CN103710599B - A kind of boron nitride strengthens creep resistance Dow metal and preparation method thereof - Google Patents

A kind of boron nitride strengthens creep resistance Dow metal and preparation method thereof Download PDF

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CN103710599B
CN103710599B CN201410018723.4A CN201410018723A CN103710599B CN 103710599 B CN103710599 B CN 103710599B CN 201410018723 A CN201410018723 A CN 201410018723A CN 103710599 B CN103710599 B CN 103710599B
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陆明军
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Guangxi Beibu Gulf Grain And Oil Technology Research Co ltd
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Abstract

The invention provides a kind of boron nitride and strengthen creep resistance Dow metal, contain according to weight percent content: Gd:0.15-0.2%, Al:0.5-0.8%, Zn:1.1-1.26%, Si:5.3-5.7%, Ca:0.3-0.4%, Sr:0.1-0.3%, Nd:0.2-0.6%, Zr:0.4-0.55%, Sn:0.8-0.9%, Be:0.05-0.15%, Mn:0.55-0.58%, Sb:0.35-0.45%, Cu:0.7-0.9%, boron nitride nanometer tube particle: 1-15%, surplus is Mg, and described boron nitride nanometer tube particle is of a size of less than 100 μm.The present invention also proposes the preparation method of this alloy.This alloy has excellent mechanical performances and creep-resistant property.

Description

A kind of boron nitride strengthens creep resistance Dow metal and preparation method thereof
Technical field
The invention belongs to field of magnesium alloy material, especially a kind of boron nitride strengthens creep resistance Dow metal and preparation method thereof.
Background technology
Magnesium alloy as the commercial metal structural timber of most lightweight, because of its have that light specific gravity, specific tenacity specific rigidity are high, damping vibration attenuation falls that dry ability is strong, liquid condition shaping superior performance and be easy to the advantages such as recycling, is described as 21 century " green structured material ".But at present because the high-temperature creep resistance of existing magnesium alloy is poor, Long-term service temperature can not more than 120 DEG C, it is made for the manufacture of to the high motor car engine of high temperature creep property requirement and other drive disk assemblies, therefore cannot greatly to hinder the further application of magnesium alloy.Also just because of like this, research and development both at home and abroad for the heat resistance magnesium alloy with high-temperature creep resistance give great attention, and successively trial-production have studied the heat resistance magnesium alloy of the series such as Mg-Al-Si, Mg-Al-RE, Mg-Al-Ca, Mg-Al-Ca-RE, Mg-Al-Sr, Mg-Al-Sn, Mg-Zn-Al, Mg-Zn-RE, Mg-Zn-Si, Mg-Zn-Sn, Mg-Y-Nd and Mg-Sn-Ca.But, above, these obtain manufacturing experimently in the heat resistance magnesium alloy system of research, what really obtain practical application mainly concentrates on minority alloy, as the WE43 alloy of the AE42 alloy in Mg-Al-RE system, Mg-Y-Nd system and AS41 and the AS21 alloy of Mg-Al-Si system.In addition, even if these heat resistance magnesium alloys be applied also make it apply to be subject to restriction in various degree because there is problems different separately.As for AE42 alloy and WE43 alloy, its precious metal element such as RE (> 2.5%) and/or Y, Th all containing high-content, the cost of alloy is higher, and it is at present only for the contour performance engine of racing car, not widespread use on automobile.Therefore, the heat resistance magnesium alloy that research and development are novel is further necessary.
Summary of the invention
The object of this invention is to provide a kind of boron nitride and strengthen creep resistance Dow metal.It can meet the requirement of higher force performance and high-temperature creep resistance, has the corrosion resistance more much higher than existing magnesium alloy.
Another object of the present invention is to provide the preparation method that a kind of boron nitride strengthens creep resistance Dow metal.
For reaching this object, the present invention by the following technical solutions:
A kind of boron nitride strengthens creep resistance Dow metal, contain according to weight percent content: Gd:0.15-0.2%, Al:0.5-0.8%, Zn:1.1-1.26%, Si:5.3-5.7%, Ca:0.3-0.4%, Sr:0.1-0.3%, Nd:0.2-0.6%, Zr:0.4-0.55%, Sn:0.8-0.9%, Be:0.05-0.15%, Mn:0.55-0.58%, Sb:0.35-0.45%, Cu:0.7-0.9%, boron nitride nanometer tube particle: 1-15%, surplus is Mg, and described boron nitride nanometer tube particle is of a size of less than 100 μm.
Further, contain according to weight percent content: Gd:0.16%, Al:0.79%, Zn:1.25%, Si:5.84%, Ca:0.37%, Sr:0.12%, Nd:0.43%, Zr:0.545%, Sn:0.86%, Be:0.125%, Mn:0.565%, Sb:0.38%, Cu:0.725%, boron nitride nanometer tube particle: 10%, surplus is Mg, and described boron nitride nanometer tube particle is of a size of 50 μm.
Described boron nitride strengthens the preparation method of creep resistance Dow metal, comprises the following steps:
(1) raw material prepares: carry out raw material preparation according to weight percent content, described raw material is pure Mg ingot, Mg-Gd master alloy, pure Al ingot, pure Zn, Al-Si master alloy, Al-Ca master alloy, Al-Sr master alloy, Mg-Nd master alloy, Mg-Zr master alloy, pure Sn, Al-Be master alloy, Al-Mn master alloy, pure Sb, Al-Cu master alloy, boron nitride nanometer tube particle;
(2) melting: adopt gas atmosphere molten alloy in resistance furnace, smelting temperature is 740-765 DEG C, first in smelting furnace, add pure Mg ingot, after pure magnesium ingot melts completely, add Mg-Gd master alloy, pure Al ingot, pure Zn, Al-Si master alloy, Al-Ca master alloy, Al-Sr master alloy, Mg-Nd master alloy, Mg-Zr master alloy, pure Sn, Al-Be master alloy, Al-Mn master alloy, pure Sb, Al-Cu master alloy, stir after all raw materials melt completely, make alloying constituent even, by particle doped in the magnesium alloy liquation of melting for the boron nitride nano-tube being preheating to 550-650 DEG C, then stir and make its uniform composition, magnesium alloy liquation sufficient standing after doping will be stirred,
(3) refining: make smelting furnace be warming up to 780 DEG C ~ 790 DEG C alloys and carry out refining, add heat resistance magnesium alloy refining agent while stirring, refining time is 1-4 minute, 5 ~ 8 minutes are left standstill, consisting of of described heat resistance magnesium alloy refining agent: NaCl:18% ~ 26% 735 DEG C ~ 745 DEG C insulations after refining is complete; Na3AlF6:8 ~ 10%; MgCl2:30-40%; Surplus is KCl;
(4) cast: the magnesium alloy refining material of melting being cast to preheating temperature is in the swage tool of 200 ~ 300 DEG C, and pouring temperature is 725 DEG C ~ 735 DEG C; Cast gauge is Ф 450mm ~ Ф 500mm, length >=3000mm
(5) thermal treatment: foundry goods is carried out solution treatment in 430-435 DEG C of temperature range, the solution treatment time is 16 ~ 24 hours, then carry out shrend, the foundry goods after quenching to be put in the resistance furnace of 210 DEG C artificial aging 40 hours, obtained magnesium alloy blank;
(6) deformation process: a. high temperature forging cogging: heating blank to temperature is 405 DEG C ~ 445 DEG C insulation 1 ~ 2h; Carry out two to hammer cogging, be forged into the slab that thickness is 40-60mm; Reduction in pass is 20% ~ 40%, every 3-6 passage forging after annealing 1.5h, and annealing temperature is 405 DEG C ~ 445 DEG C; B. heated roll to temperature is 305-345 DEG C; C. heating slab to temperature is 455-465 DEG C, is incubated after 20-30 minute, and adopt the method for multi-pass small deformation amount that heavy plate rolling is become 2 ~ 10mm thin plate, the speed of rolls is 0.4m/s ~ 0.8 m/s; Every time roll reduction is 10% ~ 20%, melts down annealing after every time rolling, and annealing temperature is 405 DEG C ~ 445 DEG C, and annealing time is 30min ~ 40min;
(7) roll postheat treatment: the thin plate after rolling is carried out ageing treatment, and described aging treatment process is: aging temp is 225-245 DEG C, soaking time is 12-36h; Carry out second time ageing treatment at 195-215 DEG C again, aging time is 12-36h; Finally carry out third time ageing treatment at 145-175 DEG C, aging time is 12-36h.
Described boron nitride nanometer tube particle refers to that the particulate material that one or more boron nitride nano-tube is formed, its size are the size of described particle.
Advantage of the present invention is: magnesium alloy of the present invention can meet the requirement of higher force performance and high-temperature creep resistance, has the corrosion resistance more much higher than existing magnesium alloy.
Embodiment
embodiment 1
A kind of boron nitride strengthens creep resistance Dow metal, contains: Gd:0.17%, Al:0.66% according to weight percent content, Zn:1.24%, Si:5.46%, Ca:0.37%, Sr:0.185%, Nd:0.235%, Zr:0.47%, Sn:0.865%, Be:0.135%, Mn:0.565%, Sb:0.378%, Cu:0.79%, boron nitride nanometer tube particle: 4%, surplus is Mg, and described boron nitride nanometer tube particle is of a size of 40 μm, and its preparation method comprises the following steps:
(1) raw material prepares: carry out raw material preparation according to weight percent content, described raw material is pure Mg ingot, Mg-Gd master alloy, pure Al ingot, pure Zn, Al-Si master alloy, Al-Ca master alloy, Al-Sr master alloy, Mg-Nd master alloy, Mg-Zr master alloy, pure Sn, Al-Be master alloy, Al-Mn master alloy, pure Sb, Al-Cu master alloy, boron nitride nanometer tube particle;
(2) melting: adopt gas atmosphere molten alloy in resistance furnace, smelting temperature is 755 DEG C, first in smelting furnace, add pure Mg ingot, after pure magnesium ingot melts completely, add Mg-Gd master alloy, pure Al ingot, pure Zn, Al-Si master alloy, Al-Ca master alloy, Al-Sr master alloy, Mg-Nd master alloy, Mg-Zr master alloy, pure Sn, Al-Be master alloy, Al-Mn master alloy, pure Sb, Al-Cu master alloy, stir after all raw materials melt completely, make alloying constituent even; By particle doped in the magnesium alloy liquation of melting for the boron nitride nano-tube being preheating to 580 DEG C, then stir and make its uniform composition, will the magnesium alloy liquation sufficient standing after doping be stirred;
(3) refining: make smelting furnace be warming up to 780 DEG C ~ 790 DEG C alloys and carry out refining, add heat resistance magnesium alloy refining agent while stirring, refining time is 3 minutes, leaves standstill 6 minutes, consisting of of described heat resistance magnesium alloy refining agent: NaCl:19% after refining is complete 738 DEG C of insulations; Na3AlF6:9.5%; MgCl2:36%; Surplus is KCl;
(4) cast: the magnesium alloy refining material of melting being cast to preheating temperature is in the swage tool of 260 DEG C, and pouring temperature is 728 DEG C; Cast gauge is Ф 460mm, length 3000mm;
(5) thermal treatment: foundry goods is carried out solution treatment in 433 DEG C of temperature ranges, the solution treatment time is 20 hours, then carries out shrend, and the foundry goods after quenching to be put in the resistance furnace of 210 DEG C artificial aging 40 hours, obtained magnesium alloy blank;
(6) deformation process: a. high temperature forging cogging: heating blank to temperature is 435 DEG C of insulation 1.5h; Carry out two to hammer cogging, be forged into the slab that thickness is 50mm; Reduction in pass is 30%, every 4 passage forging after annealing 1.5h, and annealing temperature is 430 DEG C; B. heated roll to temperature is 325 DEG C; C. heating slab to temperature is 458 DEG C, is incubated after 25 minutes, and adopt the method for multi-pass small deformation amount that heavy plate rolling is become 3mm thin plate, the speed of rolls is 0.6 m/s; Every time roll reduction is 15%, melts down annealing after every time rolling, and annealing temperature is 425 DEG C, and annealing time is 35min;
(7) roll postheat treatment: the thin plate after rolling is carried out ageing treatment, and described aging treatment process is: aging temp is 235 DEG C, soaking time is 18h; Carry out second time ageing treatment at 205 DEG C again, aging time is 18h; Finally carry out third time ageing treatment at 155 DEG C, aging time is 18h.
embodiment 2:
A kind of boron nitride strengthens creep resistance Dow metal, contain according to weight percent content: Gd:0.17%, Al:0.66%, Zn:1.18%, Si:5.48%, Ca:0.36%, Sr:0.125%, Nd:0.46%, Zr:0.435%, Sn:0.87%, Be:0.10%, Mn:0.555%, Sb:0.38%, Cu:0.78%, boron nitride nanometer tube particle: 7%, surplus is Mg, and described boron nitride nanometer tube particle is of a size of 80 μm, described boron nitride strengthens the preparation method of creep resistance Dow metal, comprises the following steps:
(1) raw material prepares: carry out raw material preparation according to weight percent content, described raw material is pure Mg ingot, Mg-Gd master alloy, pure Al ingot, pure Zn, Al-Si master alloy, Al-Ca master alloy, Al-Sr master alloy, Mg-Nd master alloy, Mg-Zr master alloy, pure Sn, Al-Be master alloy, Al-Mn master alloy, pure Sb, Al-Cu master alloy, boron nitride nanometer tube particle;
(2) melting: adopt gas atmosphere molten alloy in resistance furnace, smelting temperature is 750 DEG C, first in smelting furnace, add pure Mg ingot, after pure magnesium ingot melts completely, add Mg-Gd master alloy, pure Al ingot, pure Zn, Al-Si master alloy, Al-Ca master alloy, Al-Sr master alloy, Mg-Nd master alloy, Mg-Zr master alloy, pure Sn, Al-Be master alloy, Al-Mn master alloy, pure Sb, Al-Cu master alloy, stir after all raw materials melt completely, make alloying constituent even; By particle doped in the magnesium alloy liquation of melting for the boron nitride nano-tube being preheating to 580 DEG C, then stir and make its uniform composition, will the magnesium alloy liquation sufficient standing after doping be stirred;
(3) refining: make smelting furnace be warming up to 788 DEG C of alloys and carry out refining, add heat resistance magnesium alloy refining agent while stirring, refining time is 3 minutes, leaves standstill 6 minutes, consisting of of described heat resistance magnesium alloy refining agent: NaCl:25% after refining is complete 740 DEG C of insulations; Na3AlF6:9%; MgCl2:34%; Surplus is KCl;
(4) cast: the magnesium alloy refining material of melting being cast to preheating temperature is in the swage tool of 220 DEG C, and pouring temperature is 730 DEG C; Cast gauge is Ф 465mm, length 3000mm
(5) thermal treatment: foundry goods is carried out solution treatment in 434 DEG C of temperature ranges, the solution treatment time is 18 hours, then carries out shrend, and the foundry goods after quenching to be put in the resistance furnace of 210 DEG C artificial aging 40 hours, obtained magnesium alloy blank;
(6) deformation process: a. high temperature forging cogging: heating blank to temperature is 440 DEG C of insulation 1.2h; Carry out two to hammer cogging, be forged into the slab that thickness is 55mm; Reduction in pass is 33.3%, every 3 passage forging after annealing 1.5h, and annealing temperature is 410 DEG C; B. heated roll to temperature is 325 DEG C; C. heating slab to temperature is 460 DEG C, is incubated after 26 minutes, and adopt the method for multi-pass small deformation amount that heavy plate rolling is become 4mm thin plate, the speed of rolls is 0.4m/s m/s; Every time roll reduction is 15%, melts down annealing after every time rolling, and annealing temperature is 440 DEG C, and annealing time is 38min;
(7) roll postheat treatment: the thin plate after rolling is carried out ageing treatment, and described aging treatment process is: aging temp is 240 DEG C, soaking time is 15h; Carry out second time ageing treatment at 200 DEG C again, aging time is 15h; Finally carry out third time ageing treatment at 160 DEG C, aging time is 15h.
embodiment 3:
A kind of boron nitride strengthens creep resistance Dow metal, contains: Gd:0.16%, Al:0.79% according to weight percent content, Zn:1.25%, Si:5.84%, Ca:0.37%, Sr:0.12%, Nd:0.43%, Zr:0.545%, Sn:0.86%, Be:0.125%, Mn:0.565%, Sb:0.38%, Cu:0.725%, boron nitride nanometer tube particle: 4%, surplus is Mg, and described boron nitride nanometer tube particle is of a size of 35 μm.。Described boron nitride strengthens the preparation method of creep resistance Dow metal, comprises the following steps:
(1) raw material prepares: carry out raw material preparation according to weight percent content, described raw material is pure Mg ingot, Mg-Gd master alloy, pure Al ingot, pure Zn, Al-Si master alloy, Al-Ca master alloy, Al-Sr master alloy, Mg-Nd master alloy, Mg-Zr master alloy, pure Sn, Al-Be master alloy, Al-Mn master alloy, pure Sb, Al-Cu master alloy, boron nitride nanometer tube particle;
(2) melting: adopt gas atmosphere molten alloy in resistance furnace, smelting temperature is 750 DEG C, first in smelting furnace, add pure Mg ingot, after pure magnesium ingot melts completely, add Mg-Gd master alloy, pure Al ingot, pure Zn, Al-Si master alloy, Al-Ca master alloy, Al-Sr master alloy, Mg-Nd master alloy, Mg-Zr master alloy, pure Sn, Al-Be master alloy, Al-Mn master alloy, pure Sb, Al-Cu master alloy, stir after all raw materials melt completely, make alloying constituent even; By particle doped in the magnesium alloy liquation of melting for the boron nitride nano-tube being preheating to 590 DEG C, then stir and make its uniform composition, will the magnesium alloy liquation sufficient standing after doping be stirred;
(3) refining: make smelting furnace be warming up to 788 DEG C of alloys and carry out refining, add heat resistance magnesium alloy refining agent while stirring, refining time is 3 minutes, leaves standstill 6 minutes, consisting of of described heat resistance magnesium alloy refining agent: NaCl:25% after refining is complete 740 DEG C of insulations; Na3AlF6:9%; MgCl2:34%; Surplus is KCl;
(4) cast: the magnesium alloy refining material of melting being cast to preheating temperature is in the swage tool of 270 DEG C, and pouring temperature is 730 DEG C; Cast gauge is Ф 465mm, length 3000mm
(5) thermal treatment: foundry goods is carried out solution treatment in 434 DEG C of temperature ranges, the solution treatment time is 18 hours, then carries out shrend, and the foundry goods after quenching to be put in the resistance furnace of 210 DEG C artificial aging 40 hours, obtained magnesium alloy blank;
(6) deformation process: a. high temperature forging cogging: heating blank to temperature is 440 DEG C of insulation 1.2h; Carry out two to hammer cogging, be forged into the slab that thickness is 55mm; Reduction in pass is 33.3%, every 3 passage forging after annealing 1.5h, and annealing temperature is 410 DEG C; B. heated roll to temperature is 325 DEG C; C. heating slab to temperature is 460 DEG C, is incubated after 26 minutes, and adopt the method for multi-pass small deformation amount that heavy plate rolling is become 4mm thin plate, the speed of rolls is 0.4m/s m/s; Every time roll reduction is 15%, melts down annealing after every time rolling, and annealing temperature is 440 DEG C, and annealing time is 38min;
(7) roll postheat treatment: the thin plate after rolling is carried out ageing treatment, and described aging treatment process is: aging temp is 240 DEG C, soaking time is 15h; Carry out second time ageing treatment at 200 DEG C again, aging time is 15h; Finally carry out third time ageing treatment at 160 DEG C, aging time is 15h.
the performance of the alloy that embodiment 1-3 obtains is listed in the table below

Claims (2)

1. a boron nitride strengthens creep resistance Dow metal, it is characterized in that: contain according to weight percent content: Gd:0.15-0.2%, Al:0.5-0.8%, Zn:1.1-1.26%, Si:5.3-5.7%, Ca:0.3-0.4%, Sr:0.1-0.3%, Nd:0.2-0.6%, Zr:0.4-0.55%, Sn:0.8-0.9%, Be:0.05-0.15%, Mn:0.55-0.58%, Sb:0.35-0.45%, Cu:0.7-0.9%, boron nitride nanometer tube particle: 1-15%, surplus is Mg, and described boron nitride nanometer tube particle is of a size of less than 100 μm.
2. boron nitride as claimed in claim 1 strengthens the preparation method of creep resistance Dow metal, it is characterized in that:
(1) raw material prepares: carry out raw material preparation according to weight percent content, described raw material is pure Mg ingot, Mg-Gd master alloy, pure Al ingot, pure Zn, Al-Si master alloy, Al-Ca master alloy, Al-Sr master alloy, Mg-Nd master alloy, Mg-Zr master alloy, pure Sn, Al-Be master alloy, Al-Mn master alloy, pure Sb, Al-Cu master alloy, boron nitride nanometer tube particle;
(2) melting: adopt gas atmosphere molten alloy in resistance furnace, smelting temperature is 740-765 DEG C, first in smelting furnace, add pure Mg ingot, after pure magnesium ingot melts completely, add Mg-Gd master alloy, pure Al ingot, pure Zn, Al-Si master alloy, Al-Ca master alloy, Al-Sr master alloy, Mg-Nd master alloy, Mg-Zr master alloy, pure Sn, Al-Be master alloy, Al-Mn master alloy, pure Sb, Al-Cu master alloy, stir after all raw materials melt completely, make alloying constituent even, by particle doped in the magnesium alloy liquation of melting for the boron nitride nano-tube being preheating to 550-650 DEG C, then stir and make its uniform composition, magnesium alloy liquation sufficient standing after doping will be stirred,
(3) refining: make smelting furnace be warming up to 780 DEG C ~ 790 DEG C alloys and carry out refining, add heat resistance magnesium alloy refining agent while stirring, refining time is 1-4 minute, 5 ~ 8 minutes are left standstill, consisting of of described heat resistance magnesium alloy refining agent: NaCl:18% ~ 26% 735 DEG C ~ 745 DEG C insulations after refining is complete; Na 3alF 6: 8 ~ 10%; MgCl 2: 30-40%; Surplus is KCl;
(4) cast: the magnesium alloy refining material of melting being cast to preheating temperature is in the swage tool of 200 ~ 300 DEG C, and pouring temperature is 725 DEG C ~ 735 DEG C; Cast gauge is Ф 450mm ~ Ф 500mm, length >=3000mm;
(5) thermal treatment: foundry goods is carried out solution treatment in 430-435 DEG C of temperature range, the solution treatment time is 16 ~ 24 hours, then carry out shrend, the foundry goods after quenching to be put in the resistance furnace of 210 DEG C artificial aging 40 hours, obtained magnesium alloy blank;
(6) deformation process: a. high temperature forging cogging: heating blank to temperature is 405 DEG C ~ 445 DEG C insulation 1 ~ 2h; Carry out two to hammer cogging, be forged into the slab that thickness is 40-60mm; Reduction in pass is 20% ~ 40%, every 3-6 passage forging after annealing 1.5h, and annealing temperature is 405 DEG C ~ 445 DEG C; B. heated roll to temperature is 305-345 DEG C; C. heating slab to temperature is 455-465 DEG C, is incubated after 20-30 minute, and adopt the method for multi-pass small deformation amount that heavy plate rolling is become 2 ~ 10mm thin plate, the speed of rolls is 0.4m/s ~ 0.8 m/s; Every time roll reduction is 10% ~ 20%, melts down annealing after every time rolling, and annealing temperature is 405 DEG C ~ 445 DEG C, and annealing time is 30min ~ 40min;
(7) roll postheat treatment: the thin plate after rolling is carried out ageing treatment, and described aging treatment process is: aging temp is 225-245 DEG C, soaking time is 12-36h; Carry out second time ageing treatment at 195-215 DEG C again, aging time is 12-36h; Finally carry out third time ageing treatment at 145-175 DEG C, aging time is 12-36h.
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