The chemical extraction of niobium and titanium carbonitride precipitates from microalloyed steels was studied. Steel samples and chemically synthesized reference nanoparticles were subjected to commonly used extraction protocols, and conditions were systematically varied. High acid concentrations led to particle etching with losses above 10%; long extraction times and small etchant volumes led to the formation of dense SiOx networks that engulfed the extracted particles. The addition of surfactants was found to reduce agglomeration and limit etching. We developed an optimized extraction protocol that can extract and retain particles with diameters below 10 nm with reduced etching and negligible network formation. The resulting particle dispersions are suitable both for efficient electron microscopy of large particle numbers in a single run and colloidal analysis of large numbers of particles in dispersion.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
The standard uses 5 g of steel that are dissolved in 100 mL HCl (6 mol L−1) and later filled up with 150 mL water.
V ∼ r3: a reduction of 15% in volume/mass goes along with a reduction of approx. 5% in radius.
For an image resolution with 2 pixels/nm and a particle size of 30 nm, the error in size determination is 1.6%.
Vega MI, Medina SF, Quispe A et al (2005) Influence of TiN particle precipitation state on static recrystallisation in structural steels. ISIJ Int 45:1878–1886. https://doi.org/10.2355/45.1878
Nishioka K, Ichikawa K (2012) Progress in thermomechanical control of steel plates and their commercialization. Sci Technol Adv Mater 13:023001. https://doi.org/10.1088/1468-6996/13/2/023001
Baker TN (2016) Microalloyed steels. Ironmak Steelmak 43:264–307. https://doi.org/10.1179/1743281215Y.0000000063
Gladman T (1997) The physical metallurgy of microalloyed steels. The Institute of Materials, London
Craven AJ, He K, Garvie LAJ, Baker TN (2000) Complex heterogeneous precipitation in titanium–niobium microalloyed Al-killed HSLA steels—I. (Ti, Nb)(C, N) particles. Acta Mater 48:3857–3868. https://doi.org/10.1016/S1359-6454(00)00194-4
Craven AJ, He K, Garvie LAJ, Baker TN (2000) Complex heterogeneous precipitation in titanium–niobium microalloyed Al-killed HSLA steels—II. Non-titanium based particles. Acta Mater 48:3869–3878. https://doi.org/10.1016/S1359-6454(00)00193-2
Courtois E, Epicier T, Scott C (2006) EELS study of niobium carbo-nitride nano-precipitates in ferrite. Micron 37:492–502. https://doi.org/10.1016/j.micron.2005.10.009
Lee Y, De Cooman BC (2014) TiN/NbC compound particle formation during thin slab direct rolling of HSLA steel. Steel Res Int 85:1158–1172. https://doi.org/10.1002/srin.201300280
Xie ZJ, Ma XP, Shang CJ et al (2015) Nano-sized precipitation and properties of a low carbon niobium micro-alloyed bainitic steel. Mater Sci Eng A 641:37–44. https://doi.org/10.1016/j.msea.2015.05.101
Li Z, Liu D, Zhang J, Tian W (2013) Precipitates in Nb and Nb–V microalloyed X80 pipeline steel. Microsc Microanal 19:62–65. https://doi.org/10.1017/S1431927613012348
Béreš M, Weirich TE, Hulka K, Mayer J (2004) TEM investigations of fine niobium precipitates in HSLA steel. Steel Res Int 75:753–758
Klinkenberg C, Hulka K, Bleck W (2004) Niobium carbide precipitation in microalloyed steel. Steel Res Int 11:744–752
Tirumalasetty GK, van Huis MA, Fang CM et al (2011) Characterization of NbC and (Nb, Ti)N nanoprecipitates in TRIP assisted multiphase steels. Acta Mater 59:7406–7415. https://doi.org/10.1016/j.actamat.2011.08.012
Mukherjee T, Stumpf WE, Sellars CM (1968) Quantitative assessment of extraction replicas for particle analysis. J Mater Sci 3:127–135. https://doi.org/10.1007/BF00585479
Shen YF, Wang CM, Sun X (2011) A micro-alloyed ferritic steel strengthened by nanoscale precipitates. Mater Sci Eng A 528:8150–8156. https://doi.org/10.1016/j.msea.2011.07.065
Bonevich JE, Haller WK (2010) NIST—NCL joint assay protocol, PCC-X: measuring the size of nanoparticles using transmission electron microscopy (TEM). National Institute of Standards and Technology, Gaithersburg, MD. https://ws680.nist.gov/publication/get_pdf.cfm?pub_id=854083. Accessed 19 Dec 2018
Rice SB, Chan C, Brown SC et al (2013) Particle size distributions by transmission electron microscopy: an interlaboratory comparison case study. Metrologia 50:663–678. https://doi.org/10.1088/0026-1394/50/6/663
