CN1442502A - Method of preparing large non crystal/fiber composite material and tis equipment - Google Patents
Method of preparing large non crystal/fiber composite material and tis equipment Download PDFInfo
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- CN1442502A CN1442502A CN 03121417 CN03121417A CN1442502A CN 1442502 A CN1442502 A CN 1442502A CN 03121417 CN03121417 CN 03121417 CN 03121417 A CN03121417 A CN 03121417A CN 1442502 A CN1442502 A CN 1442502A
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Abstract
A process and equipment for preparing great non-crystal/fibre composition block is disclosed. Its equipment features that its heater is composed of a Mo layer and 6 reflecting layers, the mould made of quartz glass or graphite is arranged in said heater and is pneumatically drawn by a drawing mechanism under it, a cooling water tank is under the mould, and a dual-wall design is used for flowing cooling water between two walls and holding Ga-In or Ga-In-Sn alloy in the center. Its advantages are high control capability, less pollution to molten body and low cost.
Description
Technical field
The invention provides a kind of prepare high-strength and high ductility large block amorphous/the vacuum seepage castmethod and the relevant device thereof of fibre composite.
Background technology
Phase earlier 1990s, 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 restriction of high speed cooling conditions, the routine casting technology under the speed of cooling condition that can reach (～10
1K/s) prepare block non-crystalline alloy material, made the research of amorphous alloy and application stride into a brand-new era.Utilize technology such as water cooled copper mould casting, high undercooling method, spray to cast-suction casting method and suspension blowing process to prepare block non-crystalline alloy materials such as Zr base, Pd base, La base, Fe base, Mg base and Ti base at present, as 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.
Compare with traditional crystal alloy material, bulk amorphous material has obvious advantages aspect the multinomial use properties, mainly show as bulk amorphous alloys and have high strength and Young's modulus, have very high fracture toughness property under the effect of high speed load, having tangible self-sharpening and Adiabatic Shear destructiveness during at the penetration metal.But the density of existing bulk amorphous alloys is all at 7g/cm
3Below, requiring the occasion of high-strength, high tenacity and kinetic energy for some, the proportion of existing bulk amorphous alloys is obviously not enough, and toughness also awaits further raising.The breakthrough of bulk amorphous alloys system and technology of preparing in recent years, for adding particle and fiber reinforcement mutually, preparing large block amorphous matrix material provides brand-new, effective important synthesizing mean.
Preparation technology is the key factor that can restriction bulk amorphous alloys/fibre composite successful.Current preparation is large block amorphous/and the method for fibre composite mainly is that melt oozes casting.P.B.Dandliker, R.D.Conner and W.L.Johnson.J.Mater.Res.13 (1998) 2896 utilize this method to prepare tungsten fiber and Stainless Steel Wire enhanced Zr
41.2Ti
13.8Cu
12.5Ni
10Be
22.5Large block amorphous matrix material.The ultimate principle of this method is: will put into the silica tube bottom after the fibre reinforcement cleaning; then the mother alloy of melting under the high-purity argon gas protective condition is inserted silica tube top; branch initial heating and seepage flow heating two stages are by certain speed heating and reach balance; the high-purity argon gas that feeds some MPa acts on the alloy liquid level and keeps for some time; the abundant infiltrated fiber of alloy liquid is increased in the body, in the saturated salt solution of quenching fast then.The shortcoming of this method is only quartz crucible to be vacuumized with applying argon gas and utilize the saturated common salt water quenching, makes that the size of the fiber reinforcement amorphous alloy composite material that obtains can not be very big, has seriously restricted the engineering range of application of material.
Summary of the invention
The objective of the invention is to: provide a kind of high tough large block amorphous/preparation method of fibre composite, design the new vacuum seepage casting equipment of a cover, and utilize this equipment to prepare high tough large block amorphous/fibre composite, with as high-strength, high-ductility and kinetic energy material.
The vacuum seepage castmethod and the equipment that prepare large block amorphous/fibre composite are provided.Vacuum seepage casting schematic diagram such as accompanying drawing 1.Equipment mainly is made of following part: mechanical pump 1, lobe pump 2, molecular pump 3, valve 4, last chamber bell 5, bell locking mechanism 6, last furnace chamber 7, molybdenum sheet heating element 8, thermopair 9, conducting copper 10, supply transformer 11, following chamber fire door 12, following furnace chamber 13, cylinder assembly 14, workplatform 15, water-cooled cooling tank 16, tungsten fiber 17, radiation screen 18, mould 19, mother alloy 20, external high-purity argon gas 21.
The inventive point of this equipment is: heating element 6 is made up of 1 layer of molybdenum sheet and 6 layers of radiation shield, and Heating temperature can reach 1600 ℃, and can be incubated 120 hours under this temperature.Mould 19 is placed in the heating element, the bottom links to each other with haulage gear, mould adopting quartz glass or graphite manufacturing, the outside dimension of mould is 10～50mm, highly be 200～500mm, silica glass and graphite jig general headquarters adopt necking down design, necking down endoporus 2～5mm, mould adopts pneumatic mode traction 14, and the top speed that mould descends is 0.5m/s.Cooling trough 16 places the below of mould, adopts double wall design, logical water coolant in the middle of the double-walled, and centre portions is put into Ga-In, and the Ga-In-Sn alloy to realize the quick cooling of mould, adopts dynamic seal between mould and the cooling tank, flows out to prevent cool metal liquid.
Method of the present invention is as follows: at first in electric arc furnace with bulk amorphous alloys element Zr; Ti; Cu; Al; Be; Nb; Ta; W; Fe; Co; Ni; C; P; B; 4～7 kinds of elements among the Pd are in following ratio (atomic percent) Zr:40～80% of preparing burden; Ti:5～10%; Cu:5～50%; Al:3～20%; Be:5～25%; Nb:2～15%; Ta:1～10%; W:1～10%; Co:1～10%; Ni:5～50%; C:1～10%; P:5～20%; B:1～10%; Pd:5～60%, molten joining adopted the high-purity argon gas protection in the process.Pack into the tungsten fiber of abundant cleaning and mother alloy in the silica tube 19 and be placed in the furnace chamber 7 locking bell locking mechanism 6 and following chamber fire door 12.Order is driven mechanical pump 1 and lobe pump 2, to 1 * 10
-2Open molecular pump 3 after the Pa vacuum tightness again, valve-off 4-1 opens valve 4-3 simultaneously, takes out upper and lower furnace chamber vacuum to condition of high vacuum degree 5 * 10
-3～5 * 10
-4Pa;
Switch power supply, rate of heating heating tungsten fiber 17 and mother alloy 19 with 1-10K/min, utilize thermopair 9 to carry out thermometric and temperature control simultaneously, heating makes 19 fusings and overheated 100～200 ℃ rapidly to 800～1000 ℃ of temperature, opening air valve 4-5 is 99.8% argon gas and pressurize 2～60min to the purity of filling 2～5GPa on the alloy liquid, and alloy liquid is infiltrated between the tungsten fiber 17 of solid matter; Then, reduce cylinder assembly 14-2, silica tube is quenched rapidly in the water-cooled cooling tank 16 that high cooling power heat-eliminating medium is housed, simultaneously powered-down; When furnace temperature is reduced to 80～100 ℃, stop to vacuumize, open purging valve and make the air admission vacuum chamber, open down vacuum chamber fire door 12, reduce workplatform 15 with cylinder assembly 14-1 and take out sample.
The invention has the advantages that: 1, the present invention adopts melt temperature control technique and unique quartz molds design, can control mother alloy fusing, temperature of superheat, overheated time and with tungsten fiber infiltration temperature and time, help preparing tungsten fiber/amorphous composite; 2, adopt molecular pump to replace diffusion pump, adopt the heat-eliminating medium of high cooling power to replace saturated aqueous common salt, make whole technological process all under high vacuum environment, carry out, the oxidation of alloy and the influence of other factors have been avoided, thereby just can make tungsten fiber/bulk amorphous alloys matrix material with the material of ordinary purity, greatly reduce manufacturing cost; 3, because the increase of vacuum chamber, so be particularly suitable for the preparation of large size tungsten fiber/bulk amorphous alloys matrix material.
Description of drawings:
Fig. 1 be of the present invention large block amorphous/fibre composite seepage flow castmethod and equipment synoptic diagram, wherein mechanical pump 1, lobe pump 2, molecular pump 3, valve 4, last chamber bell 5, bell locking mechanism 6, last furnace chamber 7, molybdenum sheet heating element 8, thermopair 9, conducting copper 10, supply transformer 11, following chamber fire door 12, following furnace chamber 13, cylinder assembly 14, workplatform 15, water-cooled cooling tank 16, tungsten fiber 17, radiation screen 18, mould 19, mother alloy 20, external high-purity argon gas 21.
Fig. 2 is the thick Zr of 6mm for the diameter of the present invention's preparation
57Nb
5Al
10Cu
15.4Ni
12.6The longitudinal section of the bar-shaped sample of bulk amorphous alloys/fibre composite.
Fig. 3 is Zr
57Nb
5Al
10Cu
15.4Ni
12.6Bulk amorphous alloys/fibre composite bar cross section SEM photo.
Fig. 4 is Zr
57Nb
5Al
10Cu
15.4Ni
12.6Bulk amorphous alloys/fibre composite bar cross section X-ray diffractogram.
Embodiment:
Select highly purified 5 kinds of pure metal for use, i.e. Zr (99.99wt%), Ni (99.95wt%), Cu (99.95wt%), Al (99.95wt%), Nb (99.99wt%).By atomic percent be: Zr is 57, and Cu is 15.4, and Ni is 12.6, and Al is 10, and Nb is the allotment of 5 ratio, is under the protection of 99.8% high-purity argon gas in purity, 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.With diameter is that the tungsten fiber of 250 μ m smoothes out with the fingers that to be cut into length after straight be 100mm, for guaranteeing the well distributed of tungsten fiber, avoids the density inequality, and tungsten filament is also wanted appropriate some bendings that have.Clean the zone of oxidation on tungsten filament surface earlier with NaOH solution, and then use ultrasonic cleaning: cleaned 10 minutes in acetone earlier, the back was cleaned 5 minutes in ethanol.
Tungsten fiber is put into quartz molds, the mother alloy of fritter is put in the necking down that then silica tube at the above 40mm of tungsten fiber place to be made a diameter be 2mm again, utilizes device as shown in Figure 1, principle of work is prepared Zr as shown in Figure 2 as described above
57Nb
5Al
10Cu
15.4Ni
12.6The bar-shaped sample of bulk amorphous alloys/fibre composite.
Utilize the microtexture of scanning electron microscope (SEM) observation sample.The SEM sample makes with 2% HF aqueous solution etch, and the etch time is 5～10 seconds.The SEM image of sample vertical section as shown in Figure 2.The SEM image of sample cross can see that as shown in Figure 3 white portion is a tungsten fiber in the image, and other is organized almost is amorphous phase, not significantly reaction at the interface completely.Utilize X-ray diffractometer check, diffraction spectra as shown in Figure 4, in addition a lot of tungsten peak that superposeed on the diffraction peak of amorphous phase on the curve, has only the very low W of very a spot of intensity
2The Zr peak.3 explanations in conjunction with the accompanying drawings, amorphous phase and tungsten fiber do not have tangible surface reaction at the interface, in conjunction with better, can determine that this sample is tungsten fiber/bulk amorphous alloys matrix material.
Claims (2)
1, a kind of vacuum seepage castmethod for preparing large block amorphous/fibre composite, it is characterized in that: at first in electric arc furnace with bulk amorphous alloys element Zr, Ti, Cu, Al, Be, Nb, Ta, W, Fe, Co, Ni, C, P, B, 4～7 kinds of elements among the Pd are by following atomic percent batching Zr:40～80%, Ti:5～10%, Cu:5～50%, Al:3～20%, Be:5～25%, Nb:2～15%, Ta:1～10%, W:1～10%, Co:1～10%, Ni:5～50%, C:1～10%, P:5～20%, B:1～10%, Pd:5～60%, molten joining adopted the high-purity argon gas protection in the process; Pack into the tungsten fiber of abundant cleaning and mother alloy in the silica tube (19) and be placed in the furnace chamber (7), lock bell locking mechanism (6) and following chamber fire door (12); Order is driven mechanical pump (1) and lobe pump (2), to 1 * 10
-2Open molecular pump (3) after the Pa vacuum tightness again, valve-off (4-1) is opened valve (4-3) simultaneously, takes out upper and lower furnace chamber vacuum to condition of high vacuum degree 5 * 10
-3-5 * 10
-4Pa; Switch power supply, rate of heating heating tungsten fiber (17) and mother alloy (19) with 1-10K/min, utilize thermopair (9) to carry out thermometric and temperature control simultaneously, to 800-1000 ℃ of temperature post-heating make (19) fusing and overheated 100-200 ℃, opening air valve (4-5) is 99.8% argon gas and pressurize 2-60min to the purity of filling 2-5GPa on the alloy liquid, and alloy liquid is infiltrated between the tungsten fiber (17) of solid matter; Then, reduce cylinder assembly (14-2), silica tube is quenched in the water-cooled cooling tank (16) that high cooling power heat-eliminating medium is housed, simultaneously powered-down; When furnace temperature is reduced to 80-100 ℃, stop to vacuumize, open purging valve and make the air admission vacuum chamber, open down vacuum chamber fire door (12), reduce workplatform (15) with cylinder assembly (14-1) and take out sample.
2, a kind of according to the described preparation of claim 1 large block amorphous/equipment of fibre composite, by mechanical pump (1), lobe pump (2), molecular pump (3), valve (4), last chamber bell (5), bell locking mechanism (6), last furnace chamber (7), molybdenum sheet heating element (8), thermopair (9), conducting copper (10), supply transformer (11), following chamber fire door (12), following furnace chamber (13), cylinder assembly (14), workplatform (15), water-cooled cooling tank (16), tungsten fiber (17), radiation screen (18), quartz molds (19), mother alloy (20), external high-purity argon gas (21) constitutes; It is characterized in that: heating element (6) is made up of 1 layer of molybdenum sheet and 6 layers of radiation shield, mould (19) is placed in the heating element, the bottom links to each other with haulage gear, mould adopting quartz glass or graphite manufacturing, outside dimension 10～the 50mm of mould, height 200～500mm, silica glass and graphite jig general headquarters adopt the necking down design, necking down endoporus 2～5mm, mould adopts pneumatic mode traction (14); Cooling trough (16) places the below of mould, adopts double wall design, logical water coolant in the middle of the double-walled, and centre portions is put into Ga-In, and the Ga-In-Sn alloy adopts dynamic seal between mould and the cooling tank.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100354448C (en) * | 2004-07-02 | 2007-12-12 | 大连理工大学 | Cu base Cu-Zr-Ti group block non-crystal alloy |
| CN100457934C (en) * | 2007-03-16 | 2009-02-04 | 北京科技大学 | Method for preparing porous blocks of metallic glass by electrochemical eroding metal fibers |
| CN101418386B (en) * | 2007-10-26 | 2010-06-23 | 中国科学院金属研究所 | Equipment for preparing multifunctional amorphous composite material |
| CN101787505A (en) * | 2010-02-12 | 2010-07-28 | 中国航空工业集团公司北京航空制造工程研究所 | Preparation method of continuous fiber reinforcing titanium matrix composite |
| CN101941065A (en) * | 2010-09-14 | 2011-01-12 | 南昌大学 | Method forming endogenic crystal plasticized block amorphous base composite material |
| CN101956148A (en) * | 2010-10-22 | 2011-01-26 | 无锡南理工科技发展有限公司 | Dual composite high strength and toughness block amorphous alloy and preparation method thereof |
| CN102463339A (en) * | 2010-11-10 | 2012-05-23 | 北京航空航天大学 | Manufacturing method and device of alloy pipes |
| CN104668503A (en) * | 2013-11-30 | 2015-06-03 | 中国科学院金属研究所 | Amorphous alloy member cast forming device and process |
| CN105803238A (en) * | 2016-03-23 | 2016-07-27 | 中国科学院力学研究所 | Experiment device for preparing amorphous alloy foam materials |
| CN105821351A (en) * | 2016-03-23 | 2016-08-03 | 中国科学院力学研究所 | Amorphous alloy preparation method and amorphous cenosphere composite foam |
| CN110724847A (en) * | 2019-12-04 | 2020-01-24 | 河南科技大学 | Method for preparing bicontinuous phase composite material by pressureless infiltration |
| CN114406245A (en) * | 2022-01-25 | 2022-04-29 | 沈阳工业大学 | Equipment and method for preparing carbon fiber aluminum-based composite material by seepage casting process |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100354448C (en) * | 2004-07-02 | 2007-12-12 | 大连理工大学 | Cu base Cu-Zr-Ti group block non-crystal alloy |
| CN100457934C (en) * | 2007-03-16 | 2009-02-04 | 北京科技大学 | Method for preparing porous blocks of metallic glass by electrochemical eroding metal fibers |
| CN101418386B (en) * | 2007-10-26 | 2010-06-23 | 中国科学院金属研究所 | Equipment for preparing multifunctional amorphous composite material |
| CN101787505A (en) * | 2010-02-12 | 2010-07-28 | 中国航空工业集团公司北京航空制造工程研究所 | Preparation method of continuous fiber reinforcing titanium matrix composite |
| CN101787505B (en) * | 2010-02-12 | 2011-12-21 | 中国航空工业集团公司北京航空制造工程研究所 | Preparation method of continuous fiber reinforcing titanium matrix composite |
| CN101941065A (en) * | 2010-09-14 | 2011-01-12 | 南昌大学 | Method forming endogenic crystal plasticized block amorphous base composite material |
| CN101956148A (en) * | 2010-10-22 | 2011-01-26 | 无锡南理工科技发展有限公司 | Dual composite high strength and toughness block amorphous alloy and preparation method thereof |
| CN102463339B (en) * | 2010-11-10 | 2014-03-19 | 北京航空航天大学 | Manufacturing method and device of alloy pipes |
| CN102463339A (en) * | 2010-11-10 | 2012-05-23 | 北京航空航天大学 | Manufacturing method and device of alloy pipes |
| CN104668503A (en) * | 2013-11-30 | 2015-06-03 | 中国科学院金属研究所 | Amorphous alloy member cast forming device and process |
| CN105803238A (en) * | 2016-03-23 | 2016-07-27 | 中国科学院力学研究所 | Experiment device for preparing amorphous alloy foam materials |
| CN105821351A (en) * | 2016-03-23 | 2016-08-03 | 中国科学院力学研究所 | Amorphous alloy preparation method and amorphous cenosphere composite foam |
| CN105821351B (en) * | 2016-03-23 | 2018-12-21 | 中国科学院力学研究所 | A kind of preparation method and amorphous Hollow Microspheres Reinforced Composite Materials foam of amorphous alloy |
| CN110724847A (en) * | 2019-12-04 | 2020-01-24 | 河南科技大学 | Method for preparing bicontinuous phase composite material by pressureless infiltration |
| CN110724847B (en) * | 2019-12-04 | 2020-10-20 | 河南科技大学 | Method for preparing bicontinuous phase composite material by pressureless infiltration |
| CN114406245A (en) * | 2022-01-25 | 2022-04-29 | 沈阳工业大学 | Equipment and method for preparing carbon fiber aluminum-based composite material by seepage casting process |
| CN114406245B (en) * | 2022-01-25 | 2024-05-31 | 沈阳工业大学 | Equipment for preparing carbon fiber aluminum-based composite material by seepage casting process |
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