NICKEL-FREE AUSTENITIC STAINLESS-STEEL POWDER COMPOSITION AND PART PRODUCED BY SINTERING BY MEANS OF THIS POWDER

Abstract

An austenitic stainless-steel powder having a nickel content of less than or equal to 0.5% by weight and a specific carbon content that is greater than or equal to 0.05% and less than or equal to 0.11% by weight. A method for manufacturing the powder by powder metallurgy and parts resulting from the manufacturing method, which have the characteristic of having a deoxidised layer on the surface of the part extending over a thickness greater than or equal to 200 μm.

Claims

1-20. (canceled)

21. An austenitic stainless-steel powder, comprising by weight: −10<Cr<25%, −5<Mn<20%, −1<Mo<5%, −0.05≤C≤0.11%, −0≤Si<2%, −0≤Cu<4%, −0.5<N<1%, −0≤O<0.3%, and −0≤Ni≤0.5%, with a balance formed by iron and possible impurities each having a content of between 0 and 0.5%.

22. The powder according to claim 21, comprising by weight: −15<Cr<20%, −8<Mn<14%, −2<Mo<4%, −0.05≤C≤0.11%, −0≤Si<1%, −0≤Cu<0.5%, −0.5<N<1%, −0≤O<0.2%, −0≤Ni≤0.5%, with a balance formed by iron and possible impurities each having a content of between 0 and 0.5%.

23. The powder according to claim 21, comprising by weight: −16.5≤Cr≤17.5%, −10.5≤Mn≤11.5%, −3≤Mo≤3.5%, −0.05≤C≤0.11%, −0≤Si≤0.6%, −0≤Cu≤0.5%, −0,5<N<1%, −0≤O<0.2%, −0≤Ni≤0.5%, with a balance formed by iron and possible impurities each having a content of between 0 and 0.5%.

24. The powder according to claim 22, comprising by weight: −16.5≤Cr≤17.5%, −10.5≤Mn≤11.5%, −3≤Mo≤3.5%, −0.05≤C≤0.11%, −0≤Si≤0.6%, −0≤Cu≤0.5%, −0,5<N<1%, −0≤O<0.2%, −0≤Ni≤0.5%, with a balance formed by iron and possible impurities each having a content of between 0 and 0.5%.

25. The powder according to claim 21, which is in the form of particles having a diameter D90 of less than or equal to 150 μm.

26. The powder according to claim 22, which is in the form of particles having a diameter D90 of less than or equal to 150 μm.

27. The powder according to claim 23, which is in the form of particles having a diameter D90 of less than or equal to 150 μm.

28. The powder according to claim 24, which is in the form of particles having a diameter D90 of less than or equal to 150 μm.

29. A part, comprising the powder according to claim 21, wherein: the part comprises a deoxidised layer on a surface of the part, the deoxidised layer comprises oxides having a diameter of less than or equal to 2 μm with a surface fraction of less than or equal to 0.1%, and the deoxidised layer has a thickness greater than or equal to 200 μm.

30. The part according to claim 29, wherein the deoxidised layer has a thickness greater than or equal to 250 μm.

31. The part according to claim 29, wherein the deoxidised layer has a thickness greater than or equal to 300 μm.

32. The part according to claim 29, wherein the deoxidised layer has a relative density greater than or equal to 99%.

33. The part according to claim 30, wherein the deoxidised layer has a relative density greater than or equal to 99%.

34. The part according to claim 31, wherein the deoxidised layer has a relative density greater than or equal to 99%.

35. The part according to claim 29, wherein the oxides are manganese oxides and/or mixed manganese and silicon oxides.

36. The part according to claim 29, which is a horological external part or a gemwork or jewellery article.

37. The part according to claim 36, wherein the external part is selected from the list consisting of a middle, a bottom, a bezel, a push-piece, a bracelet link, a bracelet, a tongue buckle, a dial, a hand, a crown and a dial index.

