn the powder into a compact solid state.

1) Sample preparation

The sample has to be in a little container that is able to resist high pressures and temperatures and does not allow the sample to leak. The following method fulfils these objectives:

A 39 mm carbon layer was assembled in the shape of a hollow cylinder and introduced within the die, a graphite-based cylindrical container which had a 12mm hole in the shape of a cylinder. Afterwards, a tiny graphite cap was put on the bottom of the cylinder. Moreover, 4g of the mixture were poured within the die and another tiny graphite cap put at the top of the powder.

After that, both parts of the hole are covered with graphite punches with pressurize to make the powder more compact. Finally, an insulating surface is attached to the outer part of the die with some threads. An image showing the final assembly is displayed:

SPS Sample Holder

51

2) SPS sintering

The sample was introduced within the experiment chamber and fixed from the top to the bottom with the help of some carbon plates. The experiment was run in vacuum conditions. Different samples were run for each mixture, with different concentrations, pressure and temperature conditions for each one. The starting temperature is set at 600C because at lower temperatures it would be easier to control some of the SPS parameters. This is because at lower temperatures the difference of the obtained signals wavelength from the sample (due to the radiation emission at different temperatures) is lower than at higher temperatures and thus more difficult to control by the SPSs detector.

The following parameters were set on the SPS:

- Starting temperature: 600C - Heating rate: 100C/ min. - Final temperatures: 1550C, or 1600C, or 1650C, or 1700C, or 1750 C or 1800C - The final temperatures were kept for 3 min, after which the samples were cooled down until 1500 C and later on the equipment was turned off. - Operation pressure: Either 50 or 75 MPa

When the final temperatures are reached, the sintering process is kept at these temperatures for 3min., after which the sintering is complete and the temperature is slowly decreased until 1500C in order to reduce the building up of thermal tensions that leads to brittleness in the sample. Afterwards the equipment can be safely disconnected and let cool down. A graph plotting the change in the operating temperature for some final temperatures is displayed:

52

SPS sintering conditions


1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400 300 200 100 0 0 1 2 3 4 5 6 7 8 9 10 11

Temperature (C)

Final T = 1600C Final T = 1700C Final T = 1800C Heating ratio = 100C/min

12

13

14

15

Time (min.)

Graph plotting the temperature sintering conditions

Once the experiment has been run, the different parameters have been plotted in the computer software. The broad peaks that are drawn by the displacement parameter correspond to the sample sintering. The sample must be held into the chamber until it cools down to approximately 500C.

3) Sample conditioning for Powder X-Ray Measurements

For X-ray characterization, only the material corresponding to the sample can be present, thus being necessary to remove the graphite layer from it. Therefore the samples were polished and sawed so as to use only a part of it and leave the rest intact for further tests and measurements. Eventually, the fragment of the solid sample which was to be used for the upcoming X-ray test was turned into powder for that purpose by smashing it with a sledgehammer and stored safely afterwards. Once the powder is obtained, it must be grinded down to the micrometric scale using a mortar and spread out over a thin silicon plate which does not reflect the X-ray beams. Now the X-ray test can be carried out.

53

Laboratory polishing equipment

Laboratory Saw blade

Laboratory Sledgehammer and mortar

54

10.4 - Powder X-Ray analysis Once the 2 range of measurement was set from 20 to 120 and the test run for 30min. approximately. When the test is over, an X-ray diffractogram is displayed. After selecting the most important peaks, these must be compared with the database to carry out a so called phase analysis. This process will provide the phases present in the material and further characterization.

All the samples were analyzed via X-Ray diffraction to study mainly the presence of both cubic and hexagonal lattice in the sample. To do so the different peaks from the diffractogram were classified as belonging to either the cubic or the hexagonal form by comparing them when TaN cubic and hexagonal databases. Once the peaks were identified, the percentages could be found accurately from the distribution of the peaks by carrying out Rietveld Analysis, which takes into account the whole diffractogram. The results from the Rietveld Analysis are presented in the tables of the next chapter.

10.5 Theoretical density calculation

The theoretical density values have been looked up in different articles. Since different density values were found for the same compound, it was decided to calculate an average value of them all for the different compounds.

Hexagonal Tantalum Nitride (TaN) Density (g/cm3) 14.31 14.29 14.34 14.31 Average (g/cm3)

Title Ta N, eine neue Hochdruckform von Tantalnitrid Die Nitride des Tantals An X-ray study of the tantalum-nitrogen system

1 of its Authors Brauer, G.P Zapp, K.H. Schoenberg, N.

55

Cubic Tantalum Nitride (TaN)

Title Das kubische Tantalmononitrid(B1Typ) und seine Mischbarkeit mit den isotypen Uebergangsmetallnitriden und -carbiden The crystal structures of new superconducting materials obtained by high pressure treatment

1 of its Authors Gatterer, J.

Density (g/cm3) 15.93

Average (g/cm3)

15.79 Popova, S.V. 15.65

Cubic Tantalum Carbide (TaC) Density (g/cm3) Average (g/cm3)

Title Formation of cubic solid solutions in the Mo-Nb-C and Mo-Ta-C systems by the carbonization of oxides in the plasma arc Hochschmelzende Systeme mit Hafniumkarbid und -nitrid Thermal expansions of some carbides and tessellated stresses in steel The pseudo-binary systems of uranium carbide with zirconium carbide, tantalum carbide, and niobium carbide

1 of its Authors

Matsumoto, O.

14.5

Nowotny, H.

14.5 14.49

Stuart, H.

14.5

Brownlee, L.D.

14.5

56

Cubic Titanium Nitride (TiN) Density (g/cm3) 5.32 Average (g/cm3)

Title The preparation of Na Cl-type Til-x Alx N solid solution Non-stoichiometry of titaniumnitride plates prepared by chemical vapour deposition X ray diffraction study of dynamic characteristics of crystal lattices of some interstitial phases. Coefficients of thermal expansion of titanium carbonitrides

1 of its Authors Inamura, S.

Takashi Goto

5,39 5.38

Samsonov, G.V.

