PRODUCTION OF

CHROMIUM BORIDE (CRB , CRB2 )

506111437 BRA GIRI

Prof.Dr. Onuralp YCEL

Prof.Dr. Filiz INAR AHN

CONTENTS
1. Generel Information About CHROMIUM BORIDE (CrB , CrB2 ) 2. Production of CHROMIUM BORIDE (CrB , CrB2 ) 2.1. Mechanochemical Synthesis 2.2. Solid state Reaction 2.3. Molten Salt Method 2.4. Low Temperature Synthesis of Chromium Borides 2.5. Chromium Borides by Combustion Synthesis Involving Borothermic and Aluminothermic Reduction of Cr2O3 3. Suppliers and Price of CHROMIUM BORIDE (CrB , CrB2 ) 4. References

1. GENEREL INFORMATION ABOUT CHROMIUM BORIDE (CRB , CRB2 )

Borides of transition metals have attracted considerable interest for their various unique properties. Among these borides, chromium boride (CrB) is currently of great technological importance because of its high melting point, high chemical stability, high hardness and strength. So it has found applications in structure materials. Chromium borides are used in plasma technology and for high-performance electrodes in electron microscopes, metal matrix composites (MMCs), cutting tools and cermets for machining aluminum. For the CrB system, six chromium borides (Cr2B, Cr5B3,CrB, Cr3B4, CrB2, and CrB4) shown in next figure . Among them,CrB2 is the most stable compound with a melting point of 2200 C and is a potential candidate as the structural material, hard coating on cutting tools, and protective layer on mechanical parts to resist wear and corrosion.

1. GENEREL INFORMATION ABOUT CHROMIUM BORIDE (CRB , CRB2 )

1. GENEREL INFORMATION ABOUT CHROMIUM BORIDE (CRB , CRB2 )

CrB

CrB2

Formula Weight Color

Theoretical Density (Kg/m3 X 10-3 ) Crystal Structure Thermal Expansion Coefficient (10-6/K)*

62.81 6,14 tetragonal 12.3

73.62 Gray
5,20 hexagonal 10.5

Thermal Conductivity (W/M. K) **

20.1

31.8

2. PRODUCTION OF CHROMIUM BORIDE (CRB , CRB2 ) 2.1. MECHANOCHEMICAL SYNTHESIS

Ball-milling of elemental powder mixtures without external heat application has been processed as a mechanism for the mechanochemical synthesis of high melting point compounds. Chromium and amorphous boron elemental powder mixtures at atomic ratios of 1:1 and 1:2 were processed for 10-40h in a planetary ball-mill. CrB2 was formed at a low yield after 10-30h of milling the 1:2 mixture using tungsten carbide balls. However, a single phase of CrB2 was found by XRD, after the as-milled Cr-B (1:2) mixture was annealed at 900 C for 2h. A single phase of CrB was formed by annealing the Cr-B (1:1) mixture at 1000 C for 2h. Ballmilling of the elemental powder mixtures before annealing significantly reduced the reaction temperature necessary for chromium boride synthesis. The as-milled Cr-B (1:2) mixture contained fewer contaminations (tungsten and cobalt) than the as milled Cr-B (1:1) mixture. The lattice parameters of the chromium borides obtained agree with previously reported measurements.

2. PRODUCTION OF CHROMIUM BORIDE (CRB , CRB2 ) 2.2. SOLID STATE REACTION

Chromium boride powders can be synthesized at 600 C through a solid-state reaction. The synthesis is carried out in an autoclave by using CrCl3 , Mg and MgB2 as reactants.The Xray powder diffraction pattern indicates the formation of orthorhombic CrB. Trassion electron microscopy image shows that typical CrB crystallites are compossed of floss-like particles with less than 10 nm in diameter and about 50-100 nm in leght.

2CrCl3 + MgB2 + 2Mg

2 CrB + 3 MgCl2

2. PRODUCTION OF CHROMIUM BORIDE (CRB , CRB2 ) 2.3. MOLTEN SALT METHOD A molten salt (anhydrous aluminum trichloride) method to prepare CrB nanorods via a reductionboronation route at 650 C in an autoclave be described as follows,

CrCl3 + B + 3Na

CrB +3NaCl

Below the temperature of 500 C, the weight gain almost has not changed. From 500 to 1000 C, the weight gain of CrB nanorods experiences four different steps. Below the temperature of 630 C, the weight gain increases gradually, which indicates that the sample is oxidized by oxygen slowly forming chromium oxide and boron oxides. When the temperature is within 630660 C, the weight gain increases significantly indicating that the sample is oxidized rapidly forming oxide layer gradually at the surface of the nanorods.

2. PRODUCTION OF CHROMIUM BORIDE (CRB , CRB2 ) 2.3. MOLTEN SALT METHOD

If the temperature was higher than 700 C, the diameters of the CrB nanorods increased obviously. An optimum reaction temperature for the CrB nanorods was about 650 C. The reaction time must be sufficient to ensure the process of boronation. It was found that 10 h was needed for the synthesis of nanorods.

2. PRODUCTION OF CHROMIUM BORIDE (CRB , CRB2 ) 2.4. LOW TEMPERATURE SYNTHESIS OF CHROMIUM BORIDES

Commercially available chromium acetate, Cr(CH3COO)3 and boron powder were used as starting materials. The boron powder was purified by refluxing in acid to an ethanolic solution of chromium acetate, boron was added .The resulting dispersion was sonicated for 2 h and evaporated to make a dry mass.
The product was further annealed in inert atmosphere under three different conditions (i) 400 C for 12 h, (ii) 600 C for 12 h and (iii) 400 C for 6 h and subsequently at 1000 C for 12 h in an argon atmosphere.

2. PRODUCTION OF CHROMIUM BORIDE (CRB , CRB2 ) 2.4. LOW TEMPERATURE SYNTHESIS OF CHROMIUM BORIDES

2. PRODUCTION OF CHROMIUM BORIDE (CRB , CRB2 ) 2.4. LOW TEMPERATURE SYNTHESIS OF CHROMIUM BORIDES

a - On heating the mixture of chromium acetate and boron at 400 C, powder X-ray diffraction shows the formation of poorly crystalline CrB . b - Further heating of the product at 600 C leads to improvement in the crystallinity. c - Synthesis of CrB at ambient pressure can be achieved above 1400 C and pure phases of CrB have been obtained only at 1600 C

2. PRODUCTION OF CHROMIUM BORIDE (CRB , CRB2 ) 2.4. LOW TEMPERATURE SYNTHESIS OF CHROMIUM BORIDES

Chromium boride (CrB) nanowires obtained at 400 C

Chromium boride (CrB) nanoparticles obtained at 600 C Chromium diboride nanoparticles obtained at 1000 C

2. PRODUCTION OF CHROMIUM BORIDE (CRB , CRB2 ) 2.5. CHROMIUM BORIDES BY COMBUSTION SYNTHESIS INVOLVING BOROTHERMIC AND ALUMINOTHERMIC REDUCTION OF CR2O3 A variety of transition metal borides have been produced from their constituent elements through combustion synthesis in the mode of self-propagating hightemperature synthesis (SHS). When direct combustion between the metal and boron is not feasible due largely to insufcient exothermicity, the SHS process involving borothermic reduction of metaloxides has been considered as an alternative of preparing the corresponding chromium borides. On the preparation of chromium borides, CrB2 has been the most produced phase. Obtained CrB and CrB2 in pure form by milling chromium and boron powders in a planetary ball mill for 2040 h, followed by annealing at 900 1000 C for 2 h. Conducted borothermic reduction of Cr2O3 at 1600 C to produce CrB2. Through self-propagating combustion involving reduction of Cr2O3 by amorphous boron.

2. PRODUCTION OF CHROMIUM BORIDE (CRB , CRB2 ) 2.5. CHROMIUM BORIDES BY COMBUSTION SYNTHESIS INVOLVING BOROTHERMIC AND ALUMINOTHERMIC REDUCTION OF CR2O3
Chromiumoxide Cr2O3 ,amorphous boron, and Al powders were employed as the starting materials to prepare two types of the powder mixtures. One is composed of Cr2O3 and boron with a molar composition of Cr2O3+ xB. The other type of the sample adopts Al as the reducing agent and is formulated by the molar proportion of Cr2O3+ 2Al + yB . The synthesis process of the Cr2O3B sample essentially combines the reduction of Cr2O3 by B to form elemental Cr and B2O3 as a by product and the interaction between the reduced Cr and B to yield boride compounds. On the other hand, chromium borides are produced along with Al2O3 from the samples containing Cr2O3, Al, and B powders. The following reactions are two examples of the formation of CrB and CrB2 from stoichiometric Cr2O3B and Cr2O3AlB samples, respectively. CrO3 + 4B Cr2O3 + 2Al + 4B 2CrB + B2O3 2CrB2 + Al2O3

3. SUPPLIERS AND PRICE OF CHROMIUM BORIDE (CRB , CRB2 )

Alfa Aesar / CHINA

www.alfa.com

Energy Chemical / CHINA

Aladdin Reagents / CHINA Guangzhou WeiBo / CHINA ABCR / GERMANY Service Chemical / GERMANY Price of Alfa Aesar ;

www.energy-chemical.com
www.aladdin-e.com www.weibochem.com www.abcrestore.com www.chemos-group.com

-325 Mesh Powder form 100gr price is 141 Euro.

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