38. A watch, comprising the part according to claim 37.

39. A method for manufacturing an austenitic stainless-steel part, the method comprising: providing the powder according to claim 21, producing a blank comprising the powder, wherein the blank has substantially the form of the austenitic stainless-steel part, and sintering the blank in an atmosphere comprising a nitrogen carrier gas at a temperature of between 1000 and 1500° C. for a time of between 1 and 10 hours to cause a carbothermic reaction between oxides and the carbon present in the blank and to densify the blank.

40. The method according to claim 39, wherein the sintering takes place in two steps with a first step performed at a temperature of between 1000 and 1200° C. for a time of between 30 minutes and 5 hours, followed by a second step performed at a temperature of between 1200 and 1500° C. for a time of between 1 and 10 hours.

41. The method according to claim 39, wherein the blank is produced by injection moulding, extrusion, pressing, or additive manufacturing.

42. The method according to claim 39, further comprising a forging step after the sintering.

43. The method according to claim 39, further comprising a hot isostatic compression step after the sintering.

44. The method according to claim 39, further comprising, after the sintering, a surface transformation of the austenitic stainless steel into a surface of a ferritic or dual-phase ferritic+austenite structure, and a transformation of the surface of the ferritic or dual-phase ferrite+austenite structure into an austenitic structure, so as to form, on the surface of the part, a densified layer having a greater density than that of a core of the part, wherein the densified layer formation is achieved by using at least one of the following steps: fixing the temperature so that the part has a ferrite+austenite dual-phase or completely ferritic structure on the surface and the nitrogen and the carbon which stabilize the austenitic phase are allowed to diffuse in the solid and are released into the atmosphere; fixing the partial pressure of the nitrogen carrier gas, or operating under an atmosphere devoid of nitrogen, so as to reduce the quantity of nitrogen on the surface of the part by denitriding, and thus forming an austenite+ferrite or completely ferritic structure on the surface; and fixing the partial pressure of a carbon carrier gas so as to reduce the quantity of carbon on the surface of the parts by decarburisation or using a decarburising atmosphere, if the alloy already contains carbon, so that the part has an austenite+ferrite dual-phase or completely ferritic structure at equilibrium.

45. The method according to claim 44, wherein the carbon carrier gas is CO or CH.sub.4, and wherein the decarburising atmosphere is H.sub.2.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0014] Other features and advantages of the present invention will emerge from the reading of the following detailed description referring to the following figures.

[0015] FIG. 1 illustrates schematically the transition between the deoxidised layer and the remainder of the part according to the invention, and

[0016] FIGS. 2A and 2B show respectively a metallographic section of a part according to the prior art and of a part according to the invention.

DESCRIPTION OF THE INVENTION

[0017] The invention relates to an austenitic stainless-steel powder and more specifically an austenitic stainless-steel powder comprising nitrogen in order to reduce or even dispense with nickel, known for the allergenic character thereof. According to the invention, this austenitic stainless-steel powder includes a specific carbon content selected for optimising the carbothermic reaction on the surface of the part during sintering thereof. The invention also relates to a method for manufacturing, by powder metallurgy, mechanical parts with a technical and/or aesthetic function and more specifically of a decorative article. More particularly, the mechanical part may be a horological external part selected from the non-exhaustive list comprising a middle, a bottom, a bezel, a push-piece, a bracelet link, a bracelet, a tongue buckle, a dial, a hand, a crown and a dial index. It may also be a gemwork or jewellery article.

