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Niobium carbide for wear protection - tailoring its properties by processing and stoichiometry
(2016)
Niobium carbide is a hardly explored carbide but its functional profile shows a high potential for wear protection and tribological applications, which are currently dominated by tungsten carbide. Surprisingly little information is available on niobium carbide (NbC). Niobium carbide can be either synthesized by carbothermal conversion of Nb2O5 or be metallurgically grown and leached out. Furthermore, NbC hardmetal grades can be bonded by all known metallic binders and processed and sintered in exactly the same way as WC-based hardmetals. Niobium is today largely available. NbC can be efficiently produced, provides comparably low friction in many relevant tribo-contacts and displays low wear. NbC and Nb2O5 have so far no REACH classification related to human toxicology and are not listed as substances of very high concern contrary to WO3 and Co3O4. This contribution demonstrates the key characteristics of NbC and discusses its sustainability and reliable value chain.
Substitution of tungsten carbide by niobium carbide as cutting materials and for wear protection
(2016)
Several phases, like Nb₄ C₃ , Nb₆C₅ and other short and long range ordered phases occur in the region of homogeneity of NbCₓ (0.75 ≤ x ≤ 1.0) in the binary phase diagram. Properties, like micro-hardness, hot hardness, sliding wear resistance, elastic modulus and toughness can be tailored by the C/Nb ratio, the addition of secondary carbides and the type of binder. Supporting results from different grades with varying C/Nb ratio or binder types were illuminated. Thus, the NbC system offers to producers a wider process window, than WC. The impact of these tailored properties on sliding wear and cutting performance was illuminated by tribological and machining results.
Niobium is today largely available. NbC can be synthesized by carbothermal conversion of Nb₂O₅ or be metallurgically grown and leached out, provides comparably low friction in many relevant tribo-contacts and displays low wear. NbC and Nb₂O₅ have so far no REACH classification related to human toxicology and are not listed as substances of very high concern contrary to WO₃ and Co₃ O₄ .
Niobium is today largely available. The initial NbC grade was substoichiometric, SPS sintered and cobalt bonded (NbC0.88-12Co SPS). The NiMo-bonded stoichiometric NbC1.0 grades enable the subtituion of cobalt by nickel, SPS by conventional sintering and NbC0.88 by NbC1.0 in view of functional properties. Nickel bonded NbC grades have improved toughnesses versus cobalt bonded NbC grades, but lose hardness. NiMo and NiMo2C bonded NbC1.0 grades compensated the loss in hardness while keeping the toughness.
Research and development of WC grades is 90 years ahead of niobium carbide-based hard materials, which showed already as light-weight and unexplored material a very high potential for many technical applications, especially for wear protection and machining. NbC evoluted recently from lab scale to pilot scale, especially in areas where established WC-based materials are causing economic, environmental or technical concerns. Benchmark trials of NbC-based hard metals indicated already a favorable performance in machining of steel components.
The sales of niobium carbide (NbC) have grown in the last years, but NbC is still a hidden carbide and mainly used as grain growth inhibitor in hard metals. In the present work it was shown that the progress in the key properties, like HV30, KIC and strength, followed by machining and tribological results of the respective NbC grades.
The CCQM-K148.a comparison was coordinated by the BIPM on behalf of the CCQM Organic Analysis Working Group for NMIs and DIs which provide measurement services in organic analysis under the CIPM MRA. It was undertaken as a "Track A" comparison within the OAWG strategic plan. CCQM-K148.a demonstrates capabilities for assigning the mass fraction content of a solid organic compound having moderate molecular complexity, where the compound has a molar mass in the range (75 - 500) g/mol and is non-polar (pKow < −2), when present as the primary organic component in a neat organic solid and where the mass fraction content of the primary component in the material is in excess of 950 mg/g.
Participants were required to report the mass fraction of Bisphenol A present in one supplied unit of the comparison material. Participants using a mass balance method for the assignment were also required to report their assignments of the impurity components present in the material. Methods used by the seventeen participating NMIs or DIs were predominantly based on either stand-alone mass balance (summation of impurities) or qNMR approaches, or the combination of data obtained using both methods. The results obtained using thermal methods based on freezing-point depression methods were also reported by a limited number of participants. There was excellent agreement between assignments obtained using all three approaches to assign the BPA content.
The assignment of the values for the mass fraction content of BPA consistent with the KCRV was achieved by most of the comparison participants with an associated relative standard uncertainty in the assigned value in the range (0.1 - 0.5)%.
KEY COMPARISON
Under the auspices of the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM) a key comparison, CCQM K55.c, was coordinated by the Bureau International des Poids et Mesures (BIPM) in 2012. Twenty National Measurement Institutes or Designated Institutes and the BIPM participated. Participants were required to assign the mass fraction of valine present as the main component in the comparison sample for CCQM-K55.c. The comparison samples were prepared from analytical grade L-valine purchased from a commercial supplier and used as provided without further treatment or purification.
Valine was selected to be representative of the performance of a laboratory's measurement capability for the purity assignment of organic compounds of low structural complexity [molecular weight range 100300] and high polarity (pKOW > –2).
The KCRV for the valine content of the material was 992.0 mg/g with a combined standard uncertainty of 0.3 mg/g. The key comparison reference value (KCRV) was assigned by combination of KCRVs assigned from participant results for each orthogonal impurity class. The relative expanded uncertainties reported by laboratories having results consistent with the KCRV ranged from 1 mg/g to 6 mg/g when using mass balance based approaches alone, 2 mg/g to 7 mg/g using quantitative 1H NMR (qNMR) based approaches and from 1 mg/g to 2.5 mg/g when a result obtained by a mass balance method was combined with a separate qNMR result.
The material provided several analytical challenges. In addition to the need to identify and quantify various related amino acid impurities including leucine, isoleucine, alanine and a-amino butyrate, care was required to select appropriate conditions for performing Karl Fischer titration assay for water content to avoid bias due to in situ formation of water by self-condensation under the assay conditions. It also proved to be a challenging compound for purity assignment by qNMR techniques.
There was overall excellent agreement between participants in the identification and the quantification of the total and individual related structure impurities, water content, residual solvent and total non-volatile content of the sample. Appropriate technical justifications were developed to rationalise observed discrepancies in the limited cases where methodology differences led to inconsistent results.
The comparison demonstrated that to perform a qNMR purity assignment the selection of appropriate parameters and an understanding of their potential influence on the assigned value is critical for reliable implementation of the method, particularly when one or more of the peaks to be quantified consist of complex multiplet signals.