5.39

Alyamovskii, S.I

5.4

10.6 Archimedes method

This method consists of weighing with a set of scales the weight of the sample when it is both dry and wet. To determine the density, a relation between the weight of the dry sample and that of the sample when it is immersed in water is used:

d calc. ( g / cm 3 )

dry weight dry weight wet weight

Once the experimental density is known, it can be compared with the theoretical value to obtain a degree of compactness of the sample.

Compactnes s

Calculated density Theoretica l Density

57

In order to measure the compactness, the proportions of each compound used to prepare the mixtures must be taken into account when it comes to calculate the theoretical density of each tablet.

Set of scales used for the Archimedes Method

To measure the theoretical densities, the density values from cubic and hexagonal TaN must be used as well as the values of the dopant which is supposed to solve within the TaN cubic lattice. Therefore, the hexagonal phase is supposed to be formed of pure TaN whereas the cubic presents a 5% amount of the cubic dopant (either TaC or TiN). The percentages corresponding to the hexagonal and the cubic lattices were obtained from X-Ray diffraction by using Rietveld Refinement and exposed in the X-Ray diffraction tables.

Therefore, a formula to calculate the theoretical density for each of the samples is displayed below:

dTheor .

d Hex.TaN * %Hex.

(1 x) * dCub .TaN

x * d dopant * %Cub .

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11 - Results and discussion


In this chapter all the obtained results are shown as well as their conclusion which could be drawn from them. These results are presented in the form of graphs, tables and images for the different techniques applied to the samples (SPS sintering, X-Ray diffraction and Scanning Electron microscopy).

11.1 SPS sintering results

In the following graphs both the sample displacement (shrinkage or expansion) and the sintering temperature are plotted against time for different processes which go up to different final temperatures as shown in the following plots taken as examples of such a process:

SPS sintering ABCR TaN at 75 MPa and 1800 C


2000 1800 1600 1.4 1.2 1 0.8 0.6 0.4 0.2 0 -0.2 -0.4 -0.6 0 5 10 Time (min.) 15 20 Temperature Displacement

Temperature (C)

1400 1200 1000 800 600 400 200 0

Sample synthesized from the starting powder ABCR TaN at 75MPa and a final temperature of 1800 C

59

SPS sintering ALFA TaC 0.05N0.95 at 75MPa and 1800C


2000 1800 1600 1.2 1 0.8 0.6 0.4 0.2 0 -0.2 0 5 10 Time (min.) 15 20

Temperature (C)

1400 1200 1000 800 600 400 200 0

Temperature Displacement

Sample synthesized from the starting powder ALFA TaN mixed with TaC with a 5% molar ratio, at 75MPa and a final temperature of 1800 C

SPS sintering ALFA TaC 0.05N0.95 at 75 Mpa and 1500C


1600 1400 1200 1

0.8

Temperature (C)

1000 800 600 400 200 0 0 2 4 6 8 10 12 14 Time (min.)

0.6 Temperature Displacement

0.4

0.2

-0.2

Sample synthesized from the starting powder ALFA TaN mixed with TaC with a 5% molar ratio, at 75MPa and a final temperature of 1500 C 60

SPS sintering ALFA TaN at 75 Mpa and 1500C


1600 1400 1200 0.8

0.6

Temperature (C)

1000 800 600 400 200 0 0 2 4 6 8 10 12 14 Time (min.)

0.4 Temperature Displacement

0.2

-0.2

-0.4

Sample synthesized from the starting powder ALFA TaN mixed at 75MPa and a final temperature of 1500 C

SPS sintering ALFA TaC 0.05N0.95 at 75 Mpa and 1550C


1800 1600 2 1400 2.5

Temperature (C)

1200 1000

1.5 Temperature Displacement

1 800 600 400 0 200 0 0 2 4 6 8 Time (min.) 10 12 14 16 -0.5 0.5

Sample synthesized from the starting powder ALFA TaN mixed with TaC with a 5% molar ratio, at 75MPa and a final temperature of 1550 C

61

SPS sintering ABCR Ta0.95Ti0.05N at 75MPa and 1550C


1800 1600 1400 1.5 2

Temperature (C)

1200 1 1000 800 0.5 600 400 200 0 0 2 4 6 8 Time (min.) 10 12 14 16 -0.5 0 Temperature Displacement

Sample synthesized from the starting powder ABCR TaN mixed with TiN with a 5% molar ratio, at 75MPa and a final temperature of 1550 C

11.2 SPS sintering discussion

The displacement plotted in the different graphs can give an overview of the processes taking place to the sintering powder at each of the stages and therefore this parameter will be taken into account in this discussion. In the very beginning of the sintering, it can be seen that in some graphs there is a negative slope which is thought to be related to the graphite expansion of the dyes used in the SPS equipment. This tendency is seen in all graphs except for number 5.

On the other hand, the steep slope detected within the time gap from 6 minutes to 10 minutes in most graphs is due to the shrinkage of the powder when it is sintered as a compact solid tablet. There are also sudden ups and downs which actually make the slope change wit no apparent reason. These are present all over the plotting and appear only because the pressure was adjusted manually at some stages (both increased and decreased) so as not to put a lot of strain in the equipment and carry out the sintering properly.

62

To complete the assessment, it can also be seen that the sintering is over at temperatures close to 1550C, as can be seen from the graphs which reach up to this final temperature. At this stage there is no change in the displacement and therefore a horizontal tendency is observed in the displacement when the temperature is stabilized at 1550C. There can also be seen some steep decreases at the final stage in the displacement due to the fact that the equipment was turned off at this very moment making the displacement value drop radically.

11.3 - Powder X-Ray diffraction results

1) Starting powders

The different starting TaN powders from both companies (ABCR and ALFA) and the used dopants (TaC and TiN) were analysed with X-Ray diffraction and from the corresponding diffractograms the cubic lattice percentage of the TaN powders could be found out by Rietveld Refinement, since it is logical to know which is the cubic lattice presence in the raw material when the main objective is to assess its synthesis. The diffractograms and corresponding results are the following.