[0018] The nickel-free austenitic stainless-steel powder according to the invention comprises by weight: [0019] −10<Cr<25%, [0020] −5<Mn<20%, [0021] −1<Mo<5%, [0022] −0.05≤C≤0.11%, [0023] −0≤Si<2%, [0024] −0≤Cu<4%, [0025] −0≤N<1%, [0026] −0≤O<0.3%,
the balance consisting of iron and any impurities. Any impurities means elements the purpose of which is not to modify the property or properties of the alloy but the presence of which is unavoidable since they result from the powder manufacturing method. Any impurities such as B, Mg, Al, P, S, Ca, Sc, Ti, V, Co, Ni, Zn, Se, Zr, Nb, Sn, Sb, Te, Hf, Ta, W, Pb and Bi may in particular each be present in a concentration by mass of less than or equal to 0.5%. Within the meaning of the present invention, nickel-free austenitic stainless-steel therefore means an alloy not containing more than 0.5% as mass percentage of nickel. Advantageously, the nickel-free austenitic stainless-steel powder according to the invention furthermore has a diameter D90 of less than or equal to 150 μm.

[0027] Preferentially, the nickel-free austenitic stainless-steel powder according to the invention comprises by weight: [0028] −15<Cr<20%, [0029] −8<Mn<14%, [0030] −2<Mo<4%, [0031] −0.05≤C≤0.11%, [0032] −0≤Si<1%, [0033] −0≤Cu<0.5%, [0034] −0≤N<1%, [0035] −0≤O<0.2%,
the balance consisting of iron and any impurities as aforementioned.

[0036] More preferentially, the nickel-free austenitic stainless-steel powder according to the invention comprises by weight: [0037] −16.5≤Cr≤17.5%, [0038] −10.5≤Mn≤11.5%, [0039] −3≤Mo≤3.5%, [0040] −0.05≤C≤0.11%, [0041] −0≤Si≤0.6%, [0042] −0≤Cu≤0.5%, [0043] −0≤N<1%, [0044] −0≤O<0.2%,
the balance consisting of iron and any impurities as aforementioned.

[0045] The method for manufacturing the part consists in producing, by means of the aforementioned metal powder, a blank having substantially the form of the part to be manufactured, and then sintering this blank. The blank may be produced by injection moulding (MIM, standing for metal injection moulding), pressing, extrusion or additive manufacturing. More precisely, in the case of injection moulding, the blank may be produced by means of a mixture, also referred to as feedstock, comprising the metallic powder and an organic binder system (paraffin, polyethylene, etc.). Next, the feedstock is injected and the binder is eliminated by dissolving in a solvent and/or by thermal degradation.

[0046] The blank is sintered in an atmosphere comprising a nitrogen carrier gas (N.sub.2 for example) at a temperature of between 1000 and 1500° C., preferably at a temperature of between 1100 and 1400° C., even more preferentially at a temperature of between 1200 and 1300° C., for a time of between 1 and 10 hours, preferably for a time of between 1 and 5 hours. The characteristics of the sintering cycle, particularly the temperature and the partial pressure of nitrogen, are dependent in particular on the composition of the alloy and are fixed so as to obtain a completely austenitic structure after sintering. It will be stated that the nitrogen content of the part can be adjusted by changing the nitrogen partial pressure of the atmosphere. In addition to the nitrogen, other gases may be used in the sintering atmosphere, such as hydrogen and argon.

[0047] The sintering cycle may be implemented in a single step in the aforementioned temperature and time ranges. It can also be envisaged implementing the sintering cycle in two steps with a first step in a range of temperatures between 1000 and 1200° C. for a time of between 30 minutes and 5 hours, followed by a second step in a range of temperatures of between 1200 and 1500° C., preferably between 1200 and 1300° C., for a time of between 1 and 10 hours. This first stage makes it possible to optimise the carbothermic reduction of the manganese oxides and/or of the mixed oxides of manganese and silicon and thus to obtain a deeper deoxidised layer.

[0048] After sintering the nickel-free austenitic stainless-steel powder according to the invention, supplementary heat treatments may be implemented on the sintered components such as for example a hot isostatic compression treatment to eliminate any residual porosity to the maximum possible extent.

[0049] A supplementary heat treatment may also consist in eliminating the residual surface porosity of the sample. Thus, in accordance with the application EP17202337.6, the supplementary heat treatment may consist in treating the sintered part to transform the austenitic structure into a ferritic or dual-phase ferrite+austenite structure on the surface of the part, and next to once again transform the ferritic or dual-phase ferrite+austenite structure into an austenitic structure so as to form a denser layer on the surface of the part. Moreover, after the sintering step, the part may be subjected to a finishing treatment by stamping, also termed forging.

