WO2014058893A1 - Verres en vrac de nickel-phosphore-bore portant du molybdène - Google Patents

Verres en vrac de nickel-phosphore-bore portant du molybdène Download PDF

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Publication number
WO2014058893A1
WO2014058893A1 PCT/US2013/063902 US2013063902W WO2014058893A1 WO 2014058893 A1 WO2014058893 A1 WO 2014058893A1 US 2013063902 W US2013063902 W US 2013063902W WO 2014058893 A1 WO2014058893 A1 WO 2014058893A1
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alloy
atomic percent
metallic glass
glass
metallic
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PCT/US2013/063902
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English (en)
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Jong Hyun Na
Michael Floyd
Glenn GARRETT
Marios D. Demetriou
William L. Johnson
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Glassimetal Technology, Inc.
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Publication of WO2014058893A1 publication Critical patent/WO2014058893A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel

Definitions

  • the present disclosure is directed to nickel-phosphorous-boron (Ni-P-B) alloys bearing molybdenum (Mo) and optionally niobium (Nb) capable of forming bulk glassy rods with diameters of 1 mm or greater.
  • Ni-P-B alloys bearing Mo, Nb, and Mn capable of forming bulk metallic glass rods with diameters of at least 1 .5 mm and as large as 3 mm or greater.
  • Ni-based P and B bearing bulk glasses Due to the attractive engineering properties of Ni-based P and B bearing bulk glasses, such as high strength, toughness, bending ductility, and corrosion resistance, it is desirable to develop other families of such alloys that incorporate different transition metals in order to explore the possibility of even better engineering performance.
  • This disclosure provides bulk glass forming Ni-Mo-Nb-P-B alloys capable of forming a bulk metallic glass rod with a diameter of 3 mm.
  • Such bulk metallic glass rods can be formed when the molten alloy is processed by water quenching while contained in a fused silica tube having a wall thickness not larger than 0.3 mm.
  • Ni-Mo-Nb-P-B alloys that can include a small fraction of Mn. These alloys have better glass forming ability compared to the alloys free of Mn.
  • Ni-Mo-Nb-Mn-P-B alloys are capable of forming metallic glass rods with diameters of at least 2 mm, and as large as 3 mm or larger when processed by melt water quenching in fused silica tubes having wall thickness of 0.5 mm.
  • the metallic glasses have high yield strength and high notch toughness.
  • the disclosure is directed to an alloy or a metallic glass comprising an alloy represented by the following formula (subscripts denote atomic percent):
  • a is between 2 and 12
  • c is between 14 and 19
  • a + b is between 7 and 9.
  • a is between 3 and 5 and b is between 3 and 5.
  • c + d is between 18.5 and 20.5.
  • c is between 16 and 17 and d ⁇ s between 2.75 and 3.75.
  • up to 1 atomic % of P is substituted by Si.
  • up to 2 atomic % of Mo is substituted by Fe, Co, Mn, W, Cr, Ru, Re, Cu, Pd, Pt, V, Ta, or combinations thereof.
  • Ni is substituted by Fe, Co, Mn, W, Cr, Ru, Re, Cu, Pd, Pt, V, Ta, or combinations thereof.
  • the alloys are capable of forming amorphous rods of diameter of at least 1 mm when rapidly quenched from the molten state.
  • the melt of the alloy is fluxed with a reducing agent prior to rapid quenching.
  • the temperature of the alloy melt prior to quenching is at least 100 degrees above the liquidus temperature of the alloy.
  • the temperature of the alloy melt prior to quenching is at least 1 100 °C.
  • rapid quenching is achieved by water-quenching a quartz tube containing the molten alloy.
  • the thickness of the quartz-tube wall is between 0.1 and 0.5 mm.
