CN1754974A - Amorphous alloy excelling in fatigue strength - Google Patents
Amorphous alloy excelling in fatigue strength Download PDFInfo
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- CN1754974A CN1754974A CNA2005101132831A CN200510113283A CN1754974A CN 1754974 A CN1754974 A CN 1754974A CN A2005101132831 A CNA2005101132831 A CN A2005101132831A CN 200510113283 A CN200510113283 A CN 200510113283A CN 1754974 A CN1754974 A CN 1754974A
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- mother alloy
- amorphous alloy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
Abstract
The invention provides an amorphous alloy which can not only keep excellent characteristics of high rigidity, high strength, excellent process performance and high erosion resistance and so on of Zr-based or Hf-based amorphous alloy, but also have high fatigue strength and excellent damping property. The composition of the amorphous alloy is shown by a general formula: XaMbAlc( in the formula, x stands for one or two elements selected from Zr and Hf, M stands for at least one element selected from Ni, Nb, Cu, Fe, Co, and Mn, a, b and c are atom percentages that a is more than or equal to 25 and less than or equal to 85, b is more than or equal to 5 and less than or equal to 70 and c is more than 0 and less than or equal to 35), the amorphous alloy which contains amorphous phase of 50-100 percent (volume ratio) contains hydrogen.
Description
Technical field
The present invention relates to a kind of high rigidity, high strength, excellent processability, have high anti-corrosion and fatigue strength height, the good amorphous alloy of damping property.
Background technology
Amorphous alloy is also referred to as metallic glass, has high strength, and generally its tensile strength is about stainless 3 times, 2 times of the Ti alloy, and solidity to corrosion height, Young's modulus are low, thereby receives very big concern as Industrial materials.
In known amorphous alloy, the amorphous alloy (opening flat 3-158446 communique) of the non-crystalline state platform gold known Zr of having, Hf-M (M=Ni, Cu, Fe, Co, Mn)-Al system that processing characteristics is good referring to the spy, the temperature range of its glass transformation temperature (Tg) and Tc (Tx) is the wider range in supercooled liquid zone, has the good characteristic of high rigidity, high strength, high heat resistance, high anti-corrosion.
But, above-mentioned amorphous alloy and present low, the existing problems of the material when conduct is used for bearing pulsating stress for a long time of metallic glass fatigue strength of carrying out general Study.And, because metallic glass is the flawless material that does not have dislocation that general crystalline metal contains etc. in the material when observing microtexture, therefore in case material is applied vibration, because this vibration can not be subjected to the obstruction of dislocation etc., therefore long-time continuous is vibrated, and promptly has the problem of vibration damping difference.
Therefore, the object of the present invention is to provide a kind of amorphous alloy, can keep aforementioned have the Zr base of high rigidity, high strength, excellent processing characteristics, high anti-corrosion or the superperformance of Hf base amorphous alloy, have fatigue strength height, vibration damping excellent characteristic again.
For achieving the above object, the invention provides a kind of amorphous alloy, it is characterized in that, its composition is represented with following general formula: X
aM
bAl
c(here, X represents to be selected from one or both elements among Zr and the Hf, and M represents to be selected from least a element among Ni, Nb, Cu, Fe, Co and the Mn, and a, b, c are atomic percents, 25≤a≤85,5≤b≤70,0＜c≤35.), contain in the amorphous alloy of amorphous phase of 50～100% (volume ratios) and contain hydrogen.
Amorphous alloy of the present invention, with the temperature range with the glass transformation temperature (Tg) formed shown in the above-mentioned general formula and Tc (Tx) is that the amorphous alloy of the wider range in supercooled liquid zone is a matrix, make it hydrogeneous, therefore have the good characteristic of high rigidity, high strength, high heat resistance, high anti-corrosion, in addition obviously show following characteristics and effect.
-because fatigue strength increases substantially, therefore the long-term reliability as material improves.
The raising of-vibration damping also can decay rapidly even apply vibration, and the sound that sends diminishes.
Amorphous alloy of the present invention is a matrix to have the amorphous alloy of forming shown in the above-mentioned general formula, wherein contains hydrogen.Compare less (0.3 of its atomic radius of the hydrogen that exists in the metallic glass with other atoms metal; Oxygen and nitrogen are 0.74 ), so hydrogen can move in metallic glass, during the be full of cracks development that caused by fatigure failure, hydrogen accumulates in the top of fatigue cracking, because this part hardens, thereby obtains stoping the effect of the development of fatigure failure.
Make the method that contains hydrogen in the metallic glass, can suitably carry out by when being equipped with mother alloy (preform), in the inert atmosphere gas that uses, adding hydrogen with the raw material molten solution system.
Zr, Hf as the metallic glass main raw material are very easy oxidized, so raw material must melt in inert atmosphere gas.The present invention uses the inert atmosphere gas (rare gas element) that is mixed with hydrogen when this preform of preparation, evenly sneak into hydrogen in preform, can be made into the metal glass product that finally contains some hydrogen.The hydrogeneous metallic glass that this method is made can provide its fatigue strength, vibration damping to increase substantially, and has the amorphous alloy material as the reliability of Applied Materials.
If the hydrogen richness in the metallic glass is very few, then be difficult to assemble at fatigure failure be full of cracks top end hydrogen, this part is difficult to sclerosis, thereby is difficult to stop the development of fatigure failure, so hydrogen richness had better not be very few.On the other hand, if hydrogen richness is too high, then the binding capacity of Zr, Hf and hydrogen atom increases, and the result generates the hydride of Zr, Hf and becomes fragile easily, so hydrogen richness had better not be too high.Hydrogen richness is different because of the difference that alloy is fine into, and in general the weight content of hydrogen is advisable with about 0.005～10% in the metallic glass.
To the hydrogen richness in the metallic glass mainly is to control by the amounts of hydrogen that preparation is adjusted in the rare gas element during mother alloy, but also can the control arbitrarily by adjusting other condition such as fusing time, temperature of fusion.Oxygen level in the manufacturing processed in the metallic glass preferably is controlled at weight ratio below 1%.Be higher than at 1% o'clock, oxide compound contained in the metallic glass increases, and makes that material is easy to become fragile, and therefore preferably is no more than 1%.In addition because if the oxygen level height, oxygen contained in the hydrogen that concentrates on the be full of cracks top end when fatigure failure develops and the metallic glass reacts, and the hydrogen that suppresses the be full of cracks development generates water, outside the discharge metallic glass.
As mentioned above, the matrix alloy of amorphous alloy of the present invention is to be made up of general formula X aM
bAl
c(in the formula, X represents to be selected from one or both elements among Zr and the Hf, and M represents to be selected from least a element among Ni, Nb, Cu, Fe, Co and the Mn, and a, b, c are atomic percents, 25≤a≤85,5≤b≤70,0＜c≤35.) amorphous alloy expression, that contain 50～100% (volume ratio) amorphous phase.Wherein the reason that is limited in the above-mentioned scope of atomic percent a, b, the c of element X, M and Al is, if be in outside the above-mentioned scope then be difficult to decrystallized, for example, utilize the industrial chilling means of liquid quench method etc. to be difficult to obtain to contain at least the alloy of 50% (volume ratio) amorphous phase.
Preparation has above-mentioned composition, contains the mother alloy of hydrogen, makes this melt liquid quench solidification with the liquid quench method, thereby can make amorphous alloy of the present invention.So-called liquid quench method is the but method of molten alloy of chilling rapidly, for example can adopt following method preparation.
(1) roll method, double roller therapy
Obtain 10 by these two kinds of methods
4～10
6The speed of cooling of K/ about second.When adopting single-roller method, double roller therapy etc. to make strip, be that 30～3000mm, speed of rotation are that for example copper or the steel roll of certain speed of the scope of about 300～10000rpm sprays the hydrogenous in advance melt liquid with above-mentioned composition to diameter by nozzle bore.The easy like this various thin band materials of making wide about 1～300mm, thick about 5～500 μ m.
(2) spin processes in the rotation liquid
Utilize when spin processes is made the thin wire material in the rotation liquid, pass through jet hole, utilize the argon gas back pressure, spray hydrogenous in advance melt liquid in the solution heat-eliminating medium of dark about 10～100mm that dependence centrifugal force keeps in the cylinder of about 50～500rpm rotation, can easily make filament material with above-mentioned composition.At this moment, spend from the angle preferably about 60～90 that constitutes between the melt liquid of nozzle ejection and the solution heat-eliminating medium liquid level, the relative velocity ratio of the melt liquid of ejection and solution heat-eliminating medium liquid level is preferably 0.7～0.9.
