EP4217331A1 - Keramischer gegenstand - Google Patents

Keramischer gegenstand

Info

Publication number
EP4217331A1
EP4217331A1 EP21742675.8A EP21742675A EP4217331A1 EP 4217331 A1 EP4217331 A1 EP 4217331A1 EP 21742675 A EP21742675 A EP 21742675A EP 4217331 A1 EP4217331 A1 EP 4217331A1
Authority
EP
European Patent Office
Prior art keywords
weight
ceramic phase
percentage
article according
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21742675.8A
Other languages
English (en)
French (fr)
Inventor
Bernard Bertheville
Yann Fallet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Swatch Group Research and Development SA
Original Assignee
Swatch Group Research and Development SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Swatch Group Research and Development SA filed Critical Swatch Group Research and Development SA
Publication of EP4217331A1 publication Critical patent/EP4217331A1/de
Pending legal-status Critical Current

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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/58007—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides
    • C04B35/58014—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides based on titanium nitrides, e.g. TiAlON
    • C04B35/58021—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides based on titanium nitrides, e.g. TiAlON based on titanium carbonitrides
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Definitions

  • the present invention relates to an article and in particular to a component for covering or movement in watchmaking, made of a composite material consisting solely of ceramic phases. It also relates to its manufacturing process.
  • trim components are made of composite ceramic materials which have the advantage, among other things, of having very high hardnesses which guarantee their ability not to be scratched.
  • the literature mainly refers to composites made up mainly of an oxide such as alumina to which carbides are added. It may, for example, be composites comprising by weight 70% A ⁇ Os and 30% TiC used as reinforcement. These composites have the characteristic of presenting little or no metallic luster compared to other materials such as stainless steels or cermets, which can be a disadvantage for decorative items where this luster is sought.
  • a way of solving this problem consists, for example to produce cermets based on TiN or TiCN, in adding a metallic element acting as a metallic binder.
  • a metallic element acting as a metallic binder For example, an addition of a few percent of nickel or cobalt allows consolidation at lower temperatures, typically around 1500°C.
  • these elements have the disadvantage of being highly allergenic, limiting their use to articles not intended to be in contact with the skin.
  • the object of the present invention is to overcome the aforementioned disadvantages by proposing a ceramic material, also called composite, with a composition and a manufacturing process optimized to meet the following criteria:
  • - have a minimum hardness of 500 HV30, preferably minimum of 800 HV30 and more preferably minimum of 1000 HV30 for applications requiring very good scratch resistance, while having sufficient toughness with, preferably, a KiC greater than or equal to 2.5 MPa.m 1/2 .
  • the present invention proposes an article made of a material consisting of several ceramic phases, said material comprising: - a majority ceramic phase comprising nitrides and/or carbonitrides of one or more elements of group IVB, namely Ti, Zr and Hf, and/or of group VB, namely V, Nb and Ta, said phase majority ceramic being present in a percentage by weight of between 60 and 98%,
  • At least one minority ceramic phase with either a single minority ceramic phase formed of zirconium and/or aluminum silicide, or several minority ceramic phases formed respectively of carbides of one or more group IVB elements (Ti, Zr, Hf), group VB (V, Nb, Ta) and group VIB (Cr, Mo, W), and zirconium oxides and/or aluminum oxides, said at least minority ceramic phase being present in its entirety in a percentage by weight of between 2 and 40%.
  • group IVB elements Ti, Zr, Hf
  • group VB V, Nb, Ta
  • group VIB Cr, Mo, W
  • zirconium oxides and/or aluminum oxides said at least minority ceramic phase being present in its entirety in a percentage by weight of between 2 and 40%.
  • the composite material thus developed has, after polishing, a metallic luster similar to that observed in stainless steels or cermets using nickel or cobalt as a metallic binder.
  • These composites have other advantages of being devoid of allergenic elements such as Ni. They also have high hardnesses and sufficient tenacity for the production of trim components while being non-magnetic.
