STEEL SUITABLE FOR PLASTIC MOULDING TOOLS

Abstract

A pre-alloyed powder having a composition consisting of, in weight % (wt. %): C, 0.02-0.04; Si, 0.1-0.4; Mn, 0.1-0.5; Cr, 11-13; Ni, 7-10; Cr+Ni, 19-23; Mo, 1-25; Al, 1.4-2.0; N, 0.01-0.75. Optionally, the pre-alloyed powder contains: Cu, 0.05-2.5; B, 0.002-2.0; S, 0.01-0.25; Nb, 0.01 max; Ti, 2 max; Zr, 2, max; Ta, 2 max; Hf, 2 max; Y, 2 max; Ca, 0.0003-0.009; Mg, 0.01 max; O, 0.003-0.80; and REM, 0.2 max. Fe and impurities comprise the balance.

Claims

1. A pre-alloyed powder having a composition consisting of, in weight % (wt. %): TABLE-US-00010 Min Max C  0.02  0.04 Si  0.1  0.4 Mn  0.1  0.5 Cr 11 13 Ni  7 10 Cr + Ni 19 23 Mo  1 25 Al  1.4  2.0 N  0.01  0.75 optionally Cu  0.05  2.5 B  0.002  2.0 S  0.01  0.25 Nb  0.01 Ti  2 Zr  2 Ta  2 Hf  2 Y  2 Ca  0.0003  0.009 Mg  0.01 O  0.003  0.80 REM  0.2, and Fe and impurities balance.

2. The pre-alloyed powder according to claim 1, fulfilling at least one of the following requirements: TABLE-US-00011 Min Max C  0.025  0.035 Si  0.15  0.40 Mn  0.15  0.50 Cr 11.5 12.5 Ni  8.5 10.0 Cr + Ni 20 23 Mo  1.0  2.0 Al  1.5  1.9 N  0.01  0.15, and S  0.01  0.03.

3. The pre-alloyed powder of claim 1, not being alloyed with S, fulfilling at least one of the following requirements: TABLE-US-00012 Min Max N  0.01  0.04 Cu  0.5  2.1 Cr + Ni 20.5 22.0 Mo  1.2  1.6 S  0.01 Ti  0.01 Zr  0.01 Ta  0.01 Hf  0.01, and Y  0.01.

4. The pre-alloyed powder according to claim 1, fulfilling the following requirements: TABLE-US-00013 Min Max C  0.025  0.035 Si  0.15  0.40 Mn  0.15  0.50 Cr 11.5 12.5 Ni  8.5 10.0 Cr + Ni 20 23 Mo  1.0  2.0 Al  1.5  1.9, and N  0.01  0.15.

5. The pre-alloyed powder according to claim 5, wherein powder particles of the pre-alloyed powder are produced by gas atomizing, wherein at least 80% of the powder particles have a size in the range of 5 to 150 μm, and wherein the pre-alloyed powder fulfils at least one of the following requirements: TABLE-US-00014 Powder size distribution (in μm):  5 ≤ D10 ≤35 20 ≤ D50 ≤55 D90 ≤80 Mean sphericity, SPHT ≥0.85 Mean aspect ratio, b/l ≥0.85,  wherein SPHT=4πA/P.sup.2, where A is the measured area covered by a particle projection and P is the measured perimeter/circumference of the particle projection and the sphericity (SPHT) is measured by a Camsizer in accordance with ISO 9276-6, and wherein b is the shortest width of the particle projection and 1 is the longest diameter.

6. The pre-alloyed powder according to claim 5, wherein at least 90% of the powder particles have a size in the range of 10 to 100 μm and wherein the powder fulfils at least one of the following requirements: TABLE-US-00015 Powder size distribution (in μm): 10 ≤ D10 ≤30 25 ≤ D50 ≤45 D90 ≤70 Mean sphericity, SPHT ≥0.90, and Mean aspect ratio, b/l ≥0.88.

7. The pre-alloyed powder according to claim 1, wherein a maximum particle size of the powder is 500 μm.

8. The pre-alloyed powder according to claim 1, wherein, for additive manufacturing, powder particles of the pre-alloyed powder have a particle size in a range of 5-150 μm.