Masuda H, Gotoh K (1999) Study on the sample size required for the estimation of mean particle diameter. Adv Powder Technol 10:159–173. https://doi.org/10.1016/S0921-8831(08)60447-1
Cunningham TR, Price RJ (1933) Determination of nonmetallic inclusions in plain carbon and manganese steels iodine and nitric acid extraction methods. Ind Eng Chem Anal Ed 5:27–29. https://doi.org/10.1021/ac50081a018
Klinger P, Koch W (1938) Beitrag zur elektrolytischen Bestimmung von nichtmetallischen Einschlüssen im Stahl. Arch für das Eisenhüttenwes 11:569–582. https://doi.org/10.1002/srin.193801061
Inoue R, Ueda S, Ariyama T, Suito H (2011) Extraction of nonmetallic inclusion particles containing MgO from steel. ISIJ Int 51:2050–2055
Garside JE, Rooney TE, Belli JJJ (1957) The alcoholic-iodine method for the extraction of inclusions from steel. J Iron Steel Inst 185:95–103
Fernandes M, Cheung N, Garcia A (2002) Investigation of nonmetallic inclusions in continuously cast carbon steel by dissolution of the ferritic matrix. Mater Charact 48:255–261. https://doi.org/10.1016/S1044-5803(02)00246-2
Lu J, Ivey D, Henein H (2006) Quantification of nano-sized precipitates in microalloyed steels by matrix dissolution. In: Proceedings of international pipeline conference, pp 635–642. https://doi.org/10.1115/ipc2006-10600
Lu J, Ivey DG, Henein H et al (2008) Extraction and characterization of nano-precipitates in microalloyed steels. In: Proceedings of the international pipeline conference, Calgary, pp 85–94
Lu J, Wiskel JB, Omotoso O et al (2011) Matrix dissolution techniques applied to extract and quantify precipitates from a microalloyed steel. Metall Mater Trans A 42:1767–1784. https://doi.org/10.1007/s11661-010-0579-6
Hegetschweiler A, Kraus T, Staudt T (2017) Colloidal analysis of particles extracted from microalloyed steel. Metall Ital 109:23–28
Wiskel J, Lu J, Omotoso O et al (2016) Characterization of precipitates in a microalloyed steel using quantitative X-ray diffraction. Metals (Basel) 6:90. https://doi.org/10.3390/met6040090
Rivas AL, Vidal E, Matlock DK, Speer JG (2008) Electrochemical extraction of microalloy carbides in Nb-steel. Rev Metal 44:447–456. https://doi.org/10.3989/revmetalm.0771
ASTM E194-10 (2015) Standard test method for acid-insoluble content of copper and iron powders, West Conshohocken
Pierson HO (1996) Carbides of group IV: titanium, zirconium, and hafnium carbides. In: Pierson HO (ed) Handbook of refractory carbides and nitrides: properties, characteristics, processing and applications. Noyes Publications, Westwood, p 362
Pierson HO (1996) Carbides of group V: vanadium, niobium and tantalum carbides. In: Pierson HO (ed) Handbook of refractory carbides and nitrides: properties, characteristics, processing and applications. Noyes Publications, Westwood, p 362
Pierson HO (1996) The refractory nitrides. In: Pierson HO (ed) Handbook of refractory carbides and nitrides. Noyes Publications, Westwood, pp 156–162
Kosolapova TY (2012) Carbides. Springer, Boston
Lengauer W (2000) Transition metal carbides, nitrides, and carbonitrides. In: Riedel R (ed) Handbook of ceramic hard materials. Wiley, Weinheim, pp 202–252
Giordano C, Erpen C, Yao W et al (2009) Metal nitride and metal carbide nanoparticles by a soft urea pathway. Chem Mater 21:5136–5144. https://doi.org/10.1021/cm9018953
Read S, Gibbs R, Parker B (1990) Extraction and characterization of precipitates formed in a niobium HSLA steel. Mater Forum 14:304–307
Duan J, Gregory J (2003) Coagulation by hydrolysing metal salts. Adv Colloid Interface Sci 100–102:475–502. https://doi.org/10.1016/S0001-8686(02)00067-2
The authors would like to thank Eduard Arzt for his continuing support of the project. Andrea Jung is also acknowledged for the elementary analysis, Kathrin Alt for particle dissolution experiments, and Bastian Philippi for Matcalc Simulations.
This work was funded by the “AG der Dillinger Hüttenwerke” in Germany and a patent for a particle extraction procedure aided by a dispersant was submitted.
Electronic supplementary material
Below is the link to the electronic supplementary material.
About this article
Cite this article
Hegetschweiler, A., Staudt, T. & Kraus, T. An improved method for the matrix dissolution extraction of nanoparticles from microalloyed steel. J Mater Sci 54, 5813–5824 (2019). https://doi.org/10.1007/s10853-018-03263-0