  • they can be shaped by conventional powder metallurgy processes such as pressing or injection or by various processes dedicated to the manufacture of three-dimensional parts such as, for example, 3D printing in order to obtain near-net-shape pieces. Parts of more or less complex shape can be finally consolidated at temperatures between 1400 and 1900°C under atmospheric pressure, under vacuum or under partial gas pressure, i.e. without resorting to significant pressure.
  • FIG. 1 represents a timepiece comprising a middle part made with the ceramic material according to the invention.
  • the present invention relates to an article made of a composite material consisting solely of ceramic phases.
  • the article may be a decorative article such as an integral part of watches, jewellery, bracelets, etc. or more generally an external part of a portable element such as a shell of a mobile telephone.
  • this article can be a covering part such as a middle part, a back, a bezel, a crown, a bridge, a pusher, a bracelet link, a dial, a hand, a dial index , etc
  • a middle part made with the ceramic material according to the invention is represented in FIG. 1. It can also be a component of the movement such as a plate or an oscillating weight.
  • the ceramic material comprises a majority phase composed of nitrides and/or carbonitrides of one or more elements chosen from Ti, Zr, Hf, V, Nb and Ta, and one or more minority phases.
  • the latter can be either zirconium and/or aluminum silicide, or a combination of carbides of one or more elements chosen from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W and of zirconium (Zr) and/or aluminum (Al) oxides.
  • the majority phase is composed of titanium nitrides and/or titanium carbonitrides.
  • the minority phase or phases are respectively composed either of zirconium silicide and/or aluminum or a combination of tungsten and/or vanadium carbides and zirconium and/or aluminum oxides
  • the majority phase is present in a percentage by weight of between 60 and 98% and all of the minority phases are present in a percentage by weight of between 2 and 40%.
  • the majority phase is present in a percentage by weight of between 65 and 97%, more preferably between 70 and 96% by weight, and even more preferably between 75 and 95%.
  • all of the minority phases are present in a percentage by weight preferably between 3 and 35%, more preferably between 4 and 30% and even more preferably between 5 and 25%.
  • the nitrides and carbonitrides are preferably present respectively in a percentage of between 20 and 70% by weight , more preferably between 25 and 60%, relative to the total weight of the ceramic material.
  • the ceramic material comprises two minority phases respectively of carbides of one element or several elements chosen from among Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W and oxides (Al2O3 and/or ZrCh), they are respectively and preferably present in a percentage of between 3 and 35% by weight, more preferably between 5 and 25%, relative to the total weight of the ceramic material.
  • the ceramic article is produced by sintering starting from a mixture of powders.
  • the manufacturing process comprises the steps consisting of: a) Making a mixture with the various ceramic powders, possibly in a humid environment.
  • the starting powders preferably have a d50 of less than 45 ⁇ m.
  • the mixture can optionally be carried out in a grinder, which reduces the d50 of the particles of the powder to a size of the order of a few microns ( ⁇ 5 ⁇ m) after grinding.
  • Powders of nitrides and/or carbonitrides of one or more elements elements chosen from Ti, Zr, Hf, V, Nb and Ta are present in a percentage by weight for all of these powders of between 60 and 98%, preferably between 65 and 97%, more preferably between 70 and 96 % and even more preferably between 75 and 95%.
  • Powders of zirconium silicide and/or aluminum silicide or powders of carbides of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W and of zirconium and/or aluminum oxides are present in a percentage by weight of between 2 and 40%, preferably between 3 and 35%, more preferably between 4 and 30%, even more preferably between 5 and 25%.
  • the mixture of powders may comprise by weight one of the following distributions for a total of 100%:
  • a second mixture comprising the aforementioned mixture and an organic binder system (paraffin, polyethylene, etc.) can be produced.
  • a second mixture comprising the aforementioned mixture and an organic binder system (paraffin, polyethylene, etc.) can be produced.
  • c) Forming a blank by giving the mixture the shape of the desired article, for example, by injection or pressing or by 3D printing.
  • d) Sintering the blank under partial gas pressure, under vacuum or under atmospheric pressure at a temperature between 1200 and 2100°C, preferably between 1400 and 1900°C for a period between 10 minutes and 20 hours, preferably between 15 minutes and 3 hours. This step can be preceded by a debinding step in a temperature range of between 60 and 500° C.
  • the mixture includes a binder system.
  • the compositions according to the invention allow sintering under low pressure, the present invention does not exclude that the sintering is carried out by SPS (Spark Plasma Sintering) or by sinter-HIP, followed or not by HIP (Hot Isostatic Pressure) consolidation.
  • SPS Spark Plasma Sintering
  • HIP Hot Isostatic Pressure
  • the blank thus obtained is cooled and polished. It can also be machined before polishing to obtain the desired article.
  • the article resulting from the manufacturing process comprises the majority phase and the minority phase or phases in percentages by weight close to those of the starting powders.
  • small variations in composition and percentages between the base powders and the material resulting from sintering cannot be ruled out following, for example, contamination or transformations during sintering.
  • carbides could react with nitrides to form carbonitrides.
  • the article has a CIELAB color space (conforms to CIE n°15, ISO 7724/1, DIN 5033 Part 7, ASTM E-1164) with a luminance component L*, representative of how the material reflects light , between 60 and 85 and, preferably, between 65 and 80, and more preferably between 70 and 75.
  • the article is yellow in color and has an a* component (red component) between +1 and +7 and a b* component (yellow component) between +20 and +35.
  • the article is pink-red in color and has an a* component of between +2 and +15 and a b* component of between +2 and +10.
  • the ceramic material has a hardness HV30 greater than or equal to 500, preferably between 800 and 1800 depending on the types and percentages of the constituents. It has a toughness KiC greater than or equal to 2 and preferably greater than or equal to 2.5 MPa.m 1/2 with values that can go up to 8 MPa.m 1/2 , the toughness being determined on the basis of measurements the lengths of the cracks at the four extremities of the diagonals of the hardness impression according to the formula: with P being the applied load (N), a being the half-diagonal (m) and / being the measured crack length (m).
  • HV30 hardness measurements were carried out on the surface of the samples and the toughness was determined on the basis of the hardness measurements as described previously.
  • TiN titanium nitride
  • ZrSi2 zirconium silicide
  • this composite was densified by Spark Plasma Sintering (SPS). The hardness measured is 1328 Vickers (HV30) and the toughness 4.3 MPa.m 1/2 .
  • TiN titanium nitride
  • ZrSi2 zirconium silicide
  • This 90TiN-10ZrSi2 composite was densified by both SPS and conventional sintering. When it is sintered by conventional sintering, a drop in hardness is observed compared to SPS sintering, going from 1302 to 863 Vickers but retaining good toughness (4.2 versus 4.4 MPa.m 1/2 ). On the other hand, by conventional sintering, a much better luster is obtained with a higher luminance index (L*) (74.5 versus 66.2). Conventional sintering also makes it possible to obtain a more yellow tint with a slightly higher value of the yellow component b*.
  • TiCN titanium carbonitride
  • ZrSi2 zirconium silicide
  • TiN titanium nitride
  • Al2O3 aluminum oxide
  • TiN titanium nitride
  • ZrC zirconium dioxide
  • This composite has a maximum hardness of 1187 Vickers and a measured luminance L* of 72.9.
  • the color of such a ceramic composite is yellow, with a* and b* index values of 1.48 and 26.0 respectively.
  • Replacing aluminum oxide (example 4) with zirconium dioxide therefore increases the hardness by 249 Vickers.
  • TiN titanium nitride
  • ZrC zirconium dioxide
  • This composite has a hardness of 1275 Vickers and a measured luminance L* of 71.8.
  • the color of such a ceramic composite is yellow, with a* and b* values of 2.9 and 23.4 respectively.
  • Replacing tungsten carbide (example 5) with vanadium carbide therefore increases the hardness by about 7%.
  • TiN titanium nitride
  • TiCN titanium carbonitride
  • ZrCh zirconium dioxide
  • Such a composite has a pink-red coloring with indices a* and b* of values 7.52 and 8.02 respectively.
  • the hardness measured is very high, ie 1727 Vickers, and almost identical to that obtained by SPS sintering. This increase results directly from the addition of tungsten carbide.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)
EP21742675.8A 2020-09-25 2021-07-28 Keramischer gegenstand Pending EP4217331A1 (de)

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PCT/EP2021/071130 WO2022063462A1 (fr) 2020-09-25 2021-07-28 Article en ceramique

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EP3974405A1 (de) 2022-03-30
WO2022063462A1 (fr) 2022-03-31

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