9. The pre-alloyed powder according to claim 8, wherein the particle size is in a range of 10-100 μm.

10. The pre-alloyed powder according to claim 9, wherein a mean of the particle size is in a range of 25-45 μm.

11. The pre-alloyed powder according to claim 1, wherein, for metal injection molding, powder particles of the pre-alloyed powder have a particle size with a maximum of 50 μm.

12. The pre-alloyed powder according to claim 1, wherein, for thermal spraying, powder particles of the pre-alloyed powder have a particle size in a range of 32-125 μm.

13. The pre-alloyed powder according to claim 1, wherein, for overlay welding, powder particles of the pre-alloyed powder have a particle size in a range of 45-250 μm.

Description

DETAILED DESCRIPTION

[0046] The importance of the separate elements and their interaction with each other as well as the limitations of the chemical ingredients of the claimed alloy are briefly explained in the following. All percentages for the chemical composition of the steel are given in weight % (wt. %) throughout the description. The amount of hard phases is given in volume % (vol. %). Upper and lower limits of the individual elements can be freely combined within the limits set out in the claims.

[0047] Carbon (0.02-0.04%)

[0048] Carbon is effective for improving the strength and the hardness of the steel. However, if the content is too high, the steel may be difficult to machine after cooling from hot working. C should be present in a minimum content of 0.02%, preferably at least 0.025%. The upper limit for carbon is 0.04%, preferably 0.035%. The nominal content is 0.030%.

[0049] Silicon (0.1-0.4%)

[0050] Silicon is used for deoxidation. Si is also a strong ferrite former. Si is therefore limited to 0.45%. The upper limit may be 0.40, 0.35, 0.34, 0.33, 0.32, 0.31, 0.30, 0.29 or 0.28%. The lower limit may be 0.12, 0.14, 0.16, 0.18 or 0.20%. Preferred ranges are 0.15-0.40% and 0.20-0.35%.

[0051] Manganese (0.1-0.5%)

[0052] Manganese contributes to improving the hardenability of the steel. If the content is too low then the hardenability may be too low. At higher sulphur contents manganese prevents red brittleness in the steel. Manganese shall therefore be present in a minimum content of 0.10%, preferably at least 0.15, 0.20, 0.25 or 0.30%. The steel shall contain maximum 0.5% Mn, preferably maximum 0.45, 0.40 or 0.35%. A preferred range is 020-0.40%.

[0053] Chromium (11-13%)

[0054] Chromium is to be present in a content of at least 11% in order to make the steel stainless and to provide a good hardenability in larger cross sections during the heat treatment. However, high amounts of Cr may lead to the formation of high-temperature ferrite, which reduces the hot-workability. The lower limit may be 11.2, 11,4, 11.6 or 11.8%. The upper limit Cr is 13% and the amount of Cr may be limited or 12.8, 12.6, 12.4 or 12.2%. A preferred range is 11.5-12.5%.

[0055] Nickel (7-10%)

[0056] Nickel is an austenite stabilizer, which supresses the formation of delta ferrite. Nickel gives the steel a good hardenability and toughness. Nickel is also beneficial for the machinability and polishability of the steel. Nickel is essential for the precipitation hardening as it together with Al form minute intermetallic NiAl-particles during aging. However, excess Ni additions may result in too high an amount of retained austenite. The lower limit may therefore be 7.2, 7.4, 7,6, 7.8, 8.0, 8.2, 8.4, 8.6, 8.8, 9.0 or 9.1%. The upper limit may be 10.0, 9.8, 9.6 or 9.4%. A preferred range is 8.5-10 or 9.0-9.5%.

[0057] Chromium+Nickel (19-23%)

[0058] In order to obtain an optimized strength and toughness it is desirable, that the total content of Cr and Ni is 19-23%. The lower amount may be 19.5, 20.0, 20,5 20.6, 20.7, 20.8 or 20.9%. The upper limit may be 22.8, 22.7, 22.6, 22.5, 22.4, 22.3, 22.2, 22.1, 22.0, 21.9, 21.8, 21.7, 21.6, 21.5, 21.4 or 21.3% A preferred range is 20.5-22.0%, preferably 20.5-22.0, most preferably 20.8-21.7%.

[0059] Molybdenum (1-25%)

[0060] Mo in solid solution is known to have a very favourable effect on the hardenability. Molybdenum is a strong carbide forming element and also a strong ferrite former. A controlled amount of Mo in the matrix counteracts the formation of reverted austenite during aging. For this reason the amount of Mo should be 1-2%. The lower limit may be 1.1, 1.2, 1.3 or 1.4%. The upper limit may be 1.9, 1.8, 1.7, 1.6, or 1.5%.

[0061] Molybdenum can also be used in higher amounts in combination with Boron in order to obtain a desired amount of hard borides of the type M.sub.2M′B.sub.2, where M and M′ stand for metals. In the present case M is Mo and M′ is Fe. However, the boride may contain minor amounts of other elements such as Cr and Ni. However, in the following boride will simply be referred to as Mo.sub.2FeB.sub.2.

[0062] The maximum content of molybdenum is therefore 25%. However, when using high Mo contents for forming borides, then the contents of Mo and B should be balanced such that the content of Mo in solid solution in the matrix remains in the range of 1-2%.

[0063] Aluminium (1.4-2.0%)

[0064] Aluminium is used for precipitation hardening in combination with Ni. The upper limit is restricted to 2.0% in order to avoid the formation of too much delta ferrite. The upper limit may be 1.95, 1.90, 1.85, 1.80 or 1.75%. The lower limit may be 1.45, 1.50, 1.55, 1.60 or 1.65%.

[0065] Nitrogen (0.01-0.75%)

[0066] Nitrogen is a strong austenite former and also a strong nitride former. N may be used in in an amount of up to 0.75% in Nitride Dispersion Strengthened (NDS) alloys. NDS alloys can be produced with basically the same techniques as ODS alloys.

[0067] However, for non-NDS applications the nitrogen content may be restricted to 0.15%.

[0068] The inventors of the present invention have surprisingly found that nitrogen can be deliberately added to the steel without impairing the polishability, provided that the size of at least 80 vol. % of AlN particles present in the matrix is limited to not more than 4 μm. Preferably, the said size may restricted to 3 μm, 2 μm or even 1 μm. The small size of the nitrides also results in a grain refining effect. The lower limit for N may then be 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019 or 0.02%. The upper limit may be 0.14, 0.12, 1.10, 0.08, 0.06, 0.05, 0.04 or 0.03%. However, if the material is in powder form and intended for production of moulds or dies by the use of AM, then it is to be considered that a too high nitrogen content may result in too high an amount of retained austenite. Accordingly, for applications where the amount of austenite in structure is to be limited, then the upper limit of nitrogen can be set to 0.040, 0.035, 0.030, 0.025 or 0.020%.

[0069] Copper (0.05-2.5%)

[0070] Cu is an optional element, which may contribute to increase the hardness and the corrosion resistance of the steel. The ε-Cu phase formed during aging not only reinforces the steel by precipitation hardening, but also affects the precipitation kinetics of the intermetallic phases. In addition thereto, it would appear that additions of Cu result in a slower growth of the intermetallic phase (NiAl) at higher working temperatures. The upper limit for Cu may be 2.3, 2.1, 1.9,1.7, 1.5, 1.3, 1.1, 0.9, 0.7, 0.5, 0.3 or even 0.2%. The lower limit for Cu may 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9%.

[0071] However, it is not possible to extract copper from the steel once it has been added. This makes the scrap handling more difficult. For this reason, copper is an optional element and needs not be added. The maximum allowable impurity content can be 0.2, 0.15 or 0.10%.

[0072] Boron (0.002-2.0%)

[0073] Boron is an optional element that can be used in small amounts in order to increase the hardenability and to improve the hot workability of the stainless steel. The upper limit may then be set to 0.007, 0.006, 0.005 or 0.004%.

