Sintering Mechanisms of Functionally Graded Cemented Carbides

Abstract:

Functionally graded cemented carbides of two types are described. The functionally graded cemented carbides of the first type are of the WC-Co system and comprise gradients of WC grain sizes and/or Co contents. The functionally graded cemented carbides of the second type are Ti-and N-containing cemented carbides comprising gradients of nitrogen, cobalt and Ti-based cubic carbides. Special features and applications of the functionally graded cemented carbides of the both types are presented. Sintering mechanisms explaining the gradient formation in the functionally graded cemented carbides of the both types are summarized.

• Periodical: Materials Science Forum (Volume 835)
• Pages: 116-198
• DOI: https://doi.org/10.4028/www.scientific.net/MSF.835.116
• Online since: January 2016
• Authors: Igor Konyashin*, Walter Lengauer
• Keywords: Cemented Carbides, Cobalt Gradient, Fracture Toughness, Functionally Graded Materials, Hardness, Sintering, Sintering Mechanisms

References

[1] V.I. Tretyakov, Metal-ceramic cemented carbides, Metallurgizdat, Moscow, 1962 (in Russian).

[2] V.I. Tretyakov, Bases of materials science and technology of fabrication of sintered cemented carbides, Metallurgiya, Moscow, 1975 (in Rusian).

[3] U. Fischer, E. Hartzell, J. Akerman, US patent 4, 743, 515 (1988).

[4] B. Aronsson, T. Hartzell, J. Aakerman, Structure and properties of dual carbide for rock drilling. In Proceedings of Adv. Hard Mater. Prod. Conf., 1988, Shrewsbury, UK: MPR Publ. Serv. Ltd., p.19/1 – 19/6.

[5] H. Suzuki, K. Hayashi, Y. Taniguchi, The beta-free layer near the surface of vacuum-sintered tungsten carbide-beta-Co alloys containing nitrogen, Trans. Jpn. Inst. Met.; 22(11)(1981)758-764.

DOI: 10.2320/matertrans1960.22.758

[6] M. Schwarzkopf, H.E. Exner, H.F. Fischmeister, W. Schintlmeister, Kinetics of compositional modification of (W, Ti)C-WC-Co alloy surfaces. Mater. Sci. Eng. A; A105/106(1988)225-231.

DOI: 10.1016/0025-5416(88)90500-9

[7] K. Tsuda, A. Ikegaya, K. Isobe, M. Kitagawa, T. Nomura, Development of functionally graded sintered hard materials. Powder Met., 39(4)(1996)296-300.

DOI: 10.1179/pom.1996.39.4.296

[8] W. Lengauer, K. Dreyer, Functionally graded hardmetals, J. Alloys Compd., 338(1-2) (2002)194-212.

DOI: 10.1016/s0925-8388(02)00232-3

[9] W. Lengauer, K. Dreyer, Tailoring hardness and toughness gradients in functional gradient hardmetals (FGHMs), Int. J. Refractory Met. Hard Mater., 24(2006)155-161.

DOI: 10.1016/j.ijrmhm.2005.03.008

[10] C. Colin, L. Durant, et al., Processing of functional-gradient WC-Co cermets by powder metallurgy, Int. J. Refractory Met. Hard Mater., 12(1993-1994)145-152.

DOI: 10.1016/0263-4368(93)90064-m

[11] S. Rassbach, S. Moseley, W. Böhlke, Metallurgical fundamentals of macroscopic gradient hardmetals. In Proc. 17th Int. Plansee Seminar, L. Sigl, P. Rödhammer, H. Wildner (Eds. ), V. 2, Reutte, 2009, Austria: Plansee Group, 2009, p.48/1 – 48/13.

[12] I. Konyashin, B. Straumal, S. Hlawatschek, B. Ries, et al. Functionally Graded Cemented Carbides Obtained on the Basis of Capillarity Phenomena, Part II. Co drifts at various WC grain sizes and carbon contents, submitted to J. Mater. Sci., (2015).

DOI: 10.1016/j.matlet.2015.12.038

[13] M. Greenfield, US Patent 5, 623, 723 (1997).