[0050] After the sintering step, and before the finishing treatments, the parts may also be subjected to a surface densification treatment by forming ferrite from the surface. This is because since the diffusion of the alloy elements in the centred cubic structure of the ferrite is approximately two orders of magnitude greater than the diffusion of the elements in the centred face cubic structure of the austenite, the densification is much great when ferrite is present. To form the ferrite on the surface of the parts, several solutions are possible:

[0051] A. Fixing the temperature so that the alloy has on the surface a ferrite+austenite dual-phase or completely ferritic structure. On the surface, the nitrogen and the carbon that stabilise the austenitic phase diffuse in the solid and can be released into the atmosphere, which facilitates the formation of ferrite, in which the solubility of the carbon and nitrogen is much lower than in the austenite phase. At the core, where the concentration of nitrogen and carbon has not been reduced by diffusion through the surface, the composition of the alloy remains unchanged since the porosity was closed during the first step. Preferably, the temperature will be fixed so as to have a ferrite+austenite dual-phase or completely ferritic structure on the surface and a completely austenitic structure at the core, but it is possible, depending on the alloy and the parameters used during these first two sintering steps, that a little ferrite may also form in the core during this step.

[0052] B. Fixing the partial pressure of the nitrogen carrier gas, or even operating under an atmosphere devoid of nitrogen, so as to reduce the quantity of nitrogen on the surface of the parts by denitriding and thus form an austenite+ferrite or completely ferritic structure on the surface. In the core, where the nitrogen concentration has not been reduced by diffusion through the surface, the composition of the alloy remains unchanged and the structure stays completely austenitic.

[0053] C. Fixing the partial pressure of the carbon carrier gas, which is for example CO or CH.sub.4, so as to reduce the quantity of carbon on the surface of the parts by decarburisation or more simply using a decarburising atmosphere, for example with H.sub.2, if the alloy already contains carbon. Once again, the atmosphere must be selected so that the alloy has an austenite+ferrite dual-phase or completely ferritic structure at equilibrium. In the core, where the concentration of carbon has not been reduced by diffusion through the surface, the composition of the alloy remains unchanged and the structure stays completely austenitic.

[0054] D. Using any Combination of Solutions A, B and C.

[0055] In summary, during this stage, the aim is to form ferrite on the surface of the parts so as to obtain a very dense layer. As this ferrite forms in particular by denitriding and/or decarburisation, which are phenomena of diffusion in the solid, the thickness of this densified layer containing ferrite, for a given composition, depends on the temperature, the duration of the stage and the partial pressures of the nitrogen and/or carbon carrier gases. In the core, where the concentration of nitrogen and carbon has not been reduced by diffusion through the surface, the composition and therefore the structure remain unchanged since the porosity was closed during the first step. However, if the temperature is different between the first and the second step, it is possible that a little ferrite also forms in the core although the composition remains unchanged.

[0056] The parts obtained with the nickel-free austenitic stainless-steel powder according to the invention have, after sintering, a deoxidised surface layer the thickness of which is at least 200 μm, this thickness preferably being greater than or equal to 250 μm and, more preferentially, greater than or equal to 300 μm. In this deoxidised layer, the diameter of the oxides that are substantially circular in shape is less than 2 μm and the total surface or volume fraction of the oxides is less than 0.1%. FIG. 1 illustrates schematically the transition between the deoxidised layer 1 of thickness e and the remainder 2 of the part 3 including oxides 4 with a greater size and surface fraction. The demarcation line between the so-called deoxidised layer and the rest of sintered part and thus the thickness of the deoxidised layer can be determined easily under optical microscopy from one or more metallographic sections. Likewise, the surface or volume fraction of oxides can be determined by analysing optical microscopy images of polished sections of the part. The surface fraction corresponds to the ratio between the surface occupied by the oxides and the total surface area of the deoxidised layer analysed. The volume fraction can be deduced from the surface fraction by supposing that the oxides are circular in shape. It will be specified that this transition between the deoxidised layer and the rest of the sintered part can be observed only if the parts have at least on the surface an almost zero porosity, i.e. a relative density greater than or equal to 99%. This is because, when high porosity is present, it will be difficult to differentiate the oxides from the pores under optical microscopy.