[0074] Boron can also be used in higher amounts as a hard phase-forming element. B should then be at least 0.2% so as to provide the minimum amount of 3% hard phase Mo.sub.2FeB.sub.2. The amount of B is limited to 2.0% for not making the alloy too brittle. The lower limit may be set to 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4 or 1.5%. The upper limit may be set to 1.4, 1.5, 1.6, 1.7, 1.8 or 1.9%.

[0075] Sulphur (0.01-0.25%)

[0076] S may optionally be added in order to improve the machinability of the steel. If S is used for this purpose, then S is deliberately added to the steel in an amount of 0.01-0.25%. At higher sulphur contents there is a risk for red brittleness. Moreover, high sulphur contents may have a negative effect on the fatigue properties and on the polishability of the steel. The upper limit shall therefore be 0.25%, preferably 0.1% most preferably 0.03%. A preferred range is 0.015-0.030%. However, if not deliberately added, then the amount of S is restricted to impurity contents as set out below.

[0077] Niobium (≤0.01%)

[0078] Nb is a strong carbide and nitride former. The content of this elements should therefore be limited in order to avoid the formation of undesired carbides and nitrides. The maximum amount of Nb is therefore 0.01%. Nb is preferably limited to 0.005%.

[0079] Ti, Zr, Ta, Hf and Y (≤2%)

[0080] These elements may form compounds with C, B, N and/or O. They can be used to produce an Oxide Dispersion Strengthened (ODS) or a Nitride Dispersion Strengthened (NDS) alloy. The upper limit is then 2% for each of these elements. The upper limit may be 1.5, 1.0, 0.5 or 0.3%. However, if these elements are not deliberately added for making an ODS alloy, then the upper limit may be 0.1, 0.05, 0.01 or 0.005%.

[0081] Ca, Mg, O and REM (Rare Earth Metals)

[0082] These elements may optionally be added to the steel in the claimed amounts for different reasons. These elements are commonly used to modify the non-metallic inclusion and/or in order to further improve the machinability, hot workability and/or weldability of the steel. The oxygen content is then preferably limited to 0.03%. However, if Oxygen is used in order to form an Oxide Dispersion Strengthened (ODS) alloy, then the upper limit may be as high as 0.80%. The oxide can be admixed to a powder of be formed in-situ, e.g. by gas atomizing, in particular by using Gas Atomizing Reaction Synthesis (GARS) or during an Additive Manufacturing (AM) method, in particular through atmospheric reaction in Liquid Metal Deposition (LMD).

[0083] Impurity Elements

[0084] P, S and O are the main impurities, which may have a negative effect on the mechanical properties of the steel. P may therefore be limited to 0.05, 0.04, 0.03 0.02 or 0.01%.

[0085] If sulphur is not deliberately added, then the impurity content of S may be limited to 0.05, 0.04, 0.003, 0.001, 0.0008, 0.0005 or even 0.0001%.

[0086] The alloys of the present invention can be produced by any suitable method. Non-limiting examples of suitable methods include: [0087] a) Conventional melt metallurgy followed by casting and hot working. [0088] b) Powder Metallurgy (PM).

[0089] PM powders can be produced by conventional gas- or water- atomization of pre-alloyed steel. The powders can be used for thermal spraying, overlay welding, additive manufacturing (AM) or Metal Injection Moulding (MIM).

[0090] However, if the powder shall be used for AM, then gas-atomization is the preferred atomization method, because it is important to use a technique, that produces powder particles having a high degree of roundness and a low amount of satellites. In particular, the close-coupled gas atomization method can be used for this purpose.

[0091] Powders produced by PM can be consolidated by Hot Isostatic Pressing (HIP) and/or by extrusion. The materials can be used as compacted or after subsequent hot working.

[0092] The maximum size of the powder particles should normally be limited to 500 μm and, depending on the intended use, specific powder fractions may be used. For AM the maximum size range is 5-150 μm, and the preferred size range is 10-100 μm with a mean size of about 25-45 μm. For MIM the preferred maximum size is 50 μm, for thermal spraying preferred ranges is 32-125 μm and 20-90 μm and for overlay welding the preferred range is 45-250 am.