[14] J. Glätzle, R. Kösters, W. Glätzle, US Patent Application US2004/0009088 (2004).

[15] M. Collin, S. Norgren, Hardness gradients in WC-Co created by local addition of Cr3C2. In Proc. 16th Int. Plansee Seminar,G. Kneringer, P. Rödhammer, H. Wildner (Eds. ), 2005, V. 2., Reutte, Austria: Plansee Group, p.227 – 241.

[16] I. Konyashin, S. Hlawatschek, B. Ries, F. Lachmann, A. Sologubenko, T. Weirich. A New Approach to Fabrication of Gradient WC-Co Hardmetals, Int. J. Refractory Met. Hard Mater., 28 (2010) 228–237.

DOI: 10.1016/j.ijrmhm.2009.10.003

[17] I. Konyashin, S. Hlawatschek , B. Ries, F. Lachmann, T. Weirich, F. Dorn, A. Sologubenko. On the Mechanism of WC Coarsening in WC-Co Hardmetals with Various Carbon Contents. Int. J. Refractory Met. Hard Mat., 27 (2009) 234–243.

DOI: 10.1016/j.ijrmhm.2008.09.001

[18] I. Konyashin, S. Hlawatschek, B. Ries, F. Lachmann. Gradient WC-Co Structures Obtained by Regulated WC Re-Crystallization without Using Grain Growth Inhibitors. In Proc. 17th Int. Plansee Seminar, L. Sigl, P. Rödhammer, H. Wildner (Eds. ), 2009, V. 2,. Reutte, Austria: Plansee Group, p.6.

[19] H. Exner, H. Fischmeister, Gefügevergröberung in zweiphasigen Legierungen, Z. Metallkunde, 5(1966)187.

DOI: 10.1515/ijmr-1966-570304

[20] L. Skolnick, The kinetics of solution of tungsten carbide in molten cobalt, in: Kingery N, (Ed. ), Kinetics of High Temperature Processes, Technology Press MIT, 1959, 92.

DOI: 10.7551/mitpress/4061.003.0018

[21] H. Grewe, Einige Überlegungen zum Wachstum der Gefügekomponenten in einer Hartmetall-Legierung mit 11% Co, DEW-Technische Berichte, 13 (1973) 35.

[22] C. Buhsmer, P. Crayton, Carbon self-diffusion in tungsten carbide. J Mater Sci, 6(1971)981.

DOI: 10.1007/bf00549949

[23] I. Konyashin, Cemented carbides for mining construction and wear parts, in V.K. Sarin (Editor-in-Chief) and D. Mari & L. Llanes (Vol. Eds. ), Comprehensive Hard Materials, Elsevier Ltd, 2014. p.425–451.

DOI: 10.1016/b978-0-08-096527-7.00015-5

[24] I. Konyashin, B. Ries, F. Lachmann, A. T. Fry, A novel sintering technique for fabrication of functionally gradient WC–Co cemented carbides, J. Mater. Sci., 47 (2012), 7072-7084.

DOI: 10.1007/s10853-012-6516-x

[25] L. Zhang, Y. Wang, X. Yu et al. Crack propagation characteristics and toughness of functionally graded WC-Co cemented carbides. Int. J. Refract. Met. Hard Mater. 26(2008)295–300.

DOI: 10.1016/j.ijrmhm.2007.07.002

[26] Y. Liu Y, H. Wang, Z. Long, P. Liaw, J. Yang, B. Huang, Microstructural evolution and mechanical behaviors of graded cemented carbides. Mater. Sci. Eng. A, 426(2006) 346-354.

DOI: 10.1016/j.msea.2006.04.018

[27] Y. Liu, H. Wang, J. Yang, et al. Formation mechanism of cobalt-gradient structure in WC-Co hard alloy. J. Mater. Sci. 39, (2004)4397-4399.

DOI: 10.1023/b:jmsc.0000033437.75050.5d

[28] O. Eso, Z. Fang, A. Griffo, Liquid phase sintering of functionally graded WC-Co composites. Int. J. Refractory Met. Hard Mater., 23(2005)233-241.

DOI: 10.1016/j.ijrmhm.2005.04.017

[29] O. Eso, P. Fan, Z. Fang, A kinetic model for cobalt gradient formation during liquid phase sintering of functionally graded WC-Co. Int. J. Refractory Met. Hard Mater. 26(2008)91-97.

DOI: 10.1016/j.ijrmhm.2007.02.004

[30] O. Eso, P. Fan, Z. Fang, Kinetics of cobalt gradient formation during the liquid phase sintering of functionally graded WC-Co. Int. J. Refractory Met. Hard Mater., 25(2007)286-292.

DOI: 10.1016/j.ijrmhm.2006.07.002

[31] A. Maximenko, G. Roebben, J. Van Der Biest, Modelling of metal-binder migration during liquid-phase sintering of graded cemented carbides, Mater. Process Technol., 160(2005)261-369.

DOI: 10.1016/j.jmatprotec.2004.06.023

[32] A. F Lisovsky, Some problems on the technical use of the phenomenon of metal melts imbibition of sintered composites, Powder Met. Int., 19(1987)18-21.

[33] D. V. Suetin, I. R Shein, A. L. Ivanovskii, Structural, electronic and magnetic properties of η carbides (Fe3W3C, Fe6W6C, Co3W3C and Co6W6C) from first principles calculations, Physica B, 404(2009)3544-3549.

DOI: 10.1016/j.physb.2009.05.051

[34] Z. Fang, O. Eso, Liquid phase sintering of functionally graded WC-Co composites. Scripta Mater., 52(2005)785-791.

DOI: 10.1016/j.scriptamat.2004.12.008

[35] I. Konyashin, S. Hlawatschek, B. Ries. Engineered Surfaces on Cemented Carbides Obtained by Tailored Sintering Techniques. Surf. Coat. Technol., 258(2014)300-309.

DOI: 10.1016/j.surfcoat.2014.09.009

[36] I. Konyashin, B. Ries, F. Lachmann, A. T. Fry. Gradient Hardmetals: Theory and Practice. International Journal of Refractory Metals and Hard Materials, 36(2013)10-21.

DOI: 10.1016/j.ijrmhm.2011.12.010

[37] I. Konyashin S. Hlawatschek1, B. Ries , B. Baretzky, A. Mazilkin, Functionally Graded Cemented Carbides Obtained on the Basis of Capillarity Phenomena. Part II. Co Drifts at Various WC Grain Sizes and Carbon Contents, submitted to J. Mater. Sci. (2015).

DOI: 10.1016/j.matlet.2015.12.038

[38] I. Konyashin, B. Ries, F. Lachmann A hard-metal body. PCT Patent Application WO2010/097784A1, (2010).

[39] I. Konyashin, B. Ries, F. Lachmann, PCT Patent Application WO2010/103418A1 (2010).

[40] J. Guo, F. Wang et al., A novel approach for manufacturing functionally graded cemented tungsten carbide composites, Advanced in Powder Metallurgy & Particulate Materials, 2010, Metal Powder Industries Federation, Princeton, NJ, USA, 8/29-8/39.

[41] J. Guo, P. Fan, Z Fang, A new method for making graded WC-Co by carburizing heat treatment of fully densified WC-Co. Proc. 17th Int. Plansee Seminar, L. Sigl, P. Rödhammer, H. Wildner (eds. ), Reutte, 2009, V. 2, p.50/1 – 50/6.

[42] Z. Fang, P. Fan, J. Guo, US Patent Application US2010/0101368A1 (2010).

[43] B. Roebuck, M.G. Gee, R. Morrell. Hardmetals – microstructural design, testing and property maps. In: Kneringer G, Rödhammer P, Wildner H (Eds. ), Proceedings of the 15th International Plansee Seminar, 2001, Reutte, Plansee Group, Vol. 4, pp.245-266.

DOI: 10.1016/s0261-3069(01)00073-5

[44] I. Konyashin, B.B. Straumal, S. Hlawatschek, B. Ries, B. Baretzky, K. Kolesnikova, A. Mazilkin, Functionally Graded Cemented Carbides Obtained on the Basis of Capillarity Phenomena. Part III: A Mechanism Explaining Co Drifts in Cemented Carbides with Various Carbon Contents, submitted to J. Mater. Sci. (2015).

DOI: 10.1016/j.matlet.2015.12.038

[45] J. Gurland, L. Norton. Role of the binder phase in cemented tungsten carbide-cobalt alloys, J. Metals Trans., 4(1952)1051-6.

DOI: 10.1007/bf03397768

[46] L. Ramqvist, Wetting of metallic carbides by liquid copper, nickel, cobalt, and iron, Int. J. Powder Met., 1(1965)2-20.

[47] B.B. Straumal, I. Konyashin, B. Ries, K.I. Kolesnikova, A.A. Mazilkin, A.B. Straumal, A.M. Gusak, B. Baretzky. Pseudopartial wetting of WC/WC grain boundaries in cemented carbides. Mater. Let., 147(2015)105–108.

DOI: 10.1016/j.matlet.2015.02.029

[48] N. K Sharma, I. D Wards, H. L., Fraser, W. S. Williams, SREM analysis of grain boundaries in cemented carbides. J. American Ceram. Soc., 63(1980)194–196.

[49] A. Henjered, M. Hellsing, G. Nouet, A. Dubon, J. Laval, Quantitative microanalysis of carbide/carbide interfaces in WC-Co base cemented carbides. Mater. Sci. Technol., 2(1994)847–855.

DOI: 10.1179/mst.1986.2.8.847

[50] J. Weidow, H. -O. Andrén. Grain and phase boundary segregation in WC–Co with TiC, ZrC, NbC or TaC additions, Int. J. Refractory Met. Hard Mater., 29(2011)38–43.

DOI: 10.1016/j.ijrmhm.2010.06.010

[51] I. Konyashin, S. Hlawatschek, B. Ries, F. Lachmann, M. Vukovic, Cobalt capping on WC–Co hardmetals. Part I: A mechanism explaining the presence or absence of cobalt layers on hardmetal articles during sintering, Int. J. Refractory Met. Hard Mater., 42(2014).

DOI: 10.1016/j.ijrmhm.2013.08.016

[52] I. Konyashin, S. Hlawatschek, B. Ries, F. Lachmann, M. Vukovic, Cobalt Capping: A Technique for Improving the Transverse Rupture Strength, Fracture Toughness and Wettability by Braze Alloys of WC-Co Hardmetals, Proc. 18th Int. Plansee Seminar, L. Sigl, H. Kestler, J. Wagner (eds. ), Reutte, 2013, V. 2, p. HM4-HM25.

DOI: 10.1016/j.ijrmhm.2013.08.016

[53] D.S. Janisch, W. Lengauer, K. Rödiger, K. Dreyer, H. van den Berg, Cobalt capping: why is sintered hardmetal sometimes covered with binder? Int. J. Refractory Met. Hard Mater., 28(2010)466–471.

DOI: 10.1016/j.ijrmhm.2010.02.006

[54] J. Guo, P. Fan, X. Wang, Z. Z. Fang, Formation of Co-capping during sintering of straight WC–10 wt. % Co. Int. J. Refract Met. Hard Mate. r, 28(2010)317–323.

DOI: 10.1016/j.ijrmhm.2009.11.005

[55] E. Sachet, W. -D. Schubert, G. Mühlbauer, J. Yukimura, Y. Kubo, On the formation and in situ observation of thin surface layers of cobalt on sintered cemented carbides. Int. J. Refract Met. Hard Mater., 31(2012)96–108.

DOI: 10.1016/j.ijrmhm.2011.09.012

[56] C.R. Comer, US Patent No. US2004211493, (2004).

[57] Y. Taniguchi, H. Sasaki, M. Ueki, K. Kobori, Japan Patent No. 87-86314817 63169356, (1988).

[58] J. Baldoni, S. Bennett, US Patent 5310605 (1994).

[59] N. Minori, T. Masaaki, N. Toshio, US Patent 4911989 (1990).

[60] I. Konyashin, B. Ries, F. Lachmann. PCT Patent Application WO2012/098102A1 (2012).

[61] K.A. Thorsen. Aluminium contamination of cemented carbides during sintering, Advances in Powder Metallurgy & Particulate Materials, 8(1992)45-60.

[62] K. A Thorsen,. H Fordsmand,. P. L. Praestgaard, K. A Thorsen, H. Fordsmand, P. L. Praestgaard, An explanation of wettability problems when brazing cemented carbides, Welding Research, 63(10)(1984)308-315.

[63] A. Lisovsky, Thermodynamics of isolated pores filled with liquid in sintered composite materials Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science, 25A(4)(1994)733-740.

DOI: 10.1007/bf02665450

[64] I. Konyashin, S. Hlawatschek, B. Ries, F. Lachmann, M. Vukovic, Cobalt capping on WC–Co hard metals. Part II: A technology for fabrication of Co coated articles during sintering, Int. J. Refractory Met. Hard Mater., 42(2014)136–141.

DOI: 10.1016/j.ijrmhm.2013.08.015

[65] I. Konyashin, Healing of Surface Defects in Hard Materials by Thin Coatings. Vacuum Sci. Technol. A, 14(2)(1996)447-452.

DOI: 10.1116/1.580104

[66] I. Konyahsin, CVD Coated Hardmetals - Causes of Transverse Rupture Strength Decrease. Functional Mater., l(1994)106-110.

[67] A. Eder, W. Lengauer, K. Dreyer, H. van den Berg, H. -W. Daub, D. Kassel, Phase formation during sintering of functionally graded hardmetals. Proc. 16th Plansee Seminar 2005, Vol. 3, pp.81-94.

[68] W. Lengauer, Diffusional control of the near-surface microstructure in functional gradient hardmetals. Materialwiss. Werkstofftechn., 36(10)(2005)460-466.

DOI: 10.1002/mawe.200500906

[69] D. Janisch, W. Lengauer, A. Eder, K. Dreyer, K. Rödiger, H. -W. Daub, D. Kassel, H. van den Berg, Nitridation sintering of WC-Ti(C, N)-Ta(C, N)C-Co hardmetals, Int. J. Refractory Met. Hard Mater., 36(2013)22-30.

DOI: 10.1016/j.ijrmhm.2011.12.013

[70] W. Lengauer, Transition Metal Carbides, Nitrides and Carbonitrides. In: Handbook of Ceramic Hard Materials, Vol. I, pp.202-252, ed. R. Riedel, Wiley-VCH, Weinheim (2000).

DOI: 10.1002/9783527618217.ch7

[71] R. Frykholm, M. Ekroth, B. Jansson, J. Ågren, H. -O. Andrén, A new labyrinth factor for modelling the effect of binder volume fraction on gradient sintering of cemented carbides. Acta Mater., 51(2003)1115-1121.

DOI: 10.1016/s1359-6454(02)00515-3

[72] R. Frykholm, B. Jansson, H. -O. Andrén, The influence of carbon content on formation of carbo-nitride free surface layers in cemented carbides, Int. J. Refractory Met. Hard Mater.,; 20(2002)345-353.

DOI: 10.1016/s0263-4368(02)00034-3

[73] J. Glühmann, M. Schneeweiß, H. van den Berg, D. Kassel, K. Rödiger, K. Dreyer, W. Lengauer, Functionally graded WC-Ti(C, N)-(Ta, Nb)C-Co hardmetals: metallurgy and performance, Int. J. Refractory Met. Hard Mater., 36(2013)38-45.

DOI: 10.1016/j.ijrmhm.2011.12.009

[74] A. Eder, W. Lengauer, K. Dreyer, H. van den Berg, H. -W. Daub, D. Kassel D, Gradient microstructure engineering in hardmetals. Proc. 16th Plansee Seminar 2005, Vol. 3, pp.120-135.

[75] D. Janisch, W. Lengauer, K. Rödiger, K. Dreyer, H. van den Berg, Novel fine-grained hardmetals by use of multiphase powder precursors and reactive nitrogen sintering, Int. J. Refractory Met. Hard Mater.,; 28(2010)362-369.

DOI: 10.1016/j.ijrmhm.2009.11.012