(3) casting die
When making metal glass product, at first in inert atmosphere, utilize the lonely fusing of electricity to wait melting method that above-mentioned metallic glass raw material is evenly melted, make preform (mother alloy) in advance, carry out die casting, make metal glass product with this preform with casting die.At this moment, use the rare gas element that is mixed with hydrogen, can in preform, evenly sneak into hydrogen, can make above-mentioned preform of sneaking into hydrogen as inert atmosphere.Then, use as the special device of putting down in writing in the flat 2001-246451 communique of opening, this preform is supplied with the sleeve pipe that can move freely towards the cast gate front and back of metal pattern with cooling way, the heat fused preform, be ejected into above-mentioned metal pattern by the plunger that is free to slide that is located in the aforementioned sleeve pipe, cast, in this metal pattern, by cooling off, form the distinctive amorphous structure of metallic glass at the mistake cool region.In addition, metal pattern can cool off, and also can not cool off, and according to the volumetric ratio of cavity dimension and mould bases, even the heating of metal mould, molten metal also can fully cool off in addition.
In addition, also have following method except aforesaid method, (4) also can use sputtering method to make film, can also prepare the chilling powder with various atomizations, the gunite of (5) high pressure gas spray method etc.At this moment,, make and contain hydrogen in the atmosphere gas, or when target material melts, make fusing contain hydrogen in the atmosphere, can make equally in the metallic glass film of generation and contain hydrogen for sputtering method.In addition, for atomization, use hydrogen-containing gas, just can make in the metallic glass powder and contain hydrogen as spray gas.
Whether the quick cooling alloy of making is non-crystalline state, can be by X-ray diffraction method commonly used, see whether exist distinctive Ha ロ one pattern of non-crystalline state to judge.And, if heat this amorphous microstructure, crystallization (this temperature is called Tc) then takes place more than specific temperature.
Below, an example of employed device when preparing metal glass product with casting die in the description of drawings aforesaid method.
Fig. 1 is to an example that Figure 4 shows that the employed vacuum melting injection molding device for molding of preparation metal glass product, and among the figure, symbol 1 is a metal pattern, by fixedly counterdie 2 and movable patrix 3 are formed.Counterdie 2 with cast gate 4 is fixed on the main platform 7, and main platform 7 has circular peristome 6 in the place corresponding with cast gate 4, and between them with containment member 8 sealings of O type ring etc.Parallel vertical is provided with a plurality of tie-rods 9 on the main platform 7, and its upper end is fixedly installing shaft collar 10.Tie-rod 9 is 4 in the present embodiment, is not limited to this certainly, also can be 3 or 2.The movable plate 11 that is arranged on this tie-rod 9 can utilize matched moulds cylinder 12 liftings that are arranged on the shaft collar 10.Below movable plate 11, by fixing part 13 and transom 14 (also can fuse) with fixing part 13, movable patrix 3 is fixed, this movable patrix 3 have with the surface of separation of fixing counterdie 2 on the die cavity 5 that forms, this movable patrix 3 is accompanied by the lifting of movable plate 11 and lifting.In addition, form metal pattern venting hole 15 at the prescribed position of movable plate 11 and stationary member 13, in addition movable plate 11, stationary member 13, transom 14, movable patrix 3 and fixedly counterdie 2 all pass through containment member 8 each other and seal.
In addition, metal pattern 1, (example among the figure is a pair of to insert a plurality of exsertile injector poles 16 in die cavity 5, also can be according to the die cavity number) for more than three, the union lever 17 of these injector poles 16 passes movable plate 11 and stationary member 13, utilize upward execute device and stopping device (not shown), be complementary above the lower surface of each injector pole 16 and the metal die cavity 5.In addition, after injection molding is finished, when movable plate 11 rises to upper dead point, the upper surface of union lever 17 with just be connected with its lower surface that is arranged on the cylinder rod 19 of the injection cylinder 18 on the shaft collar 10 matchingly, make injection cylinder 18 actions, cylinder rod 19 pushes union lever 17, and injector pole 16 is projection in die cavity 5.
And, below movable plate 11, the vacuum (-tight) housing 20 of the tubular that hangs down round movable patrix 3, sealed member 8 is fixing, on the other hand, on main platform 7, sealing is fixed on correspondence position with support 21 same sealed members 8, and when movable plate 11 descends, movably patrix 3 is when fixing counterdie 2 matched moulds, vacuum (-tight) housing 20 outsides are slidingly connected at the inner face of sealing with support 21 by containment member 8, thereby form airtight injection forming portion space X.
In addition, the moulded products with the cantilever 23 of can be approaching to injection forming portion with specified altitude, retreating is installed on the prescribed position on the main platform 7 and discharges cylinder 22.
On the other hand, below main platform 7, the vacuum chamber 24 that is provided with for airtight formation heat fused portion's space Y is supported by frame 48.Covering gate 26 utilizes the action of gate cylinder 25 to be slidingly connected at the action of advancing, retreating below the main platform 7, make peristome 6 close and open, thereby realize the blocking between the heat fused portion space Y in above-mentioned injection forming portion space X and the vacuum chamber 24 and be communicated with.
In vacuum chamber 24, with peristome 6 matched positions of the cast gate 4 of fixing counterdie 2 and main platform 7 under, injection cannula 27 cylindraceous is set, its inside has and is free to slide the injection plunger 28 that sets, and this injection plunger 28 moves by the injection cylinder 29 that is arranged on vacuum chamber 24 bottoms.In addition, the lower end of injection cannula 27 is fixed on the collar supports member 30, and this collar supports member 30 moves cylinder 31 by sleeve pipe and moves, carries out lifting by 32 guiding of sleeve pipe mobile guide bar.Thus, move cylinder 31 actions by sleeve pipe and make 30 liftings of collar supports member, injection cannula 27 just rises to the cast gate 4 of metal pattern 1, descends behind the arrival starting position.
In addition, being provided with high-frequency induction heating around the top of injection cannula 27 uses coil 34 as heater means.Certainly heater means is not limited only to high-frequency induction heating, also can adopt other known heating means such as resistive heating.
And be provided with the mother alloy feedway 35 that the lateral opening portion 33 with above-mentioned injection cannula 27 is complementary in the vacuum chamber 24.This mother alloy feedway 35 is made up of following parts: the mother alloy that is arranged on the height location that can be connected with the lateral opening portion 33 of above-mentioned injection cannula 27 is supplied with road cylindrical shell 36, be arranged on the mother alloy box 37 on this mother alloy supply road cylindrical shell 36, the mother alloy that is free to slide that is arranged in the above-mentioned supply road cylindrical shell 36 is supplied with plunger 38, and the mother alloy supply cylinder 39 that makes its action, supply with plunger 38 and the mother alloy supply cylinder 39 of its action is played a role as the pressure mobile means with mother alloy, promptly the mother alloy piece A that drop to from mother alloy box 37 in the mother alloy supply road cylindrical shell 36 are forced to move in injection cannula 27.
Because when mother alloy is supplied with plunger 38 and will be fallen mother alloy and supply with nethermost mother alloy piece A in the road cylindrical shell 36 and supply with injection cannula 27, supplying with plunger 38 by mother alloy closes the peristome 45 of erecting bed 40, so, pile up at the molten mother alloy piece A that receives in the hopper 42 of mother alloy with stratiform and can not drop in the mother alloy supply road cylindrical shell 36, in case mother alloy is supplied with plunger 38 and is retreated, the peristome 45 of erecting bed 40 will be opened, mother alloy piece A just can drop on mother alloy and supply with in the road cylindrical shell 36, prepares next time and supplies with.So, the mother alloy piece A that mother alloy holds in the hopper 42 fall in order, and all in accordance with regulations timed interval is supplied with injection cannula 27 for each.After mother alloy held hopper 42 and empties, rotating disk 41 turned over predetermined angular, next mother alloy is held hopper 42 be arranged on and supply with the position.
Above-mentioned mother alloy feedway 35 is installed on the slip lid 46 of vacuum chamber 24, and this lid 46 is arranged on the guide rail 47 and can be free to slide, and pulling lid 46 just can be pulled out whole mother alloy feedway 35.Thus, after using whole mother alloys to hold mother alloy piece A reaction-injection mouldings in the hopper 42 to finish, open the room air valve 53 that connects vacuum chamber 24, remove vacuum state (at this moment, the vacuum evacuating system L2 of vacuum chamber 24 cuts off), draw back lid 46, taking-up mother alloy box 37 is also changed, and operation once just can be supplied with the preparation of a plurality of mother alloy piece A well.In addition, when vacuum chamber 24 covered lid 46, the top that mother alloy is supplied with road cylindrical shell 36 just in time with around the lateral opening portion 33 of injection cannula 27 was connected, and seals with containment member 8 between lid 46 and the vacuum chamber 24.
In addition, in the mother alloy feedway, also can be transported to the top to the mother alloy that mother alloy holds in the hopper, the mother alloy that is transported to the top is transplanted on the sleeve pipe top by means of transporting such as cantilevers, mother alloy be dropped in the sleeve pipe from the top by elevating lever etc.
The pipeline L1 (metal pattern exhaust line) of the vacuum evacuating system L of vacuum pump 50 (being made of diffusion pump and rotary pump) is connected to the metal pattern venting hole 15 that is formed by movable plate 11 and stationary member 13, exhaust reaches the specified vacuum degree in reaction-injection moulding portion space X, another pipeline L2 is connected with vacuum chamber 24, and exhaust reaches the specified vacuum degree in heat fused portion space Y.In addition, in order to remove the vacuum state of reaction-injection moulding portion space X, metal pattern exhaust line L1 is connected with metal pattern pressure lock 54, simultaneously, also be connected with vacuum gas holder 51, in the moment of movable patrix 3 matched moulds behind the fixing counterdie 2, reaction-injection moulding portion space X can reach vacuum state.
In addition, vacuum chamber 24 also is connected with inert gas container 52, can be according to the kind of employed mother alloy, heat fused under inert atmospheres such as Ar.Symbol 55～59 is a magnetic valve.
Below, the reaction-injection moulding operation of using said apparatus to carry out is described.
＜mother alloy is supplied with operation 〉
At first, draw back lid 46, be installed in mother alloy box 37 on the mother alloy feedway 35 as mentioned above after, close lid 46, be under the closing condition at room air valve 53, open magnetic valve 58, the heat fused portion space Y in the vacuum chamber 24 are vacuumized.At this moment, cover valve 26 closures, mother alloy supply unit and heat fused portion are contained in the vacuum chamber 24 in together.
After the mother alloy of mother alloy box 37 holds hopper 42 and is arranged on prescribed position, mother alloy supply cylinder 39 just begins action, from mother alloy hold hopper 42 fall mother alloy supply with in the road cylindrical shell 36 mother alloy piece A as shown in Figure 1, supply with plunger 38 by mother alloy and push in the injection cannula 27.
＜heat fused operation 〉
Then injection cylinder 29 actions, as shown in Figure 2, injection plunger 28 is pushed into the melting area with mother alloy piece A.Herein, high-frequency induction heating is with passing through electric current in the coil 34, and mother alloy piece A is heated fusing.At this moment, movably patrix 3 and fixedly counterdie 2 matched moulds, the reaction-injection moulding portion space X in the vacuum (-tight) housing 20 reach vacuum, can carry out reaction-injection moulding.
＜reaction-injection moulding operation 〉
After melt liquids in the injection cannula 27 reach specified temperature (temperature measuring can be adopted the thermopair of setting injection plunger 28 in or adopt proper methods such as radiation thermometer among the embodiment hereinafter described), with high-frequency induction heating coil 34 demagnetizations, 25 actions of gate cylinder, open and cover valve 26, reaction-injection moulding portion space X is communicated with heat fused portion space Y.In this stage, sleeve pipe moves cylinder 31 and injection cylinder 29 action simultaneously immediately, injection cannula 27 and injection plunger 28 rise, as shown in Figure 3, the upper end of injection cannula 27 is close to around the cast gate 4 that box belongs to mould 1, simultaneously, is filled in the metal die cavity 5 by the melt liquid injection of injection plunger 28 pressurizations of rising predetermined distance, absorb heat by metal pattern 1, thereby quench solidification is shaped.At this moment, metal pattern 1, from becoming the terminal injection portion of melt liquid stream, by metal pattern venting hole 15 exhausts of movable plate 11, thereby melt liquid stream taking advantage of evacuation circuit to be filled in the metal die cavity 5, so bubble is difficult to be involved in.
＜moulded products is discharged operation 〉
After reaction-injection moulding finished, as shown in Figure 4, injection cannula 27 retreated to original position with injection plunger 28, covers gate 26 and closes, and magnetic valve 55 cuts out, and after metal pattern pressure lock 54 is opened, promoted movable plate 11 by matched moulds with cylinder 12, opened metal pattern 1.Movable plate 11 1 arrives upper dead points, and union lever 17 upper surfaces of injector pole 16 just join with cylinder rod 19 lower surfaces of injection cylinder 18.In this stage, the moulded products B that solidifies is from movable patrix 3 and fixedly break away from the counterdie 2, so injection cylinder 18 actions, makes injector pole 16 outstanding downwards, on moulded products B breaks away from, falls fixedly counterdie 2 from movable patrix 3.Then, moulded products is discharged cylinder 22 actions, and cantilever 23 advances, behind the clamping moulded products B, draw back, and B gets outside the device with moulded products.At this moment, magnetic valve 56,57 is opened, and vacuum gas holder 51 joins with vacuum pump 50, and the time of utilizing metal pattern to open operation is improved the vacuum tightness in the vacuum gas holder 51.