[0093] The AM methods of prime interest are Liquid Metal Deposition (LMD), Selective Laser Melting (SLM) and Electron Beam (EB) melting. The powder characteristics are also of importance for AM. The powder size distribution measured with a Camsizer according to ISO 4497 should fulfil the following requirements (in m): [0094] 5≤D10≤35 [0095] 20≤D50≤55 [0096] D90≤80

[0097] Preferably, the powder should fulfil the following size requirements (in μm): [0098] 10≤D10≤30 [0099] 25≤D50≤45 [0100] D90≤70

[0101] Even more preferred is that the coarse size fraction D90 is limited to ≤60 μm or even≤55 μm.

[0102] The sphericity of the powder should be high. The sphericity (SPHT) can be measured by a Camsizer and is definined in ISO 9276-6. SPHT=4πA/P.sup.2, where A is the measured area covered by a particle projection and P is the measured perimeter/circumference of a particle projection. The mean SPHT should be at least 0.80 and can preferably be at least 0.85, 0.90, 0.91, 0.92 0.93, 0.94 or even 0.95. In addition, not more than 5% of the particles should have a SPHT≤0.70. Preferably said value should be less than 0.70, 0.65, 0.55 or even 0.50. In addition to SPHT, the aspect ratio can be used in the classifying of the powder particles. The aspect ratio is defined as b/l, wherein b is the shortest width of the particle projection and 1 is the longest diameter. The mean aspect ratio should preferably be at least 0.85 or more preferably 0.86, 0.87, 0.88, 0.89, or 0.90.

[0103] The inventive alloy is a precipitation hardenable steel having a martensitic matrix, which may comprise other microstructural constituents such as delta ferrite and austenite. The austenite may comprise retained and/or reverted austenite.

[0104] The inventive alloy can be hardened by aging in the temperature range of 425-600° C. to a desired hardness in the range of about 34-56 HRC.

[0105] The amount of delta ferrite should preferably be restricted to ≤7 vol. %, preferably ≤5 vol. %, more preferably ≤3 vol. % for not impairing the hot workability.

[0106] The austenite consists of retained and/or reverted austenite, in the following, austenite. Pre-alloyed powder produced by atomizing may contain substantial amounts of austenite but the amount of austenite in finished parts may be reduced to a lower level by solution heat treatment and/or ageing, if there is a fear that the austenite content is so high that it could lead to problems, e.g., with respect to dimensional stability. The amount of austenite in the microstructure may therefore be limited to 22, 20, 18, 16, 14, 12, 10, 8, 6, 4 or 2 vol. %. However, austenite has a positive effect on the mechanical properties of the material, in particular the toughness, and is therefore a desired microstructural constituent in many applications.

[0107] The inventive alloy can be hardened by aging in the temperature range of 425-600° C. to a desired hardness in the range of about 34-56 HRC.

Example 1

[0108] Conventional Processing.

[0109] An alloy was produced in conventional way by induction melting, casting and forging. The alloy had the composition (in wt. %): C: 0.03, Si: 0.3, Mn: 0.2, Cr: 12.0, Ni: 9.3, Mo: 1.4, Al: 1.7, N: 0.017, balance Fe and impurities. The inventive alloy was compared to a commercially available steel of the type steel PH 13-8Mo (Böhler N709). The comparative alloy had the following nominal composition (in wt. %): C: 0.03, Si: ≤0.08, Mn: ≤0.08, Cr: 12.7, Ni: 8.1, Mo: 2.2, Al: 1.1, balance Fe.

[0110] The inventive alloy differs from the comparative steel mainly in higher amounts of Mn, Si, Al and N and lower amounts of Mo dissolved in the matrix.

[0111] The inventive steel and the comparative steel were both hardened to 50 HRC and subjected to un-notched impact testing using a standard specimen size of 10 mm×10 mm×55 μmm. The inventive alloy was found to have an un-notched impact strength of 255 J, whereas the impact strength of the known steel was only 120 J.

[0112] The reason for this difference is presently not fully understood. However, it would appear that small differences in the matrix composition lead to differences in the precipitation kinetics such that the type and distribution of the precipitates are different. The lower content of Mo may also result in a reduced risk of the formation of reverted austenite during the heat treatment and thereby also a reduced risk for the precipitation of Mo— and Cr-rich carbides. The addition of Al may result in a grain refinement that is beneficial for the toughness. Hence, it would appear plausible that one or more of these factors in combination result in an improved toughness of the inventive steel.

Example 2

[0113] Powder Production.

[0114] A base alloy having the composition similar to the alloy of Example 1 was produced in conventional way by induction melting, casting and forging. A ESR-remelted bar of the alloy was subjected to vacuum induction melting and closed couple gas atomization processing in order to obtain a powder suitable for AM processing. The gas to metal weight ratio during the atomization was 3:1. In order to avoid oxygen contamination, high purity (6N) nitrogen gas was used for the atomization. The particles obtained were examined with respect to size and shape by dynamic image processing according to ISO 13322-2. The powder was sieved in order to remove particles larger than 50 μm and smaller than 20 μm. The sieved powder was found to have the following size distribution: D10: 23 μm, D50: 34 μm and D90: 49 μm. The mean sphericity was 0.95 and the mean aspect ratio was 0.93. The powder had an oxygen content of 0.021% and a nitrogen content of 0.013%. The morphology of this powder was examined by Scanning Electron Microscopy (SEM and the powder was found to be almost fully spherical with a very low amount of satellites.

[0115] The Apparent Density (AD) was 4.3 g/cm.sup.3 and the Tap Density (TD) was 5.2 4.3 g/cm.sup.3.

[0116] Accordingly, the powder produced would be expected to be suitable for AM processing.

Example 3

[0117] Additive Manufacturing.

[0118] The suitability of this powder for AM was tested by building a part by SLM in an EOS M290 system using the following processing parameters: Layer thickness 30 μm, laser power 170 W, scan speed 1250 μmm/s, hatch distance 0.10 μmm. The hatch mode was stripes.

[0119] The as-built samples thus obtained had a density of 99.4% of the theoretical density (TD) and a hardness of 35 HRC at room temperature. The amount of austenite was about 23% in the sample. An examination in SEM using EBSD revealed that the austenite phase was extremely fine in size and dispersed at the boundaries of the martensite blocks.

[0120] The influence of the thermal treatment of the built sample was examined. After ageing at 525° C. for 4 h the amount of austenite was reduced to 16 vol. %. However, an intermediate solution treatment at 850° C. for 30 μminutes reduced the amount of austenite to 4 vol. %. The hardness of the solution annealed and aged sample was 50 HRC.

[0121] Hence, the solution annealed and the aged sample have the same hardness as the conventionally produced sample of Example 1. The reason for this might be, that the conventionally produced sample also has an austenite content of about vol. 4%. It was therefore decided to compare the mechanical properties of the solution treated and aged AM sample with the properties of the conventionally produced steel in Example 1.

[0122] The strength and elongation values were measured by uniaxial tensile testing and the impact toughness was measured by the Charpy V-notch test. The results are given below in Table 1. It can be seen that the material produced by AM has a considerably higher Impact toughness than the conventionally produced material and that the other mechanical values are comparable.

TABLE-US-00009 TABLE 1 Results of the mechanical testing. Impact Rm Rp.sub.02 Elongation toughness Sample (MPa) (MPa) A5 (%) (J) Conv. (EX. 1) 1700 1600 10  3 (S-T)  6 (L-T) AM (EX. 3). 1700 1640  9 19 Perpendicular to build plate AM (EX.3) 1650 1560 10 22 Parallel to build plate

[0123] The corrosion and wear testing revealed that the two materials are equally good. The polishability was also examined and it was found that the AM material exhibits an excellent polishability. It was possible to achieve a comparably good high quality gloss surface for both materials, although the oxygen content was about 10 times higher for the AM material. However, surprisingly it was found that the AM material was much easier to polish in that the AM-material could be polished to the same gloss with fewer steps in a shorter time.

[0124] The steel of the present invention is useful in large moulds or dies requiring a good corrosion resistance and a uniform hardness. The steel of the present invention is particular for making articles by AM.