CN116875841A - Large-specification tin-phosphor bronze bar and preparation method thereof - Google Patents
Large-specification tin-phosphor bronze bar and preparation method thereof Download PDFInfo
- Publication number
- CN116875841A CN116875841A CN202310876570.6A CN202310876570A CN116875841A CN 116875841 A CN116875841 A CN 116875841A CN 202310876570 A CN202310876570 A CN 202310876570A CN 116875841 A CN116875841 A CN 116875841A
- Authority
- CN
- China
- Prior art keywords
- tin
- phosphor bronze
- bar
- temperature
- size
- 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.)
- Pending
Links
- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 88
- BSPSZRDIBCCYNN-UHFFFAOYSA-N phosphanylidynetin Chemical compound [Sn]#P BSPSZRDIBCCYNN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000010974 bronze Substances 0.000 title claims abstract description 83
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 61
- 239000000956 alloy Substances 0.000 claims description 61
- 238000000137 annealing Methods 0.000 claims description 54
- 238000001125 extrusion Methods 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000003723 Smelting Methods 0.000 claims description 26
- 238000005266 casting Methods 0.000 claims description 26
- 238000012545 processing Methods 0.000 claims description 25
- 230000032683 aging Effects 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 21
- 239000000498 cooling water Substances 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 238000009749 continuous casting Methods 0.000 claims description 14
- 210000001787 dendrite Anatomy 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910017888 Cu—P Inorganic materials 0.000 claims description 6
- 229910017985 Cu—Zr Inorganic materials 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910017827 Cu—Fe Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 description 72
- 239000010949 copper Substances 0.000 description 33
- 238000005728 strengthening Methods 0.000 description 23
- 238000004321 preservation Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000006104 solid solution Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000002918 waste heat Substances 0.000 description 5
- 230000006698 induction Effects 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000005482 strain hardening Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910009038 Sn—P Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/002—Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/02—Making uncoated products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
- B22D11/004—Copper alloys
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0075—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for rods of limited length
-
- 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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Extrusion Of Metal (AREA)
Abstract
The invention discloses a large-size tin phosphor bronze bar, which consists of the following components in percentage by weight: 7-10wt%, P:0.15-0.35wt%, fe:0.03 to 0.2 weight percent, zr:0.003-0.1wt% of Pb less than or equal to 0.007wt% and the balance of Cu and impurities; fe in large-size tin-phosphor bronze bar 3 The P phase size is below 100nm, and the distribution number is not less than 3000/mm 2 ，Cu 3 The P phase size is below 60nm, and the distribution number is not less than 1000/mm 2 Parallel to the pullIn the extending direction<111>The directional texture area accounts for 60-75 percent and is parallel to the stretching direction of the bar<100>The directional texture area accounts for 25-40 percent; the large-size tin-phosphor bronze bar has good mechanical properties. The invention also discloses a preparation method of the large-size tin phosphor bronze bar.
Description
Technical Field
The invention belongs to the technical field of copper alloy, and particularly relates to a large-specification tin-phosphor bronze bar and a preparation method thereof.
Background
Tin-phosphorusA ternary alloy with Cu, sn and P as main alloy elements has the characteristics of good conductivity, corrosion resistance, high strength and the like.The bar is mainly used for manufacturing precision springs, electric connectors, wiring terminals and the like, and the tensile strength of the bar with small specification can easily reach 600Mpa or even 1000Mpa; />The large-size bar is generally used for processing mechanical parts bearing high load, such as parts of aircrafts in the aviation field, missiles and other aircrafts, pipelines, valves and the like in the chemical engineering field and the ocean engineering field.
Because tin phosphor bronze belongs to deformation-reinforced copper alloy, high strength is realized mainly by work hardening with large deformation.
Chinese patent publication No. CN114875270a discloses a method for preparing tin-phosphor bronze alloy, comprising: a tin-phosphor bronze alloy according to claim 1; 2) Casting: drawing and casting the blank in a horizontal continuous casting mode, wherein the drawing speed is 0.2-1.0 m/min, the drawing pitch is 1-3 mm, and the reverse pushing length is as follows: 0.1-0.5 mm, cooling water pressure: 0.5-0.8 MPa, cooling water inlet temperature: 15-25 ℃, and the water outlet temperature is: the casting temperature is controlled at 1190-1220 ℃ at 20-40 ℃; 3) Homogenizing and annealing: homogenizing annealing treatment is carried out on the blank, and the annealing temperature range is as follows: 680-720 ℃, the heat preservation time is 6-10 h, quenching treatment is carried out on the homogenized blank after reaching the heat preservation time, and the water inlet time after discharging from the furnace is controlled within 30 s; 4) The first stretching: stretching the blank after the homogenization annealing, wherein the processing rate is controlled to be 10-35%; peeling after stretching, wherein the peeling amount is 0.2-1 mm; 5) Intermediate high temperature annealing: annealing the stretched blank, wherein the annealing temperature range is as follows: the temperature is 520-600 ℃ and the heat preservation time is 2-5 h; 6) Second stretching: stretching the blank subjected to intermediate high-temperature annealing, wherein the second stretching processing rate is controlled to be 30-60%; 7) Intermediate low temperature annealing: annealing the stretched blank, wherein the annealing temperature range is as follows: the temperature is between 350 and 450 ℃ and the heat preservation time is between 3 and 10 hours; 8) And (3) stretching a finished product: stretching the blank subjected to intermediate low-temperature annealing, wherein the stretching of a finished product is performed in 2-4 passes, and the processing rate of each pass is controlled as follows: 10-30%, and the total processing rate of stretching is 40-70%; 9) Stress relief annealing: and (3) carrying out stress relief annealing on the finished bar, and carrying out atmosphere protection, wherein the heating speed is controlled to be 5-10 ℃/min, the heat preservation temperature is controlled to be 150-200 ℃, and the heat preservation time is 4-12 h.
