CN1348017A - Method and equipment of preparing massive great-specific weight Zr-W-base amorphous alloy - Google Patents

Method and equipment of preparing massive great-specific weight Zr-W-base amorphous alloy Download PDF

Info

Publication number
CN1348017A
CN1348017A CN 01136482 CN01136482A CN1348017A CN 1348017 A CN1348017 A CN 1348017A CN 01136482 CN01136482 CN 01136482 CN 01136482 A CN01136482 A CN 01136482A CN 1348017 A CN1348017 A CN 1348017A
Authority
CN
China
Prior art keywords
vacuum chamber
alloy
bulk amorphous
amorphous alloys
amorphous alloy
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.)
Granted
Application number
CN 01136482
Other languages
Chinese (zh)
Other versions
CN1123647C (en
Inventor
惠希东
王艳丽
宋西平
林均品
林志
陈国良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology Beijing USTB
Original Assignee
University of Science and Technology Beijing USTB
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to CN 01136482 priority Critical patent/CN1123647C/en
Publication of CN1348017A publication Critical patent/CN1348017A/en
Application granted granted Critical
Publication of CN1123647C publication Critical patent/CN1123647C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Landscapes

  • Manufacture And Refinement Of Metals (AREA)

Abstract

The massive amorphous alloy has the components (in atomicity percentage): Zr 40-60, Cu 5-25, Ni 5-20, Al 2-10, W 5-15 and B2-10. The suspension smelting and double chamber casting equipment for producing the alloy consists of mechanical pump, diffusion pump, air valve, vacuum chamber, elevator, water cooled copper mold, upper and lower connection and sealing structure, suspension coil, quartz glass crucible, thermocouple, power supply and other parts. The amorphous alloy of the present invention has specific weight of 7.5-8.0 g/cu cm, 15-20 % greater than that of traditional Zr-base massive amorphous alloy. The suspension smelting can purify and homogenize melt and the double chamber casting can raise melt filling speed, simplify mold design and manufacture and lower manufacture cost.

Description

A kind of method and apparatus for preparing massive great-specific weight Zr-W-base amorphous alloy
Technical field:
The invention provides the suction pouring preparation method and the relevant device thereof of a kind of tungstenic great-specific weight Zr-W-Cu-Ni-Al-B bulk amorphous alloys.
Background technology:
Since nineteen sixty Duwez adopts the melt supercooled technology to prepare the Au-Si amorphous alloy first, amorphous alloy is with its particular structure and good performance, attracting scientific workers strongly, and at first obtaining industrial application at aspects such as transformer fe core material, catalyst materials.Yet, because necessary condition of fast cooling (＞10 when formed by at that time various amorphous alloys 6K/s) restriction, amorphous alloy quite can only exist with low-dimensional forms such as powder, silk, strips in one period of length afterwards, have weakened giving full play to of amorphous alloy performance potential greatly, have also limited being extensive use of of amorphous alloy simultaneously.Up to the nineties, A.Inoue, T Zhang and T.Masumoto.Mater.Trans., JIM, 30 (1989), 965 and A.Peker and W.L.Johnson, Appl.Phys.Lett., 63 (1993), 2342 pass through design of alloy, broken through the high speed cooling limitation, the routine casting technology under the speed of cooling condition that can reach (10 1-10 -2K/s) prepared massive metal glass material.
The development of block amorphous alloy over past ten years, it basically mainly is the development of bulk amorphous alloys system, up to now, the bulk amorphous alloys system that has been found that has: alloy systems such as Zr base, Ln base, Ti base, Cu base, Fe base, M base and Pd base, find that wherein maximum is Zr base large amorphous alloy system, representative alloy has: M.I.Petrzhik, V.V.Moloksnov, T.N.Mikhailova, Y.K.Kovneristyi, Mater.Sci.Forum, 269-272 (1998), the Zr of 791 preparations 40Ti 10Cu 50Bulk amorphous alloys; A.Inoue, D.Kawase, A.P.Tai.Mater.Sci.Eng., A178 (1994), the Zr of 255 preparations 60Al 10Cu 30Bulk amorphous alloys; A.Kubler, J.Eckert, A.Kirchner andSchultz.Mater.Sci.Forum, 269-272 (1998), the Zr of 767 preparations 65Al 10Ni 10Cu 15Bulk amorphous alloys; C.Fan, A.Takeuchi and A.Inoue.Mater.Trans., JIM, the Zr of 40 (1999), 42 preparations 60Al 10Cu 20Pd 10Bulk amorphous alloys; A.Leonhard, L.Q.Xing, M.Heilmaier and Schultz Nanostructure Materials, the Zr of 10 (1998), 805 preparations 57Al 10Ni 8Cu 20Ti 5Bulk amorphous alloys; A.Peker and W.L.Johnson Appl.Phys.Lett., the Zr of 63 (1993), 2342 preparations 40Ti 14Ni 11Cu 10Be 25Bulk amorphous alloys; A.Inoue, T.Shibataand T.Zhang.Mater.Trans., JIM, the Zr of 36 (1995), 1420 preparations 60Al 10Co 3Ni 9Cu 18Bulk amorphous alloys.But the density of existing Zr base large amorphous alloy is all at 7g/cm 3Below, for some occasion that requires high-strength, high tenacity and kinetic energy, the Zr base large amorphous alloy still has certain gap.
Preparation technology also is the key factor that can the restriction bulk amorphous alloys successful.The large block amorphous method of current preparation mainly contains following several: pressure model casting, atomizing amorphous powder extrusion process, directional solidification method, water quenching and vacuum suction casting technique etc.A.Inoue.Mater.Trans. for example, JIM, 36 (1995), 866 utilize the pressure model casting to prepare the Mg-Ln-TM amorphous of block, Ln-Al-TM amorphous and Zr base block amorphous alloy etc.The ultimate principle of this method is: by high-frequency induction heating fusing, fire plug certain speed and pressure under hydraulic action moves forward mother alloy, and molten metal is squeezed in the copper mold under the protection of argon gas, relies on strong water-cooled and forms bulk amorphous.A.Inoue, Zhang Tao, US5740854 have proposed arc melting and have added the method for inhaling casting and prepare bulk amorphous alloy, and its basic functional principle is: the method fusing mother alloy that at first utilizes arc melting, copper mold divides two chambeies up and down, and the copper mold cavity of resorption is in the vacuum state of sealing.After the mother alloy fusing, open the baffle plate between copper mold up and down, in the water cooled copper mould below liquid alloy is inhaled under the pull of vacuum effect, the strong cold-working that relies on water cooled copper mould is with preparing bulk amorphous alloy, the shortcoming of this equipment is that copper mold is made complexity, both consider the shape of sample, considered the vacuum-sealing problem of copper mold again.
The objective of the invention is to propose a kind of great-specific weight Zr-W-Cu-Ni-Al-B large-block amorphous alloy component, design the new suspended smelting of a cover and add two chambers suction casting machines, and the high specific gravity Zr bulk amorphous alloys bar and the sheet material that utilize this equipment to prepare to contain W, with as high-strength, high-ductility with have the kinetic energy material.
Summary of the invention:
1, the design of large-block amorphous alloy component, following three aspects have mainly been considered in the design of alloying constituent: (1) is in order to obtain bulk amorphous alloys, at first based on Zr-Ni-Cu-Al, (2) focus on the proportion that consideration improves alloy then, we choose the main adding elements of W as the new alloy system for this reason.(3) after W adds, might cause the rising of alloy melting point and the raising of certain compound formation ability, thereby reduce amorphous formation ability, cold theory is crossed on the polynary short-range order farmland that proposes according to us for this reason, by calculating, select B to add element as the another kind of new alloy system.So the composition proportion (atomic percent, as follows) of new alloy system is: Zr is 40-60, and Cu is 5-25, and Ni is 5-20, and Al is 2-10, and W is 5-15, and B is 2-10.The proportion of this bulk amorphous alloys can reach 7.5～8.0g/cm 3, than the based bulk amorphous raising 15～20% of traditional Z r,
