CN105246642B - 延性的含硼镍基焊接材料 - Google Patents
延性的含硼镍基焊接材料 Download PDFInfo
- Publication number
- CN105246642B CN105246642B CN201480013693.6A CN201480013693A CN105246642B CN 105246642 B CN105246642 B CN 105246642B CN 201480013693 A CN201480013693 A CN 201480013693A CN 105246642 B CN105246642 B CN 105246642B
- Authority
- CN
- China
- Prior art keywords
- welding
- containing nickel
- nickel
- boron
- welding material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000003466 welding Methods 0.000 title claims abstract description 97
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 67
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 38
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 35
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 68
- 239000000956 alloy Substances 0.000 claims abstract description 68
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005219 brazing Methods 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 230000008439 repair process Effects 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 239000011888 foil Substances 0.000 claims abstract description 3
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000013078 crystal Substances 0.000 claims description 15
- 229910001119 inconels 625 Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 5
- 208000013201 Stress fracture Diseases 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000005304 joining Methods 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 2
- 229910052748 manganese Inorganic materials 0.000 claims 2
- 239000011572 manganese Substances 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 15
- 229910000601 superalloy Inorganic materials 0.000 description 13
- 229910001011 CMSX-4 Inorganic materials 0.000 description 12
- 238000005253 cladding Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910001026 inconel Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 208000010392 Bone Fractures Diseases 0.000 description 2
- 206010017076 Fracture Diseases 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- -1 WGB Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 229910000819 inconels 713 Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004372 laser cladding Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000013206 minimal dilution Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