The above patent achieves an increase in tensile strength by deformation strengthening and work hardening, however for large gauge bar, particularlyThe strength through deformation reinforcement of the large-size bar is difficult to achieve the desired high strength. When the large-size bar is stretched at a large processing rate, the work hardening effect of the metal at the bar core is smaller than that of the surface metal, the tensile strength of the bar core of the large size is improved, and the larger processing rate is needed, so that the problem is that the tensile stress of the surface metal of the bar exceeds the strength limit to cause transverse cracks, and therefore the strength of the large-size bar cannot be improved by deformation strengthening and work hardening methods.
Disclosure of Invention
The invention provides a large-specification tin-phosphor bronze bar with higher strength and better plasticity.
The invention provides a large-specification tin phosphor bronze bar, which consists of the following components in percentage by weight: 7-10wt%, P:0.15-0.35wt%, fe:0.03 to 0.2 weight percent, zr:0.003-0.1wt%, impurity Pb less than or equal to 0.007wt%, other impurities less than 0.5wt% and Cu for the rest;
the large-size tin-phosphor bronze bar comprises Fe 3 P phase and Cu 3 P phase, the Fe 3 The distribution number of P phases is not less than 3000/mm 2 The Cu is 3 The distribution number of P phases is not less than 1000/mm 2 ；
The diameter of the large-specification tin-phosphor bronze bar isThe above.
Further, the large-sized tin-phosphor bronze bar further comprises a delta phase, wherein the size of the delta phase is less than 1 mu m, and the distribution quantity of the delta phase is not more than 10/mm 2 。
Further, the Fe 3 The size of the P phase is 100nm or less, and the Cu is 3 The size of the P phase is below 60 nm.
The structure of the large-specification tin-phosphor bronze bar provided by the invention comprises Cu besides a matrix phase alpha phase 3 P、Fe 3 P、Fe 2 P and delta phases, the mechanical property of the large-size tin phosphor bronze bar is affected by Cu 3 P、Fe 3 P、Fe 2 The effects of P and delta phases, therefore, control of Cu is required 3 P、Fe 3 P、Fe 2 The size and distribution number of the P, delta phases. Cu (Cu) 3 P and Fe 3 P、Fe 2 P is a strengthening phase, which is a phase beneficial to alloy strength, wherein Fe 2 P is a granular solid solution strengthening phase at high temperature, fe 3 P is a network strengthening phase precipitated from Fe 2 P is converted from Fe 3 The strengthening effect of the P precipitation phase is far better than that of F 2 P solid solution phase. Cu (Cu) 3 The P phase is also a low-temperature precipitated phase, and the strengthening effect sequence of the three strengthening phases is as follows: fe (Fe) 3 P＞Cu 3 P＞Fe 2 P, therefore, improve the intensity of big specification tin phosphor bronze rod, need regulate and control the size and the distribution quantity of four kinds of looks, the regulation and control direction is: the size of four phases is reduced as much as possible, and Fe is improved 3 P-phase number and Cu 3 The number of P phase and Fe reduction 2 Number of P and delta phases. Thus in the present invention Fe 3 The P phase size is controlled below 100nm, and the distribution number is not less than 3000/mm 2 ；Cu 3 The P phase size is controlled below 60nm, and the distribution number is not less than 1000/mm 2 . The delta phase is a brittle phase and is a harmful phase in tin phosphor bronze, the deformation strengthening effect of the tin phosphor bronze and the plasticity of the alloy are weakened, and the size and the quantity of the delta phase are reduced as much as possible, so that in the invention, the size of the delta phase is controlled to be less than 1 mu m, and the distribution quantity is not more than 10 pieces/mm 2 。
Sn: sn has strong solidification in CuThe higher the Sn content, the higher the strength of the Sn-P bronze. When the Sn content is less than 7%, the solid solution strengthening effect of Sn has small contribution to improving the alloy strength, and further does not play a role of pinning dislocation and fixing the dislocation, but with the increase of the Sn content, cu and Sn form hard and brittle delta phases, and the delta phases are Cu and Sn form Cu 31 Sn 8 The compound has negative effect on improving the strength of the tin phosphor bronze. When the Sn content exceeds 10%, the number of δ phases increases, the size becomes large, and even the case of aggregation of δ phases occurs, the strength of tin phosphor bronze is lowered instead. Therefore, in the tin-phosphor bronze alloy of the present invention, the Sn content is controlled to be in the range of 7 to 10%.
P: p and Cu are easy to form and can form A in coherent order 3 Intermetallic compound B of Cu 3 P, when the P content is less than 0.15%, P hardly forms sufficient Cu with Cu and Fe 3 P、Fe 3 A P strengthening phase, wherein the strength of the alloy is improved through second phase precipitation strengthening; when the P content exceeds 0.35%, cu 3 P forms a triple eutectic (alpha+delta+Cu) with the alpha and delta phases 3 P) causes hot shortness of the alloy, and is liable to cause cracking of the tin phosphor bronze during heat processing or heat treatment, so that the P content in the tin phosphor bronze of the present invention is not more than 0.35%.