Sample Starting TaN powder (ABCR) Starting TaN powder (ALFA_1) Starting TaN powder (ALFA_2)

Cubic TaN (%) 27.3 100 10.4

Hexagonal TaN (%) 72.7 0 69.8

Ta2N 0 0 19.8

Percentages of the different phases present in the TaN starting powders from ABCR and ALFA companies

63

X-Ray diffractograms carried out to the powders of the pure Tantalum Nitrides and dopants used to create the samples

Two different powder bottles of 50g each were bought from the ALFA company. It can be seen from the percentage results that the first powder bought from that company (labelled as ALFA 1) showed better properties since it presented no cubic phase whatsoever and therefore the cubic phase could be sintered completely from the hexagonal TaN phase. However, the second bottle (called ALFA 2) presented some cubic phase and what is more it presented a vast amount of a different phase (Ta2N) whose behaviour in the sintering was totally unknown. Therefore it was decided that using this powder to synthesize samples should be avoided, and the samples were synthesized using both ABCR and ALFA powder (the first bottle). However, not as many samples as wanted could be synthesized with this ALFA powder because there were only 50 grams and as seen with the second bottle it was difficult to find another powder with the same phases from the same company ( ALFA 1 and ALFA 2 presented different phases even though they were acquired from the same manufacturer).

64

2) SPS sintered samples

The following are some tables with the cubic and hexagonal percentages of the TaN phases detected by X-Ray diffraction and assessed using the Rietveld method. From these tables, different graphs were also plotted to compare different variables that influence the cubic transformation of the hexagonal TaN which allow some conclusions to be drawn. Eventually, it was also considered relevant to plot diffractograms for each of the sintered series at different temperatures and for the starting materials as follows.

ABCR POWDER (TixTa1-xN)

Sample TixTa1-xN (x =0.05, 1600C, 50MPa) (ABCR TaN) TixTa1-xN (x =0.05, 1700C, 50MPa) (ABCR TaN) TixTa1-xN (x =0.05, 1800C, 50MPa) (ABCR TaN) TixTa1-xN (x =0.05, 1550C, 75MPa) (ABCR TaN) TixTa1-xN (x =0.05, 1600C, 75MPa) (ABCR TaN) TixTa1-xN (x =0.05, 1650C, 75MPa) (ABCR TaN)

Cubic %

Hexagonal %

Ti

37.3

59.5

3.2

93.9

6.1

97.1

2.9

26.6

73.4

59.5

37.3

3.2

86.6

12.3

1.1

65

TixTa1-xN (x =0.05, 1700C, 75MPa) (ABCR TaN) TixTa1-xN (x =0.05, 1800C, 75MPa) (ABCR TaN) TixTa1-xN (x =0.03, 1600C, 75MPa) (ABCR TaN) TixTa1-xN (x =0.03, 1700C, 75MPa) (ABCR TaN) TixTa1-xN (x =0.03, 1800C, 75MPa) (ABCR TaN) 100 0 0 96.2 3.8 0 29.4 70.6 0 98.2 1.8 0 97.5 2.5 0

ABCR POWDER (TaCxN1-x)

Sample TaCxN1-x (x =0.05, 1600C, 50MPa) (ABCR TaN) TaCxN1-x (x =0.05, 1700C, 50MPa) (ABCR TaN) TaCxN1-x (x =0.05, 1800C, 50MPa) (ABCR TaN) TaCxN1-x (x =0.05, 1550C, 75MPa) (ABCR TaN)

Cubic %

Hexagonal %

TaC %

57.2

40.8

95.9

2.2

1.9

97.1

2.8

57.6

42.4

66

TaCxN1-x (x =0.05, 1600C, 75MPa) (ABCR TaN) TaCxN1-x (x =0.05, 1650C, 75MPa) (ABCR TaN) TaCxN1-x (x =0.05, 1700C, 75MPa) (ABCR TaN) TaCxN1-x (x =0.05, 1800C, 75MPa) (ABCR TaN) 96.3 0.1 3.6 98 2 0 51.9 48.1 0 44.2 55.2 0.6

PURE ABCR POWDER

Sample TaN (ABCR) starting powder Pure TaN (ABCR) (1600C, 75Mpa) Pure TaN (ABCR) (1700C, 75Mpa) Pure TaN (ABCR) (1800C, 75Mpa)

Cubic % 27.3 32.2

Hexagonal % 72.7 67.8

97.1

2.9

100

67

ALFA 1 POWDER (TaCxN1-x)

Sample TaCxN1-x (x =0.05, 1500C, 75MPa) (ALFA TaN) TaCxN1-x (x =0.05, 1550C, 75MPa) (ALFA TaN) TaCxN1-x (x =0.05, 1600C, 75MPa) (ALFA TaN) TaCxN1-x (x =0.05, 1700C, 75MPa) (ALFA TaN) TaCxN1-x (x =0.05, 1800C, 75MPa) (ALFA TaN)

Cubic %

Hexagonal %

TaC %

Ta

23.2

76.8

30

69.1

0.9

60.6

38.5

0.9

96.6

3.4

100

PURE ALFA 1 POWDER

Sample Pure TaN (Alfa) TaN Alfa (1500C, 75Mpa) TaN Alfa (1600C, 75Mpa) TaN Alfa (1700C, 75Mpa) TaN Alfa (1750C, 75Mpa)

Cubic % 0 8.1

Hexagonal % 100 91.9

12.1

87.9

93.4

6.6

98

68

3) Plotted graphics with observations

GRAPH 1

Cubic percentages of Ta0.95 Ti0.05 N at different pressures (with ABCR TaN)


100 90 80

Cubic phase (%)

70 60 50 40 30 20 10 0 1500 1550 1600 1650 1700 1750 1800 TaTiN at 75MPa TaTiN at 50 MPa

Temperature (C)

Observations 1:

There is a trend which shows that the higher the temperature the higher the conversion into the cubic phase. Moreover, this effect seems to be more significant at lower temperatures due to the fact that at higher temperatures both the sample temperature and exposition time have been higher. That is why from 1700 C forward there seem to be no significant effects on the cubic percentage.

There also seems that a higher pressure helps considerably to boost the cubic conversion, especially at lower temperatures for the reasons mentioned before.

69

GRAPH 2

Cubic percentages of TaC0.05N0.95 at different pressures (with ABCR TaN)


100 90 80
Cubic phase (%)

70 60 50 40 30 20 10 0 1500 1550 1600 1650 1700 1750 1800 TaCN at 75MPa TaCN at 50 MPa TaCN (1550C,75MPa)

Temperature (C)

Observations 2:

A higher synthesis temperature always entails a higher cubic percentage in the sample. It must be pointed out that the samples taken at 75MPa at 1600C and 1650C respectively belonged to a different mixture than the remaining three from the same series at 1550C, 1700C and 1800C.

On the one hand maybe the value of 1550 C at 75 MPa should be discarded because it seems to be wrong. On the other hand, it seems like the input pressure is not an important asset over 1700 C and comparison at 1600 C of both pressures just does not add up since it should be the other way round (75MPa higher than 50MPa). However, the trend was perfect with the TiTaN series (graphic 1), and not much more information can be extracted from this graph.

70

GRAPH 3

Cubic percentages of TaxTi1-x N at 75MPa with different dopant concentrations x (with ABCR TaN)
100 90 80

Cubic phase (%)

70 60 50 40 30 20 10 0 1500 1550 1600 1650 1700 1750 1800 Temperature (C) x = 0.05 x = 0.03

Observations 3)

A higher synthesis temperature always entails a higher cubic percentage in the sample. Nevertheless, no considerable changes occur at temperatures over 1700 C.

The dopant (TiN with a cubic arrangement) seems to help the TaN adopt a cubic arrangement, as can be seen in the graph, especially at the low temperature of 1600C, where the fact that both the temperature and the reaction time have been considerably low allow the dopant concentration to show its effect on the cubic transformation. Therefore, there seems to be a trend which exposes that the higher the dopant concentration the higher the cubic percentage in the sample.

71

GRAPH 4

Comparison of the Cubic percentages of TaC0.05N0.95 and Ta0.95Ti0.05N at 50MPa (with ABCR TaN)
100 90 80

Cubic phase (%)

70 60 50 40 30 20 10 0 1550 1600 1650 1700 1750 1800 TaCN at 50MPa TaTiN at 50 MPa

Temperature (C)

Observations 4:

A higher synthesis temperature always entails a higher cubic percentage in the sample. Nevertheless, no considerable changes occur at temperatures over 1700 C.

It can be assessed from the graph that the type of dopant (TaC or TiN) is not significant when assessing the cubic percentage. The reason for that seems to be both present a cubic arrangement, and, in the same concentrations on the sample have the same effect on the final cubic percentage.

72

GRAPH 5

Comparison of the Cubic percentages of TaC0.05N0.95 ,Ta0.95Ti0.05N and pure TaN powder at 75MPa (with ABCR TaN)
100 90 80

Cubic phase (%)

70 60 50 40 30 20 10 0 1500 1550 1600 1650 1700 Pure TaN at 75MPa TaCN (1550C,75MPa) 1750 1800 TaCN at 75 MPa TaTiN at 75 MPa

Temperature (C)

Observations 5:

A higher synthesis temperature always entails a higher cubic percentage in the sample, apart from the value at 1500C which could be wrong. Nevertheless, no considerable changes occur at temperatures over 1700 C.

It can be seen that the values of the cubic percentages for TaN to which dopant has been added are higher than those of the pure TaN, which shows the dopant has actually an effect on the conversion especially at low temperatures. Moreover, for all samples but that at 1550C, whose value maybe is wrong, it seems that the cubic percentage is higher for those samples doped with TiN instead of TaC, but no conclusions could be drawn up from this fact since as mentioned before two different mixtures were used at different times to prepare the TaCN series and maybe those could just be experimental errors.

73

GRAPH 6

Comparison of the Cubic percentages of the two TaN powders (ABCR and ALFA) at 75MPa and their pure forms with no SPS sintering.
100 90 80

Cubic phase (%)

70 60 50 40 30 20 10 0 1450 1500 1550 1600 1650 1700 ALFA TaN with no SPS sintering ABCR TaN with no SPS sintering ABCR TaN powder ALFA TaN powder

1750

1800

Temperature (C)

Observations 6:

On the one hand, it was determined by X-Ray diffraction that the starting TaN powder from the ABCR company had considerable cubic content (around 27%) whereas the TaN from the ALFA company did not present any cubic phase whatsoever. Therefore, it is only logical that at low temperatures (where the effect of temperature and reaction time is not that significant) the cubic percentage is higher for the ABCR powder, as can be seen for both powders at 1600C. At higher temperatures the values of the percentages become stable at high values and this former presence of a cubic phase in the ABCR powder does not seem so significant. It must also be remarked that without the help of any dopant both powders reached very high values in cubic percentage, even the ALFA powder with no cubic phase in the very beginning. Therefore it seems logical to say that temperature and overall reaction time seem to be the most significant assets for the synthesis of the cubic form of TaN.

74

GRAPH 7

Comparison of the Cubic percentages of TaC0.05N0.95 at 75MPa with ABCR and ALFA TaN

100 90 80

Cubic phase (%)

70 60 ABCR TaCN 50 40 30 20 10 0 1450 1500 1550 1600 1650 1700 1750 1800 ALFA TaCN TaCN (1550C , 75MPa)

Temperature (C)

Observations 7:

Both series show again very similar values at temperatures over 1700C showing temperature is a considerable asset. Unexpectedly, it seems that the cubic percentage seems to be higher for the ALFA series than for its ABCR counterpart ( see samples at 1600C), which just does not add up with the premonitions since ABCR had a higher cubic content in the beginning and that tendency should be charted throughout the synthesis, especially at low temperatures. However, it is unclear and filling up with more samples would be necessary to make such a statement.