[0057] To illustrate the effect of the carbon on the deoxidation of the nickel-free austenitic stainless-steel powders, parts formed by MIM (metal injection moulding) from two powders (D90=16 μm) having different carbon concentrations were sintered at the same time in the same furnace. Metallographic sections were produced to measure and compare the thickness of the deoxidised layer between the two parts. Sintering was implemented in a reducing atmosphere comprising 75% N.sub.2 and 25% H.sub.2 at a pressure of 850 mbar with a first stage at 1200° C. for 3 hours followed by a second stage at 1300° C. for 2 hours. A comparative sample was produced by means of a powder comprising 0.03% by weight carbon. More precisely, this is an Fe-17Cr-11Mn-3Mo-0.5Si-0.1O-0.5N-0.03C (% by weight) powder. A view under optical microscopy of a cross-section of the sample after polishing is shown in FIG. 2A. A transition line between the deoxidised layer 1 and the remainder 2 of the sample is clearly observed. The thickness of the deoxidised layer is approximately 196 μm. Measurements performed on several sections showed that the values are substantially similar from one section to another.

[0058] A sample according to the invention was produced by means of a powder comprising 0.07% by weight carbon. More precisely, this is an Fe-17Cr-11Mn-3Mo-0.5Si-0.1O-0.5N-0.07C (% by weight) powder. A view under optical microscopy of a cross-section of the sample after polishing is shown in FIG. 2B. A transition line between the deoxidised layer 1 and the remainder 2 of the sample is also clearly observed. The thickness of the deoxidised layer is appreciably greater, with a value of approximately 335 μm.

[0059] Tests were also performed with a powder comprising 0.18% by weight carbon, i.e. an Fe-17Cr-11Mn-3Mo-0.5Si-0.1O-0.5N-0.18C (% by weight) powder. The decarburisation resulting from the reaction of the carbon with the hydrogen of the atmosphere caused very great differences in carbon concentration within the same load, i.e. starting from the same powder composition, with differences with regard to the microstructure of the parts as a consequence.

[0060] It goes without saying that the present invention is not limited to the above description and that various modifications and simple variants can be envisaged without departing from the scope of the invention as defined by the accompanying claims. It will have been understood from the above that the present invention relates to the sintering of parts by means of nickel-free austenitic stainless-steel powders and that the aim thereof is to procure such parts that have a surface layer as thick as possible devoid of its oxides to the maximum extent. Nevertheless, such steels comprise high manganese concentrations. However, manganese is a component having a strong affinity for oxygen and the oxides that it forms can be eliminated only at temperatures of around the sintering temperatures. However, at the sintering temperature, the porosity closes rapidly, which makes it more difficult to eliminate the oxides wherein the manganese is included. Faced with this problem, the Applicant has shown that nickel-free austenitic stainless-steel compositions containing a concentration of carbon at least equal to 0.05% by weight and not exceeding 0.11% by weight made it possible to obtain sintered parts with a surface layer having a lower concentration of oxides and the thickness of which is greater than what has been observed on sintered parts obtained by means of known nickel-free austenitic stainless steels. It has in fact been observed that, for carbon concentrations of between 0.05% and 0.11% by weight, the presence of carbon makes it possible to deoxidise the sintered parts to a greater depth while avoiding a problematic decarburisation, this deoxidation being further reinforced by the fact that it can be implemented at temperatures lower than the sintering temperatures, for which the density is still low and the pores relatively open.