  • a wire made of the metallic glass having a diameter of 1 mm can undergo macroscopic plastic bending under load without fracturing
  • the disclosure is also directed to alloy or metallic glass Ni72.slvlO4Nb4Pi6.08B3.12, Ni72.3M08Pi 6.5B32, Ni72.3M04Nb4Pi6.5B32, Ni72.3M03.5Nb4.5Pi6.5B32, Ni72.3M04Nb4Pi6.2B35, Ni72.3M03Nb5Pi6.5B32, Ni72.3M04.5Nb3.5Pi6.5B32, Ni72.3M05Nb3Pi6.5B32, Ni72.3M04Nb4P17.2B25, and
  • a method for forming a metallic glass article includes melting an alloy comprising at least Ni, Mo, P, and B and optionally Nb with a formula Ni (10 o-a-t>-c-d ) lvlo a Nb b P c B £i , where an atomic percent of
  • molybdenum (Mo) a is between 2 and 12
  • an atomic percent of niobium (Nb) b is between 0 and 8
  • an atomic percent of phosphorus (P) c is between 14 and 19
  • an atomic percent of boron (B) d ⁇ s between 1 and 4 and the balance is nickel (Ni).
  • the method also includes quenching the molten alloy at a cooling rate sufficiently rapid to prevent crystallization of the alloy.
  • the disclosure is directed to an alloy, or a metallic glass comprising an alloy, represented by the following formula (subscripts denote atomic percent):
  • a is between 1 and 5
  • b is between 3 and 5
  • d is between 16 and 17, and
  • e is between 2.75 and 3.75
  • the largest rod diameter of the metallic glass according to Eq. (2) that can be formed when processed by water quenching the high temperature melt in a fused silica tube having wall thickness of 0.5 mm is at least 1 .5 mm.
  • a + c of the alloy or metallic glass according to Eq. (2) is between 3 and 5, while c is between 0.5 and 1 .5, and wherein the largest rod diameter that can be formed with an amorphous phase is at least 2 mm.
  • a + c of the alloy or metallic glass according to Eq. (2) is between 3.5 and 4.5, while c is between 0.75 and 1 .25, and wherein the largest rod diameter that can be formed with an amorphous phase is at least 2.5 mm.
  • up to 1 atomic percent of P of the alloy or metallic glass according to Eq. (2) is substituted by Si.
  • up to 2 atomic percent of Ni of the alloy or metallic glass according to Eq. (2) is substituted by Fe, Co, W, Ru, Re, Cu, Pd, Pt, or combinations thereof.
  • the melt of the alloy according to Eq. (2) is fluxed with a reducing agent prior to rapid quenching.
  • the temperature of the alloy melt according to Eq. (2) prior to quenching is at least 200 °C above the liquidus temperature.
  • the temperature of the alloy melt according to Eq. (2) prior to quenching is at least 1200°C.
  • the compressive yield strength of the metallic glass according to Eq. (2) is at least 2200 MPa.
  • the stress intensity at crack initiation (i.e. the notch toughness) of the metallic glass according to Eq. (2) when measured on a 2 mm diameter rod containing a notch with length between 0.75 and 1 .25 mm and root radius between 0.1 and 0.15 mm is at least 60 MPa m 1 2 .
  • a wire made of such metallic glass according to Eq. (2) having a diameter of 1 mm can undergo macroscopic plastic deformation under bending load without fracturing catastrophically.
  • the disclosure is also directed to an alloy, or a metallic glass comprising an alloy, selected from Ni72.3Mo3.5Nb4Mno.5Pi6.5B32, Ni 7 2.3Mo3Nb4Mn 1 P 16 .5B 3 .2, and
  • FIG. 1 provides a data graph showing the effect of Mo atomic concentration on the glass forming ability of the Ni-Mo-P-B alloys.
  • FIG. 2 provides a data graph showing calorimetry scans for sample Ni-Mo-P-B metallic glasses from Table 1 with varying Mo atomic concentration (Arrows from left to right designate the glass-transition and liquidus temperatures).
  • FIG. 3 provides a data graph showing the effect of Nb atomic concentration on the glass forming ability of the Ni-Mo-Nb-P-B alloys.
  • FIG. 4 provides an X-ray diffractogram verifying the amorphous structure of a 2.9 mm rod of sample metallic glass Ni 72 . 3 M0 4 Nb 4 Pi 6 . 5 B 3 2 .
  • FIG. 5 provides a data graph showing calorimetry scans for sample Ni-Mo-Nb-P-B metallic glasses with varying Nb atomic concentration. Arrows designate the liquidus temperatures.
  • FIG. 6 provides a data graph showing the effect of B atomic concentration on the glass forming ability of the Ni-Mo-Nb-P-B alloys.
  • FIG. 7 provides a data graph showing the calorimetry scans for sample Ni-Mo-Nb- P-B metallic glasses with varying B atomic concentration. Arrows designate the liquidus temperatures.
  • FIG. 8 provides a data graph showing the effect of metalloid atomic concentration on the glass forming ability of the Ni-Mo-Nb-P-B alloys.
  • FIG. 9 provides an image showing a plastically bent 1 mm amorphous rod of sample metallic glass N i72.3M05Nb3Pi6.5B3 2.
  • FIG. 10 provides a plot showing the effect of substituting Mo by Mn on the glass forming ability of alloy Ni 72.3 Mo 4 -xNb 4 Mn x P 16.5 B 3 .2.
  • FIG. 1 1 provides a plot showing calorimetry scans for sample metallic glass Ni 72.3 Mo 4 -xNb 4 Mn x P 16.5 B 3 .2. Arrows from left to right designate the glass-transition and liquidus temperatures, respectively.
  • FIG. 12 provides an optical image of an amorphous 3 mm rod of example metallic glass Ni72.3Mo3Nb 4 Mn 1 P 16 .5B3.2.
  • FIG. 13 provides an X-ray diffractogram verifying the amorphous structure of a 3 mm rod of example metallic glass Ni 72.3 Mo 3 Nb 4 Mn 1 P 16.5 B 3 .2.
  • FIG. 14 provides a compressive stress-strain diagram for sample metallic glass
  • FIG. 15 provides an optical image of a plastically bent 1 mm metallic glass rod of sample metallic glass Ni7 2 .3Mo 3 Nb 4 Mn 1 P 16 .5B3.2.
  • FIG. 16 provides a plot showing the corrosion depth versus time in 6M HCI solution of a 2 mm metallic glass rod having composition Ni 72.3 Mo 3 Nb 4 Mn 1 P 16 5 B 3 2.
  • Embodiments described herein may provide Ni-Mo-P-B, Ni-Mo-Nb-P-B, or Ni-Mo- Nb-Mn-P-B alloys.
  • the alloys are capable of forming bulk glassy rods with diameters of 1 mm or greater.
  • Mo substituting Ni and optionally the addition of Nb substituting Mo in the disclosed ranges promote bulk-glass formation in Ni-P-B alloys.
  • the Nb containing Ni-Mo-Nb-P-B alloys have better glass forming ability than the Ni-Mo-P-B alloys.
  • the relative B and P contents affect the glass forming ability (GFA), as does the total metalloid content in relation to the total metal content.
  • GFA glass forming ability
  • Mn substituting Mo further promotes bulk-glass formation in Ni-Mo-Nb-P-B alloys.
  • the Mn containing Ni-Mo-Nb-Mn-P-B alloys have better glass forming ability than the Ni-Mo-Nb-P-B alloys.
  • glassy rods of sample metallic glasses with diameters up to 1 mm can be plastically bent.
  • the glass-forming ability of each alloy may be assessed by determining the maximum or "critical" rod diameter in which the amorphous phase can be formed when processed by the method described herein, which is, water quenching the molten alloy in quartz capillaries. Since quartz is known to retard heat transfer, the quartz thickness is a critical parameter associated with the glass-forming ability of the sample alloys. Therefore, to quantify the glass-forming ability of each of the sample alloys, the critical rod diameter, d c , is reported in conjunction with the associated quartz thickness, t w , of the capillary used to process the alloy.
  • Quartz capillaries with wall thicknesses that were about 10% of the tube inner diameter were used for processing the sample Ni-Mo-Nb-P-B alloys.
  • Table 1 shows sample Ni-Mo-P-B and Ni-Mo-Nb-P-B metallic glasses that satisfy the disclosed metallic glass composition formula, Eq. (1 ), along with the associated glass forming ability and
  • Table 1 Sample metallic glasses Ni-Mo-P-B and Ni-Mo-Nb-P-B compositions and the associated glass forming ability of the corresponding glass forming alloys
  • Samples 1 -7 are Ni-Mo-P-B metallic glasses, in which the P and B contents are held constant while Ni is substituted by Mo, according to the formula Ni 80 .3-xMOxPi 6. 5 B 3 2 , where x denotes the Mo content. Ni was substituted by Mo in the range from 3% to 9%. Of these samples, sample 5 reveals a peak in d c of 1 .5 mm at 7.5% Mo.
  • the GFA data for samples 1 -7 are also presented graphically in FIG. 1 .
  • FIG. 2 provides a data graph showing calorimetry scans for sample Ni-Mo-P-B metallic glasses (samples 1 -6) from Table 1 with varying Mo atomic concentration, according to the formula Ni 80 .3-xMOxPi 6. 5 B 3 2 , where x denotes the Mo content.
  • the arrows from left to right designate the glass-transition and liquidus temperatures, respectively.
  • Differential scanning calorimetry reveals that increasing the Mo content raises the glass transition temperature, but does not substantially influence the liquidus temperatures.
  • Samples 8-15 are Ni-Mo-Nb-P-B metallic glasses, in which the Ni, P, and B contents are held constant while Mo is substituted by Nb, according to the formula N172.3M08- x Nb x P 16 . 5 B 3 .2, where x denotes the Nb content.
  • samples 8-15 have d c ranging from 1 .3 mm to 1 .6 mm, which is larger than the d c values of 0.1 mm to 1 .2 mm of samples 1 -7.
  • Sample 12 has d c of 2.9 mm such that the content of Mo and Nb are 4% for each.
  • the GFA data for samples 8- 15 are presented graphically in FIG. 3.
  • Ni72.3M04Nb4Pi6.5B32 was verified by x-ray diffraction.
  • FIG. 4 provides an X-ray diffractogram revealing no sharp peaks, which indicates absence of any crystals in the sample.
  • FIG. 5 provides a data graph showing calorimetry scans for sample metallic glasses Ni-Mo-Nb-P-B with varying Nb atomic concentration (samples 8-15), according to the formula Ni72.3M08-xNbxPi6.5B32, where x denotes the Nb content.
  • the arrows from left to right designate the glass-transition and liquidus temperatures, respectively. As shown, the glass transition temperatures of the metallic glasses do not change much with varying Nb content, but the liquidus temperatures change with varying Nb content.
  • the differential scanning calorimetry reveals that the Nb substitution does not substantially influence the glass transition temperature, but the melting behavior is considerably influenced, as the liquidus temperatures go through a minimum at about 3-4%, which is near a Nb content of 4%. Again, lower liquidus temperature as illustrated in the calorimetry scan implies an improved potential for glass-forming ability.
  • Samples 12 and 16-23 are also metallic glasses Ni-Mo-Nb-P-B in which the Ni, Mo, Nb contents are held constant while P is substituted by B, according to the formula Ni72.3M04Nb4P19.7 xBx, where x denotes the B content.
  • sample 12 shows a peak in d c of 2.9 mm at B content of 3.2%.
  • the GFA data for samples 12 and 16- 23 are presented graphically in FIG. 6.
  • FIG. 7 provides a data graph showing the calorimetry scans for sample metallic glasses Ni-Mo-Nb-P-B with varying B atomic concentration according to the formula Ni72.3M04Nb4P19.7 xBx, where x denotes the B content (samples 17, 19, 20, and 22).
  • the arrows from left to right designate the glass-transition and liquidus temperatures, respectively.
  • the glass transition temperature of the metallic glasses is not greatly affected by varying the B content.
  • the differential scanning calorimetry reveals that the liquidus temperature goes through a minimum near the B content of 3%. Again, lower liquidus temperature, as illustrated in the calorimetry scan, implies an improved potential for glass-forming ability.
  • Samples 12 and 24-27 are also Ni-Mo-Nb-P-B metallic glasses in which the Mo and Nb content is held constant while the total metalloid content is varied with the Ni content according to the formula Ni 9 2-xMo4Nb 4 (Po.8376Bi 624)x, where x denotes the B content. Shifting the metalloid content in the alloy is shown to influence glass-forming ability. Out of these samples, sample 25 shows a peak in d c of 3.0 mm at metalloid content of 19.2% B. This GFA data is presented graphically in FIG. 8.
  • Samples 28-30 are also Ni-Mo-Nb-P-B metallic glasses, in which the Ni, P and B content is held constant while Mo is substituted by Nb, according to the formula Ni72.sM07.5- x Nb x P 16.5 B 3 .2, where x denotes the Nb content.
  • This GFA data shows that substitution of Mo by Nb when the total Mo and Nb content is 7.5 instead of 8 does not offer any improvement in GFA.
  • Samples 30-31 are Ni-Mo-Nb-P-B-Si metallic glasses in which the Ni, Mo, Nb, and B content is held constant while P is substituted by Si, according to the formula
  • FIG. 9 provides an image showing a plastically bent 1 mm amorphous rod of sample metallic glass Ni72.3M05Nb3Pi 6.5B3 2. This demonstrates that the metallic glass Ni72.3M05Nb3Pi 6.5B3 2 rod of 1 mm diameter is able to undergo macroscopic plastic bending under load without fracturing catastrophically.
  • the glass forming ability of the alloy is enhanced.
  • the critical rod diameter determined by processing in fused silica with a wall thickness of 0.5 mm is increased from about 1 mm for the Mn-free alloy to about 3 mm or more.
  • the Ni-Mo- Nb-P-B composition includes about 4 atomic percent Mo, about 4 atomic percent Nb, between 16 and 17 atomic percent P, between 3 and 3.5 atomic percent B, and the balance is Ni.
  • An atomic percent of Mn between 0.5 and 1 .5 substitutes Mo in this Ni-Mo-Nb-P-B composition.
  • Sample metallic glasses showing the effect of substituting Mo by Mn.
  • Metallic glasses having the formula N i72.3M04-xNb4MnxPi 6.5B3 2 are presented in Table 2 and FIG. 10.
  • Mn atomic percent is between 0.5 and 1 .5
  • metallic glass rods with diameters greater than 2 mm can be formed.
  • Mn atomic percent is at about 1
  • 3-mm diameter metallic glass rods can be formed.
  • Differential calorimetry scans for sample metallic glasses in which Mo is substituted by Mn are presented in FIG. 1 1 .
  • the alloy exhibiting the highest glass-forming ability is Sample 35 (Ni 72 . 3 M0 3 Nb 4 Mn 1 Pi 6 . 5 B 3 2 ).
  • the alloy is capable of forming metallic glass rods of up to 3 mm in diameter.
  • An image of a 3 mm diameter metallic glass rod having the composition Ni 72 . 3 M0 3 Nb 4 Mn 1 Pi 6 . 5 B 3 2 rod is shown in FIG. 12.
  • An x-ray diffractogram taken on the cross section of a 3 mm diameter Ni 72 . 3 M0 3 Nb 4 Mn 1 Pi 6 . 5 B 3 2 rod verifying its amorphous structure is shown in FIG. 13.
  • the compressive yield strength, a y is the measure of the material's ability to resist non-elastic yielding.
  • the yield strength is the stress at which the material yields plastically. A high o y ensures that the material will be strong.
  • the stress intensity factor at crack initiation i.e. the notch toughness
  • K q is the measure of the material's ability to resist fracture in the presence of a notch.
  • the notch toughness is a measure of the work required to propagate a crack originating from a notch.
  • a high K q ensures that the material will be tough in the presence of defects.
  • Bending ductility is a measure of the material's ability to deform plastically and resist fracture in bending in the absence of a notch or a pre-crack. A high bending ductility ensures that the material will be ductile in a bending overload.
  • Hardness is a measure of the material's ability to resist plastic indentation. A high hardness will ensure that the material will be resistant to indentation and scratching.
  • a plastic zone radius, r p defined as K q 2 /na y 2 , is a measure of the critical flaw size at which catastrophic fracture is promoted.
  • the plastic zone radius determines the sensitivity of the material to flaws; a high r p designates a low sensitivity of the material to flaws.
  • sample metallic glass Ni72 .3 Mo 3 Nb 4 Mn 1 P16.5B3.2 (Sample 35) is presented in Table 3.
  • the stress-strain diagram for sample metallic glass Ni72.3Mo3Nb 4 Mn 1 P 16 .5B3.2 is presented in FIG. 14.
  • the metallic glasses are capable of undergoing plastic bending in the absence of fracture for diameters up to at least 1 mm.
  • An optical image of a plastically bent amorphous rod at 1 -mm diameter section of example metallic glass is presented in FIG. 15.
  • the metallic glasses Ni-Mo Nb-Mn-P-B also exhibit a corrosion resistance.
  • the corrosion resistance of example metallic glass Ni72. 3 M0 3 Nb 4 Mn 1 Pi 6 .5B32 is evaluated by immersion test in 6M HCI.
  • a plot of the corrosion depth versus time is presented in FIG. 16.
  • the corrosion depth at approximately 673 hours is measured to be about 4.7 micrometers.
  • the corrosion rate is estimated to be 0.068 mm /year.
  • the corrosion rate of all metallic glasses according to the current disclosure is expected to be under 1 mm/year.
  • the alloys or alloy ingots can be produced by inductive melting of the elemental constituents in a quartz tube (i.e. fused silica tubes) under an inert atmosphere.
  • the purity levels of the constituent elements were Ni 99.995%, Mo 99.95%, Nb 99.95%, Mn 99.9998%, P 99.9999%, and B 99.5%.
  • the melting crucible may alternatively be a ceramic such as alumina or zirconia, graphite, or a water-cooled hearth made of copper or silver.
  • Metallic glass rods can be produced from the alloy ingots by re-melting the alloy ingots in quartz tubes in a furnace at 1 100°C or higher, e.g. between 1200 °C and 1400°C, under inert atmosphere, e.g. under high purity argon. Subsequently, the quartz tube containing the alloy melt can be rapidly quenched in a room-temperature water bath.
  • the bath could be iced water or oil.
  • Metallic glass articles in general can be alternatively formed by injecting or pouring the molten alloy into a metal mold.
  • the mold can be made of copper, brass, or steel, among other materials.
  • the wall thickness of the quartz tubes ranged from 0.06 mm to 0.5 mm.
  • Fused silica is generally a poor thermal conductor. Slightly increasing the thickness of the tube wall slows the heat removal rate during the melt quenching process, thereby limiting the diameter of a rod that can be formed with an amorphous phase by a given composition.
  • the alloy for example, the alloy
  • Ni72. 3 M0 4 Nb 4 Pi 6 .5B32 is capable of forming amorphous 3 mm diameter rods (Sample 12 in Table 1 ) when processed by water quenching the high temperature melt in a fused silica tube having wall thickness of 0.3 mm.
  • the alloy Ni72. 3 M0 4 Nb 4 Pi 6 .5B32 is capable of forming metallic glass rods of only 1 mm in diameter.
  • the alloy ingots can be fluxed with a reducing agent.
  • the ingots can be remelted in a quartz tube under inert atmosphere along with a reducing (fluxing) agent.
  • the alloy melt can be brought in contact with the molten reducing agent to allow the two melts to interact for about a time period of at least 1000 seconds (e.g. between 1 and 12 hours) at a temperature of about 1 100°C or higher (e.g. between 1200 °C and 1400 °C), and the alloy melt can be subsequently cooled by water quenching.
  • each alloy was assessed by determining the maximum rod diameter in which the amorphous phase of the alloy (i.e. the metallic glass phase) can be formed when processed by the method described above. X-ray diffraction with Cu- ⁇ radiation was performed to verify the amorphous structure of the alloys.
  • the notch toughness of sample metallic glasses was performed on 2-mm diameter rods.
  • the rods were notched using a wire saw with a root radius of between 0.10 and 0.13 ⁇ to a depth of approximately half the rod diameter.
  • the notched specimens were placed on a 3-point bending fixture with span distance of 12.7 mm and carefully aligned with the notched side facing downward.
  • the critical fracture load was measured by applying a monotonically increasing load at constant cross-head speed of 0.001 mm/s using a screw- driven testing frame. At least three tests were performed, and the variance between tests is included in the notch toughness plots.
  • the stress intensity factor for the geometrical configuration employed here was evaluated using the analysis by Murakimi (Y. Murakami, Stress Intensity Factors Handbook, Vol. 2, Oxford: Pergamon Press, p. 666 (1987)). Test Methodology for Measuring Compressive Yield Strength
  • sample metallic glasses were evaluated by immersion tests in hydrochloric acid (HCI).
  • HCI hydrochloric acid
  • a rod of metallic glass sample with initial diameter of 1 .99 mm, and a length of 22.55 mm was immersed in a bath of 6M HCI at room temperature.
  • the density of the metallic glass rod was measured using the Archimedes method.
  • the corrosion depth at various stages during the immersion was estimated by measuring the mass change with an accuracy of ⁇ 0.01 mg.
  • the corrosion rate was estimated assuming linear kinetics.
  • Ni-Mo-P-B, Ni-Mo-Nb-P-B, or Ni-Mo-Nb-Mn-P-B alloys with controlled ranges of Mo, Nb, Mn, and metalloids P and B have good glass forming ability, as they are capable of forming bulk metallic glass rods with diameters as large as 3 mm or larger.
  • the metallic glasses formed from the alloys also demonstrate high strength, hardness, toughness, bending ductility, and corrosion resistance.
  • the combination of high glass-forming ability and the mechanical and corrosion performance of the bulk Ni-based metallic glasses make them candidates for various applications.
  • the disclosed alloys may be used in applications such as consumer electronics, dental and medical implants and instruments, luxury goods, and sporting goods, among many other applications.

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Abstract

L'invention concerne des alliages de Ni-Mo-P-B, Ni-Mo-Nb-P-B et Ni-Mo-Nb-Mn-P-B pouvant former des objets de verre métallique. Les objets de verre métallique peuvent avoir des dimensions latérales dépassant 1 mm et d'au moins 3 mm. L'invention concerne également des procédés de formation des verres métalliques.
PCT/US2013/063902 2012-10-08 2013-10-08 Verres en vrac de nickel-phosphore-bore portant du molybdène WO2014058893A1 (fr)

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US11371108B2 (en) 2019-02-14 2022-06-28 Glassimetal Technology, Inc. Tough iron-based glasses with high glass forming ability and high thermal stability

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US9957596B2 (en) 2013-12-23 2018-05-01 Glassimetal Technology, Inc. Bulk nickel-iron-based, nickel-cobalt-based and nickel-copper based glasses bearing chromium, niobium, phosphorus and boron
US10000834B2 (en) 2014-02-25 2018-06-19 Glassimetal Technology, Inc. Bulk nickel-chromium-phosphorus glasses bearing niobium and boron exhibiting high strength and/or high thermal stability of the supercooled liquid
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WO2017058670A1 (fr) 2015-09-28 2017-04-06 Glassimetal Technology, Inc. Procédé de traitement de surface pour verres métalliques à base de nickel visant à réduire la libération de nickel
US11905582B2 (en) 2017-03-09 2024-02-20 Glassimetal Technology, Inc. Bulk nickel-niobium-phosphorus-boron glasses bearing low fractions of chromium and exhibiting high toughness

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US11371108B2 (en) 2019-02-14 2022-06-28 Glassimetal Technology, Inc. Tough iron-based glasses with high glass forming ability and high thermal stability

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