2, provide method and apparatus, absorbing and casting device schematic diagram such as the accompanying drawing 1 that adopts suspended smelting to add two chambers suction casting preparation Zr-W-Ni-Cu-Al-B.Equipment mainly is made of following part: (1) mechanical pump, (2) diffusion pump, (3) air valve; (4) vacuum chamber, (5) lifting table, (6) water cooled copper mould; (7) connect sealed structure (adding water jacket) up and down, (8) suspended coil, (its top is for containing melt for (9) quartz glass crucibles; the bottom is a thrust-augmenting nozzle), (10) stopper, mechanism draws the cork (11); (12) protection gas air inlet purging valve, (13) thermopair, (14) power supply; (15) fire door, (16) are the vacuum chamber venting port down.
Principle of work is as follows: at first in electric arc furnace various constituent elements are joined by predetermined one-tenth fractional melting, molten joining adopted argon shield in the process.Mother alloy is packed in the silica tube, open mechanical pump (1) and diffusion pump (2), open air valve (3)-1 (3)-2, be evacuated to condition of high vacuum degree; Then, close (3)-1, continue to take out down vacuum chamber; Simultaneously, fill the protection argon gas for last vacuum chamber.Switch power supply, mother alloy in the quick fused quartz glass pot, utilize thermocouple temperature measurement simultaneously, behind alloy melting,, start the mechanism that draws the cork (11) and mention stopper (10) to preset temperature, melt is owing to be subjected to the effect of vacuum chamber pressure reduction up and down, fill type fast and solidify, stop at last vacuumizing, open down vacuum chamber venting port (16) and make vacuum chamber under the air admission, open fire door (15), reduce lifting table (5) sampling.
The invention has the advantages that:
1, the proportion of this bulk amorphous alloys can reach 7.5～8.0g/cm 3, be particularly suitable for making the material that requires to have kinetic energy;
2, the intensity of bulk amorphous alloys can reach 1600Mpa, is much higher than crystalline material;
3, the suspended smelting method of the present invention's employing can play the effect of even purification, thereby just can make bulk amorphous alloys to the material with ordinary purity, arrives the manufacturing cost that has reduced bulk amorphous alloys.
4, adopt dual-vacuum chamber to inhale the casting process method, gas clean-up greatly improves the filling velocity of melt, has simplified die design and manufacturing processed, is convenient to die change.
5, because the increase of vacuum chamber, so be particularly suitable for the preparation of large size bulk amorphous alloys.
Description of drawings:
Fig. 1 is that suspended smelting of the present invention adds dual-vacuum chamber suction casting machine synoptic diagram; (1) mechanical pump wherein; (2) diffusion pump; (3) air valve, (4) vacuum chamber, (5) lifting table; (6) water cooled copper mould; (7) connect sealed structure (adding water jacket) up and down, (8) suspended coil, (its top is for containing melt for (9) quartz glass crucibles; the bottom is a thrust-augmenting nozzle); (10) stopper, (11) mechanism that draws the cork, (12) protection gas air inlet purging valve; (13) thermopair; (14) power supply, (15) fire door, (16) are the vacuum chamber venting port down.
Fig. 2 is 3 for the diameter of the present invention's preparation, the thick Zr of 5mm 55.2Cu 14.8Ni 8.5Al 6.4W 10B 5The bulk amorphous alloys bar.
Fig. 3 is Zr 55.2Cu 14.8Ni 8.5Al 6.4W 10B 5The X-ray diffractogram of bulk amorphous alloys bar.
Fig. 4 is Zr 55.2Cu 14.8Ni 8.5Al 6.4W 10B 5The SEM image of bulk amorphous alloys bar.
Fig. 5 is Zr 55.2Cu 14.8Ni 8.5Al 6.4W 10B 5The TEM image of bulk amorphous alloys bar.
Fig. 6 is Zr 55.2Cu 14.8Ni 8.5Al 6.4W 10B 5Compression fracture curve after bulk amorphous alloys bar and the annealing thereof, X-coordinate is strain, and ordinate zou is the intensity of compressive stress, and unit is Mpa.
Embodiment:
Select highly purified 6 kinds of pure metal for use, i.e. Zr (99.9999wt%), Ni (99.999wt%), Cu (99.99wt%), Al (99.999wt%), W (99.99wt%), B (99.9999wt%).With atomic percent be: Zr is 55.2, and Cu is 14.8, and Ni is 8.5, and Al is 6.4, and W is 10, and B is the allotment of 5 ratio, under the high-purity argon gas protection, uses the purification technique of liquid mother alloy, utilizes arc melting method and makes mother alloy.In order to ensure the homogeneity of each constituent element in the mother alloy, mother alloy is by remelting three times.The surface of mother alloy spindle is polished away surperficial oxide skin by mechanical grinding, is crushed to fritter then and uses the alcohol wash surface.These mother alloy fritters are placed in the silica tube, utilize device as shown in Figure 1, and principle of work is prepared Zr as shown in Figure 2 as described above 55.2Cu 14.8Ni 8.5Al 6.4W 10B 5Bar, the proportion of this bar is through being measured as 7.82g/cm 3, higher by 20.3% than the proportion of other Zr base large amorphous alloy of having reported.Utilize the X-ray diffractometer check, diffraction spectra has only a roomy diffraction peak as shown in Figure 3 on the curve, and therefore not tangible the and corresponding diffraction peak existence of crystallization phases can confirm that this bar is an amorphous alloy.
Utilize the microtexture of scanning electron microscope (SEM) and transmission electron microscope (TEM) observation sample.The SEM sample makes with 2% HF aqueous solution etch, and the etch time is 5～10 seconds, and the TEM sample prepares with ion milling, and preparation temperature is 250K.The SEM of this bar image and TEM image shown in accompanying drawing 4 and accompanying drawing 5, can see that organizing almost completely of showing in the image is made up of single amorphous phase respectively, and be on all four on this and the X-ray diffraction spectrum result.
The mechanical property of bulk amorphous alloys is tested at normal temperatures with Gleeble1500 and is obtained.Accompanying drawing 6 is Zr 55.2Cu 14.8Ni 8.5Al 6.4W 10B 5Large block amorphous and through 773K, 1min annealing after the stress under compression strain curve.As seen, bulk amorphous alloys shows high intensity, and its breaking tenacity is 1.78Gpa, plasticity and recoverable strain preferably, and its plastic elongation rate and recoverable strain are respectively 0.6% and 1.7%.After 773K, 1min annealing, structural relaxation has taken place in tissue, but does not make large block amorphous intensity generation obvious variation, and just plasticity slightly reduces.

Claims (2)

1, a kind of method for preparing tungstenic great-specific weight Zr-W-Cu-Ni-Al-B bulk amorphous alloys is characterized in that:
A. the design of large-block amorphous alloy component, the composition proportion (atomic percent, as follows) that new bulk amorphous alloys is is: Zr is 40-60, and Cu is 5-25, and Ni is 5-20, and Al is 2-10, and W is 5-15, and B is 2-10, and the proportion of this alloy is 7.5～8.0g/cm 3
B. the preparation method of bulk amorphous alloys mainly is: at first in electric arc furnace various constituent elements are joined by predetermined one-tenth fractional melting, molten joining adopted argon shield in the process, mother alloy is packed in the silica tube, open mechanical pump (1) and diffusion pump (2), open air valve (3)-1 (3)-2, be evacuated to condition of high vacuum degree; Then, close (3)-1, continue to take out down vacuum chamber; Simultaneously, fill protection argon gas, switch power supply for last vacuum chamber; mother alloy in the quick fused quartz glass pot; utilize thermocouple temperature measurement simultaneously, behind alloy melting,, start the mechanism that draws the cork (11) and mention stopper (10) to preset temperature; melt is owing to be subjected to the effect of vacuum chamber pressure reduction up and down; fill type fast and solidify, stop at last vacuumizing, open down vacuum chamber venting port (16) and make vacuum chamber under the air admission; open fire door (15), reduce lifting table (5) sampling.
2, a kind of device for preparing tungstenic great-specific weight Zr-W-Cu-Ni-Al-B bulk amorphous alloys; it is characterized in that: by (1) mechanical pump; (2) diffusion pump; (3) air valve, (4) vacuum chamber, (5) lifting table; (6) water cooled copper mould; (7) connect sealed structure (adding water jacket) up and down, (8) suspended coil, (its top is for containing melt for (9) quartz glass crucibles; the bottom is a thrust-augmenting nozzle); (10) stopper, (11) mechanism that draws the cork, (12) protection gas air inlet purging valve; (13) thermopair; (14) power supply, (15) fire door, (16) vacuum chamber venting port are down formed.
CN 01136482 2001-10-19 2001-10-19 Method and equipment of preparing massive great-specific weight Zr-W-base amorphous alloy Expired - Fee Related CN1123647C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 01136482 CN1123647C (en) 2001-10-19 2001-10-19 Method and equipment of preparing massive great-specific weight Zr-W-base amorphous alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 01136482 CN1123647C (en) 2001-10-19 2001-10-19 Method and equipment of preparing massive great-specific weight Zr-W-base amorphous alloy

Publications (2)

Publication Number Publication Date
CN1348017A true CN1348017A (en) 2002-05-08
CN1123647C CN1123647C (en) 2003-10-08

Family

ID=4673693

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 01136482 Expired - Fee Related CN1123647C (en) 2001-10-19 2001-10-19 Method and equipment of preparing massive great-specific weight Zr-W-base amorphous alloy

Country Status (1)

Country Link
CN (1) CN1123647C (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102278881A (en) * 2011-08-12 2011-12-14 上海理工大学 Vacuum induction melting furnace capable of realizing rapid solidification
CN101644537B (en) * 2009-09-03 2012-07-18 张保国 Double-chamber vacuum oriented smelting furnace and use method thereof
CN105112819A (en) * 2015-09-14 2015-12-02 西北工业大学 Method for regulating micro structure of Ti-Zr-Nb-Cu-Be-system amorphous composite material
CN105397030A (en) * 2015-11-13 2016-03-16 山东农业大学 Method for improving heat stability and abrasion resistance of hollow conical amorphous alloy
CN109530702A (en) * 2018-11-16 2019-03-29 广东劲胜智能集团股份有限公司 A kind of amorphous alloy mobile phone center molding machine and its forming method
CN109612275A (en) * 2019-01-28 2019-04-12 徐州金虹钢铁集团有限公司 A kind of technique of suspension smelting furnace and its smelting metal
CN109654877A (en) * 2019-01-28 2019-04-19 徐州金虹钢铁集团有限公司 A kind of method of the smelting in suspension mechanism and its smelting metal of metal smelting-furnace
CN112916832A (en) * 2021-01-25 2021-06-08 中国科学院金属研究所 Vacuum suction casting device and method for high-melting-point, high-activity and high-purity alloy

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101644537B (en) * 2009-09-03 2012-07-18 张保国 Double-chamber vacuum oriented smelting furnace and use method thereof
CN102278881A (en) * 2011-08-12 2011-12-14 上海理工大学 Vacuum induction melting furnace capable of realizing rapid solidification
CN105112819A (en) * 2015-09-14 2015-12-02 西北工业大学 Method for regulating micro structure of Ti-Zr-Nb-Cu-Be-system amorphous composite material
CN105397030A (en) * 2015-11-13 2016-03-16 山东农业大学 Method for improving heat stability and abrasion resistance of hollow conical amorphous alloy
CN109530702A (en) * 2018-11-16 2019-03-29 广东劲胜智能集团股份有限公司 A kind of amorphous alloy mobile phone center molding machine and its forming method
CN109612275A (en) * 2019-01-28 2019-04-12 徐州金虹钢铁集团有限公司 A kind of technique of suspension smelting furnace and its smelting metal
CN109654877A (en) * 2019-01-28 2019-04-19 徐州金虹钢铁集团有限公司 A kind of method of the smelting in suspension mechanism and its smelting metal of metal smelting-furnace
CN112916832A (en) * 2021-01-25 2021-06-08 中国科学院金属研究所 Vacuum suction casting device and method for high-melting-point, high-activity and high-purity alloy

Also Published As

Publication number Publication date
CN1123647C (en) 2003-10-08

Similar Documents

Publication Publication Date Title
Xia et al. Binary Ni–Nb bulk metallic glasses
CN106567015B (en) A kind of CuZr base lump non-crystalline alloy and its preparation method and application
CN101774009B (en) Device and method for shaping amorphous alloy thin-wall slim pipe
CN1123647C (en) Method and equipment of preparing massive great-specific weight Zr-W-base amorphous alloy
CN111118414B (en) Method for preparing copper-based amorphous alloy from standard blister copper
CN1442254A (en) Spray casting-suction casting method and equipment for preparing large non crystal alloy
CN107236913B (en) A kind of zirconium-base amorphous alloy and preparation method thereof
CN106591743A (en) High-plasticity zirconium base amorphous alloy and preparation method thereof
CN103668010B (en) A series of Zr Al Ni Cu block amorphous alloys with born of the same parents' shape microstructure
CN102146550A (en) Nickel-free zirconium alloy with amorphous structure easily formed by pouring melt copper mould
Yokoyama et al. Nanocrystalline Zr-based bulk glassy alloys with high flexural strength
CN103589882A (en) Blocky high-entropy metallic glass and preparation method thereof
CN102952969B (en) Large-size Zr standard crystal material and preparation method thereof
CN1442502A (en) Method of preparing large non crystal/fiber composite material and tis equipment
CN109022906B (en) Preparation method of TiAl intermetallic compound containing rare earth element Er
CN109468548A (en) A kind of width supercooling liquid phase region zirconium-base amorphous alloy
CN110358962A (en) A kind of large scale rule billet infusibility high-entropy alloy and preparation method thereof
CN106222585B (en) A kind of siliceous Cu base bulk metallic glass composite material and its preparation process
CN104911513A (en) Large size ZrTi quasicrystal material and preparation method thereof
CN101665893B (en) Amorphous bulk composite as-cast tough phase crystal spheroidizing method and special device thereof
CN108977738A (en) A kind of hydrogeneous titanium-based block amorphous alloy
CN112658268B (en) Rare earth modified TiAl alloy powder for additive manufacturing and preparation method thereof
CN101347830A (en) Method for improving massive amorphous alloy plasticity by controlling solidification condition
CN103122429A (en) Massive aluminum base noncrystal/nanocrystal composite material and preparation method thereof
CN101148711B (en) Method for preparing Mg-base large-block amorphous alloy

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee