Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C33/00—Making ferrous alloys
  • C22C33/02—Making ferrous alloys by powder metallurgy
  • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
  • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
  • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/56—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.7% by weight of carbon
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process

Definitions

• the invention relates to a material comprising an iron based alloy containing C, B, Cr, Ni, Si and Mo.
• the material or alloy may be used for producing formed products, casted products, coatings, parts, coated parts, wires, electrodes, powders and powder mixtures.
• EP 1 788 104 A1 discloses a material for producing parts or coatings adapted for high wear and friction-intensive applications.
• the material comprises a nickel based alloy with the addition of hard particles such as WC.
• Iron-based self-fluxing alloys are an alternative group of lower cost materials and many materials have been found that exhibit reasonable wear resistance.
• Such an iron-based alloy is known from DE 197 33 306 C1. It discloses an iron- based thermal coating material.
• the alloy is used as additive material, in the form of a mixture, a gas atomized alloy, an agglomerated metal powder, a core-filled wire, a core-filled strip, a sintered strip or a cast sheathed rod electrode and used for thermal coating of components exposed to friction.
• a preferred composition of the alloy for applying a low friction and low wear layer for a sliding component pairing with good fatigue and impact resistance is as follows (by weight): 20-25% Mn, 13-20% Cr, 0.1 -2% Ni, 3-6% W, 0.1 -0.15% C, 1.5-2.5% B, balance Fe.
• An- other preferred composition of the alloy for applying a low friction layer with high abrasion resistance and higher thermal loading capacity is as follows (by weight): 18-25% Mn, 13-25% Cr, 0.1 -2% Ni, 3-5% W, 0.1 -0.15% C, 4-6% B, balance Fe.
• DE 199 01 170 A1 discloses another iron alloy with high carbon, boron, vanadium, chromium, molybdenum and nickel contents.
• the following composition is proposed (by weight): 2.0-4.0 % C, 2.0-4.5 % B, 0.5-3.5 % Si, 6.0-15.0 % Cr, 1.5- 7.5 % Mo, 6.0-14.0 % V, 0-3.0 % W, 0-1.5 % Mn, 0-2.0 % Cu, 2.0-7.0 % Ni, balance Fe and impurities.
• the alloy is used for internal hard facing of metal cylinders by centrifugal casting or hot isostatic pressing.
• CA 2 416 950 A1 discloses a material for the manufacture of parts and tools for use at elevated temperature, comprising an iron-based alloy comprising C, Si, Mn, Cr, Ni and N in certain concentrations.
• the alloy is cold formed to a hardness of at least 230 HB.
• the object is achieved by a material comprising an alloy containing 13 to 16 percent by weight nickel (Ni), 13.5 to 16.5 percent by weight of chromium (Cr), 0.5 to 3 percent by weight of molybdenum (Mo), 3.5 to 4.5 percent by weight of silicon (Si), 3.5 to 4 percent by weight of boron (B), 1.5 to 2.1 percent by weight of carbon ( C) and 0.2 to 0.5 percent by weight of copper (Cu), balance iron (Fe).
• Ni nickel
• Cr chromium
• Mo molybdenum
• Si silicon
• B boron
• Cu copper
• Fe balance iron
• the material comprises an iron based alloy with the further components C, B, Cr, Ni, Si and Mo.
• the material includes the pure alloy and coatings with a composition of the alloy.
• the alloy contains only C, B, Cr, Ni, Si and Mo as major components besides the main component Fe. Generally the alloy contains traces or minor amounts of other elements, which are generally common impurities. Less preferred, the alloy may contain other elements in concentrations, which do not alter its chemical behavior significantly. Such optional additives are named accompanying elements.
• the alloy is useful for producing either coatings on a metal substrate or for producing formed products, casted products, coatings, parts, coated parts, wires, electrodes or powders.
• the alloy consists of 13 to 16 percent by weight (wt.-%) nickel (Ni), 13.5 to 16.5 percent by weight of chromium (Cr), 0.5 to 3 percent by weight of molybdenum (Mo), 3.5 to 4.5 percent by weight of silicon (Si), 3.5 to 4 percent by weight of boron (B) and 1.5 to 2.1 percent by weight of carbon ( C),, balance iron (Fe) and possible impurities.
• Impurities are normally present and are generally unavoidable.
• the content of impurities in the alloy is generally less than 1 percent by weight, preferably less than 0.5 percent by weight and most preferred less than 0.2 percent by weight. All weight percentages mentioned are based on the weight of the total composition, which is 100 percent by weight. All numerical values are approximate values.
• the alloy may contain one or more accompanying elements.
• the content of an accompanying element in the alloy is generally less than 3 percent by weight, preferably less than 2 percent by weight and most preferred less than 1 percent by weight.
• the whole content of accompanying ele- ments in the alloy is generally less than 5 percent by weight, preferably less than 3 percent by weight and most preferred less than 2 percent by weight.
• a preferred composition of the alloy is 13 to 14 percent by weight of nickel (Ni), 14 to 16 percent by weight of chromium (Cr), 1 to 3 percent by weight of molybdenum (Mo), 3.5 to 4.5 percent by weight of silicon (Si), 3.5 to 4 percent by weight of boron (B), 1.8 to 2.1 percent by weight of carbon (C) and 0.2 to 0.5 percent by weight of copper (Cu), balance iron (Fe) and possible impurities.
• the alloy has an unusual good corrosion resistance in mixed corrosion conditions where most Ni-based or Fe-based wear resistant materials do not satisfy. It is remarkable that the Fe-based alloy contains no addition of other hard particles to increase its hardness, such as Tungsten Carbide (WC).
• WC Tungsten Carbide
• the alloys have a hardness in the range of 35 HRC to 60 HRC, particularly in the range of 55 HRC to 60 HRC, typically around 58 HRC, which is unusually low for such a wear resistant material. It gives an advantage in processing and operation as it makes the alloy less sensitive to cracking.
• the unit “HR” represents the so called “Rockwell hardness”.
• HRB B scale
• HRC C scale
• the method for measuring hardness according to Rockwell is specified in DIN EN ISO 6508- ASTM E-18.
• Rockwell hardness numbers are not proportional to Vickers hardness readings, but there exist conversion tables, according to which the above range of 35 to 60 HRC is corresponding a Vickers hardness of between 345 and 780 HV/10.
• the alloys generally have a melting point in the range of 1.000 to 1.150° C, typically around 1080° C. This a very low melting temperature for such an alloy with these properties, which reduces costs in processing and gives application advantages.
• the alloy is produced in the conventional manner by melting of the components or blending of powders or compounds.
• the alloy can be cast to products of any shape.
• the alloy is used for the production of parts or coatings on parts, which are generally metal substrates or metal parts, especially made of steel.
• Metal parts are e.g. rotors, sleeves, bearings, screws, blades, etc.
• the material in particular the alloy, is preferably used for the production of wires, filling wires, bands, strand-shaped products, electrodes, powders, pastes, slurries, or cast bar material, which are used e.g. for casting, welding, plasma transferred arc welding (PTA), plasma powder build-up welding or arc welding, brazing, flame spraying, in particular high-speed flame spraying (HVOF), sinter fusing and similar processes.
• PTA plasma transferred arc welding
• HVOF high-speed flame spraying
• the invention also comprises a process for applying a material according to the invention for the production of coatings with a high level of resistance to corrosion and wear on a workpiece by a thermal coating process, in which the coating material in powder form is alloyed and atomized from the melt or agglomerated from various alloyed and non-alloyed metal powders.
• the coatings or protective layers of the alloy on parts, in particular metal parts are produced preferably by conventional methods of applying a powder by pouring, casting, dipping, spraying, spinning followed by a thermal fusion treatment or by thermal methods like flame spraying, and preferably by high velocity flame spraying (HVOF), or by plasma transferred are welding.
• a powder by pouring, casting, dipping, spraying, spinning followed by a thermal fusion treatment or by thermal methods like flame spraying, and preferably by high velocity flame spraying (HVOF), or by plasma transferred are welding.
• HVOF high velocity flame spraying
• Such coatings can be produced as mentioned above in the thermal processes by using materials containing the alloy, like powders, wires, electrodes or other conventional forms, or by applying two or more materials, which deviate in the composition from the resulting final alloy, where the materials are separate or mixed, e.g. different electrodes or mixed powders, resulting in a coating with the composition of the alloy.
• Such coatings or protective layers serve to give protection from wear and corrosion in the chemical industry, the pharmaceutical industry, the paper industry, the glass industry, power industry, cement industry, waste and recycling, pulp and paper industry and the plastics-processing industry. Coated parts are also used advantageously for oil and gas exploration applications.
• the coating has a thickness in the range of 0.1 to 20 mm, preferably 1 to 10 mm.
• Fig. 1 a diagram on the degree of volume loss in a standardized abrasion testing (ASTM G65) in dependence upon the alloy composition
• Fig.2 a diagram on the degree of weight loss in a standardized corrosion test in contact with HCI in dependence upon the Ni content of the X5 alloy
• Fig.3 a diagram on the degree of weight loss in a standardized corrosion test in contact with HNO 3 in dependence upon the Ni content of the X5 alloy.
• Example 1 (Sample X5)
• Powder B (which is a Fe-based alloy) was blended with varying wt% of Powder A (which is a Ni based wear resistant alloy which is also designated by No. "53606”) and then fused at 1.080 C. It was found that there was an optimal % of powder A for wear and corrosion results that lay between 10 and 40 weight % and that best results were obtained with 15% of Powder A mixed with Powder B
• the 3 curves are wear rate data points obtained from the same fused mixtures but tested with the ASTM G65 method at three independent test series (different times and places).
• the volume loss is plotted on the y-axis in [mm 3 ] in dependence of the content of the Powder A in [wt%].
• a characteristical low volume loss and therefore best wear resistance were obtained with about 15% of Powder A mixed with Powder B.
• X5 is a Fe-based alloy containing no addition of other hard particles to increase its hardness, such as Tungsten Carbide (WC).
• Table 2 shows the composition of the X5 alloy in comparison with an Fe-based alloy as it is disclosed in DE 199 01 170 A1. It is obvious that the Ni-content of the X5-alloy is higher and its V-content is lower (namely zero) and the carbon and chrome levels are also different.
• the balance is Fe (in the case of X5 the Fe balance is 57 wt%).
• the X5 alloy has a melting temperature of 1080° C. and low hardness of 58 HRC.
• Alloy X5 achieved the same G65 wear resistance result as the established 12112 is a surprise and a breakthrough, as the 12112 needs to have 35% of expensive WC added to achieve this value and an expensive Ni-based matrix. Alloy X5 is an Fe-based product and has no WC present.
• specimens with near cylindrical shape were prepared by melt- ing of the test material in ceramic crucibles and cut into sliced with two exposed circular surfaces. The measurement of weight and surface area was recorded.
• test material are the above mentioned Fe-based powder B (table 1 ) and Ni- powders A (table 1 , No. 53606) as well as powders of standard Ni-based alloys known as "12496" and ,,12497"( a slight chemical modification of alloy 12496). Said Ni-based powders were mixed with the Fe-based powder B (table 1 ) at various mixing ratios.
• the slice specimens were exposed to HCI (33%), HNO 3 (55%), H 2 SO 4 (96%) and acidic acid (80%) and the weight loss after 24h, 48h and 12Oh was measured.
• the corrosion resistance as specific weight loss was determined.
• the diagram of Fig.2 illustrates the corrosion test results of three test series for different compositions exposed to HCI (33%).
• the three curves are weight loss data points obtained from the corrosion tests as explained above.
• the weight loss is plotted on the y-axis in [mg/(cm 2 x h)] in dependence of the fraction of the re- spective Ni-based A powder of the mixed powders for the preparation of the specimens.
• Fig.3 illustrates the corrosion test results of three test series for different alloys exposed to HNO 3 (55%).
• the three curves are weight loss data points obtained from the corrosion tests as explained above.
• the weight loss is plotted on the y-axis in [mg/(cm 2 x h)] in dependence of the content of the respective Ni-based A powder of the mixed powders for the preparation of the specimens.
• the results are as follows:
• Ni-based alloys (A, 12496, 12497) show good corrosion resistance against HCI.
• Fe-based do not (Powder B). With increasing content of the Ni-based powder in the respective powder blends, the corrosion resistance against HCI increases.
• Fe-based alloy (B) shows good corrosion resistance against HNO 3 .
• the corrosion resistance against HNO 3 increases.
• Ni and Fe-based alloys are resistant against acetic acid and H 2 SO 4 .
• Adding Ni-based powders (A, 12496, 12497) to Powder B improves the corrosion resistance against HCI but decreases the resistance against HNO 3 . The best balance is achieved with a Ni-based powder percentage of 5-15% as can be seen in Figs. 2 and 3.
• the optimum alloy blend of Ni-based powder into the Fe-based Powder B compo- sition is 15% (in wt% of the Ni-based powder) for HCI and HNO 3 , with the use of Powder A as the best source of Ni-based alloy.
• This 15% / 85% mix gives the composition of X5 according to this preferred embodiment of the invention.
• This X5 composition also gives the lowest G65 wear resistance results.

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