＜penetrate and circulate
After discharging moulded products, matched moulds moves once more with cylinder 12, closes metal pattern 1.Then, metal pattern pressure lock 54 cuts out, magnetic valve 55 is opened, injection forming portion space X and vacuum gas holder 51 join, and after the predischarge, magnetic valve 56 cuts out (magnetic valve 57 is in the state of opening usually), because be connected with vacuum pump 50, therefore reaction-injection moulding portion space X can reach vacuum in the extremely short time, returns to state as shown in Figure 1, enters next and penetrates circulation.
On the other hand, in the mother alloy feedway 35, supply with plunger 38 because of mother alloy and retreat and hold hopper 42 from mother alloy and fall mother alloy and supply with next mother alloy piece A in the road cylindrical shell 36, supply with plunger 38 by mother alloy and release and supply in the injection cannula 27, penetrate circulation thereby enter next.
As mentioned above, penetrate circulation automatically continuously circulation carry out, hold the mother alloy piece A that holds in the hopper 42 until each mother alloy of mother alloy box 37 and exhaust.After the mother alloy piece A of mother alloy box 37 exhausts, magnetic valve 58 closures, as indicated above after room air valve 53 is opened, draw back lid 46, change mother alloy box 37.After changing box, close lid 46, carry out aforementioned ejaculation circulation once more repeatedly.
Description of drawings
Fig. 1 supplies with operation for the local section diagrammatic side views of an example of the employed vacuum melting reaction-injection moulding of preparation metal glass product of the present invention device in order to the expression mother alloy.
Fig. 2 is the local section diagrammatic side views of device shown in Figure 1, in order to the operation of representing to move to mother alloy heat fused portion.
Fig. 3 is the local section diagrammatic side views of device shown in Figure 1, in order to the expression jeting process.
Fig. 4 is the local section diagrammatic side views of device shown in Figure 1, discharges operation in order to the expression moulded products.
Fig. 5 is the mother alloy box orthographic plan partly of the mother alloy feedway of device use shown in Figure 1.
Figure 6 shows that corresponding to hydrogeneous and not hydrogenous metallic glass sample (Zr
50Cu
40Al
10) the change curve of fatigue stress of cycle number.
Figure 7 shows that corresponding to hydrogeneous and not hydrogenous metallic glass sample (Zr
60Cu
30Al
10) the change curve of fatigue stress of cycle number.
Figure 8 shows that corresponding to hydrogeneous and not hydrogenous metallic glass sample (Zr
50Cu
30Ni
10Al
10) the change curve of fatigue stress of cycle number.
Figure 9 shows that corresponding to hydrogeneous and not hydrogenous metallic glass sample (Zr
55Cu
30Ni
5Al
10) the change curve of fatigue stress of cycle number.
Embodiment
Use the arc-melting method,, make preform (mother alloy) evenly fusing of each metallic glass raw material (Zr, Al, Cu etc.) of forming shown in the table 1.When preparing this preform, use the rare gas element of having sneaked into 3vol% hydrogen, in preform, evenly sneak into hydrogen.For making comparisons, only use the rare gas element of not sneaking into hydrogen, prepare not hydrogenous preform.
Each preform that use is made is cast (die casting) by device as shown in Figure 1, makes the metallic glass sample.
Each metallic glass sample of making is carried out fatigue test.Its result is shown in table 1 and Fig. 6～9.And in Fig. 6～9, " E " of transverse axis represents exponential function, represents 1.0 * 10 as 1.0E+01, and 1.0E+02 represents 1.0 * 10
2
Little wild formula rotating bending fatigue machine is adopted in fatigue test, adopts sinusoidal wave pulsating stress to test under the condition of stress ratio R=-1.Cycle frequency is 13Hz, and fatigue test is to carry out in room temperature, atmosphere.Use bar-shaped sample (diameter 16mm, central authorities shrink, be the log glass type, shoulder radius (shrinking the radius-of-curvature of transition portion) R=16mm, be clamped in diameter (diameter of the constriction) φ=8mm of trier chuck part, the shortest diameter phi=the 4mm of breaking portion, mark square L=20mm) as test sample, obtain the fatigue test results of smooth material (non-notch).
[table 1]
| Safe range of stress | Not hydrogeneous | Hydrogeneous | ||||||
| Cycle number | Zr 50Cu 40Al 10 | Zr 60Cu 30Al 10 | Zr 50Cu 30Ni 10Al 10 | Zr 55Cu 30Ni 5Al 10 | Zr 50Cu 40Al 10 | Zr 60Cu 30Al 10 | Zr 50Cu 30Ni 10Al 10 | Zr 55Cu 30Ni 5Al 10 |
| 2.5×10 3 | 1360 | 1250 | 1200 | 1000 | 1350 | 1210 | 1340 | 1260 |
| 6.0×10 3 | 920 | 850 | 1000 | 900 | 900 | 800 | 1120 | 1040 |
| 1.2×10 4 | 700 | 680 | 850 | 750 | 750 | 680 | 1050 | 900 |
| 2.5×10 4 | 600 | 550 | 700 | 670 | 730 | 640 | 980 | 880 |
| 1.3×10 6 | 360 | 320 | 580 | 500 | 710 | 610 | 960 | 810 |
| 1.0×10 7 | 260 | 250 | 500 | 350 | 700 | 600 | 950 | 800 |
Result shown in table 1 and Fig. 6～9 shows, compares with the sample that not hydrogenous metallic glass is made, and the corresponding safe range of stress of sample that hydrogeneous metallic glass is made and cycle number increases substantially.
Symbol description
1 metal pattern
2 fixing counterdies
3 movable patrixes
4 cast gates
5 die cavitys
11 movable plates
12 matched moulds cylinders
15 metal pattern steam vents
16 spray pole
18 injection cylinders
20 vacuum (-tight) housings
22 moulded products are discharged cylinder
24 vacuum chambers
25 gate cylinders
26 cover gate
27 injection cannula
28 injection plungers
29 injection cylinders
31 sleeve pipes move cylinder
34 high-frequency induction heating coils
35 mother alloy feedwaies
36 mother alloys are supplied with the road cylindrical shell
37 mother alloy boxes
39 mother alloy supply cylinders
42 mother alloys hold hopper
Claims (2)
1, a kind of amorphous alloy is characterized in that having with general formula X
aM
bAl
c(in the formula, X represents to be selected from one or both elements among Zr and the Hf to the composition of expression, and M represents to be selected from least a element among Ni, Nb, Cu, Fe, Co and the Mn, and a, b, c are atomic percents, 25≤a≤85,5≤b≤70,0＜c≤35.), contain in the amorphous alloy of amorphous phase of 50～100% (volume ratios) and contain hydrogen.
2, amorphous alloy as claimed in claim 1, wherein the content of the hydrogen in the amorphous alloy counts 0.005～10% with weight ratio.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004172253 | 2004-06-10 | ||
| JP2004172253A JP2005350720A (en) | 2004-06-10 | 2004-06-10 | Amorphous alloy having excellent fatigue strength |
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| Publication Number | Publication Date |
|---|---|
| CN1754974A true CN1754974A (en) | 2006-04-05 |
| CN100545294C CN100545294C (en) | 2009-09-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101132831A Expired - Fee Related CN100545294C (en) | 2004-06-10 | 2005-06-09 | The amorphous alloy of excellent in fatigue strength |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20060081310A1 (en) |
| JP (1) | JP2005350720A (en) |
| KR (1) | KR20060048249A (en) |
| CN (1) | CN100545294C (en) |
| DE (1) | DE102005027009A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418053A (en) * | 2011-12-09 | 2012-04-18 | 湖南科技大学 | Zr-Cu-Ni-Al amorphous alloy containing trace boron and preparation method thereof |
| CN103958709A (en) * | 2011-11-24 | 2014-07-30 | 萨尔布吕肯大学 | Bulk metallic glass forming alloy |
| CN108977738A (en) * | 2018-07-25 | 2018-12-11 | 沈阳工业大学 | A kind of hydrogeneous titanium-based block amorphous alloy |
| CN111996471A (en) * | 2020-08-26 | 2020-11-27 | 燕山大学 | Zirconium-based amorphous alloy and preparation method and application thereof |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7645350B1 (en) * | 2004-04-06 | 2010-01-12 | The United States Of America As Represented By The Secretary Of The Army | High-density metallic glass alloys |
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| CN101286401B (en) * | 2008-02-26 | 2010-04-21 | 东北大学 | High-heat stability amorphous soft magnetic material and preparation method |
| JP5330051B2 (en) * | 2009-03-26 | 2013-10-30 | オリンパス株式会社 | Molding apparatus and amorphous alloy molding method |
| CN102041461B (en) * | 2009-10-22 | 2012-03-07 | 比亚迪股份有限公司 | Zr-based amorphous alloy and preparation method thereof |
| KR101501068B1 (en) * | 2013-06-07 | 2015-03-17 | 한국생산기술연구원 | Zr-based amorphous alloy composition |
| US10563275B2 (en) * | 2014-10-16 | 2020-02-18 | Glassy Metal, Llc | Method and apparatus for supercooling of metal/alloy melts and for the formation of amorphous metals therefrom |
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| CN106350731B (en) * | 2016-08-30 | 2018-08-10 | 宝山钢铁股份有限公司 | A kind of cold rolling high strength steel plate and its manufacturing method with excellent phosphorus characteristic and formability |
| CN106702292B (en) * | 2016-12-12 | 2020-01-07 | 北京科技大学 | Be-free and Ni-free high-hardness Zr-based bulk amorphous alloy containing N and preparation method thereof |
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| JPS6169931A (en) * | 1984-09-14 | 1986-04-10 | Univ Osaka | Method for making intermetallic compound amorphous by chemical reaction |
| JPH07122120B2 (en) * | 1989-11-17 | 1995-12-25 | 健 増本 | Amorphous alloy with excellent workability |
| US5735975A (en) * | 1996-02-21 | 1998-04-07 | California Institute Of Technology | Quinary metallic glass alloys |
| CN1101477C (en) * | 1999-12-17 | 2003-02-12 | 中国科学院金属研究所 | Process for preparing non-crystal alloy block |
| DE10332388B3 (en) * | 2003-07-11 | 2004-08-12 | Leibniz-Institut für Festkörper- und Werkstoffforschung e.V. | Improving plastic deformability of high strength moldings of solid metallic glasses based on zirconium-, titanium- and hafnium alloys, introduces low hydrogen concentration |
| TW593704B (en) * | 2003-08-04 | 2004-06-21 | Jin Ju | Annealing-induced extensive solid-state amorphization in a metallic film |
-
2004
- 2004-06-10 JP JP2004172253A patent/JP2005350720A/en active Pending
-
2005
- 2005-06-08 KR KR1020050048735A patent/KR20060048249A/en not_active Application Discontinuation
- 2005-06-09 CN CNB2005101132831A patent/CN100545294C/en not_active Expired - Fee Related
- 2005-06-09 US US11/148,655 patent/US20060081310A1/en not_active Abandoned
- 2005-06-10 DE DE102005027009A patent/DE102005027009A1/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103958709A (en) * | 2011-11-24 | 2014-07-30 | 萨尔布吕肯大学 | Bulk metallic glass forming alloy |
| CN103958709B (en) * | 2011-11-24 | 2016-07-06 | 萨尔布吕肯大学 | Block metal glass forms alloy |
| US9506133B2 (en) | 2011-11-24 | 2016-11-29 | Universitat Des Saarlandes | Bulk metallic glass forming alloy |
| CN102418053A (en) * | 2011-12-09 | 2012-04-18 | 湖南科技大学 | Zr-Cu-Ni-Al amorphous alloy containing trace boron and preparation method thereof |
| CN108977738A (en) * | 2018-07-25 | 2018-12-11 | 沈阳工业大学 | A kind of hydrogeneous titanium-based block amorphous alloy |
| CN108977738B (en) * | 2018-07-25 | 2020-04-28 | 沈阳工业大学 | Hydrogen-containing titanium-based block amorphous alloy |
| CN111996471A (en) * | 2020-08-26 | 2020-11-27 | 燕山大学 | Zirconium-based amorphous alloy and preparation method and application thereof |
| CN111996471B (en) * | 2020-08-26 | 2021-06-29 | 燕山大学 | Zirconium-based amorphous alloy and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20060081310A1 (en) | 2006-04-20 |
| KR20060048249A (en) | 2006-05-18 |
| DE102005027009A1 (en) | 2005-12-29 |
| JP2005350720A (en) | 2005-12-22 |
| CN100545294C (en) | 2009-09-30 |
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