-
- 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
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3033—Ni as the principal constituent
- B23K35/304—Ni as the principal constituent with Cr as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/20—Bonding
- B23K26/21—Bonding by welding
- B23K26/211—Bonding by welding with interposition of special material to facilitate connection of the parts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0233—Sheets, foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
- B23K35/0261—Rods, electrodes, wires
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K9/00—Arc welding or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K9/00—Arc welding or cutting
- B23K9/16—Arc welding or cutting making use of shielding gas
- B23K9/167—Arc welding or cutting making use of shielding gas and of a non-consumable electrode
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/02—Iron or ferrous alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/18—Dissimilar materials
- B23K2103/26—Alloys of Nickel and Cobalt and Chromium
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Arc Welding In General (AREA)
- Laser Beam Processing (AREA)
- Laminated Bodies (AREA)
- Powder Metallurgy (AREA)
Abstract
延性的含硼镍基焊接材料,其包含0.4‑0.6wt.%B范围内的硼、痕量至0.04wt.%C的碳、17‑23wt.%Cr、0.35‑10wt.%Mo、0.1‑4.15wt.%Nb及余量的镍或铁和杂质,其用于制造用于由镍基、钴基和铁基合金制成的各种制品的修复的焊接和钎焊用的焊丝、焊粉和焊箔。
Description
本申请要求于2014年4月28日由Alexander B.Goncharov、Joseph Livurdi和PaulLowden正式提交的发明名称为“用于焊接超级合金的焊接材料”的第14/263,120号美国专利申请的优先权。
名义上包含20-23wt.%Cr、8-10wt.%Mo、3.15-4.15wt.%Nb、最大值为0.1wt.%C和镍及余量的杂质的镍铬合金625也称为制造成AMS 5789的625(IN625),其在高至1800°F的温度下具有良好的抗氧化性,在高至1598°F的温度下具有良好的机械性,并且提供了良好的耐水溶液腐蚀性。因此,数十年来,该合金已经被广泛用于航空航天、化学以及发电工业
而且,由于独特的冶金性能,按照AMS 5837以焊丝和焊条形式制造的Inconel 625已经通过钨极惰性气体保护焊(GTAW)、激光、电子束和等离子焊接和熔覆用于涡轮发动机组件的修复。由于平衡的化学组成,溶体硬化IN625合金具有高延性,其中高至0.1wt.%的碳不影响其延性。因此,该合金没有进一步进行费用高的纯化的冶金需要,该纯化可能增加该广泛应用的焊丝的价格。因此,市场上可获得的IN625焊丝中通常的碳含量从约0.06wt.%至约0.1wt.%变化。
IN625产生了良好的焊接,但是根据Banerjee K.,Richards N.L.和ChaturvediM.C.“Effect of Filler Alloys on Heat Affected Zone Cracking in Pre-weld HeatTreated IN-738LC Gas-Tungsten-Arc”,Metallurgical and Material Translation,第36A卷,2005年7月,pp.1881-1890所述,738、GTD 111、GTD 222、Inconel 713和一些其他具有高含量的γ'相(γ')的沉淀硬化超级合金的热影响区(HAZ)趋于微裂,也称为微开裂。