Fe: the solubility of Fe in tin phosphor bronze is very small, and trace Fe mainly forms Fe with P 2 P、Fe 3 P phase, fe and P at high temperature to form Fe 2 P is mainly, and Fe is easy to form at low temperature 3 P, by aging treatment, fe in the form of particles 2 P-direction Fe with network structure 3 P conversion, play better strengthening effect.
Zr: zr is used as a grain boundary strengthening element, and is added into the tin phosphor bronze to refine alloy grains and strengthen the grain boundary of the alloy, so that the crystal structure of the casting blank is compact. Zr is enriched in the liquid phase of the crystallization front, so that the melting point of the front component of the solid-liquid interface is reduced, the formation of supercooling of the component is promoted, alpha-Cu dendrite arms are thinned, and the distance between secondary dendrite arms is reduced; and ZrO formed by Zr and oxygen can prevent the growth of alpha-Cu crystals and contribute to the branch refinement of alpha-Cu dendrites. When the added amount of Zr in the tin phosphor bronze exceeds 0.1%, the grain refining effect becomes poor.
Further, the microstructure of the large-size tin phosphor bronze bar comprises<111>Directional texture<100>Directional texture parallel to the stretching direction of large-sized tin phosphor bronze bar<111>Directional texture area S <111> The proportion of the total area of the texture parallel to the stretching direction of the bar is 60-75 percent, and the texture is parallel to the stretching direction of the bar<100>Directional texture area S <100> The proportion of the total area of the texture parallel to the stretching direction of the bar is 25-40%.
The microstructure of the tin-phosphor bronze bar material of the invention comprises<111>And<100>the texture is realized in two directions,<111>and<100>the directional texture includes: a texture parallel to the stretching direction of the bar and a texture at an angle to the stretching direction, wherein the texture parallel to the stretching direction of the bar has the greatest effect on improving the strength of the bar,<111>the effect of the directional texture on improving the strength of the tin-phosphor bronze bar is stronger than that of the tin-phosphor bronze bar<100>Directional texture of<100>The effect of the directional texture on improving the plasticity of the tin-phosphor bronze bar is better than that of the tin-phosphor bronze bar<111>Directional texture. Thus, in the invention, by reasonable regulation<111>And<100>the distribution of the directional texture gives the obtained bar a higher strength, wherein the direction is parallel to the stretching direction of the bar<111>Directional texture area S <111> The proportion of the total area of the texture parallel to the stretching direction of the bar is controlled to be 60-75 percent<100>Directional texture area S <100> The proportion of the total area of the texture parallel to the stretching direction of the bar is 25-40%.
The invention also provides a preparation method of the large-specification tin-phosphor bronze bar, which comprises the following steps:
(1) Proportioning, smelting and casting according to the weight percentage of each component of the large-size tin-phosphor bronze bar material to obtain a master alloy cast ingot;
(2) Carrying out high-temperature annealing on the master alloy cast ingot obtained in the step (1), wherein the high-temperature annealing process comprises the following steps: preserving heat at 650-750deg.C for 4-8 hr, and then heating to 780-900deg.C for 10-40min for 5-20min;
(3) The master alloy cast ingot obtained in the water seal extrusion step (2) has extrusion speed of 2-11mm/s, extrusion ratio of 10-40 and water temperature of lower than 50 ℃;
(4) Stretching the master alloy extrusion blank obtained in the step (3) for 1-4 times to obtain a bar with set specification, wherein the total processing rate of the stretching process is more than or equal to 20%;
(5) And (3) carrying out aging annealing on the bar material obtained in the step (4), wherein the aging annealing process comprises the following steps: heating from normal temperature to 390-450 ℃ for 20-40min, preserving heat for 90-150min, cooling to 320-360 ℃ for 20-45min, and preserving heat for 60-120min;
(6) Stretching the bar obtained in the step (5) for 1-3 times again to obtain a bar with finished product specification, wherein the total processing rate of the stretching process is 10-25%;
(7) And (3) carrying out low-temperature annealing on the bar material obtained in the step (6), wherein the low-temperature annealing process comprises the following steps: heating to 170-260deg.C from normal temperature for 30-60min, and maintaining the temperature for 120-300min;
(8) And (3) straightening the bar obtained in the step (7) to obtain the large-specification tin-phosphor bronze bar.
The invention uses the heat preservation for 4-8 hours at 650-750 ℃ in the high temperature annealing process to reduce delta phase distributed among tin phosphor bronze dendrites, thereby improving the plasticity of the finally obtained tin phosphor bronze bar.
The invention provides water seal extrusion with proper extrusion ratio, the extrusion ratio is lower than 10, and the extrusion billet still maintains the cast structure of the cast ingot due to low extrusion deformation degree, and the material performance is poor. After extrusion blanks are extruded from the die, the extrusion blanks immediately enter a water seal groove to be dissolved in a line by utilizing waste heat, the water temperature in the whole process is less than 50 ℃, the higher the water temperature is, the lower the cooling strength is, and the worse the solution effect is. The water seal extrusion provided by the invention has two purposes, namely, promoting Cu 3 P and Fe 2 The P second phase is completely dissolved in the alloy matrix to separate out small-sized Cu for subsequent aging 3 Preparing a P strengthening phase; secondly, through extremely fast cooling, extrusion recrystallization grain growth is avoided, fine grain strengthening is realized, meanwhile, the plasticity of casting blanks is improved, and a foundation is provided for the large processing rate stretching of the next procedure.
