CN110042270A - The preparation method of Ultra-fine grain copper titanium alloy wire - Google Patents
The preparation method of Ultra-fine grain copper titanium alloy wire Download PDFInfo
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- CN110042270A CN110042270A CN201910334755.8A CN201910334755A CN110042270A CN 110042270 A CN110042270 A CN 110042270A CN 201910334755 A CN201910334755 A CN 201910334755A CN 110042270 A CN110042270 A CN 110042270A
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- titanium
- copper
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- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000010936 titanium Substances 0.000 claims abstract description 76
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 37
- 238000005245 sintering Methods 0.000 claims abstract description 37
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 37
- 239000011734 sodium Substances 0.000 claims abstract description 37
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000956 alloy Substances 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001125 extrusion Methods 0.000 claims abstract description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 12
- 238000005275 alloying Methods 0.000 claims abstract description 11
- 238000000462 isostatic pressing Methods 0.000 claims abstract description 7
- 230000000930 thermomechanical effect Effects 0.000 claims abstract description 7
- 238000007689 inspection Methods 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000009434 installation Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 5
- 229910001338 liquidmetal Inorganic materials 0.000 abstract 1
- 238000012797 qualification Methods 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 229910003074 TiCl4 Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000002706 hydrostatic effect Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910010038 TiAl Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- -1 rare earth metal Rare earth metal Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- B22F1/0003—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous metal compounds
-
- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The preparation method of Ultra-fine grain copper titanium alloy wire, including titanium valve preparation, powdered titanium tetrachloride is reacted with liquid metal sodium and generates nanometer titanium power；After above-mentioned titanium valve is mixed in proportion with copper powder, then plus special ratios rare-earth yttrium be mixed, isostatic pressing is at copper-titanium alloy billet；Above-mentioned copper-titanium alloy billet is placed in ceramic die, at 950 DEG C~1050 DEG C of sintering temperature, is sintered 50~70 minutes in sintering furnace, titanium, copper atom is enable to carry out complete alloying in nanoscale；By the copper titanium billet water seal extrusion through sintered alloy；Copper titanium billet through water seal extrusion is subjected to secondary thermomechanical treatment；The titanium crystalline particle of the copper-titanium alloy wire rod of product inspection qualification is 10~60nm, has intensity height, conductivity good, the characteristics such as excellent spring.
Description
Technical field
The present invention relates to the preparation of copper-titanium alloy material and technology field, a kind of specific Ultra-fine grain copper titanium alloy wire preparation side
Method.
Background technique
Copper-titanium alloy is a kind of superpower copper series alloy, compared to general copper alloy, has superelevation tensile strength, elasticity and resistance to
Hot mastication performance, also have it is good it is conductive, thermally conductive, without magnetic and impact the performances such as no-spark.It can be used for manufacturing lead frame
Material, elastic material connector, spring connector etc..In electronic information, automobile, telecommunications industry, army's industry and aircraft manufacturing
The industrial fields such as industry have a extensive future.Present copper alloy ingot blank is mainly traditional fusion casting, but traditional fusion casting without
Method casts out the as-cast grain structure of Nano grade.CN104674054A discloses a kind of high-strength copper titanium alloy and its manufacturer
Method obtains CTB alloy ingot casting by addition third alloy element Al, Sn and Zn, and TiAl Intermetallic compound is used to increase for collaboration
Phase is folded by force, the second phase of alloy is improved and folds effect, and through solution treatment, cold rolling and ageing treatment, composition and method do not pay attention to
Refine as-cast grain, the effect for improving tensile strength, elongation percentage and conductivity is unobvious.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of titanium copper ingot blank technology of preparing.
Second technical problem to be solved by this invention is to provide a kind of preparation method of Ultra-fine grain copper titanium alloy wire.
The CTB alloy of preparation has good processing performance, while alloy strength is high, and conductivity is good, excellent spring, and high temperature is resistance to answer
The features such as power relaxation property is good.
