Preparation of ultrafine WC-Co powder via fluidized bed

doi:10.1016/j.cjche.2024.04.023

中国化学工程学报 ›› 2024, Vol. 73 ›› Issue (9): 15-26.DOI: 10.1016/j.cjche.2024.04.023

Preparation of ultrafine WC-Co powder via fluidized bed

Huijun Shang¹, Hengli Li^1,2, Weijun Li², Feng Pan^1,3, Zhan Du^1,4

1. State Key Laboratory of Mesoscience and Engineering, Institute of Process Engineering, Chinese Academy of Sciences (CAS), Beijing 100190, China;
2. College of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China;
3. College of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China;
4. Chinalco Environmental Protection and Energy Conservation Group Co., Ltd., Xiong'an 071700, China

收稿日期:2024-01-19 修回日期:2024-03-12 接受日期:2024-04-22 出版日期:2024-11-21 发布日期:2024-06-05
通讯作者: Feng Pan,E-mail:fpan@ipe.ac.cn;Zhan Du,E-mail:zdu@ipe.ac.cn
基金资助:
The authors wish to gratefully acknowledge financial support from the National Natural Science Foundation of China (22078326, 21878305).

Preparation of ultrafine WC-Co powder via fluidized bed

Huijun Shang¹, Hengli Li^1,2, Weijun Li², Feng Pan^1,3, Zhan Du^1,4

1. State Key Laboratory of Mesoscience and Engineering, Institute of Process Engineering, Chinese Academy of Sciences (CAS), Beijing 100190, China;
2. College of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China;
3. College of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China;
4. Chinalco Environmental Protection and Energy Conservation Group Co., Ltd., Xiong'an 071700, China

Received:2024-01-19 Revised:2024-03-12 Accepted:2024-04-22 Online:2024-11-21 Published:2024-06-05
Contact: Feng Pan,E-mail:fpan@ipe.ac.cn;Zhan Du,E-mail:zdu@ipe.ac.cn
Supported by:
The authors wish to gratefully acknowledge financial support from the National Natural Science Foundation of China (22078326, 21878305).

摘要/Abstract

摘要： In this study, the effects of reaction parameters on the deep-reduction and carbonization process of WO₂-Co to WC-Co were studied. The results indicate that the oxygen loss rate of WO₂ is positively correlated with temperature and methane partial pressure. The partial pressure of methane has no significant effect on the formation rate of WC. The carbon content and particle size of the product increase with the increase of CH₄ partial pressure. By synergistically regulating the reaction temperature to 950 ℃, the CH₄ partial pressure to 1.25%, and the reaction time to 60 min, ultrafine WC-Co powder without η phase can be obtained. The particle size of the composite powder is 128 nm, with total carbon content of 6.16%, free carbon content of 0.4%, and residual oxygen content of 0.05%, respectively. The growth rate relationship of tungsten carbide is as follows: δ(t)=1.21×10^-13 exp $ \left(-\frac{12809.72}{T}\right) \sqrt{t}$.

关键词: Ultrafine WC-Co powder, Gas-solid reaction, Fluidization, Reaction process regulation, Growth rate equation

Abstract: In this study, the effects of reaction parameters on the deep-reduction and carbonization process of WO₂-Co to WC-Co were studied. The results indicate that the oxygen loss rate of WO₂ is positively correlated with temperature and methane partial pressure. The partial pressure of methane has no significant effect on the formation rate of WC. The carbon content and particle size of the product increase with the increase of CH₄ partial pressure. By synergistically regulating the reaction temperature to 950 ℃, the CH₄ partial pressure to 1.25%, and the reaction time to 60 min, ultrafine WC-Co powder without η phase can be obtained. The particle size of the composite powder is 128 nm, with total carbon content of 6.16%, free carbon content of 0.4%, and residual oxygen content of 0.05%, respectively. The growth rate relationship of tungsten carbide is as follows: δ(t)=1.21×10^-13 exp $ \left(-\frac{12809.72}{T}\right) \sqrt{t}$.

Key words: Ultrafine WC-Co powder, Gas-solid reaction, Fluidization, Reaction process regulation, Growth rate equation

Huijun Shang, Hengli Li, Weijun Li, Feng Pan, Zhan Du. Preparation of ultrafine WC-Co powder via fluidized bed[J]. 中国化学工程学报, 2024, 73(9): 15-26.

Huijun Shang, Hengli Li, Weijun Li, Feng Pan, Zhan Du. Preparation of ultrafine WC-Co powder via fluidized bed[J]. Chinese Journal of Chemical Engineering, 2024, 73(9): 15-26.

参考文献

[1] J.H. Kim, H.S. Yang, K.H. Baik, B.G. Seong, C.H. Lee, S.Y. Hwang, Development and properties of nanostructured thermal spray coatings, Curr. Appl. Phys. 6 (6) (2006) 1002-1006.
[2] Y.Q. Wang, G. Sayre, Commercial thermal barrier coatings with a double-layer bond coat on turbine vanes and the process repeatability, Surf. Coat. Technol. 203 (16) (2009) 2186-2192.
[3] Z.G. Ban, L.L. Shaw, Synthesis and processing of nanostructured WC-Co materials, J. Mater. Sci. 37 (16) (2002) 3397-3403.
[4] W.B. Liu, X.Y. Song, J.X. Zhang, G.Z. Zhang, X.M. Liu, Preparation of ultrafine WC-Co composite powder by in situ reduction and carbonization reactions, Int. J. Refract. Met. Hard Mater. 27 (1) (2009) 115-120.
[5] C.H. Wu, Preparation of ultrafine tungsten powders by in situ hydrogen reduction of nano-needle violet tungsten oxide, Int. J. Refract. Met. Hard Mater. 29 (6) (2011) 686-691.
[6] H.Y. Wu, Q.Y. Wang, M.L. Qin, R.W. Yin, Z.Y. Zhang, B.R. Jia, X.H. Qu, Synthesis of tungsten carbide nanopowders by direct carbonization of tungsten oxide and carbon: Effects of tungsten oxide source on phase structure and morphology evolution, Ceram. Int. 46 (7) (2020) 8787-8795.
[7] M. Zhu, X.Y. Bao, X.P. Yang, N.S. Gu, H. Wang, M.Q. Zeng, L.Y. Dai, A novel method for direct synthesis of WC-co nanocomposite powder, Metall. Mater. Trans. A 42 (9) (2011) 2930-2936.
[8] Z.G. Ban, L.L. Shaw, On the reaction sequence of WC-Co formation using an integrated mechanical and thermal activation process, Acta Mater. 49 (15) (2001) 2933-2939.
[9] P. Choongkwon, K. Jiwoong, K. Shinhoo. Effect of cobalt on the synthesis and sintering of WC-Co composite powders, J. Alloys Compd. 76 (2018) 564-571.
[10] T. Ryu, H.Y. Sohn, K.S. Hwang, Z.Z. Fang, Chemical vapor synthesis and characterization of nanosized WC-co composite powder and post-treatment, Ind. Eng. Chem. Res. 47 (23) (2008) 9384-9388.
[11] J.C. Kim, B.K. Kim, Synthesis of nanosized tungsten carbide powder by the chemical vapor condensation process, Scr. Mater. 50 (7) (2004) 969-972.
[12] C.W. Won, B.S. Chun, H.Y. Sohn, Preparation of ultrafine tungsten carbide powder by CVD method from WCl₆-C₂H₂-H₂ mixtures, J. Mater. Res. 8 (10) (1993) 2702-2708.
[13] F. Pan, J.Y. Liu, Z. Du, Q.S. Zhu, M.J. Zhang, D. Yan, S.F. Li, Reaction process of WC prepared under a CO atmosphere in a fluidized bed, Ind. Eng. Chem. Res. 60 (1) (2021) 162-172.
[14] F. Pan, Z. Du, S.F. Li, J. Li, M.J. Zhang, M.Q. Xiang, Q.S. Zhu, Preparation of nano-sized tungsten carbide via fluidized bed, Chin. J. Chem. Eng. 28 (3) (2020) 923-932.
[15] S. Cetinkaya, S. Eroglu, Thermodynamic analysis and reduction of tungsten trioxide using methane, Int. J. Refract. Met. Hard Mater. 51 (2015) 137-140.
[16] H. Lin, J.C. Sun, C.H. Li, H. He, L.Z. Qin, Q. Li, A facile route to synthesize WC-Co nanocomposite powders and properties of sintered bulk, J. Alloys Compd. 682 (2016) 531-536.
[17] M. Mardali, R. Sarraf-Mamoory, B. Sadeghi, B. Safarbali, Acrylamide route for the co-synthesis of tungsten carbide-cobalt nanopowders with additives, Ceram. Int. 42 (8) (2016) 9382-9386.
[18] G.H. Lee, S. Kang, Sintering of nano-sized WC-Co powders produced by a gas reduction-carburization process, J. Alloys Compd. 419 (1-2) (2006) 281-289.
[19] J.M. Giraudon, P. Devassine, J.F. Lamonier, L. Delannoy, L. Leclercq, G. Leclercq, Synthesis of tungsten carbides by temperature-programmed reaction with CH₄-H₂ mixtures. influence of the CH₄ and hydrogen content in the carburizing mixture, J. Solid State Chem. 154 (2) (2000) 412-426.
[20] S.Y. Park, M.C. Kim, C.G. Park, Mechanical properties and microstructure evolution of the nano WC-Co coatings fabricated by detonation Gun spraying with post heat treatment, Mater. Sci. Eng. A 449 (2007) 894-897.
[21] D.A. Stewart, P.H. Shipway, D.G. McCartney, Abrasive wear behaviour of conventional and nanocomposite HVOF-sprayed WC-Co coatings, Wear 225 (1999) 789-798.
[22] C.F. Davidson, G.B. Alexander, M.E. Wadsworth, Catalytic effect of cobalt on the carburization kinetics of tungsten, Metall. Trans. A 10 (8) (1979) 1059-1069.
[23] W.B. Zhan, H.B. Wang, S.H. Liang, X.M. Liu, X.Y. Song, Acceleration effect of cobalt on carburization of tungsten at low temperature, J. Alloys Compd. 732 (2018) 429-435.
[24] Z.Y. Zhang, Y. Zhang, M. Muhammed, The reduction of cobalt doped ammonium paratungstate to nanostructured W-Co powder, Int. J. Refract. Met. Hard Mater. 20 (3) (2002) 227-233.
[25] E.T. Zhu, J.X. Zhang, S.D. Guo, X.Y. Yang, X. Zhang, J.G. Yang, Effect of Co on morphology and preparation of in situ synthesis of WC-Co composite powders, Mater. Res. Express 6 (8) (2019) 086522.
[26] H.J. Shang, H.L. Li, W.J. Li, F. Pan, Z. Du, Pre-reduction of WO₃-Co₃O₄ by H₂-C₂H₄ in a fluidized bed, Chin. J. Chem. Eng. 66 (2024) 273-284.
[27] Stanko Popovi′c, Quantitative phase analysis by X-ray diffraction-Doping methods and applications, Crystals 10 (2020) 27-42.
[28] K.M. Reddy, T.N. Rao, K. Radha, J. Joardar, Nanostructured tungsten carbides by thermochemical processing, J. Alloys Compd. 494 (1-2) (2010) 404-409.
[29] F.C. Nava Alonso, M.L. Zambrano Morales, A. Uribe Salas, J.E. Bedolla Becerril, Tungsten trioxide reduction-carburization with carbon monoxide-carbon dioxide mixtures: Kinetics and thermodynamics, Int. J. Miner. Process. 20 (1-2) (1987) 137-151.
[30] J. Ma, S.G. Zhu, Direct solid-state synthesis of tungsten carbide nanoparticles from mechanically activated tungsten oxide and graphite, Int. J. Refract. Met. Hard Mater. 28 (5) (2010) 623-627.
[31] A.A. Burkov, S.A. Pyachin, A.V. Zaytsev, Influence of carbon content of WC-co electrode materials on the wear resistance of electrospark coatings, J. Surf. Eng. Mater. Adv. Technol. 2 (2) (2012) 65-70.
[32] H.B. Wang, X.Y. Song, X.M. Liu, Y. Gao, C.B. Wei, Y. Wang, G.S. Guo, Effect of carbon content of WC-Co composite powder on properties of cermet coating, Powder Technol. 246 (2013) 492-498.
[33] M.H. Kim, E.K. Lee, J.H. Jun, S.J. Kong, G.Y. Han, B.K. Lee, T.J. Lee, K.J. Yoon, Hydrogen production by catalytic decomposition of methane over activated carbons: kinetic study, Int. J. Hydrog. Energy 29 (2) (2004) 187-193.
[34] E. Ruckenstein, H.Y. Wang, Carbon deposition and catalytic deactivation during CO₂ reforming of CH₄ over Co/γ-Al₂O₃ catalysts, J. Catal. 205 (2) (2002) 289-293.
[35] S.H. Lim, J. Lin, Z. Luo, Z. Shen, Efficient growth of horizontally aligned single-walled carbon nanotubes by chemical vapor deposition over MgO-supported bimetallic co-based catalysts, J. Nanosci. Nanotechnol. 11 (1) (2011) 143-147.
[36] A.H. Wu, C.P. Lei, G. Liu, J.C. Tang, L.W. Hao, Effect of the morphology of raw material powders on homogeneity of tungsten and tungsten carbide nano-powders, Cemented Carbide 5 (2014) 302-308. (in Chinese).
[37] Q.W. Zhang, K.H. Shi, J.B. Gu, K.L. Dong, W. Zeng, P. Wang, Y. Liao, Effect of carbon content near the decarbonization phase boundary on the physical and mechanical properties of WC-6% Co cemented carbides, J Superhard Mater. 44 (2022) 350-357.
[38] T.Z. Huang, E.X. Wu, Y.X. Li, D. Zou, Y.Y. Xie, Effects of carbon content on WC grain growth activation energy of WC-6Co ultrafine cemented carbides, Rare Metals & Cemented Carbides 45 (2017) 57-62. (in Chinese).
[39] Y.M. Wang, L. Zhang, Y.F. Yang, K. Kondoh, L.B. Sun, Y.N. Lu, Elimination of ƞ phase in WC-Co cemented carbides during laser powder bed fusion by powder coating compensation strategy, J Am Ceram Soc. 106 (3) (2023) 1681-1693.
[40] I. Konyashin, S. Hlawatschek, B. Ries, F. Lachmann, F. Dorn, A. Sologubenko, T. Weirich, On the mechanism of WC coarsening in WC-Co hardmetals with various carbon contents, Int. J. Refract. Met. Hard Mater. 27 (2) (2009) 234-243.
[41] W.H. Chen, P.K. Nayak, H.T. Lin, M.P. Chang, J.L. Huang, Synthesis of nanostructured tungsten carbide via metal-organic chemical vapor deposition and carburization process, Int. J. Refract. Met. Hard Mater. 47 (2014) 44-48.
[42] B. Sarma, N.M. Tikekar, K.S. Ravi, Kinetics of growth of superhard boride layers during solid state diffusion of boron into titanium, Ceram. Int. 38 (2012) 6795-6805.
[43] U. Sen, Kinetics of niobium carbide coating produced on AISI 1040 steel by thermo-reactive deposition technique, Mater. Chem. Phys. 89 (2004) 189-194.
[44] H. Xu, C. Liu, V.V. Silberschmidt, S.S. Pramana, T.J. White, Z. Chen, V.L. Acoff, Behavior of aluminum oxide, intermetallics and voids in Cu-Al wire bonds, Acta Mater. 59 (2011) 5661-5673.

Preparation of ultrafine WC-Co powder via fluidized bed

Preparation of ultrafine WC-Co powder via fluidized bed

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	Congjing Ren, Peng Zhang, Qi Song, Zhengliang Huang, Yao Yang, Yongrong Yang. Particle agglomeration and inhibition method in the fluidized pyrolysis reaction of waste resin[J]. 中国化学工程学报, 2024, 67(3): 135-147.
[2]	Huijun Shang, Hengli Li, Weijun Li, Feng Pan, Zhan Du. Pre-reduction of WO₃–Co₃O₄ by H₂–C₂H₄ in a fluidized bed[J]. 中国化学工程学报, 2024, 66(2): 273-284.
[3]	Qiyao Yang, Xiaobin Qi, Qinggang Lyu, Zhiping Zhu. Experimental study on the activation of coal gasification fly ash from industrial CFB gasifiers[J]. 中国化学工程学报, 2024, 65(1): 8-18.
[4]	Qiang Zhang, Wankun Liu, Hengjun Gai, Quanhong Zhu. Extending homogeneous fluidization flow regime of Geldart-A particles by exerting axial uniform and steady magnetic field[J]. 中国化学工程学报, 2024, 65(1): 169-177.
[5]	Zhangke Ma, Yingjie Li, Boyu Li, Zeyan Wang, Tao Wang, Wentao Lei. Calcium looping heat storage performance and mechanical property of CaO-based pellets under fluidization[J]. 中国化学工程学报, 2021, 36(8): 170-180.
[6]	Juanbo Liu, Xinhua Liu, Wei Ge. EMMS-based modeling of gas-solid generalized fluidization: Towards a unified phase diagram[J]. 中国化学工程学报, 2021, 29(1): 27-34.
[7]	A. Al-Farraji, Haidar Taofeeq. Effect of elevated temperature and silica sand particle size on minimum fluidization velocity in an atmospheric bubbling fluidized bed[J]. 中国化学工程学报, 2020, 28(12): 2985-2992.
[8]	Yunsong Yu, Chen Zhang, Zaoxiao Zhang, Geoff Wang. Characterizing the catalyst fluidization with field synergy to improve the amine absorption for CO₂ capture[J]. 中国化学工程学报, 2019, 27(7): 1608-1617.
[9]	Musango Lungu, Haotong Wang, Jingdai Wang, Ronald Ngulube, Yongrong Yang, Fengqiu Chen, John Siame. Assessment of the TFM in predicting the onset of turbulent fluidization[J]. 中国化学工程学报, 2019, 27(5): 979-992.
[10]	Nouman Ahmad, Yujie Tian, Bona Lu, Kun Hong, Haifeng Wang, Wei Wang. Extending the EMMS/bubbling model to fluidization of binary particle mixture: Formulation and steady-state validation[J]. Chinese Journal of Chemical Engineering, 2019, 27(1): 54-62.
[11]	Hongbing Mo, Bao Xu, Chuanbao Luo, Tao Zhou, Jiangrong Kong. Aggregation and fragmentation of agglomerates in a fluidized bed of mixed nanoparticles by adding FCC coarse particles[J]. Chinese Journal of Chemical Engineering, 2018, 26(12): 2531-2536.
[12]	Zheng Zou, Yunlong Zhao, Hu Zhao, Libo Zhang, Zhaohui Xie, Hongzhong Li, Qingshan Zhu. CFD simulation of solids residence time distribution in a multi-compartment fluidized bed[J]. Chinese Journal of Chemical Engineering, 2017, 25(12): 1706-1713.
[13]	R. K. Padhi, D. T. K. Dora, Y. K. Mohanty, G. K. Roy, B. Sarangi. Hydrodynamics of three-phase fluidization of homogeneous ternary mixture in a conical conduit-Experimental and statistical analysis[J]. , 2016, 24(10): 1335-1343.
[14]	Xiaolin Zhu, Qiang Zhang, YaoWang, Fei Wei. Review on the nanoparticle fluidization science and technology[J]. Chinese Journal of Chemical Engineering, 2016, 24(1): 9-22.
[15]	Cheng Wu, Yongxiang Gao, Youwei Cheng, Lijun Wang, Xi Li. Solid concentration and velocity distributions in an annulus turbulent fluidized bed[J]. Chinese Journal of Chemical Engineering, 2015, 23(7): 1077-1084.