The purpose of the first stretching provided by the invention is to increase the dislocation density in the alloy and promote Cu 3 P、Fe 3 And the second phase P is dispersed and precipitated during aging annealing, the size of the second phase P is reduced, and the area ratio is increased.
The purpose of aging annealing provided by the invention promotes Cu 3 P、Fe 3 The P second phase is separated out from the alloy matrix, thereby improving the strength of the alloy. Due to Cu 3 P、Fe 3 Peak temperature of P phase precipitation is different, cu 3 The peak temperature of P phase precipitation is around 340 ℃, fe 3 The peak temperature of the P phase precipitation is near 420 ℃, so that the tin-phosphor bronze alloy adopts a sectional aging process, the temperature of the first section is quickly increased to 390-450 ℃ after 20-40min, and the temperature is kept for 90-150min; the second stage is cooled to 320-360 ℃ after 20-45min, and then is kept for 60-120min.
The purpose of the second stretching provided by the invention is two: firstly, the strength of the alloy is improved through deformation strengthening; secondly, the ratio of textures parallel to the bar stretching directions <111> and <100> is controlled by the stretching processing rate, because the processing rate is increased, the ratio of the textures in the <111> direction is increased, the ratio of the textures in the <100> direction is reduced, the stretching pass influences the textures, and under the condition of the constant total processing rate, the fewer passes, the more easily the textures parallel to the bar stretching direction are formed, but the fewer passes, the bar stretching deformation is difficult, and on the contrary, the cracks are formed on the surface of the bar due to the overlarge pass processing rate.
The combination of the technological parameters of low-temperature annealing and the Sn content provided by the invention further improves the strength of the tin-phosphor bronze, and under the action of low temperature and long time, the dislocation in the material is redistributed and the number of movable dislocation is reduced due to the result of the comprehensive actions of the partial aggregation of Sn atoms with proper content on the stacking fault surface and ordered strengthening. The annealing temperature and the annealing time are very important, the annealing temperature is too low, dislocation cannot be redistributed, the annealing temperature is too high, and the annealing temperature exceeds the initial recrystallization temperature of the alloy, so that the strength of the alloy cannot be improved, and the strength of the alloy is reduced due to recrystallization.
Further, the specific steps of the step (1) are as follows:
smelting a tin ingot, a Cu-P intermediate alloy and a Cu-Fe intermediate alloy according to the weight percentage of each component of the large-size tin-phosphor bronze bar, wherein the smelting temperature is 1100-1280 ℃, and after the content of Sn, P and Fe reaches a set range, adding the Cu-Zr intermediate alloy for smelting after smelting;
and casting the alloy obtained by smelting by adopting a vertical semi-continuous casting or horizontal continuous casting method to obtain a master alloy cast ingot.
Further, the alloy obtained by smelting is cast by adopting a vertical semi-continuous casting or horizontal continuous casting method, and the casting process comprises the following steps:
the casting temperature is 1140-1280 ℃, the water inlet temperature of cooling water is 20-35 ℃, the cooling water pressure is 0.2-0.5Mpa, and the cooling water flow is 10-18m 3 And/h, the water outlet temperature is 25-45 ℃, and the traction speed is 40-100mm/min.
Further, the master alloy cast ingot obtained in the step (1) is dendrite, and the spacing of the dendrite is 5-15 mu m. The smaller the dendrite spacing, the finer the structure, the smaller the delta phase size distributed among dendrites, and the easier the delta phase is to be eliminated when the ingot is annealed at high temperature.
Further, the grain size of the master alloy ingot obtained in the step (3), namely a tin phosphor bronze extrusion billet, is controlled below 0.030 mm. The smaller the grain size, the more grain boundaries, and the more grains in different directions, and thus the greater the plastic deformation resistance, the higher the strength of the alloy.
Further, in the master alloy extrusion blank obtained in the step (3), namely the tin-phosphor bronze extrusion blank, the recrystallized grains are required to have the twin crystal area accounting for 50-70% of the total area of the grains. The twinning boundary can play a hardening role after the twinning, but the twinning boundary can reduce the plasticity of the alloy, and the tin-phosphor bronze alloy further needs to keep better plasticity while realizing high strength, so that when the material is acted by external force, a part of energy can be absorbed, brittle cracks are avoided in the material, and the durability of the part is improved.
Further, the mechanical properties of the large-size tin phosphor bronze bar with the diameter of more than phi 40mm are shown in table 1:
TABLE 1 mechanical property requirement of large-size tin phosphor bronze rod
| Specification range mm | Tensile strength Mpa | Elongation A50% |
| 40-50 | 600 | 8 |
| 50-60 | 540 | 12 |
| ＞60 | 480 | 16 |
Compared with the prior art, the invention has the beneficial effects that:
(1) As the strengthening phase in the large-size tin-phosphor bronze bar material provided by the invention, namely Fe 3 P phase and Cu 3 The P phase is distributed in a large-size tin phosphor bronze bar in a large quantity, so that the large-size tin phosphor bronze bar has high strength.
(2) The strengthening phase in the large-size tin-phosphor bronze bar material provided by the invention is Fe 3 P phase and Cu 3 The size of the P phase is smaller, so that the strengthening phase can be dispersed in the matrix, and the strength of the large-size tin-phosphor bronze bar is improved.
(3) The delta phase in the large-size tin phosphor bronze bar provided by the invention has smaller size, and the distribution quantity in the large-size tin phosphor bronze bar is smaller, so that the influence of brittleness delta on the strength of the large-size tin phosphor bronze bar is reduced, and the strength of the large-size tin phosphor bronze bar is further improved.
(4) The large-size tin-phosphor bronze bar provided by the invention has the advantages that the proportion of the texture area in the <111> direction parallel to the bar stretching direction to the total texture area parallel to the bar stretching direction is higher, so that the strength of the large-size tin-phosphor bronze bar is improved.
(5) The invention provides a method for preparing a large-size tin phosphor bronze bar, which can prepare a large-size tin phosphor bronze bar with higher strength, wherein a strengthening phase is completely dissolved in an alloy matrix by a water seal extrusion method, a small-size and large-size strengthening phase is prepared for subsequent aging precipitation, and Cu is respectively treated by aging annealing in stages 3 P、Fe 3 The P phase is separated out from the matrix, the number of movable dislocation is reduced through the combination effect of low-temperature annealing and Sn content, and the strength of the large-size tin-phosphor bronze bar is further increased.
Drawings
FIG. 1 is a photograph showing a metallographic structure of a large-sized tin-phosphor bronze bar material prepared in example 1 of the present invention;
fig. 2 is a photograph showing a metallographic structure of a large-sized tin-phosphor bronze bar material prepared in comparative example 1 of the present invention.
Detailed Description
Aiming at the problems that the tensile strength of the existing large-specification tin phosphor bronze bar with the diameter of more than 40mm is low, the requirement of the aerospace and ocean engineering field on the high strength of materials cannot be met, the large-specification high-strength tin phosphor bronze bar is designed and developed, the defects of the prior art are overcome, and the requirement of the special field on the high strength of materials is met. The invention is described in further detail below with reference to the embodiments of the drawings.
The invention provides 4 examples and 2 comparative examples, the specific compositions are shown in Table 2.
Example 1
A specification isThe preparation method of the high-strength tin-phosphor bronze bar comprises the following steps:
1) Smelting and casting: and (3) preparing materials according to the required components, sequentially adding an electrolytic plate, a tin ingot and a Cu-P intermediate alloy into an induction furnace for smelting, wherein the smelting temperature is 1100-1280 ℃, after all metals are molten, testing the contents of Sn, P and Pb as impurities to be qualified, adding the Cu-Zr intermediate alloy, testing the components of the alloy again to be qualified, and transferring the alloy into a heat preservation furnace. Casting ingot by vertical semi-continuous casting method, and casting ingot diameterCasting temperature: 1170-1210 ℃, cooling water inlet temperature: 22-25 ℃, cooling water pressure: 0.4Mpa, cooling water flow: 15m 3 And/h, water outlet temperature: 30-35 ℃, traction speed: 75mm/min.
2) And (3) high-temperature heating: the heating is carried out in two stages, wherein the heating temperature in the first stage is as follows: 700 ℃, and the heat preservation time is up to the temperature: 6h; second stage heating temperature: and (3) heating to 860-880 ℃ for 25min on the basis of the temperature of the first stage, preserving heat for 15min, and discharging from the furnace for extrusion.
3) And (3) water seal extrusion: extrusion billet specification:extrusion speed: 4-8mm/s, extrusion ratio: 13. after extrusion blanks are extruded from the die, waste heat is immediately utilized to enter a water seal groove for online solid solution, and water temperature is: 17-42 ℃.
4) Stretching: after the extruded blank is pickled, the extruded blank is continuously stretched to a reserved specification in 3 passesAnd (3) die matching process:processing rate: 27.43%.
5) Aging annealing: adopting a sectional aging process, rapidly heating to 370 ℃ after 25min in the first section, and preserving heat for 120min; the second stage is cooled to 350 ℃ after 30min, and then is kept for 90min.
6) Stretching: the wire blank after aging annealing is stretched to the specification of a finished product by 2 timesAnd (3) die matching process:the processing rate is controlled at 16.63%.
7) And (3) low-temperature annealing: annealing temperature: 200 ℃, and the temperature is increased from normal temperature to the temperature: 30min, heat preservation time: 240min.
8) Straightening: straightening on a two-roll straightener.
9) And (5) checking.
As shown in FIG. 1, the crystal grains were uniform in size, the average grain size was 0.020mm, the small black spots were delta phases, and the average size of the delta phases was 0.6. Mu.m.
Example 2
A specification isThe preparation method of the high-strength tin-phosphor bronze bar comprises the following steps:
1) Smelting and casting: and (3) preparing materials according to the required components, sequentially adding an electrolytic plate, a tin ingot and a Cu-P intermediate alloy into an induction furnace for smelting, wherein the smelting temperature is 1100-1280 ℃, after all metals are molten, testing the contents of Sn, P and Pb as impurities to be qualified, adding the Cu-Zr intermediate alloy, testing the components of the alloy again to be qualified, and transferring the alloy into a heat preservation furnace. Casting ingot by adopting a horizontal continuous casting method, wherein the diameter of the ingot is equal to that of the ingotCasting temperature: 1180-1220 ℃, cooling water inlet temperature: 26-29 ℃, cooling water pressure: 0.38Mpa, cooling water flow: 13m 3 And/h, water outlet temperature: 32-36 ℃, traction speed: 80mm/min.
2) And (3) high-temperature heating: the heating is carried out in two stages, wherein the heating temperature in the first stage is as follows: 680 ℃, and the heat preservation time after reaching the temperature: 7h; second stage heating temperature: and (3) heating to the temperature of 840-870 ℃ for 25min on the basis of the temperature of the first stage, preserving heat for 15min, and discharging from the furnace for extrusion.
3) And (3) water seal extrusion: extrusion billet specification:extrusion speed: 4.2-7.7mm/s, extrusion ratio: 15.3. after extrusion blanks are extruded from the die, waste heat is immediately utilized to enter a water seal groove for online solid solution, and water temperature is: 21-46 ℃.
4) Stretching: after the extruded blank is pickled, the extruded blank is continuously stretched to a reserved specification in 3 passesAnd (3) die matching process:processing rate: 25.78%.
5) Aging annealing: adopting a sectional aging process, rapidly heating to 420 ℃ in the first section for 25min, and then preserving heat for 100min; the second stage is cooled to 330 ℃ after 35min, and then the temperature is kept for 120min.
6) Stretching: stretching the wire blank after ageing annealing for 3 times to the specification of a finished productAnd (3) die matching process:the processing rate is controlled at 20.28%.
7) And (3) low-temperature annealing: annealing temperature: 230 ℃, from normal temperature to the temperature time: 30min, heat preservation time: 120min.
8) Straightening: straightening on a two-roll straightener.
9) And (5) checking.
Example 3
A specification isThe preparation method of the high-strength tin-phosphor bronze bar comprises the following steps:
1) Smelting and casting: and (3) preparing materials according to the required components, sequentially adding an electrolytic plate, a tin ingot and a Cu-P intermediate alloy into an induction furnace for smelting, wherein the smelting temperature is 1100-1280 ℃, after all metals are molten, testing the contents of Sn, P and Pb as impurities to be qualified, adding the Cu-Zr intermediate alloy, testing the components of the alloy again to be qualified, and transferring the alloy into a heat preservation furnace. Casting ingot by adopting a horizontal continuous casting method, wherein the diameter of the ingot is equal to that of the ingotCasting temperature: 1200-1240 ℃, cooling water inlet temperature: 18-23 ℃, cooling water pressure: 0.35Mpa, cooling water flow: 12m 3 And/h, water outlet temperature: 22-25 ℃, traction speed: 60mm/min.
2) And (3) high-temperature heating: the heating is carried out in two stages, wherein the heating temperature in the first stage is as follows: 750 ℃, and preserving the temperature for a period of time after reaching the temperature: 5h; second stage heating temperature: heating to 800-850 ℃ for 15min on the basis of the temperature of the first stage, preserving heat for 10min, and discharging from the furnace for extrusion.
3) And (3) water seal extrusion: extrusion billet specification:extrusion speed: 4-7mm/s, extrusion ratio: 11.5. after extrusion blanks are extruded from the die, waste heat is immediately utilized to enter a water seal groove for online solid solution, and water temperature is: 25-42 ℃.
4) Stretching: after the extruded blank is pickled, the extruded blank is continuously stretched to a reserved specification in 3 passesAnd (3) die matching process:processing rate: 24.89%.
5) Aging annealing: adopting a sectional aging process, rapidly heating to 450 ℃ in the first section for 25min, and preserving heat for 90min; the second stage is cooled to 320 ℃ after 35min, and then is kept for 90min.
6) Stretching: the wire blank after aging annealing is stretched to the specification of a finished product by 2 timesAnd (3) die matching process:the processing rate is controlled at 14.79%.
7) And (3) low-temperature annealing: annealing temperature: 250 ℃, and the temperature is raised from normal temperature to the temperature: 45min, heat preservation time: 180min.
8) Straightening: straightening on a two-roll straightener.
9) And (5) checking.
Example 4
A specification isThe preparation method of the high-strength tin-phosphor bronze bar comprises the following steps:
1) Smelting and casting: and (3) preparing materials according to the required components, sequentially adding an electrolytic plate, a tin ingot and a Cu-P intermediate alloy into an induction furnace for smelting, wherein the smelting temperature is 1100-1280 ℃, after all metals are molten, testing the contents of Sn, P and Pb as impurities to be qualified, adding the Cu-Zr intermediate alloy, testing the components of the alloy again to be qualified, and transferring the alloy into a heat preservation furnace. Casting ingot by adopting a horizontal continuous casting method, wherein the diameter of the ingot is equal to that of the ingotCasting temperature: 1200-1240 ℃, cooling water inlet temperature: 28-31 ℃, cooling water pressure: 0.42Mpa, cooling water flow: 18m 3 And/h, water outlet temperature: 36-40 ℃, traction speed: 60mm/min.
2) And (3) high-temperature heating: the heating is carried out in two stages, wherein the heating temperature in the first stage is as follows: 720 ℃, and preserving the temperature for a period of time after reaching the temperature: 6h; second stage heating temperature: 780-820 ℃, heating to the temperature for 10min on the basis of the temperature of the first stage, preserving heat for 15min, and discharging from the furnace for extrusion.
3) And (3) water seal extrusion: extrusion billet specification:extrusion speed: 4-7.5mm/s, extrusion ratio: 10.6. extrusionAfter the pressed compact is extruded from the die, the pressed compact immediately enters a water seal groove for on-line solid solution by utilizing waste heat, and the water temperature is as follows: 29-50 ℃.
4) Stretching: after the extruded blank is pickled, the extruded blank is continuously stretched to a reserved specification in 2 passesAnd (3) die matching process:processing rate: 21.74%.
5) Aging annealing: adopting a sectional aging process, rapidly heating to 430 ℃ after 25min in the first section, and preserving heat for 90min; the second stage is cooled to 350 ℃ after 30min, and then is kept for 90min.
6) Stretching: stretching the wire blank after ageing annealing for 1 pass to the specification of a finished productAnd (3) die matching process:the processing rate is controlled at 11.26%.
7) And (3) low-temperature annealing: annealing temperature: 180 ℃, and the temperature is increased from normal temperature to the temperature: 30min, heat preservation time: 300min.
8) Straightening: straightening on a two-roll straightener.
9) And (5) checking.
Comparative example 1
The chemical composition was controlled as in example 1, and the results of the structure and properties of the bar of Φ42mm produced by the conventional process route of "smelting→horizontal continuous casting Φ54→homogenizing annealing (680 ℃/6 h) →multi-pass continuous drawing Φ42→straightening→checking" are shown in table 3, the metallographic structure is shown in fig. 2, the crystal grains are coarser, the average grain size is 0.040mm, the black spots are the delta phase, and the average size of the delta phase is 4.3 μm.
Comparative example 2
Commercially available QSN8-0.3And (5) bar material.
The following examination was performed on the microstructures of the 4 examples and 2 comparative examples, and the results are recorded in table 3.
Performance analysis:
grain size: the metallographic sample is prepared according to the specification of GB/T13298, and the grain size measurement is measured according to the comparison method of GB/T6394-2017 (metal average grain size measurement method), namely the grain size is evaluated by comparison with a standard rating chart;
observing the phase occupation ratio, the phase size and the phase distribution quantity by using a scanning electron microscope;
texture area ratio: observation and measurement were performed using a scanning electron microscope back-scattered electron diffraction (EBSD).
Tensile strength Rm and elongation a50: according to GB/T228.1-2021 section 1 Metal tensile test: room temperature test method.
The following performance tests were performed on 4 examples and 2 comparative examples, and the results are recorded in table 4.
TABLE 2 chemical compositions of examples 1-4, comparative examples 1-2
TABLE 3 grain size, phase size, number of distributions per unit area, texture area ratio of examples 1-4 and comparative examples 1-2
TABLE 4 tensile Strength and elongation for examples 1-4 and comparative examples 1-2
Claims (10)
1. The large-size tin phosphor bronze bar is characterized by comprising the following components in percentage by weight: 7-10wt%, P:0.15-0.35wt%, fe:0.03 to 0.2 weight percent, zr:0.003-0.1wt%, impurity Pb less than or equal to 0.007wt%, other impurities less than 0.5wt% and Cu for the rest;
the large-size tin-phosphor bronze bar comprises Fe 3 P phase and Cu 3 P phase, the Fe 3 The distribution number of P phases is not less than 3000/mm 2 The Cu is 3 The distribution number of P phases is not less than 1000/mm 2 ；
The diameter of the large-specification tin phosphor bronze bar is more than phi 40 mm.
2. The large-sized tin phosphor bronze rod according to claim 1, further comprising a delta phase having a size of 1 μm or less, the delta phase being distributed in an amount of not more than 10/mm 2 。
3. The large format tin phosphor bronze rod according to claim 1, wherein the Fe 3 The size of the P phase is 100nm or less, and the Cu is 3 The size of the P phase is below 60 nm.
4. The large format tin phosphor bronze rod according to claim 1, wherein the microstructure of the large format tin phosphor bronze rod comprises a <111> direction texture and a <100> direction texture;
wherein, the drawing direction of the large-specification tin phosphor bronze bar is parallel to<111>Directional texture area S <111> Occupying the area of<111>The proportion of the total area of the directional texture is 60-75 percent;
parallel to the direction of stretching of the bars<100>Directional texture area S <100> Occupying the area of<100>The proportion of the total area of the directional texture is 25-40%.
5. A method for producing a large-sized tin-phosphor bronze rod according to any one of claims 1 to 4, comprising:
(1) Proportioning, smelting and casting according to the weight percentage of each component of the large-size tin-phosphor bronze bar material to obtain a master alloy cast ingot;
(2) Carrying out high-temperature annealing on the master alloy cast ingot obtained in the step (1), wherein the high-temperature annealing process comprises the following steps: preserving heat at 650-750deg.C for 4-8 hr, and then heating to 780-900deg.C for 10-40min for 5-20min;
(3) The master alloy cast ingot obtained in the water seal extrusion step (2) has extrusion speed of 2-11mm/s, extrusion ratio of 10-40 and water temperature of lower than 50 ℃;
(4) Stretching the master alloy extrusion blank obtained in the step (3) for 1-4 times to obtain a bar with set specification, wherein the total processing rate of the stretching process is more than or equal to 20%;
(5) And (3) carrying out aging annealing on the bar material obtained in the step (4), wherein the aging annealing process comprises the following steps: heating from normal temperature to 390-450 ℃ for 20-40min, preserving heat for 90-150min, cooling to 320-360 ℃ for 20-45min, and preserving heat for 60-120min;
(6) Stretching the bar obtained in the step (5) for 1-3 times again to obtain a bar with finished product specification, wherein the total processing rate of the stretching process is 10-25%;
(7) And (3) carrying out low-temperature annealing on the bar material obtained in the step (6), wherein the low-temperature annealing process comprises the following steps: heating to 170-260deg.C from normal temperature for 30-60min, and maintaining the temperature for 120-300min;
(8) And (3) straightening the bar obtained in the step (7) to obtain the large-specification tin-phosphor bronze bar.
6. The method for preparing the large-size tin-phosphor bronze bar according to claim 5, wherein the specific steps of the step (1) are as follows:
smelting a tin ingot, a Cu-P intermediate alloy and a Cu-Fe intermediate alloy according to the weight percentage of each component of the large-size tin-phosphor bronze bar, wherein the smelting temperature is 1100-1280 ℃, and after the content of Sn, P and Fe reaches a set range, adding the Cu-Zr intermediate alloy for smelting;
and casting the alloy obtained by smelting by adopting a vertical semi-continuous casting or horizontal continuous casting method to obtain a master alloy cast ingot.
7. The method for preparing the large-size tin-phosphor bronze bar according to claim 6, wherein the alloy obtained by smelting is cast by adopting a vertical semi-continuous casting or horizontal continuous casting method, and the casting process is as follows:
the casting temperature is 1140-1280 ℃, the water inlet temperature of cooling water is 20-35 ℃, the cooling water pressure is 0.2-0.5Mpa, and the cooling water flow is 10-18m 3 And/h, the water outlet temperature is 25-45 ℃, and the traction speed is 40-100mm/min.
8. The method for preparing a large-sized tin-phosphor bronze bar according to claim 1, wherein the master alloy ingot obtained in the step (1) is dendrite, and the pitch of the dendrite is 5-15 μm.
9. The method for producing a large-sized tin-phosphor bronze rod according to claim 1, wherein the grain size of the master alloy ingot obtained in the step (3) is controlled to be 0.030mm or less.
10. The method for preparing a large-sized tin-phosphor bronze bar according to claim 1, wherein the twin area in the recrystallized grains of the master alloy extrusion blank obtained in the step (3) is 50-70% of the total area of the grains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310876570.6A CN116875841A (en) | 2023-07-18 | 2023-07-18 | Large-specification tin-phosphor bronze bar and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310876570.6A CN116875841A (en) | 2023-07-18 | 2023-07-18 | Large-specification tin-phosphor bronze bar and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116875841A true CN116875841A (en) | 2023-10-13 |
Family
ID=88267659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310876570.6A Pending CN116875841A (en) | 2023-07-18 | 2023-07-18 | Large-specification tin-phosphor bronze bar and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116875841A (en) |
-
2023
- 2023-07-18 CN CN202310876570.6A patent/CN116875841A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022062335A1 (en) | Copper-chromium alloy strip and preparation method therefor | |
| CN109022896B (en) | High-strength high-conductivity heat-resistant Cu-Fe-Y-Mg alloy material with electromagnetic wave shielding performance and preparation method thereof | |
| CN110423927A (en) | A kind of Ultrahigh strength aluminum lithium alloy and preparation method thereof | |
| CN112899541B (en) | Quick age hardening multielement micro-alloy weak texture magnesium alloy and preparation method thereof | |
| CN111440963B (en) | High-heat-resistance high-conductivity CuCrNb-based copper alloy and preparation method thereof | |
| WO2008120237A1 (en) | Alloy composition and preparation thereof | |
| CN109182809B (en) | Low-cost high-toughness wrought magnesium alloy and preparation method thereof | |
| CN110747365B (en) | High-plasticity high-strength high-conductivity CuCrZr copper alloy and preparation method thereof | |
| CN110863120B (en) | Copper alloy for lead frame and preparation method thereof | |
| CN114277291B (en) | Al-Zn-Mg-Cu aluminum alloy extrusion material for aerospace and preparation method thereof | |
| CN113737068A (en) | High-strength and high-toughness corrosion-resistant 7xxx series aluminum alloy and processing method thereof | |
| CN112593100A (en) | Preparation method of large-size 6061 aluminum alloy plate for semiconductor equipment | |
| CN110172621B (en) | High-strength high-conductivity Al-Mg-Si alloy and preparation method thereof | |
| CN109234592B (en) | Low-temperature rolled high-strength-toughness wrought magnesium alloy and preparation method thereof | |
| CN115896509B (en) | Preparation method for constructing superfine crystal structure in magnesium alloy | |
| CN111549262A (en) | Low-resistivity high-strength aluminum alloy conductive tube and manufacturing method thereof | |
| CN116875841A (en) | Large-specification tin-phosphor bronze bar and preparation method thereof | |
| CN114318087A (en) | Al-Zn-Mg-Cu aluminum alloy for aircraft engine shell and preparation method thereof | |
| CN114427046A (en) | Short-process preparation device and preparation method of alloy | |
| CN115652136B (en) | Free-cutting copper-nickel-silicon bar and preparation method thereof | |
| US10273564B2 (en) | Aluminium based alloys for high temperature applications and method of producing such alloys | |
| CN112593114B (en) | Preparation method of high-performance Cu-Cr-Zr-Mg-Si alloy plate strip | |
| CN117960831A (en) | Isothermal extrusion process for 7000 series aluminum alloy structural members of high-speed rail vehicle body | |
| CN117965981A (en) | Ultra-light high-strength and high-toughness micro-alloyed magnesium-lithium alloy and low-temperature extrusion forming process thereof | |
| CN117604347A (en) | High-strength and high-toughness (alpha+beta) dual-phase magnesium-lithium alloy bar and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |