US3715206A - Heat resisting alloys - Google Patents

Heat resisting alloys Download PDF

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Publication number
US3715206A
US3715206A US00059169A US3715206DA US3715206A US 3715206 A US3715206 A US 3715206A US 00059169 A US00059169 A US 00059169A US 3715206D A US3715206D A US 3715206DA US 3715206 A US3715206 A US 3715206A
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alloys
alloying
alloy
hardness
ratio
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T Ito
N Komatsu
T Suzuki
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Toyota Central R&D Labs Inc
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Toyota Central R&D Labs Inc
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Priority claimed from JP6134469A external-priority patent/JPS543806B1/ja
Priority claimed from JP3946370A external-priority patent/JPS5621816B1/ja
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    • 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
    • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent

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  • the improvement resides in the selection of specific alloying ratios as determined by a certain specific polygonal area plotted on a triangular coordinate diagram of Ni, Al and Be, for general improvement of the high temperature antioxidation performance, high temperature strength and high temperature toughness of the alloys.
  • PATENTEDFEB 6 I975 SHEET 2 OF 3 Al, CLO/0 0 O m 5 $89 1 mmmzom MEASURING TEMPERATURE C PATENTEDFEB 6 1975 3,715,206
  • HEAT RESISTING ALLOYS This invention concerns highly improved heat resisting alloys representing superior antioxydation properties even at higher temperatures, as well as superior high temperature strength and toughness properties.
  • the heat resistant steel must be used in practice at a temperature range lower than 800C.
  • Heat resistant alloys containing as its main constituent Ni or C0 the practically usable temperature range will increase to about 1,000C. With higher temperatures than 1,000C, these heat resistant alloys represent generally a substantially reduced strength, as well as abruptly decreased antioxidation properties which tendency prevents these alloys from their prolonged usage.
  • fire resistant alloys containing Mo, Nb and Ta, and ceramic materials can be used at higher temperatures than 1,000C for a long time. These fire resistant alloys, however, show an inferior antioxidation performance at high temperatures so that the kind, nature and working conditions of the environmental atmosphere are limitative and/or a certain surface treatment for intensifying the antioxidation performance must preferably be applied. 1n the case of ceramic materials, considerable drawbacks will be encountered by the lack of ductility, malleability and shock resistibility, resulting in a liability to destruction when subjected to a sudden and substantial temperature change. lt may therefore be definitely concluded that conventional heat resistant materials when used in various high temperature parts and equipments represent much to be desired and must be further improved.
  • lt is the main object of the invention to provide such heat resistant alloys as capable of obviating substantially the aforementioned conventional drawbacks.
  • the ternary Ni-Al-Be alloys which can be produced by adding Be to the binary Ni Al alloys of the above kind and comprise specific alloying ratios lying within an imaginary poligonal areas as determined by specific five apexes drawn on the triangular coordinate chart of said three alloying components: Ni, Al and Be.
  • the first apex is fixed by a specific alloying ratio of Ni 48 at. Al 0.1 at. and Be 51.9 at. this first apex being referred to as l-point" hereinafter throughout the specification.
  • the second apex is fixed by a specific ratio of these three alloying components: Ni 50.1 at. Al 0.1 at. and Be 49.8 at.
  • this second apex being referred to as .l-point" hereinafter.
  • the third apex called K-point is fixed by a specific ratio of these alloying components: Ni 61 at. Al 1 1 at. and Be 28 at. 1n the similar way, the fourth apex called B- point" is determined by an alloying ratio: Ni 87 at. Al 11 at. and Be 2 at.
  • the fifth apex called C- point is determined by an alloying ratio: Ni 48 at. A at. and Be 2 at.
  • the at.% is meant by atomic percentage which may be abbreviated hereinafter only to When the hardness of the alloy should be evaluated at most, it can be selected from a polygonal area in said triangular co-ordinate chart covered by six apexes of 1, J, K, D, E and C-points.
  • the points 1, .l, K and C are same as before, while the D-point is fixed by an alloying ratio of: Ni 79% Al 1 1% and Be 10% and the 15-point by a ratio of: Ni 71%; Al 27% and Be 2%.
  • These alloys will be referred hereinafter as the second range alloys.”
  • the hardness and the toughness of the alloy When the antioxidation performance, the hardness and the toughness of the alloy must be evaluated jointly at the most, it can be selected from a polygonal area in said triangular coordinate chart covered, however, by six apexes of F, G, D, E, C and H, of which the three D, E- and C-points are same as before, while the F- point is determined by a specific alloying ratio: Ni 51%; Al 14% and Be 35%; the 6-point by: Ni 69%; Al 11% and Be 20%; and the H-point by: Ni 48%; Al 39% and Be 13%, as will be more fully described hereinafter. These alloys will be referred to as the third range alloys throughout the specification.
  • the relative strength of the alloy when it should be highly evaluated, it can be selected from a polygonal area in said triangular coordinate chart covered, however, by four apexes of A-, l-, J and 1(- points, of which the first or A-point is determined by a specific alloying ratio: Ni 48%; Al 11% and Be 41%, while the remaining three points 1, J and K are same as before.
  • These alloys will be referred to hereinafter throughout the specification as the fourth range alloys.”
  • FIG. 1 is a Ni-Al-Be triangular coordinate diagram showing a plurality of test specimen alloys used in the experiments carried out on heat resistant Ni-AlBe als.
  • FIG. 2 is a Ni-AlBe triangular coordinate diagram showing several different areas of oxidation weight increase of Ni-Al-Be alloyes appearing on the said diagram.
  • FIG. 3 is a Ni-Al-Be triangular coordinate diagram showing several different areas of room temperature hardness of Ni-Al-Be alloys appearing on the said diagram.
  • FIG. 4 is a chart of the harness of various alloying materials used for the preparation of the heat resistant Ni-Al-Be alloy according to the invention, being plotted against measured temperature.
  • FIG. 5 is a Ni-AlBe triangular coordinate diagram showing several different areas of toughness of Ni-Al-Be alloys appearing on the said diagram.
  • FIG. 6 is a NiAl-Be triangular coordinate diagram showing several different composition ranges of the heat resisting alloys proposed by the present invention.
  • the left-hand and right-hand sides represent the nickel content and the beryllium content, respectively, while the bottom side represents the aluminum content.
  • the alloying materials were electrolytic nickel, high purity aluminum, metallic beryllium, Ni-Be alloy and Al-Be alloy. These materials were melted together by a specifically selected melting process to be described below and then moulded into samples which were subjected to tests.
  • argon was used after addition of a small quantity of hydrogen, for avoiding otherwise encountered oxydation.
  • the molten alloy was cast into a copper moulds.
  • the specimen of 8 mm 41, 5 mm long was measured by weighing it on a chemical balance in units of 0.01 mg. Then, the specimen is put on a ceramic boat made of alumina and kept at 1,200C for 5 hours in an electric furnace, and cooled down in open air atmosphere. The specimen was weighed again and the weight increase was determined. These values were expressed in terms of weight increase, mg, divided by the surface area of the specimen, cm and classified into four categories as shown in the following Table l. The results are also shown graphically in FIG. 2, as attached respectively with l, m, n and 0.
  • Ni A1 alloy having a ratio of: Ni 50% and Al 50%, and a Ni Al alloy having a ratio of: Ni and A1 25%, are also shown. These conventional alloys are also plotted on other triangular coordinate diagrams shown and to be described.
  • the specimen was heated up to 1,200C and the hardness was measured at each temperature increase increment of 100C on a Vickers micro-hardness tester loaded with 300 grs.
  • test results are plotted on the chart shown in FIG. 4 which has been prepared with a logarithmic hardness scale, l-lv, and an arthmetic temperature scale, C, as shown.
  • the novel Ni-Al-Be alloys K2 K7 and K10 K1 represent three to five times higher values of room temperature hardness.
  • the conventional alloys as representatively expressed by Specimens K and K show a rather inferior maximum allowable temperature of 800 900C for keeping its hardness Hv: 100.
  • the maximum allowable temperature amounts to higher than 900C for representing the hardness lower than Hv 100.
  • the critical temperature value amounts to as high as 1,000 1,100C.
  • the improved alloys according to this invention when having a superior room temperature hardness in the order of Hv 400 or higher, can show I-lv 100 even at 900C which performance is substantially superior over the comparative conventional heat resisting alloys.
  • the impressing load applied on to the specimen was varied successively from 1 through 5, I0, 20 and 30 to 50 kgs., and at each specific load application, three impressions were formed on the specimen so as to well investigate possible development of cracks around each of the impressions.
  • the degree of toughness of the alloy was determined in terms of the load, X kgs. implied at that time.
  • the toughness increases generally with decrease of aluminum content. It will be further observed from the diagram that the addition of beryllium to the corresponding binary Ni-Al alloys can provide a substantial improvement in the toughness of the alloy.
  • alloying material for supplying Ni-, Aland Becomponent, electrolytic nickel, high purity aluminum, metallic beryllium, nickel-beryllium alloy and aluminum beryllum alloy were used, which may, however, include small amounts of Fe, Si, Cu, Co and the like impurities.
  • these impurities amount only to 0.2 0.4 percent in total.