根据A.Gontcharov,J.Liburdi,P.Lowden等“Self Healing Fusion WeldingTechnology”,GT2014-26412,Proceedings of ASME Turbo Expo 2014:TurbineTechnical Conference and Exposition,2014年6月16至20日,Dussseldorf,Germany,用硼改性Inconel 625降低了由GTD111和Inconel 738和GTD 111镍基超级合金上的激光熔覆产生的焊接的HAZ中的熔解温度和液化开裂。这些焊接处在1800°F的温度下只有19.7%的延伸率,这实际上限制了拉拔工艺用于制造焊丝。
因此,需要对硼改性的Inconel 625焊接材料进行额外的改善,以允许使用标准的拉拔工艺进行焊丝的制造,且与Inconel 625的标准化学组成无显著偏差。所述焊丝能在沉淀硬化超级合金上产生无裂纹的焊接,其钎焊接头及焊接接头的屈服强度及断裂应力特性超过标准Inconel 625合金的相关特性,这同样是本构思的一个目标。
发明概述
我们已经发现,为了达到使用标准的拉拔工艺及挤压工艺制造焊丝所需要的延性,在含0.4-0.6wt.%的硼(B)、17-23wt.%的铬(Cr)、8-10wt.%的钼(Mo)、0.1-4.15wt.%的铌(Nb)的镍基合金中的碳含量不应超过约0.04wt.%,以避免或最小化碳化物的形成。
除以上所述之外,本发明的焊接材料还产生了具有优异的屈服强度、延性和断裂应力特性的无裂纹焊接,其超过了使用标准IN625焊丝所产生的焊接的机械性能。
根据所述的优选实施方案,本发明的焊接材料可被制成焊丝和钎焊丝、焊粉和焊箔的形式。
本发明的焊接材料可用于各种制品的连接和修复,包括由多晶的、定向凝固的以及单晶的镍基合金、钴基合金和铁基合金制造的涡轮发动机组件。
由于该合金的高延性和降低的熔解温度,本发明的焊接材料可用于由大间隙钎焊、Liburdi粉末冶金技术产生的材料以及复合材料的TIG钎焊和连接。
附图说明
图1是用于GTAW-MA焊接和TIG钎焊的切割成条状的焊丝的照片。
图2是使用包含0.4wt.%B和0.02wt.%C的焊条在GTD 111母材上产生的被覆熔接的显微照片,其描绘了在底部的无裂纹HAZ和在顶部堆立的焊接,其中,1为焊缝金属,2为熔合线以及3为由GTD 111超级合金制造的母材。
图3是在应用于Inconel 738超级合金的表面的Mar M24-Amdry775大间隙钎焊材料上产生的被覆熔接的显微照片,其中1为焊缝金属,2为熔合线以及3为由WGB制造的母材。
图4是在CMSX-4上的被覆熔接的显微照片,其描绘了无裂纹焊接且无任何证据表明单晶基材重结晶,其中,1为焊缝金属,2为熔合线以及3为由CMSX-4单晶合金制造的母材。
标准首字母缩略词
AMS-航空航天材料规格(标准)
ASTM-美国材料与试验协会(标准)
AWS-美国焊接协会(标准)
HAZ-热影响区
NDT-无损检测
PWHT-焊后热处理
RA-拉伸试验中减少的样本面积
UTS-极限抗拉强度
IN625-Inconel 625镍基合金
GTAW-MA-钨极惰性气体保护焊-手动的
GTAW-ME-钨极惰性气体保护焊-机械的
LBW-激光焊接
EBW-电子束焊接
PAW-等离子弧焊接
TIG-钨极惰性气体
WGB-大间隙钎焊
LPMTM-Liburdi粉末冶金工艺和商标
HPT-高压涡轮
术语的词汇表
Amdry 775-具有高铬含量的扩散钎焊合金,其具有强大的抗氧化性和耐腐蚀性,以及含硼作为熔化抑制剂,其提供了均匀的沉积物。
硼化物-由两种元素组成的化合物,其中硼是更具有电负性的元素。硼与金属元素和非金属元素形成硼化物。
CMSX-4材料-超高强度单晶合金
稀释-由焊珠中的母材或先前的焊接金属的混合所引起的焊接材料的化学组成的变化,其是通过焊珠中的基体金属或先前的焊接金属的百分比而测量的。
延性-金属和合金在不断裂的情况下被拉伸、伸展或成形的能力。
开裂-破裂表面的仅具有轻微分离(张开位移)的小的裂纹状中断。所述的前缀大-或微-表示相对大小。
钨极惰性气体保护焊(GTAW)-根据AWS定义,其是通过使用在钨电极(非消耗型)和也称作母材的工件之间的电弧加热金属而产生金属接合的电弧焊接工艺。从气体或气体混合物获得屏蔽。可以或可以不使用压力以及可以或可以不使用填充金属。
GTD 111-由通用电气公司开发的镍基超级合金。
INCONEL 738-真空浇注并沉淀硬化的镍基合金。
激光焊接和熔覆(LBW)-根据AWS定义,其是使用通过分别冲击接缝或母材上的集中相干光束的应用而获得的热量产生金属的接合的焊接工艺。
液化开裂-在液化材料的凝固过程中由边界成分的熔化引起的小裂纹。
LPM材料-包含基于黄铜的基质(braze based matrix)并以诸如Mar M247和Inconel 738等固相高温填充粉末形式呈现的材料。
MAR M-247-沉淀硬化的高γ'镍基超级合金。
Inconel 738-沉淀硬化的高γ'镍基超级合金。
钨极惰性气体钎焊-由钨电极维持电弧并使用惰性气体防止空气接近的焊接方法。