75

GRAPH 8

Comparison of the Cubic percentages of TaC0.05 N0.95 and pure TaN powder at 75MPa (with ALFA TaN)
100 90 80

Cubic phase (%)

70 60 50 40 30 20 10 0 1450 1500 1550 1600 1650 1700 1750 1800 ALFA TaCN ALFA TaN

Temperature (C)

Observations 8:

In this graph the effect of the dopant in the sintering can be seen, being more significant at low temperatures. In fact, at the lowest temperature in the graph (1500C) the doped TaN has already transformed more of its hexagonal lattice into cubic than the pure TaN. Moreover, it can be seen that when temperature is increased (up to 1600C) the increasement of the cubic percentage is radical for the doped TaN whereas its pure form remains still stable. The data plotting seems relevant and therefore it must be emphasized that the dopant is a considerable asset for the transformation of the hexagonal lattice into cubic within a considerably low range of temperatures. This effect is especially considerable taking into account that the starting TaN powder (Alfa) had no present cubic lattice whatsoever.

76

X-Ray diffractograms from the series TaC0,05N0,95 synthesized at 50MPa with ABCR TaN

X-Ray diffractograms from the series TaC0,05N0,95 synthesized at 75MPa with ABCR TaN

77

X-Ray diffractograms from the series Ta0,95Ti0,05N synthesized at 50MPa with ABCR TaN

X-Ray diffractograms from the series Ta0.95Ti0.05N synthesized at 75 MPa with ABCR TaN

78

X-Ray diffractograms from the series Ta0.97Ti0.03N synthesized at 75 MPa with ABCR TaN

X-Ray diffractograms from the series of pure ABCR TaN synthesized at 75MPa

79

X-Ray diffractograms from the series TaC0.05N0.95 synthesized at 75 MPa with ALFA TaN

X-Ray diffractograms from the series of pure ALFA TaN synthesized at 75 MPa

80

11.4 - X-Ray results discussion

1) The reaction temperature is the main asset, since all the cubic percentages go up radically at temperures over 1700C and higher, whereas there is usually a considerable mixture of both phases (cubic and hexagonal) when the reaction takes place at temperatures close to 1600C. Another reason is that at higher temperatures the overall exposure time of the sample to high pressures and temperatures is increased, thus boosting the transformation.

2) It was also noticed there was a correlation between the pressure and the cubic percentage (the higher the pressure, the higher the percentage). However this parameter only had an important effect on the transformation at low temperatures around 1600 C. and therefore should be considered less important than parameters such as temperature and exposure time.

3) The added dopants (TaC, TiN) were supposed to boost the synthesis into the cubic form of TaN in all the range of temperatures. However, like pressure, they had a low effect on the cubic percentages at temperatures over 1700C and higher, and only were significant at lower temperatures around 1600C. There were questions as to whether the reason for this was that the starting powder presented a significant cubic percentage before the synthesis which would allow the cubic phase to grow without the need of a dopant with a cubic lattice arrangement such as TaC or TiN. However, this was clearly not the case since those samples synthesized with the starting ALFA powder (which presented no cubic phase at all) behaved likewise.

4) This SPS sintering method seems reliable since all the samples had a considerably high cubic percentage as shown in the X-Ray diffractrograms after the synthesis. It should also be remarked that special consideration must be taken at the final temperature reached in the sintering because it seems to be the main asset in the transformation along with exposure time.

81

11.5 - Density measurements results

These measurements were carried out using the Archimedes method. The dry and wet weight were obtained by weighing the sample in an air environment and drawn in water respectively.. The different types of densities along with the compactness were obtained by application of the formulas exposed in the experimental chapter (Archimedes method).

ABCR POWDER (TixTa1-xN) Dry weight (g) 1.3827 Wet weight (g) 1.2731 Calculated Density ( g/cm3 ) 12.61 Cubic TaN (%) 39.7 Hexagonal TaN (%) 60.3 Theoretical Density ( g/cm3 ) 14.90 Compactness (%) 84.6

Sample name Ta0.95Ti0.05N (50MPa,1600C) (ABCR TaN) Ta0.95Ti0.05N (50MPa,1700C) (ABCR TaN) Ta0.95Ti0.05N (50MPa,1800C) (ABCR TaN) Ta0.95Ti0.05N (75MPa,1550C) (ABCR TaN) Ta0.95Ti0.05N (75MPa,1600C) (ABCR TaN) Ta0.95Ti0.05N (75MPa,1650C) (ABCR TaN) Ta0.95Ti0.05N (75MPa,1700C) (ABCR TaN) Ta0.95Ti0.05N (75MPa,1800C (ABCR TaN)) Ta0.97Ti0.03N (75MPa,1600C) (ABCR TaN) Ta0.97Ti0.03N (75MPa,1700C) (ABCR TaN) Ta0.97Ti0.03N (75MPa,1800C) (ABCR TaN)

2.7072

2.4977

12.92

93.9

6.1

15.21

84.9

0.9060

0.8368

13.09

97.1

2.9

15.24

85.9

2.2220

2.0493

12.87

26.6

73.4

14.70

87.5

1.5311

1.4127

12.93

61.4

38.6

14.90

86.8

1.8847

1.7393

12.96

87.6

12.4

15.61

83.1

1.1185

1.0325

13.01

97.5

2.5

15.25

85.3

1.4425

1.3304

12.87

98.2

1.8

15.25

84.4

1.3356

1.2339

13.13

29.4

70.6

14.65

89.6

1.3632

1.2595

13.15

96.2

3.8

15.43

85.2

2.1380

1.9742

13.05

100

15.48

84.3

82

ABCR POWDER (TaCxN1-x) Dry weight (g) 2.5442 Wet weight (g) 2.3524 Calculated Density ( g/cm3 ) 13.26 Cubic TaN (%) 57.2 Hexagonal TaN (%) 40.8 Theoretical Density ( g/cm3 ) 14.83

Sample name TaC0.05 N0.95 (50MPa,1600C) (ABCR TaN) TaC0.05 N0.95 (50MPa,1700C) (ABCR TaN) TaC0.05 N0.95 (50MPa,1800C) (ABCR TaN) TaC0.05 N0.95 (75MPa,1550C) (ABCR TaN) TaC0.05 N0.95 (75MPa,1600C) (ABCR TaN) TaC0.05 N0.95 (75MPa,1650C) (ABCR TaN) TaC0.05 N0.95 (75MPa,1700C) (ABCR TaN) TaC0.05 N0.95 (75MPa,1800C) (ABCR TaN)

Compactness (%) 89.4

2.5955

2.4001

13.28

95.9

2.2

15.40

86.3

2.3946

2.2150

13.33

97.1

15.27

87.3

2.0093

1.8588

13.35

57.6

42.4

14.86

89.8

1.9590

1.812

13.33

44.2

55.2

14.85

89.8

1.6966

1.5698

13.38

51.9

48.1

15.08

88.7

1.624

1.5024

13.36

98

15.70

85.1

1.5781

1.4598

13.33

96.3

0.1

15.16

87.3

PURE ABCR POWDER

Sample name Ta N (75MPa,1600C) (ABCR TaN) TaN (75MPa,1700C) (ABCR TaN) TaN (75MPa,1800C) (ABCR TaN)

Dry weight (g) 1.7658

Wet weight (g) 1.6392

Calculated Density ( g/cm3 ) 13.95

Cubic TaN (%) 34.5

Hexagonal TaN (%) 59.4

Theoretical Density ( g/cm3 ) 13.95

Compactness (%) 100.0

1.7870

1.6528

13.32

90.4

2.9

14.69

90.7

0.9889

0.9143

13.26

100

15.79

84.0

83

ALFA 1 POWDER (TaCxN1-x)

Sample name TaC0.05 N0.95 (75MPa,1500C) (ALFA 1 TaN) TaC0.05 N0.95 (75MPa,1550C) (ALFA 1 TaN) TaC0.05 N0.95 (75MPa,1600C) (ALFA 1 TaN) TaC0.05 N0.95 (75MPa,1700C) (ALFA 1 TaN) TaC0.05 N0.95 (75MPa,1800C) (ALFA 1 TaN)

Dry weight (g) 1.4533

Wet weight (g) 1.3489

Calculated Density ( g/cm3 ) 13.92

Cubic TaN (%) 23.2

Hexagonal TaN (%) 76.8

Theoretical Density ( g/cm3 ) 14.53

Compactness (%) 95.8

1.8047

1.6752

13.93

30.2

69.8

14.60

95.4

1.8450

1.7147

14.15

61

38.7

14.85

95.3

1.3512

1.2552

14.08

96.6

3.4

15.24

92.4

2.0982

1.9495

14.11

100

15.27

92.4

PURE ALFA 1 POWDER

Sample name TaN (75MPa,1500C) (ALFA 1 TaN) TaN (75MPa,1600C) (ALFA 1 TaN) TaN (75MPa,1700C) (ALFA 1 TaN) TaN (75MPa,1750C) (ALFA 1 TaN)

Dry weight (g) 1.6853

Wet weight (g) 1.5553

Calculated Density ( g/cm3 ) 12.96

Cubic TaN (%) 8.1

Hexagonal TaN (%) 91.9

Theoretical Density ( g/cm3 ) 14.39

Compactness (%) 90.1

2.3062

2.1410

13.96

12.1

87.9

14.43

96.8

1.5992

1.4862

14.15

93.4

6.6

15.21

93.1

1.0132

0.9413

14.09

98

15.25

92.4

84

11.6 - Density measurements discussion

These density measurements were mainly done to assess whether the compactness of the samples was high enough to allow the carrying out of some mechanical tests to the samples such as hardness measurements. In fact, this test needs a sample compactness of 95% or higher, otherwise the cracks will stop at the pores thus providing wrong values for fracture toughness.

On the other hand, unexpectedly the compactness is significantly low for most of the samples. The SPS sintering is theoretically supposed to provide with samples of at least 95% compactness but as assessed most of the samples could barely reach high enough compactness. This fact has no relevance on neither the phase analysis of the samples by XRay diffraction nor the visualization of the grain sizes from the images obtained by SEM. However, special considerations must be taken into account when selecting the samples if hardness measurements are to be carried out, since most of the samples are not eligible because they do not meet the necessary conditions in terms of compactness.

85

11.7 - Scanning Electron Microscopy (SEM) images

Different samples were visualized by SEM. The TaN powders from the chemical companies ABCR and ALFA were observed along with different samples created from these powders trying to cover the maximum possible range of different cubic percentages. The sintered samples were previously fractured, being this fracture surface the one visualized with the microscope.

Therefore the following samples ordered by cubic content percentage were tested:

Sample Starting powder TaN (ABCR) Starting powder TaN (ALFA) TaN (x =0.05, 1500C, 75MPa) (ALFA TaN) TixTa1-xN (x =0.03, 1600C, 75MPa) (ABCR TaN) TaCxN1-x (x =0.05, 1600C, 75MPa) (ABCR TaN) TaCxN1-x (x =0.05, 1600C, 75MPa) (ALFA TaN) TixTa1-xN (x =0.05, 1800C, 75MPa) (ABCR TaN) TaCxN1-x (x =0.05, 1800C, 75MPa) (ALFA TaN)

Cubic % 27,3 100

8.1

29.4

44.2

60.6

61.4

100

86

The following images were obtained from the SEM:

ABCR TaN POWDER

SEM Figure 1. ABCR TaN Starting powder 500X Backscattered electrons Image

SEM Figure 2. ABCR TaN 3000X (1) Secondary Electrons Image

87

SEM Figure 3. ABCR TaN 3000X BackScattered Electrons Image

SEM Figure 4. ABCR TaN 30000X Backscattered Electrons Image

88

ALFA TaN Powder

SEM Figure 5. Alfa TaN 500X Backscattered Electrons Image

SEM Figure 6. Alfa TaN 3000X Backscattered Electrons Image

89

SEM Figure 7. Alfa TaN 30000X Backscattered Electrons Image

ABCR TaC0.05 N0.95 , 1600C,75MPa

SEM Figure 8. ABCR TaC0.05 N0.95 (1600 C, 75MPa) 500X, BackScattered Electrons Image 90

SEM Figure 9. ABCR TaC0.05 N0.95 (1600 C, 75MPa) 3000X, Secondary Electrons Image

SEM Figure 10. ABCR TaC0.05 N0.95 (1600 C, 75MPa) 3000X, BackScattered Electrons Image

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SEM Figure 11. ABCR TaC0.05 N0.95 (1600 C, 75MPa) 30000X, Secondary Electrons Image

SEM Figure 12. ABCR TaC0.05 N0.95 (1600 C, 75MPa) 30000X, BackScattered Electrons Image 92

SEM Figure 13. ABCR Ti 0.03Ta0.97N (1600C, 75Mpa) 500X, Backscattered Electrons Image

SEM Figure 14. ABCR Ti 0.03Ta0.97N (1600C, 75Mpa) 3000X, Secondary Electrons Image 93

SEM Figure 15. ABCR Ti 0.03Ta0.97N (1600C, 75Mpa) 3000X, Backscattered Electrons Image

SEM Figure 16. ABCR Ti 0.03Ta0.97N (1600C, 75Mpa) 30000X, Secondary Electrons Image 94

SEM Figure 17. ABCR Ti 0.03Ta0.97N (1600C, 75Mpa) 30000X, Backscattered Electrons Image

ABCR Ti 0.05Ta0.95N (1800C, 75Mpa)

SEM Figure 18. ABCR Ti 0.05Ta0.95N (1800C, 75Mpa), 500X, Secondary Electrons Image 95

SEM Figure 19. ABCR Ti 0.05Ta0.95N (1800C, 75Mpa), 500X, Backscattered Electrons Image

SEM Figure 20. ABCR Ti 0.05Ta0.95N (1800C, 75Mpa), 3000X, Backscattered Electrons Image

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SEM Figure 21. ABCR Ti 0.05Ta0.95N (1800C, 75Mpa), 3000X, Backscattered Electrons Image

SEM Figure 22. ABCR Ti 0.05Ta0.95N (1800C, 75Mpa), 10000X, Secondary Electrons Image 97

SEM Figure 23. ABCR Ti 0.05Ta0.95N (1800C, 75Mpa), 10000X, Backscattered Electrons Image

ALFA TaN (1500C, 75Mpa)

SEM Figure 24. ALFA TaN (1500C, 75Mpa), 150X, Backscattered Electrons Image 98

SEM Figure 25. ALFA TaN (1500C, 75Mpa), 500X, Backscattered Electrons Image

SEM Figure 26. ALFA TaN (1500C, 75Mpa), 3000X, Secondary Electrons Image

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SEM Figure 27. ALFA TaN (1500C, 75Mpa), 3000X, Secondary Electrons Image

ALFA TaC0.05 N0.95 (1600C, 75Mpa)

SEM Figure 28. ALFA TaC0.05 N0.95 (1600C, 75Mpa), 150X, Backscattered Electrons Image 100

SEM Figure 29. ALFA TaC0.05 N0.95 (1600C, 75Mpa), 500X, Backscattered Electrons Image

SEM Figure 30. ALFA TaC0.05 N0.95 (1600C, 75Mpa), 3000X, Secondary Electrons Image 101

ALFA TaC0.05 N0.95 (1800C, 75Mpa)

SEM Figure 31. ALFA TaC0.05 N0.95 (1800C, 75Mpa), 500X, Secondary Electrons Image

SEM Figure 32. ALFA TaC0.05 N0.95 (1800C, 75Mpa), 1000X, Secondary Electrons Image

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SEM Figure 33. ALFA TaC0.05 N0.95 (1800C, 75Mpa), 3000X, Secondary Electrons Image

11.8 - SEM Discussion

Images for both the starting powders and different sintered samples have been taken at different magnifications in order to assess features such as the grain size, the fracture surface and their composition.

It must be remarked that the grain size of both starting powders (ALFA and ABCR) seems to be around 1 micrometer, although it can easily gather up to create bigger conglomerates as can be seen from the pictures. Taking a closer look at the images of the synthesized samples, it can be seen that their grain size has grown when compared to the starting powders. Therefore, it seems that both factors pressure and temperature enhance the growth of the grains. However, when comparing the different samples it seems these parameters are not directly proportional to the grain growth. In other words, it seems that the lattice content (whether hexagonal or cubic) is the major asset to determine the grain size.

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As it can be seen from the images, it is in those samples that present mostly one phase (either cubic or hexagonal) that the grain size is bigger, being at the same time bigger when the phase is mostly hexagonal rather than cubic. In fact, the grain size seems to be bigger mainly for the samples created with ALFA TaN at 1500 C and 1800 C (with 8.1 % and 100% cubic content respectively). When comparing them to one another, the grain size of the former one seems to be around 8 micrometers whereas it is around 5 micrometers for the latter. The main reason for such a change seems to be that the hexagonal lattice occupies a higher volume than the cubic. On the other hand, the reason why those samples with almost only one phase possess bigger grain size seems to be that when there is a phase mixture one phase hinders the other from growing. In our case, what happens is that as the reaction goes by, the hexagonal lattice turns into cubic and when both phases are in considerable proportions the hexagonal phase hinders somehow the cubic from growing. As time goes by and the cubic lattice develops, the hexagonal one becomes less significant and no other phase hinders the cubic from growing.

When assessing the fracture surface, it must be said that both types of fractures took place in the samples: fracture through the grains and fractures through the boundaries. An example in which both mechanisms can be seen is the SEM Figure 27. Another interesting asset that can be seen from the fracture surface is the presence of porosity in the sample. The porosity distribution observed in the images seems to fit the results obtained by the density measurements. A good example is the sample synthesized at 1500C with ALFA TaN powder whose compactness was assessed to be close to 100%. In fact, there seems to be very low porosity for this sample (see SEM Figure 24). However, there does not seem to be a relation between the sintering conditions and the porosity of the samples.

On the other hand, those images obtained by backscattered electrons give an overview of the samples composition with tonalities of grey and black colours. As expected, those images present mainly bright grains due to the fact that Ta is a heavy element and is displayed quite brightly. The EDS analysis confirmed these grains consist of TaN. It can also be expected there are traces of unreacted dopant in the samples (TaC or TiN). This seems to be the case at least for the samples with TiN as a dopant, since such samples present a great deal of dark-coloured spots, which could easily be unreacted TiN (see SEM Figures 21 and 23). Therefore, it seems the samples consist of TaN with some unreacted dopant impurities.

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12 - Conclusions
Different mixtures to which different amounts of dopants (TaC and TiN) were added have been used to synthesize samples at different pressures and temperatures to cover a broad range of sintering conditions, thus being able to predict the effect of the variables on the cubic transformation.

After sample conditioning for powder X-Ray diffraction it seems that temperature and reaction time were the main assets which boosted the cubic transformation. In fact, the samples cubic lattice content was 90% or higher for all samples from 1700C forward, whereas the pressure and the amount of added cubic dopant only had an effect at lower temperatures, being quite significant at temperatures close to 1600C and lower. Moreover, both dopants seemed to play a very similar role.

The SEM visualization also confirmed the grain growth boosted by the SPS sintering which turned a nanometric starting powder into a tablet of bigger grain size, thus creating a compact. It was also confirmed by EDS that most of the tablet content was TaCN or TiTaN as expected, and some of them also presented traces of unreacted dopant, which could also be noticed by SEM in the case of TiN.

However, one of the most considerable encountered difficulties was faced when trying to control the porosity of the sintered samples. Actually, there seemed to be no connection between the applied sintering conditions and the compact samples, and whats more, in some cases the compactness turned out to be lower than expected theoretically by SPS sintering (samples should possess a compactness of 95% or higher).

Although this asset entails no problems for the assessment of the cubic transformation and the phase analysis, it could be problematic when carrying out foreseeable mechanical tests to the samples. For instance, if fracture toughness tests were to be realized to samples with porosity, the cracks would stop at the pores and wrong values for hardness would be provided.

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Therefore hardness tests could only be carried out to few of these samples, those which possess very low porosity as assessed by density measurements. Actually, such tests are scheduled to be carried out in the foreseeable future.

On the other hand, while cutting the samples to tear them asunder (one part was saved for SEM imaging and further hardness measurements whereas the other was pulverized to carry out X-Ray diffraction) it could be noticed that those samples containing mainly one type of phase (either cubic or hexagonal) seemed much easier to cut than those in which there was a mixture of both phases. Therefore, it seems that the presence of two phases truly reinforces the materials fracture toughness although no experimental values to back up such a statement were recorded.

Summing up, the SPS sintering technique turns out to be a reliable method since the synthesis parameters can be easily controlled and the samples results were quite promising in final cubic content. In fact, the hexagonal lattice was easily turned into cubic with quite ease of operation, making the application of such a process quite feasible to carry out such a transformation.

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13 - Bibliography

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7) Jianhua Ma, One simple synthesis route to nanocrystalline tantalum carbide via the reaction of tanthalum pentachloride and sodium carbonate with metallic magnesium, Materials Letters, Volume 61, Issue 17, pages 36583661, Year 2007 8) ByungRyang, Kim Mechanical properties and rapid consolidation of binderless nanostructured tantalum carbide, Ceramics International, Volume 35, Issue 8, pages 3395-3400, Year 2009 9) T.Shikama, Properties of titanium carbide and vanadium carbide mixtures as first wall coatings, Journal of Nuclear Materials, Volumes 133-134, pages 765768, Year 1985 10) Yong Choi, Stress corrosion behavior of nickel base titanium carbide cermets prepared by direct consolidation during combustion reaction in 50% aqueous sodium hydroxide solution, Journal of Materials Science, Volume 39, Issue 3, Pages 1041 1045, Year 2004 11) V.F.Loskutov, Application of Titanium Carbide coatings on iron and steels, Metal Science and Heat Treatment, Volume 21, Issue 10, pages 779-782, Year 1979 12) Essaki, Kenji Synthesis of nanoparticulate tungsten carbide under microwave irradiation , Journal of the American Ceramic Society, Volume 93, Issue 3, pages 692-695, Year 2010 13) A.G.Merzhanov, Titanium carbide produced by self-propagating hightemperature synthesis Valuable abrasive material, Powder Metallurgy and Metal Ceramics, Volume 20, Issue 10, pages 709-713, Year 1981 14) V.M.Maslov, Carbon interaction with oxygen during titanium carbide synthesis, Combustion,Explosion, and Shockwaves, Volume 19, Issue 5, pages 634-637, Year 2004 15) Lirong Tong, Synthesis of titanium carbide nano-powders by thermal plasma, Scripta Materialia, Volume 52, Issue 12, pages 1253 1258, Year 2005. 16) S. Lpez-Romero, Synthesis of TiC thin fils by CVD from toluene and titanium tetrachloride with nickel as catalyst, Matria (Rio Janeiro), Volume 12, Issue 3, Year 2007

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Webpages:

www.substech.com (Boron Nitride) www.azom.com (Silicon Nitride), (Tungsten Carbide) www.accuratus.com ( Silicon Nitride), (Boron Nitride) www.brycoat.com (Titanium Nitride) www.reade.com (Tantalum Nitride) www.americanelements.com (Carbides) www.britannica.com (Carbides) www.transtutors.com (Carbides) www.ultramet.com (Carbides) www.streetdirectory.com (Carbides) www.tungstenchina.com ( Tungsten Carbide) www.hydrocarbide.com (Tungsten Carbide) www.panalytical.com (X-Ray diffraction) http://www.mrl.ucsb.edu/ (X-Ray diffraction) http://www.icdd.com/ (X-Ray Diffraction) http://imr.chem.binghamton.edu/ (X-Ray diffraction) http://serc.carleton.edu/ (X-Ray diffraction) http://home.planet.nl/~rietv025/ (Rietveld Method) http://epswww.unm.edu/xrd/xrdclass/09-Quant-intro.pdf (Rietveld Method) http://www.mos.org (Scanning Electron Microscopy) http://www.unl.edu (Scanning Electron Microscopy) http://www.purdue.edu (Scanning Electron Microscopy) http://mee-inc.com (Scanning Electron Microscopy) http://www.sdm.buffalo.edu (Scanning Electron Microscopy) www.askmehelpdesk.com (Scanning Electron Microscopy) www.answers.com (Grinding Mill) www.britannica.com (Archimedes Principle) www.physicsprinciples.tripod.com (Archimedes Principle)

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