  • these material contained practically no contents of impurities. It should be, however, noted that the use of such high purity alloying materials was made only for best control of the alloy components which does not means that an inclusion of impurities gives always rise to the formation of inferior heat resisting alloys.
  • the hardness, the toughness and the oxidation weight increase less than 2.0 mg/sq. cm were considered in combination.
  • the limit should preferably placed at the border line between m and n range areas.
  • the lower limit of nickel content was selected to 48 percent which is defined by the line C-I shown in FIG. 6, said line passes through the 1'!- point as defined by the ratio: Ni 48%; AI 39% and Be 13%.
  • the most apparent inferior antioxidation performance of the alloy having been observed at this point H, as may be well observed from FIG. 2.
  • the aluminum content As for the aluminum content, a melting phenomenon was observed at a temperature in proximity of about 1,200C when the Al-content was selected to less than 9 percent with the nickel content amounted to over about 61 percent. It was observed that throughout the combined overall area covering 1-, n and 0"- ranges the most inferiority of antioxidation was observed at G-point shown in FIG. 2 which was defined by the alloy ratio of: Ni 69%; Al 11% and Be 20%, as was referred to hereinbefore. Therefore, with the nickel content higher than about 61 percent, the lower limit of aluminum content was selected to 11 percent which corresponds to the line B-K in FIG.6.
  • the range of the oxidation weight increase set to less than 2.0 mg/sq. cm lies rightwards from a specific point a in F1G.2, as may be well supposed from the tests on Specimens n, n,,, the rightward area relative to n representing more high aluminum contents of the inventive alloys. From this reason, the lower limiting border for attaining the oxidation weight increase set to less than 2.0 mg/sq. cm with the nickel content less than about 61 percent was fixed by the limiting line J-K shown in FIG. 6.
  • the line J-K is defined by the two points of Ni 50% and Be 50%; and Ni and Al 25%.
  • Point J and K are defined by the specific alloying ratios of Ni 50.1%, A1 0.1% and Be 49.8%, and Ni 61.0%, A1 11.0% and Be 28.0%, respectively.
  • the overall alloying range was limited by those lying within the polygonal area defined by the specific points C, I, J, K and B in FIG. 6. These points correspond to specifically selected alloying ratios, as was described hereinbefore.
  • These alloys called the first range alloys represent similar or somewhat inferior antioxidation performance in comparison with that of Ni Al or Ni Al alloys which are known to have the most efficient antioxidation performance.
  • These novel alloys represent highly superior hardness and toughness properties in combination. When, therefore, reviewing the overall performance regarding said three kinds of desirous properties, these novel alloys have a preferential performance over the conventional heat resisting alloys and can find their way of utilization as the high pressure, high temperature, high load, and thus highly valuable material in the manufacture of steam and gas turbines, jet propulsion engines, rockets, chemical plant facilities and/or the like.
  • the higher nickel content alloys included in q-range in FIG. 3 represent normal temperature hardness less than Hv 399, and somewhat inferior high temperature hardness.
  • the remaining alloys represent superior room temperature hardness higher than I-Iv 100. Therefore, these alloys can be effectively utilized as the high temperature hardness material for use in the manufacture of cutting tools, turbine blades, -disks and the like parts which must be highly of the heat resisting nature.
  • These alloys corresponds to the second range alloys defined above. In this case, the range area IJK-DE-C-I includes all the second range alloys.
  • the point D was fixed by the intersection point between the curved line connecting a first point corresponding the alloying ratio of Ni 79% and Be 21% to a second point corresponding to Ni 68% and Al 32% in FIG. 3, representing the room temperature hardness of I-Iv 400, and the straight line connecting the two points K and B.
  • the points E was fixed by the intersection point of the said first curved line with the third straight line connecting two points B and C, instead of the above points K and B in the foregoing. The selection of these points can be easily understood by observing FIG. 3 in combination with FIG. 6.
  • the q-range area in FIG. 3 showing the alloy ratios of: Ni 48-58%; Al 42-52% and Be smaller amounts, representing the hardness less than Hv 399, defines such alloys having a maximum beryllium content of about 1.8 percent and thus being deleted from inclusion within the second range alloy group.
  • novel alloys belonging to the first range are used as the material in the manufacture of such highly heat resisting parts and devices as gas turbine nozzles, combustion chamber material of that kind of turbine, suction and discharge or exhaust gas valves of automotive drive engine, various high pressure and high temperature parts of chemical and/or industrial plants, blades of jet propulsion engines, they must represent superior antioxidation performance, hardness and toughness in combination.
  • the oxydation weight increase should preferably be less than 1.0 mg/sq. cm.
  • the room temperature hardness must preferably be higher than H 400 from the same reason as that referred to hereinabove in connection with the second range alloys.
  • the toughness should be higher than that of the conventional Ni-Al alloy.
  • the second range alloys could be utilized to a satisfying degree.
  • novel Ni-Al-Be alloys should be used for the manufacture of such machine parts as of turbine blades, aircraft and rocket shells and the like which require a high relative strength
  • those alloys having a high beryllium content should preferably be selected.
  • such alloys which are covered by the still reduced polygonal area A-I-J-K-A can advantageously be used.
  • the A-point is defined as an intersecting point of an extension of the straight line.
  • These alloys are defined as the fourth range alloys, as was referred to hereinbefore.
  • the density of these alloys amounts to about 5.8 6.8 g/cub. cm which is substantially lower than these of the conventional heat resisting steel and alloy amounting generally to 8 9 g/cub. cm.
  • the high temperature hardness and toughness are higher thanconventional, thus providing higher value of relative strength.
  • novel Ni-Al-Be alloys according to this invention do not mean in any way the pure ternary alloys which may, however, contain a small mount of impurities, so far as they do not affect upon the desired effects adversely to a detrimental degree.
  • the novel alloy may include, among others, a small amount of impurities such as Fe, Si, Cu, Co and the like which are frequently included as impurities in the commercialized metallic nickel, metallic aluminum, metallic beryllium, nickelberyllium alloy, aluminum-beryllium alloy, aluminumberyllium alloy.
  • impurities such as Fe less than 1.0 wt. CuO less than 3.0 wt. and a trace of Co as frequently contained in commercial metallic nickel (Grade 3,.11S), Fe less than 1.5 wt.%; Si less than 1.5 wt. and a trace of Cu as frequently contained frequently in commercial metallic aluminum (Grade 4, HS), various small amounts of Fe, Na, Cu and the like contained frequently in commercial metallic beryllium, small amounts of Fe, Si, Cu and the like frequently contained in commercial aluminumberyllium alloy, and/or small amounts of Fe, Cu, Co and the like frequently contained in commercial nickelberyllium alloy do not affect adversely upon the desired and advantageous properties of the novel ternary alloy according to this invention.
  • alloying materials are not limited to those which have been demonstrated in the foregoing detailed description and commercially available alloying materials such as metallic nickel, metallic aluminum, metallic beryllium and alloys thereof can well be utilized within the framework of the invention.
  • the third one being defined by a third alloying ratio of Ni 61 at Al 11 at and Be 28 at.%, the
  • fourth one being defined by a fourth alloying ratio of Ni 87 at.%; Al 11 at.% and Be 2 at.%
  • the fifth one being defined by a fifth alloying ratio of Ni 48 at.%; Al 50 at.% and Be 2 at.%.
  • a heat resisting alloy consisting essentially of Ni, Al and Be, wherein the amounts thereof are defined by and included in a polygonal area on a triangular coordinate diagram of Ni, Al and Be, the polygon having six apexes of which the first one being defined by a first alloying ratio of Ni 48 at.%; A] 0.1 at.% and Be 51.9 at.%, the second one being defined by a second alloying ratio of Ni 50.1 at.%; A1 0.1 at.% and Be 49.8 at.%, the third one being defined by a third alloying ratio of Ni 61 at.%; Al 11 at.% and Be 28 at.%, the fourth one being defined by a fourth alloying ratio of Ni 79 at.%; Al 11 at.% and Be 10 at.%; the fifth one being defined by a fifth alloying ratio of Ni 71 at.%; Al 27 at.% and Be 2 at.% and the sixth one being defined by a sixth alloying ratio of Ni 48 at.%; Al 50 at.% and Be 2 at
  • a heat resisting alloy consisting essentially of Ni, Al and Be, wherein the amounts thereof are defined by and included in a polygonal area on a triangular coordinate diagram of Ni, Aland Be, the polygon having six apexes of which the first one being defined by a first a1- loying ratio of M51 at.%; Al 14 at.%and Be 35 at.%; the second one being defined by a second alloying ratio of Ni 69 at.%; Al 11 at.% and Be 20 at.%, the third one being defined by a third alloying ratio of Ni 79 at.%; Al
  • a heat resisting alloy consisting essentially of Ni, Al and Be, wherein the amounts thereof are defined by and included in a polygonal area on a triangular co-ordinate diagram of Ni, Al and Be, the polygon having four apexes of which the first one being defined by a first alloying ratio of Ni 48 at.%; Al 11 at.% and Be 41 at.%, the second one being defined by a second alloying ratio of Ni 48 at.%; A1 0.1 at.% and Be 51.9 at.%, the third one being defined by a third alloying ratioof Ni 50.1 at.%; A1 0.1 at.% and Be 49.8 at.% and the fourth one being defined by a fourth alloying ratio of Ni 61 at.%; Al 11 at.% and Be 28 at.%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
US00059169A 1969-08-02 1970-07-29 Heat resisting alloys Expired - Lifetime US3715206A (en)

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JP6134469A JPS543806B1 (US20080094685A1-20080424-C00004.png) 1969-08-02 1969-08-02
JP3946370A JPS5621816B1 (US20080094685A1-20080424-C00004.png) 1970-05-08 1970-05-08

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DE (1) DE2038509C3 (US20080094685A1-20080424-C00004.png)
FR (1) FR2058185B1 (US20080094685A1-20080424-C00004.png)
GB (1) GB1289021A (US20080094685A1-20080424-C00004.png)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5998041A (en) * 1996-03-12 1999-12-07 Ngk Insulators, Ltd. Joined article, a process for producing said joined article, and a brazing agent for use in producing such a joined article
US6093262A (en) * 1998-06-23 2000-07-25 Pes, Inc. Corrosion resistant solenoid valve
US6312534B1 (en) 1994-04-01 2001-11-06 Brush Wellman, Inc. High strength cast aluminum-beryllium alloys containing magnesium

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1685570A (en) * 1926-09-16 1928-09-25 Siemens Ag Process of improving the qualities of nickel-beryllium alloy
US2157979A (en) * 1935-08-17 1939-05-09 Cooper Wilford Beryillum Ltd Process of making alloys
US2193363A (en) * 1936-06-06 1940-03-12 Perosa Corp Process for obtaining beryllium and beryllium alloys

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1685570A (en) * 1926-09-16 1928-09-25 Siemens Ag Process of improving the qualities of nickel-beryllium alloy
US2157979A (en) * 1935-08-17 1939-05-09 Cooper Wilford Beryillum Ltd Process of making alloys
US2193363A (en) * 1936-06-06 1940-03-12 Perosa Corp Process for obtaining beryllium and beryllium alloys

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6312534B1 (en) 1994-04-01 2001-11-06 Brush Wellman, Inc. High strength cast aluminum-beryllium alloys containing magnesium
US5998041A (en) * 1996-03-12 1999-12-07 Ngk Insulators, Ltd. Joined article, a process for producing said joined article, and a brazing agent for use in producing such a joined article
US6093262A (en) * 1998-06-23 2000-07-25 Pes, Inc. Corrosion resistant solenoid valve

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FR2058185B1 (US20080094685A1-20080424-C00004.png) 1976-02-20
DE2038509A1 (de) 1971-02-18
DE2038509B2 (de) 1974-10-10
GB1289021A (US20080094685A1-20080424-C00004.png) 1972-09-13
FR2058185A1 (US20080094685A1-20080424-C00004.png) 1971-05-28
DE2038509C3 (de) 1975-05-07

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