焊粉-在产生焊接接头或被覆熔接时添加的粉末形式的焊接材料。
焊条-切割成标准长度的焊丝。
焊丝-在产生焊接接头或被覆熔接时添加的线材形式的焊接材料。
大间隙钎焊合金-含有在钎焊温度下熔化的组分和在相同温度下部分熔化或不熔化的组分的合金。该合金允许在构件之间产生“桥”。
大间隙钎焊层-提供基材上的材料覆盖物
发明详述
本发明的合金可以以焊丝和焊粉的形式使用,也可以以通过浇铸、压延、热压成形和冷成形制造的各种制品并在修复期间通过替换损坏的部分而并入这些制品的形式使用。
焊丝和焊粉形式的焊接材料是本发明合金的主要应用,因此,将在下文更详细地讨论。
关于制造焊丝,直径为0.5-3英寸的铸锭(也称为坯料)采用标准感应、电弧熔化和再熔化技术和设备在真空或氩气中生产出。然后将坯料通过使用预热进行拉延或挤压而减少至所需直径、随后通过标准的表面精加工。因此,初始铸造材料的高延性对于最小化用于通过挤压和拉延成功制造焊丝的工艺温度是必要的。
在最终加工期间,使线材经过标准的严密清洗程序,这确保采用该线材制造的焊丝和焊接不受污染。
在清洗后,将该线材切割成用于制造手动GTAW-MA用焊条所需要的长度,或将该线材对接焊接在一起并绕在卷轴上以用于自动GTAW-ME、LBM、EBM以及PAW焊接。
通过标准气体喷雾工艺制造用于激光和等离子熔覆及焊接的直径为45-75μm的焊粉。在该过程中,熔化的合金通过惰性气体喷流被雾化成细金属滴,在它们落入雾化塔期间被冷却。通过气体雾化获得的金属粉具有完美的球形和高洁净度水平。
在焊接期间,将焊粉和焊丝注入焊接熔池中,由于凝固,它们与母材融合,产生具有与焊接材料的化学组成相近的化学组成的焊接金属。为降低过热并防止HAZ开裂,使用最小稀释进行焊接和熔覆。熔覆的最佳结果是用5-15%的稀释来实现。
如本发明范围内所发现的,特定范围内的硼产生了两个有益效果,实现本发明的目的。首先,硼与特定含量的碳的组合提高了本发明的合金在1600°F-1800°F的温度范围内的延性,这允许采用标准的拉拔工艺和挤压工艺制造焊丝。
第二,在0.4wt.%至0.6wt.%范围内的硼降低了焊接材料的熔化温度和HAZ的过热,从而使在GTD 111超级合金的HAZ中的母材的液化开裂最小化或排除该液化开裂,如图1所示。
除上所述之外,由于形成立方形硼化物,硼增加了焊接的强度,参看表2和表3。
如图3所示,本发明的焊接材料的高延性和降低的熔解温度允许在钎焊接头和WGB材料上进行双面点焊(direct welding)和TIG钎焊。以及如图4所示,采用本发明的焊接材料的焊接和熔覆排除了开裂以及单晶材料的重结晶。
在GTD 111合金和WGB钎焊材料上产生的焊丝和焊接的实例
将具有表1所示的优选化学组成的本发明合金被指定为合金1和合金2以及具有增加的碳含量的合金3,其在氩气中通过等离子电弧熔炼而产生并为条棒形式,根据ASTM E-8,E-21在1200°F和1800°F下进行拉伸试验,以及根据ASTM E-139在1700°F的温度下进行应力断裂试验。如下表2和表3所示,本发明的合金显示了优异的延性,这允许采用标准的拉拔工艺和挤压工艺制造焊丝。由合金1制造的直径为0.045英寸的焊丝的实例显示于图1中。
除了优异的延性外,由于形成在延性镍基基质中均匀沉淀的细的立方形硼化物,本发明的合金的屈服强度和应力断裂特性显著地超过标准IN625合金的特性。
采用等离子电弧再熔炼由合金1制造的条棒和在相同制造条件下制造的线材的机械性能与标准的AMS 5666和AMS 5402625合金在锻造和铸造条件下的机械性能的各自比较提供于表3和表4中。如该数据所示,本发明的合金在室温下显示了优异的机械性能,其可用于制造包括涡轮发动机组件在内的各种制品。
通过采用由合金1制造的焊条进行熔覆和焊接,采用GTAW-MA焊接进行可焊性试验。在沉淀硬化的等轴的并定向凝固的GTD 111沉淀硬化型超级合金、熔敷至Inconel 738基材表面的由Mar M247填充粉末和Amdry 775钎焊材料组成的WGB层和单晶CMSX-4材料上进行熔覆。
基于GTD 111、WGB和CMSX-4合金的历史上不良的可焊性和在多种涡轮发动机组件的制造和修复中的广泛的工业应用,选择这些材料以证明本发明的焊接材料的优异特性。例如,GTD 111对在HAZ中的微裂隙高度敏感。数十年来,GTD 111一直用于制造工业燃气涡轮发动机的高压涡轮叶片(HPT)。单晶CMSX-4材料已用于制造航空涡轮发动机的HPT叶片。其易于重结晶和开裂。WGB材料已经广泛用于涡轮发动机组件的修复。由于低延性,这类材料易于应力-应变开裂。
通过分别在WGB和GTD 111、CMSX-4样品上进行单道和多道熔覆来进行焊接试验,旨在在室温下采用GTAW-MA焊接工艺产生4英寸长,0.15英寸至0.3英寸宽以及0.080英寸至0.35英寸高的堆焊。在PWHT条件下在GTD 111、WGB和CMSX-4材料上的被覆熔接的典型显微照片分别如图2、3和4所示。
通过实验选择焊接工艺参数,旨在产生稀释度为10-15%的被覆熔接:
(60-70)A的焊接电流
(13-14)V的电弧电压
(1.0-1.2)英寸/分钟的焊接速度。
在焊接之前,使由GDT 111合金制造的样品在2192°F的温度下进行预焊接退火热处理两个(2)小时,随后氩气淬火。在由WGB和CMSX-4材料制造的样品上进行焊接,无需预焊接热处理。