The preparation method of Ultra-fine grain copper titanium alloy wire, feature the following steps are included:
1) prepared by titanium valve: the weight ratio of powdered titanium tetrachloride and solid metallic sodium is 2.0~2.5:1, first by four chlorinations
Titanium is placed in plus protects to gasify in the closed steam oven of inert argon, while will make metallic sodium in metallic sodium placement vacuum drying oven
Then gaseous titanium tetrachloride and Liquid Sodium are passed through pipeline respectively and crossed to sealing reaction by liquefaction, generate displacement reaction and generate
The titanium and sodium chloride of Nano grade finally dry to obtain the pure titanium valve of nanoscale by water tower cleaning, drying tower；
2) it is molded copper titanium billet processed: rabble furnace is added in the pure titanium valve and copper powder of preparation ratio 1:30~45 by weight and is mixed, then
0.001%~0.01% rare-earth yttrium of above-mentioned raw materials total weight is added, is stirred after vacuumizing, is then carried out into press etc. quiet
It is pressed into column billet；
3) copper titanium billet is sintered: the column billet after isostatic pressing being placed in ceramic die, then billet will be housed
Ceramic die is put into sintering furnace and is sintered, and is passed through reductive hydrogen, and sintering time is 50~70 minutes, and sintering temperature controls copper
950 DEG C~1050 DEG C of the solid-liquid two-phase region temperature of titanium alloy, enables titanium, copper atom to be diffused in nano-scale range, tissue
Reach alloying；
4) water seal of copper titanium billet squeezes: extrusion speed is 7~10mm/s, squeezes 800~900 DEG C of temperature, extruding specification is Φ 18
~32mm carries out water seal quenching solution when extruded rod exports；
5) thermomechanical treatment of semi-finished product: roller bottom furnace temperature rises to 400~460 DEG C of step aging temp, and heat preservation 0.5~
1h；Then 360~390 DEG C of second level ladder aging temp is cooled the temperature to, 3h is kept the temperature, makes alloy structure crystal grain more evenly, it is conductive
Property and intensity are more preferable；
6) product inspection.
As an improvement, what the step 1) gaseous titanium tetrachloride and Liquid Sodium gasified according to weight ratio 2.2:1, titanium tetrachloride
At 200 ~ 500 DEG C, the control of metallic sodium condensing temperature is 200 ~ 500 DEG C for temperature control, and sealing reacting furnace is passed through inert argon protection.
The step 1) is cleaned by water tower, drying tower dries to obtain the pure titanium valve of dry Nano grade, is that will react life
At nano grade titanium powder and sodium chloride mixture be sent to water tower, mixture is soluble in water by water tower afterchlorinate sodium, nanometer
It is resent in drying tower after titanium powder filtering, titanium valve enters at the top of drying tower, is gradually decreased to tower bottom by helical orbit, does
Argon gas is passed through in dry tower, drying tower drying temperature is 500 ~ 700 DEG C.
As an improvement, the gross weight that rare earth element yttrium is added in the step 2 is 0.005 ~ 0.009% rare-earth yttrium of total weight,
Addition rare-earth yttrium can improve titanium and copper surface-active, and the atom of titanium and copper is promoted to spread during the sintering process, enhance sintering process
Middle alloying improves the cold and hot working plasticity of billet.
As an improvement, the step 3) copper titanium billet sintering refers to that ceramic die internal model size is consistent with ingot blank size, simultaneously
Ceramic die wall is covered with through-hole, aperture 3mm, each pitch of holes 5mm, and material is boron nitride, and ceramic die effect is to prevent billet in high temperature
It is deformed when sintering, while through-hole contacts billet by reducing atmosphere.
As an improvement, the step 4) copper titanium billet water seal extruding refers to that the billet that will reach through the burning time, high temperature takes
It is placed in holding furnace out, protective gas nitrogen is passed through in holding furnace, while by Control for Kiln Temperature at 800 ~ 900 DEG C.Then start
Water seal squeezes, and extrusion speed is 7 ~ 10mm/s, and extruding specification is 18 ~ 32mm of Φ.It is 20 ~ 40 DEG C squeezing installation water temperature at die orifice
Sink, in water seal extrusion process, extruded rod, which goes out, immediately enters quenching-in water solid solution when squeezing die orifice, it is ensured that when CTB alloy squeezes
Solid solubility.
The technological merit of this patent: it is reacted using misted chemical, i.e., gaseous titanium tetrachloride and Liquid Sodium prepare titanium valve, particle
It is tiny, uniform, reach Nano grade.Rare-earth yttrium improvement titanium is added and copper surface-active, yttrium are that content is big, inexpensive in rare earth metal
Rare earth metal, yttrium have high temperature resistant, corrosion resistance, sintering process promote the atom of titanium and copper spread, enhance it is sintered
Alloying in journey.
Detailed description of the invention
Fig. 1 a is that 2000 times of crystalline state figures are amplified in metallographic structure after the billet of embodiment 2 is sintered.
Fig. 1 b is that 10000 times of crystalline state figures are amplified in metallographic structure after the billet of embodiment 2 is sintered.
Specific embodiment
Present invention is further described in detail with reference to embodiments.
Embodiment 1
1) prepared by titanium valve: the weight ratio of commercially available powdered titanium tetrachloride and solid metallic sodium is 2.2:1, first by tetrachloro
Change titanium to be placed on plus protect in the closed steam oven of inert gas argon gas, is heated to 300 DEG C and titanium chloride gasifies；Sodium is put simultaneously
It sets in vacuum drying oven, is vacuumized, then pass to protection inert gas argon gas, and furnace temperature is risen to 320 DEG C, sodium is liquefied.So
The titanium tetrachloride of gasification and the sodium of liquid are passed through special pipeline respectively afterwards to cross to sealing reacting furnace generation displacement reaction generation
The titanium and sodium chloride of Nano grade, inert argon protection is passed through in simultaneous reactions furnace, and reaction generates nanometer titanium power and sodium chloride
Powder,
4Na+ TiCl4 → 4NaCl+ Ti。
The nanometer titanium power prepared and sodium chloride powder mixture are sent to water tower, are dissolved in by water tower afterchlorinate sodium
It in water, is resent in drying tower after nano-titanium powder filter, titanium valve enters at the top of drying tower, gradually drops by helical orbit
To tower bottom, argon gas is passed through in drying tower, drying tower drying temperature is 600 DEG C, to obtain the pure titanium powder of dry nanoscale.
2) it is molded base ingot: the pure titanium valve and copper powder of Nano grade ratio 1:40.8 by weight is mixed, while adding
The 0.005% rare-earth yttrium powder for stating raw material total amount, is stirred and waits hydrostatic compacting, is pressed into Φ 200mm billet.
3) billet is sintered: the billet of isostatic pressing being placed in the ceramic die that material is boron nitride, then base will be housed
The ceramic die of ingot is sent into sintering furnace and is sintered, while being passed through reductive hydrogen, and sintering time is 55 minutes, and sintering temperature is in titanium copper
1020 DEG C of the solid-liquid two-phase region temperature of alloy, it is ensured that can be diffused, reach in nano-scale range in sintering process titanium, copper atom
To the complete alloying of copper-titanium alloy tissue.
4) water seal squeezes: the billet that will reach through the burning time, and high temperature taking-up is placed in holding furnace, is passed through in holding furnace
Protective gas nitrogen, Control for Kiln Temperature then carry out water seal extruding at 850 DEG C, and extrusion speed is 7 ~ 10mm/s, and extruding specification is Φ
32mm；It is 20 ~ 40 DEG C of sinks squeezing installation water temperature at die orifice, in water seal extrusion process, when extruded rod goes out to squeeze die orifice immediately
It is dissolved into quenching-in water, it is ensured that solid solubility when CTB alloy squeezes.
5) thermomechanical treatment of semi-finished product: roller bottom furnace temperature rises to 450 DEG C of step aging temp, keeps the temperature 0.7h；So
After cool the temperature to 380 DEG C of second level ladder aging temp, keep the temperature 3h.
6) finished surface cleaning, surface grinding polishing aligning, product inspection.
Embodiment 2
1) prepared by titanium valve: the weight ratio of commercially available powdered titanium tetrachloride and solid metallic sodium is 2.1:1, first by four chlorinations
Titanium is placed on plus protects in the closed steam oven of inert gas argon gas, is heated to 400 DEG C and titanium chloride gasifies；Sodium is placed simultaneously
It in vacuum drying oven, is vacuumized, then passes to protection inert gas argon gas, and furnace temperature is risen to 450 DEG C, sodium is liquefied.Then
By the titanium tetrachloride of gasification and the sodium of liquid pass through respectively special pipeline cross to sealing reacting furnace generate displacement reaction generate receive
The other titanium of meter level and sodium chloride, inert argon protection is passed through in simultaneous reactions furnace, and reaction generates nanometer titanium power and sodium chloride powder
End,
4Na+ TiCl4 → 4NaCl+ Ti。
The nanometer titanium power prepared and sodium chloride powder mixture are sent to water tower, are dissolved in by water tower afterchlorinate sodium
It in water, is resent in drying tower after nano-titanium powder filter, titanium valve enters at the top of drying tower, gradually drops by helical orbit
To tower bottom, argon gas is passed through in drying tower, drying tower drying temperature is 650 DEG C, to obtain the pure titanium powder of dry nanoscale.
2) it is molded base ingot: the pure titanium valve and copper powder of Nano grade ratio 1:36.1 ratio by weight being mixed, added simultaneously
The 0.007% rare-earth yttrium powder for adding above-mentioned raw materials total amount, is stirred and waits hydrostatic compacting, and being pressed into specification is Φ 200mm base
Ingot.
3) billet is sintered: the billet of isostatic pressing being placed in the ceramic die that material is boron nitride, is then loaded into again
The billet of ceramic die is sent into sintering furnace and is sintered, while being passed through reductive hydrogen, and sintering time is 60 minutes, and sintering temperature is in titanium
1010 DEG C of the solid-liquid two-phase region temperature of copper alloy, it is ensured that it can be diffused in nano-scale range in sintering process titanium, copper atom,
Reach the complete alloying of CTB alloy tissue.
4) water seal squeezes: the billet that will reach through the burning time, and high temperature taking-up is placed in holding furnace, is passed through in holding furnace
Protective gas nitrogen, while by Control for Kiln Temperature at 870 DEG C, then start water seal extruding, extrusion speed is 7 ~ 10mm/s, squeezes rule
Lattice are Φ 30mm；Water temperature is installed for 20 ~ 40 DEG C of sinks at die orifice squeezing, in water seal extrusion process, extruded rod goes out to squeeze die orifice
When immediately enter quenching-in water solid solution, it is ensured that CTB alloy squeeze when solid solubility.
5) thermomechanical treatment of semi-finished product: roller bottom furnace temperature rises to 430 DEG C of step aging temp, keeps the temperature 1h；Then
390 DEG C of second level ladder aging temp is cooled the temperature to, 3h is kept the temperature.
6) finished surface cleaning, surface grinding polishing aligning.
Embodiment 3
1) prepared by titanium valve: the weight ratio of commercially available powdered titanium tetrachloride and solid metallic sodium is 2.5:1, first by four chlorinations
Titanium is placed on plus protects in the closed steam oven of inert gas argon gas, is heated to 450 DEG C and titanium chloride gasifies；Sodium is placed simultaneously
It in vacuum drying oven, is vacuumized, then passes to protection inert gas argon gas, and furnace temperature is risen to 500 DEG C, sodium is liquefied.Then
By the titanium tetrachloride of gasification and the sodium of liquid pass through respectively special pipeline cross to sealing reacting furnace generate displacement reaction generate receive
The other titanium of meter level and sodium chloride, inert argon protection is passed through in simultaneous reactions furnace, and reaction generates nanometer titanium power and sodium chloride powder
End,
4Na+ TiCl4 → 4NaCl+ Ti。
The nanometer titanium power prepared and sodium chloride powder mixture are sent to water tower, are dissolved in by water tower afterchlorinate sodium
It in water, is resent in drying tower after nano-titanium powder filter, titanium valve enters at the top of drying tower, gradually drops by helical orbit
To tower bottom, argon gas is passed through in drying tower, drying tower drying temperature is 650 DEG C, to obtain the pure titanium powder of dry nanoscale.
2) it is molded base ingot: the copper powder of the pure titanium valve of Nano grade and Nano grade ratio 1:34.7 by weight is mixed,
The 0.008% rare-earth yttrium powder for adding above-mentioned raw materials total amount simultaneously, is stirred and waits hydrostatic compacting, and compacting specification is Φ
200mm billet.
3) billet is sintered: the billet of isostatic pressing being placed in the ceramic die that material is boron nitride, is then loaded into again
The billet of ceramic die is sent into sintering furnace and is sintered, while being passed through reductive hydrogen, and sintering time is 65 minutes, and sintering temperature is in titanium
1030 DEG C of the solid-liquid two-phase region temperature of copper alloy, it is ensured that it can be diffused in nano-scale range in sintering process titanium, copper atom,
Reach the complete alloying of CTB alloy tissue.
4) water seal squeezes: the billet that will reach through the burning time, and high temperature taking-up is placed in holding furnace, is passed through in holding furnace
Protective gas nitrogen, while by Control for Kiln Temperature at 820 DEG C.Then start water seal extruding, extrusion speed is 7 ~ 10mm/s, squeezes rule
Lattice are Φ 25mm；Water temperature is installed for 20 ~ 40 DEG C of sinks at die orifice squeezing, in water seal extrusion process, extruded rod goes out to squeeze die orifice
When immediately enter quenching-in water solid solution, it is ensured that CTB alloy squeeze when solid solubility.
5) thermomechanical treatment of semi-finished product: roller bottom furnace temperature rises to 420 DEG C of step aging temp, keeps the temperature 1h；Then
390 DEG C of second level ladder aging temp is cooled the temperature to, 3h is kept the temperature.
6) finished surface cleaning, surface grinding polishing aligning.
Embodiment 4
1) prepared by titanium valve: the weight ratio of commercially available powdered titanium tetrachloride and solid metallic sodium is 2.1:1, first by four chlorinations
Titanium is placed on plus protects in the closed steam oven of inert gas argon gas, is heated to 350 DEG C and titanium chloride gasifies；Sodium is placed simultaneously
It in vacuum drying oven, is vacuumized, then passes to protection inert gas argon gas, and furnace temperature is risen to 480 DEG C, sodium is liquefied.Then
By the titanium tetrachloride of gasification and the sodium of liquid pass through respectively special pipeline cross to sealing reacting furnace generate displacement reaction generate receive
The other titanium of meter level and sodium chloride, inert argon protection is passed through in simultaneous reactions furnace, and reaction generates nanometer titanium power and sodium chloride powder
End,
4Na+ TiCl4 → 4NaCl+ Ti。
The nanometer titanium power prepared and sodium chloride powder mixture are sent to water tower, are dissolved in by water tower afterchlorinate sodium
It in water, is resent in drying tower after nano-titanium powder filter, titanium valve enters at the top of drying tower, gradually drops by helical orbit
To tower bottom, argon gas is passed through in drying tower, drying tower drying temperature is 620 DEG C, to obtain the pure titanium powder of dry nanoscale.
2) it is molded base ingot: the copper powder of the pure titanium valve of Nano grade and Nano grade is mixed by weight 1:32.2 ratio
It closes, while adding 0.009% rare-earth yttrium powder, be stirred and wait hydrostatic compacting, compacting specification is Φ 200mm ingot blank.Rare earth
Yttrium improves titanium and copper surface-active, promotes the atom of titanium and copper to spread in sintering process, enhances alloying in sintering process.
3) billet is sintered: the billet of isostatic pressing being placed in the ceramic die that material is boron nitride, is then loaded into again
The billet of ceramic die is sent into sintering furnace and is sintered, while being passed through reductive hydrogen, and sintering time is 60 minutes, and sintering temperature is in titanium
1025 DEG C of the solid-liquid two-phase region temperature of copper alloy, it is ensured that it can be diffused in nano-scale range in sintering process titanium, copper atom,
Reach the complete alloying of CTB alloy tissue.
4) water seal squeezes: the billet that will reach through the burning time, and high temperature taking-up is placed in holding furnace, is passed through in holding furnace
Protective gas nitrogen, while by Control for Kiln Temperature at 860 DEG C.Then start water seal extruding, extrusion speed is 7 ~ 10mm/s, squeezes rule
Lattice are Φ 28mm；Water temperature is installed for 20 ~ 40 DEG C of sinks at die orifice squeezing, in water seal extrusion process, extruded rod goes out to squeeze die orifice
When immediately enter quenching-in water solid solution, it is ensured that CTB alloy squeeze when solid solubility.
5) thermomechanical treatment of semi-finished product: roller bottom furnace temperature rises to 440 DEG C of step aging temp, keeps the temperature 1h；Then
380 DEG C of second level ladder aging temp is cooled the temperature to, 3h is kept the temperature.
6) finished surface cleaning, surface grinding polishing aligning.
Table 1 is the copper-titanium alloy band of aforementioned four embodiment compared with component and the relevant grain size of technique:
It is grain size and titanium, yttrium content and billet sintering temperature correlation: the size of grain size and receiving for titanium valve shown in table 1
Meter Du is related with billet sintering temperature.
In the metallographic microscope of example 2, black represents titanium in (a) figure, amplifies 2000 times, scale 100nm, and titanium particle is
32nm.(b) figure is 10000 times, scale 20nm of amplification, and titanium particle is 32nm.Titanium particle size is in 10~60nm in billet,
Grain size is tiny, Dispersed precipitate.
Table 2 is the performance test results of the copper-titanium alloy wire rod of above-mentioned four embodiments preparation:
2 particular product performance parameters of table
Copper-titanium alloy wire rod prepared by the present invention has intensity high as can be seen from Table 2, and conductivity is good, the spies such as excellent spring
Property.
Claims (6)
1. a kind of preparation method of Ultra-fine grain copper titanium alloy wire, feature the following steps are included:
1) prepared by titanium valve: the weight ratio of powdered titanium tetrachloride and solid metallic sodium is 2.0~2.5:1, first by four chlorinations
Titanium is placed in plus protects to gasify in the closed steam oven of inert argon, while will make metallic sodium in metallic sodium placement vacuum drying oven
Then gaseous titanium tetrachloride and Liquid Sodium are passed through pipeline respectively and crossed to sealing reaction by liquefaction, generate displacement reaction and generate
The titanium and sodium chloride of Nano grade prepare the pure titanium valve of nanoscale finally by water tower cleaning, drying tower drying；
2) it is molded copper titanium billet processed: rabble furnace is added in the pure titanium valve and copper powder of preparation ratio 1:30~45 by weight and is mixed, then
0.001%~0.01% rare-earth yttrium of above-mentioned raw materials total weight is added, is stirred after vacuumizing, is then carried out into press etc. quiet
It is pressed into column billet；
3) copper titanium billet is sintered: the column billet after isostatic pressing being placed in ceramic die, then billet will be housed
Ceramic die is put into sintering furnace and is sintered, and is passed through reductive hydrogen, and sintering time is 50~70 minutes, and sintering temperature controls copper
950 DEG C~1050 DEG C of the solid-liquid two-phase region temperature of titanium alloy, enables titanium, copper atom to be diffused in nano-scale range, tissue
Reach alloying；
4) water seal of copper titanium billet squeezes: extrusion speed is 7~10mm/s, squeezes 800~900 DEG C of temperature, extruding specification is Φ 18
~32mm carries out water seal quenching solution when extruded rod exports；
5) thermomechanical treatment of semi-finished product: roller bottom furnace temperature rises to 400~460 DEG C of step aging temp, and heat preservation 0.5~
Then 1h cools the temperature to 360~390 DEG C of second level ladder aging temp, keep the temperature 3h, make alloy structure crystal grain more evenly, conductive
Property and intensity are more preferable；
6) product inspection.
2. the preparation method of Ultra-fine grain copper titanium alloy wire according to claim 1, it is characterised in that the step 1) gas
State titanium tetrachloride and Liquid Sodium are according to weight ratio 2.2:1, and the temperature control of titanium tetrachloride gasification is at 200 ~ 500 DEG C, metallic sodium liquid
Changing temperature control is 200 ~ 500 DEG C, and sealing reacting furnace is passed through inert argon protection.
3. the preparation method of Ultra-fine grain copper titanium alloy wire according to claim 1, it is characterised in that the step 1) warp
Cross water tower cleaning, drying tower dry to obtain the pure titanium valve of dry Nano grade, be will react generation nano grade titanium powder and chlorine
Change sodium mixture and be sent to water tower, mixture is soluble in water by water tower afterchlorinate sodium, is resent to after nano-titanium powder filter
In drying tower, titanium valve enters at the top of drying tower, is gradually decreased to tower bottom by helical orbit, argon gas is passed through in drying tower, dry
Tower drying temperature is 500 ~ 700 DEG C.
4. the preparation method of Ultra-fine grain copper titanium alloy wire according to claim 1, it is characterised in that the step 2 adds
The weight for entering rare earth element yttrium is 0.005 ~ 0.009% rare-earth yttrium of total weight, improves titanium and copper surface-active, in sintering process
In promote the atom of titanium and copper spread, enhance sintering process in alloying, improve the cold and hot working plasticity of billet.
5. the preparation method of Ultra-fine grain copper titanium alloy wire according to claim 1, it is characterised in that the step 3) copper
The ceramic die internal model size of titanium billet sintering is consistent with ingot blank size, while ceramics die wall is covered with through-hole, aperture 3mm, between each hole
Away from 5mm, material is boron nitride, and ceramic die prevents billet from deforming when sintering at high temperature, while through-hole allows also Primordial Qi to contact billet.
6. the preparation method of Ultra-fine grain copper titanium alloy wire according to claim 1, it is characterised in that the step 4) copper
Titanium billet water seal extruding is the billet that will reach through the burning time, and high temperature taking-up is placed in holding furnace, and guarantor is passed through in holding furnace
Gas nitrogen is protected, while by Control for Kiln Temperature at 800 ~ 900 DEG C, then start water seal extruding, extrusion speed is 7 ~ 10mm/s, is squeezed
Specification is 18 ~ 32mm of Φ；It is 20 ~ 40 DEG C of sinks squeezing installation water temperature at die orifice, in water seal extrusion process, extruded rod goes out to squeeze
Quenching-in water solid solution is immediately entered when pressing mold mouth, it is ensured that solid solubility when CTB alloy squeezes.
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| CN114807668A (en) * | 2022-05-06 | 2022-07-29 | 浙江百川导体技术股份有限公司 | Rare earth nitride dispersion strengthening titanium-doped copper alloy and preparation method thereof |
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