在焊接之后,使由GTD 111和WGB材料产生的样品进行PWHT,其包括在2192°F的温度下退火两个(2)小时,随后在2048°F的温度下老化两个(2)小时并在1553°F下老化二十四个(24)小时。使CMSX-4样本在2048°F下应力消除一(1)个小时。
用于焊接镍基超级合金的焊接材料的可接受的组成包括如下组成:其具有足够的延性以被拉拔成线并产生在1800°F的温度下屈服强度和应力断裂特性超过IN625的特性的无裂纹焊接。
如表2所示,合金3中的增加的碳含量在1200-1800°F的温度范围内大于两倍地降低了伸长率并且使得其不能被拉拔成焊丝。
具有对应于合金1和合金2的化学组成的本发明的合金显示了优异的延性,这允许采用标准的拉拔工艺和挤压工艺制造焊丝。而且,如表3所示,在1200°F和1800°F下,合金1具有与标准625合金相比更优异的应力-断裂特性,并且分别如图2、3和4所示,合金1在GTD 111、WGB和单晶CMSX-4材料上产生无裂纹焊接。同样,如表4所示,本发明的合金在室温下具有优异的拉伸特性和延性,可以考虑将其用于涡轮发动机组件及其他制品的制造。
表1与标准IN625合金相比本发明的焊接材料的化学组成(Wt.%)
表2在电弧再熔炼条件下本发明的合金的高温拉伸特性
表3具有优选化学组成的等离子电弧熔炼的合金1和基线标准IN625合金的应力断裂特性
表4在室温下由具有优选化学组成的本发明的合金1和标准Inconel625合金制造的焊丝的机械特性
表5在1800°F下采用由合金1和IN625基线合金制造的焊丝产生的焊点的拉伸特性
表6采用由合金1和IN625基线合金制造的焊丝所产生的焊接金属的应力-断裂特性和拉伸特性
如表5和表6所示,在1800°F的温度下,使用由合金1制造的焊丝采用GTAW-MA在GTD111基材上产生的被覆熔接的机械特性超过了使用标准IN625焊丝所产生的焊接的特性。因此,包含约0.4wt.%至0.6wt.%B和痕量至最大值为0.04wt.%C的本发明的焊接材料具有优异的延性,并在GTD 111超级合金、WGB和CMSX-4单晶材料上产生了在高温下机械特性超过标准IN625基线合金的特性的无裂纹焊接,并允许采用标准的低成本和高生产力的拉拔工艺和挤压工艺制造本发明的焊丝。标准IN625合金不含硼,然而由于该合金的碳含量其确实包含一定量的碳化物。在该合金中要求小于0.04wt.%C的低碳含量以排除碳化物的形成。通常在625中所含有的0.06wt.%至约0.1wt.%的高碳含量促进碳化物的形成,这降低了延性并且影响了本发明的材料经受冷加工、拉丝和成形的能力。如以上表1和表2中的合金3所证实的,这已被实验所证实。
Claims (17)
1.延性的含硼镍基焊接材料,其包含重量百分比表示的以下元素:
a)硼:0.4-0.6wt.%
b)碳:痕量至0.04wt.%
c)铬:20-23wt.%
d)钼:8-10wt.%
e)铌:3.15-4.14wt.%
f)锰:痕量至1.5wt.%,以及
g)镍及杂质:余量,
其中所述焊接材料适于连接和修复合金,其具有等于或超过基线标准Inconel 625的应力断裂特性。
2.如权利要求1所述的延性的含硼镍基焊接材料,其还包含重量百分比表示的以下元素:
a)铁:痕量至5wt.%;以及
b)选自钛、钽、钨和硅的微合金元素,前提是所述微合金元素和锰的合计的量不超过1.5wt.%。
3.如权利要求1所述的延性的含硼镍基焊接材料,其是用于焊接的丝。
4.如权利要求1所述的延性的含硼镍基焊接材料,其是用于焊接的粉末。
5.如权利要求1所述的延性的含硼镍基焊接材料,其是用于钎焊和扩散接合的箔。
6.如权利要求1所述的延性的含硼镍基焊接材料,其用于多晶镍基、多晶钴基和多晶铁基合金的焊接。
7.如权利要求1所述的延性的含硼镍基焊接材料,其用于定向凝固的镍基、定向凝固的钴基和定向凝固的铁基合金的焊接。
8.如权利要求1所述的延性的含硼镍基焊接材料,其用于单晶镍基、单晶钴基和单晶铁基材料的焊接。
9.如权利要求1所述的延性的含硼镍基焊接材料,其用于复合材料的TIG焊接。
10.如权利要求1所述的延性的含硼镍基焊接材料,其用于通过焊接产生的制品的修复。
11.如权利要求1所述的延性的含硼镍基焊接材料,其是用于钎焊的丝。
12.如权利要求1所述的延性的含硼镍基焊接材料,其是用于钎焊的粉末。
13.如权利要求1所述的延性的含硼镍基焊接材料,其用于多晶镍基、多晶钴基和多晶铁基合金的钎焊。
14.如权利要求1所述的延性的含硼镍基焊接材料,其用于定向凝固的镍基、定向凝固的钴基和定向凝固的铁基合金的钎焊。
15.如权利要求1所述的延性的含硼镍基焊接材料,其用于单晶镍基、单晶钴基和单晶铁基材料的钎焊。
16.如权利要求1所述的延性的含硼镍基焊接材料,其用于复合材料的TIG钎焊。
17.如权利要求1所述的延性的含硼镍基焊接材料,其用于通过钎焊产生的制品的修复。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/263,120 US10414003B2 (en) | 2013-09-30 | 2014-04-28 | Welding material for welding of superalloys |
US14/263,120 | 2014-04-28 | ||
PCT/CA2014/000752 WO2015164939A1 (en) | 2014-04-28 | 2014-10-21 | A ductile boron bearing nickel based welding material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105246642A CN105246642A (zh) | 2016-01-13 |
CN105246642B true CN105246642B (zh) | 2020-05-26 |
Family
ID=54357930
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201480013693.6A Active CN105246642B (zh) | 2014-04-28 | 2014-10-21 | 延性的含硼镍基焊接材料 |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP3137253B1 (zh) |
JP (1) | JP6506389B2 (zh) |
KR (1) | KR102227534B1 (zh) |
CN (1) | CN105246642B (zh) |
CA (1) | CA2902152C (zh) |
ES (1) | ES2713006T3 (zh) |
PL (1) | PL3137253T3 (zh) |
RU (1) | RU2666822C2 (zh) |
SG (1) | SG11201508884XA (zh) |
WO (1) | WO2015164939A1 (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10625361B2 (en) * | 2017-06-14 | 2020-04-21 | General Electric Company | Method of welding superalloys |
TWI683005B (zh) * | 2018-05-24 | 2020-01-21 | 國家中山科學研究院 | 鎳基超合金銲接用之銲料 |
CN112575227B (zh) * | 2020-11-02 | 2021-12-07 | 抚顺特殊钢股份有限公司 | 一种高硅镍基合金冷轧板材的制造方法 |
CN113319418A (zh) * | 2021-06-29 | 2021-08-31 | 哈尔滨工业大学 | 一种钼铼合金无中间层扩散连接方法 |
CN114505619B (zh) * | 2022-04-19 | 2022-09-27 | 西安热工研究院有限公司 | 镍基焊丝、镍基焊丝的制造方法和镍基焊丝的焊接工艺 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3798075A (en) * | 1970-03-10 | 1974-03-19 | Carpenter Technology Corp | Method of making stainless steel containing borides |
US4363659A (en) * | 1979-06-04 | 1982-12-14 | Cabot Corporation | Nickel-base alloy resistant to wear |
GB2039950B (en) * | 1979-01-11 | 1983-06-15 | Boc Ltd | Hard alloys |
CN101121977A (zh) * | 2006-08-09 | 2008-02-13 | 中国科学院金属研究所 | 一种定向凝固镍基高温合金及其热处理工艺 |
CN101376971A (zh) * | 2007-08-31 | 2009-03-04 | 通用电气公司 | 修复镍基合金制品的方法 |
FR2935396B1 (fr) * | 2008-08-26 | 2010-09-24 | Aubert & Duval Sa | Procede de preparation d'une piece en superalliage base nickel et piece ainsi obtenue. |
CN103540928A (zh) * | 2013-09-30 | 2014-01-29 | 广州有色金属研究院 | 一种风管表面涂层的制造方法 |
CN103635284A (zh) * | 2011-03-23 | 2014-03-12 | 思高博塔公司 | 用于抗应力腐蚀裂开的细粒镍基合金及其设计方法 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB909948A (en) * | 1960-04-13 | 1962-11-07 | Rolls Royce | Method of making turbine blades |
US3632319A (en) * | 1969-07-11 | 1972-01-04 | Gen Electric | Diffusion bonding of superalloy members |
US3918964A (en) * | 1973-12-21 | 1975-11-11 | Sorcery Metals Inc | Nickel-base alloys having a low coefficient of thermal expansion |
JPS519036A (ja) * | 1974-07-10 | 1976-01-24 | Int Nickel Co | Kodonikachuseinoarusankateikoseino gannitsukerugokinoyosetsusurunonimochiiru tanrenshitayokazai |
USRE29920E (en) * | 1975-07-29 | 1979-02-27 | High temperature alloys | |
JPS5274509A (en) * | 1975-12-18 | 1977-06-22 | Mitsubishi Metal Corp | Ni-base sintered alloy |
SE428937B (sv) * | 1979-01-11 | 1983-08-01 | Cabot Stellite Europ | Nickelbaserad, hard legering eller tillsatsmaterial avsett for pasvetsning eller svetsning |
JPS57207145A (en) | 1981-06-15 | 1982-12-18 | Toshiba Corp | Wear resistant alloy |
JPS58159993A (ja) * | 1982-03-17 | 1983-09-22 | Toshiba Corp | 溶接材料 |
JPS59100248A (ja) | 1982-11-27 | 1984-06-09 | Toshiba Corp | 内燃機関のバルブおよびバルブシ−ト用Ni基合金 |
RU2078657C1 (ru) * | 1995-04-28 | 1997-05-10 | Акционерное общество "Новолипецкий металлургический комбинат" | Способ наплавки деталей металлургического оборудования |
JPH08337850A (ja) * | 1995-06-12 | 1996-12-24 | Nkk Corp | 溶接構造高温機器用オーステナイト系ステンレス鋼 |
RU2154563C1 (ru) * | 1999-04-12 | 2000-08-20 | Инженерный центр "Сплав" | Композиция для индукционной наплавки |
JP4189359B2 (ja) * | 2004-06-22 | 2008-12-03 | 岡野バルブ製造株式会社 | 防食方法 |
US20120251840A1 (en) * | 2011-03-30 | 2012-10-04 | General Electric Company | Nickel-base weld materials, processes of using, and components formed therewith |
CA2870778C (en) | 2012-10-24 | 2019-06-04 | Liburdi Engineering Limited | A composite welding wire and method of manufacturing |
RU2610198C2 (ru) * | 2012-12-05 | 2017-02-08 | Либурди Инжиниринг Лимитед | Способ наплавления и сварки плавлением сверхпрочных сплавов |
-
2014
- 2014-10-21 JP JP2017508716A patent/JP6506389B2/ja active Active
- 2014-10-21 ES ES14891039T patent/ES2713006T3/es active Active
- 2014-10-21 CA CA2902152A patent/CA2902152C/en active Active
- 2014-10-21 WO PCT/CA2014/000752 patent/WO2015164939A1/en active Application Filing
- 2014-10-21 PL PL14891039T patent/PL3137253T3/pl unknown
- 2014-10-21 SG SG11201508884XA patent/SG11201508884XA/en unknown
- 2014-10-21 EP EP14891039.1A patent/EP3137253B1/en active Active
- 2014-10-21 RU RU2015139526A patent/RU2666822C2/ru active
- 2014-10-21 CN CN201480013693.6A patent/CN105246642B/zh active Active
- 2014-10-21 KR KR1020157025629A patent/KR102227534B1/ko active IP Right Grant
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3798075A (en) * | 1970-03-10 | 1974-03-19 | Carpenter Technology Corp | Method of making stainless steel containing borides |
GB2039950B (en) * | 1979-01-11 | 1983-06-15 | Boc Ltd | Hard alloys |
US4363659A (en) * | 1979-06-04 | 1982-12-14 | Cabot Corporation | Nickel-base alloy resistant to wear |
CN101121977A (zh) * | 2006-08-09 | 2008-02-13 | 中国科学院金属研究所 | 一种定向凝固镍基高温合金及其热处理工艺 |
CN101376971A (zh) * | 2007-08-31 | 2009-03-04 | 通用电气公司 | 修复镍基合金制品的方法 |
FR2935396B1 (fr) * | 2008-08-26 | 2010-09-24 | Aubert & Duval Sa | Procede de preparation d'une piece en superalliage base nickel et piece ainsi obtenue. |
CN103635284A (zh) * | 2011-03-23 | 2014-03-12 | 思高博塔公司 | 用于抗应力腐蚀裂开的细粒镍基合金及其设计方法 |
CN103540928A (zh) * | 2013-09-30 | 2014-01-29 | 广州有色金属研究院 | 一种风管表面涂层的制造方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2902152C (en) | 2019-03-05 |
RU2015139526A (ru) | 2017-03-22 |
RU2015139526A3 (zh) | 2018-07-16 |
EP3137253B1 (en) | 2018-12-12 |
KR20160146490A (ko) | 2016-12-21 |
KR102227534B1 (ko) | 2021-03-12 |
WO2015164939A1 (en) | 2015-11-05 |
PL3137253T3 (pl) | 2019-06-28 |
ES2713006T3 (es) | 2019-05-17 |
CN105246642A (zh) | 2016-01-13 |
EP3137253A4 (en) | 2017-10-04 |
SG11201508884XA (en) | 2015-11-27 |
CA2902152A1 (en) | 2015-10-28 |
JP6506389B2 (ja) | 2019-04-24 |
EP3137253A1 (en) | 2017-03-08 |
JP2017519643A (ja) | 2017-07-20 |
RU2666822C2 (ru) | 2018-09-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102237760B1 (ko) | 초내열합금의 융접용 석출 경화형 니켈계 용접 재료 | |
JP6086992B2 (ja) | 超合金のクラッディング及び溶融溶接方法 | |
US20160167172A1 (en) | Method of cladding, additive manufacturing and fusion welding of superalloys and materialf or the same | |
EP3647442B1 (en) | High gamma prime nickel based superalloy, its use, and method of manufacturing of turbine engine components | |
CN105246642B (zh) | 延性的含硼镍基焊接材料 | |
CN112760525B (zh) | 高γ′镍基超级合金、其用途及制造涡轮发动机构件的方法 | |
EP2853339B1 (en) | Welding material for welding of superalloys | |
KR102232809B1 (ko) | 초합금의 용접을 위한 용접 재료 | |
US10493568B2 (en) | Ductile boron bearing nickel based welding material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |