CN1990892A - Multi-component heat resistance alloy and die with multi-component heat resistance alloy layer - Google Patents
Multi-component heat resistance alloy and die with multi-component heat resistance alloy layer Download PDFInfo
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- CN1990892A CN1990892A CN 200510137689 CN200510137689A CN1990892A CN 1990892 A CN1990892 A CN 1990892A CN 200510137689 CN200510137689 CN 200510137689 CN 200510137689 A CN200510137689 A CN 200510137689A CN 1990892 A CN1990892 A CN 1990892A
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Abstract
The invention relates to a multiple element thermal resistance alloy and mold containing said alloy. The weight proportion of each element in the alloy is less than 45%. The structure of alloy is amorphous, and the phonon thermal conduction essence is low, so the thermal conduction rate of said alloy is low. The alloy is characterized by thermal stability, ability to increase the thermal insulation of casting mold, to increase the shaping qualification rate and stability of metallic sheet with low fusion point, and suitability to be used as thermal- resistance coating material.
Description
Technical field
The present invention relates to a kind of thermal resistance material, particularly relate to a kind of multi-component heat resistance alloy and have the mould of multi-component heat resistance alloy layer.
Background technology
Along with the development of global communication cause, for portable device, as notebook computer Note Book, NB), mobile telephone product demands such as (Cellular Phone) with increase.These products must meet the demand of light-weight design.With the notebook computer is example, and its shell tradition is based on engineering plastics (ABS), but if replace engineering plastics with magnesium alloy, can be as shown in the table, magnesium alloy has the advantage that density is higher and young's modulus (GPa) significantly increases.In addition, but magnesium alloy also tool thermal diffusivity, ELECTROMAGNETIC OBSCURANT, and the environmental protection characteristic of recovery property.
| Density (g/cm3) | Young's modulus (GPa) | |
| ABS | 1.07 | 2.1 |
| Magnesium alloy | 1.81 | 445 |
But magnesium alloy is with the method manufacturing of die casting, and as easy as rolling off a log in cast(ing) surface generation defective, its product disqualification rate reaches 50% approximately.Taiwan is in producing apparatus energy the first in the world of NB magnesium alloy pressure-casting on the other hand, but qualified rate variance, product output energy faces main bottleneck.Why magnesium alloy pressure-casting produces many defectives, the size that key mechanism is its foundry goods as thin as a wafer, heat scatters and disappears too soon during metal freezing, and produces non-directional solidification and causes.The lost defective that causes aspect semi-solid-state shaping too soon of heat comprises during metal freezing: thermal contraction and filling are not exclusively ... Deng; The defective that causes aspect magnesium alloy pressure-casting comprises: hot tearing mould, surface oxidation, flow liner, surface hole defect and eject distortion.
Therefore, be used as heat insulating coating if spray one deck thermal resistance material (Thermal-barrier Material) on magnesium alloy pressure-casting mould (SKD61) or semi-solid-state shaping spare surface, magnesium alloy pressure-casting mould or semi-solid-state shaping spare heat when the solidifying speed of scattering and disappearing is reduced, can improve and solidify additional phenomenon.This mode meets aforesaid metal freezing theory.
In the thermal resistance material research with low heat conduction coefficient, the thermal resistance material of the overwhelming majority is a ceramic matric composite.Thermal resistance material often is used in high temperature environment such as turbine (turbine) blade or its part at present.Turbine blade or its part material often use superalloy, though the superalloy material can be high temperature resistant, under long-time the use, still can face the problem of material production fatigure failure.The most frequently used settling mode is at turbine blade or its piece surface coating one deck thermal resistance material at present.Zirconium white (ZrO
2) be to be found the oxide compound that can be used for the earliest as thermal resistance material.Along with after zirconic thermal resistance material is developed, many researchists just begin to drop into research, develop many zirconia base (ZrO
2-base) thermal resistance material.
At present the most frequently used thermal resistance material be yttria-stabilized zirconia (Yttria-Stabilized Zirconia, YSZ), in order further to reduce heat-conduction coefficient, part Study personnel add other oxide compound in YSZ, for example U.S. Pat 6,686, and 060 adds niobium oxides (Nb in YSZ
2O
5).
U.S. Pat 6,764,779 are utilized the YSZ of one deck 6～8wt% (weight percent) and the mutual storehouse of YSZ of one deck 18～22wt%, to reach the purpose that reduces heat-conduction coefficient.Have other researchist to add other oxide compound in addition in zirconium white, as U.S. Pat 6,284,323 add 5～60mol% gadolinium sesquioxide (Gd in zirconium white
2O
3), U.S. Pat 6,916,551 add Erbium trioxide (Er in zirconium white
2O
3), can obtain the thermal resistance material of low heat conduction coefficient.
Other has researchist's escape zirconium white and develops the new oxide compound that replacement, and for example U.S. Pat 6,924, and 040 at hafnia (HfO
2) adding gadolinium sesquioxide (Gd
2O
3), can obtain quite low heat-conduction coefficient equally.
U.S. Pat 6,803,135, then be with RexZr1-xOy (0＜x＜0.5,1.75＜y＜2) be coated on the metal base as thermal resistance material, Re (rhenium, rhenium) is tellurian rare elements, and rare elements has comprised cerium (Ce), praseodymium (Pr), neodymium (Nd), Yi (Pm), samarium (Sm), europium (Eu), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and gold-plating (Lu).
Except the oxide compound thermal resistance material, U.S. Pat 6,521 in 353, adds the superhard metal that a small amount of Mn, Cr make low heat conduction coefficient again with 50～80wt%WC+10wt%TiC+Co+Ni.
Above-mentioned all thermal resistance material patents all are ceramic matric composites, especially based on oxide ceramic material.Be not difficult to find that thermal resistance material uses considerable rare elements from above-mentioned thermal resistance material, this increases material cost undoubtedly.
In numerous patents, U.S. Pat 6,756,131 composition comprise Ni, Co (0.1～12wt%), Cr (10～30wt%), Al (4～15wt%), Y (0.1～5wt%), Re (0.5～10wt%), Hf (0～0.7wt%) and Si (0～1.5wt%), though make the thermal resistance material of alloy with the pure metal element fully, yet still add considerable rare elements in the material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of multi-component heat resistance alloy, so as to the disclosed use rare elements of solution prior art, and the problem of increase material cost.
Another object of the present invention is to provide a kind of mould, make die casting or semi-solid-state shaping spare heat when the solidifying speed of scattering and disappearing reduce, can improve the additional problem of solidifying with multi-component heat resistance alloy layer.
Mould with multi-component heat resistance alloy layer of the present invention comprises metal base, and coating multi-component heat resistance alloy layer thereon.
According to the described mould with multi-component heat resistance alloy layer of preferred embodiment of the present invention, metal base is included as the metal base of thin ancient piece of jade, round, flat and with a hole in its centre casing die casting and the metal base of semi-solid shaping die.
Multi-component heat resistance alloy of the present invention, include cobalt (Co), chromium (Cr), iron (Fe), nickel (Ni), silicon (Si) and titanium (Ti), wherein the weight percent of cobalt element is the total a% (6%≤a%≤41%) that forms of alloy, the weight percent of chromium element is the total b% (5%≤b%≤36%) that forms of alloy, the weight percent of ferro element is the total c% (4%≤c%≤38%) that forms of alloy, the weight percent of nickel element is the total d% (5%≤d%≤44%) that forms of alloy, the weight percent of element silicon is the total e% (2%≤e%≤20%) that forms of alloy, and the weight percent of titanium elements is the total f% (3%≤f%≤29%) that forms of alloy, and a%+b%+c%+d%+e%+f%≤100%.
According to the described multi-component heat resistance alloy of preferred embodiment of the present invention, comprising aluminium (Al) element or zirconium (Zr) element.And the weight percent of aluminium element is the g% of the total composition of alloy, 2%≤g%≤25%, and a%+b%+c%+d%+e%+f%+g%≤100%.The weight percent of zr element is the total h% that forms of alloy, 6%≤h%≤43%, and a%+b%+c%+d%+e%+f%+h%≤100%.
The present invention makes with the pure metal element fully, does not also add to appoint and closes rare elements, can reduce the manufacturing cost of thermal resistance material.
Multi-component heat resistance alloy of the present invention, still trends towards forming amorphous structure, and has low heat-conduction coefficient after the plasma spray technology as the thermal barrier coatings material.
Multi-component heat resistance alloy of the present invention, when replacing aluminium element with zr element, except the heat of zirconium in theory pass coefficient than aluminium little, in reality as the thermal barrier coatings material, after the plasma spray technology, still trend towards forming amorphous structure, and have low heat-conduction coefficient.
Multi-component heat resistance alloy of the present invention is the metallic substance of tool amorphous structure and low heat conduction coefficient, can offer a kind of metallic substance of industry with thermostability and tool low heat conduction coefficient, increase the heat retaining property of casting forming mould, promote the shaping qualification rate and the stability of low melting point sheet metal sheet and semi-solid-state shaping spare.
A kind of multi-component heat resistance alloy of the present invention can utilize the plasma spray technology, the multi-component alloy powder of tool low heat conduction coefficient is sprayed for example on magnesium alloy pressure-casting mould (SKD61), with the additional properties that solidifies of raising magnesium alloy, and then improve magnesium alloy pressure-casting shaping qualification rate problem.
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Description of drawings
Fig. 1 is the data of multi-component heat resistance alloy embodiment A 1 to A8 of the present invention and hardness value thereof, fracture length measurement;
Fig. 2 is the X-ray diffraction chart of multi-component heat resistance alloy embodiment A 1 to A8 of the present invention;
Fig. 3 a is each the element mol ratio of multi-component heat resistance alloy embodiment A 1 to A8 of the present invention and the factor response diagram of hardness relation;
Fig. 3 b is each the element mol ratio of multi-component heat resistance alloy embodiment A 1 to A8 of the present invention and the factor response diagram of fracture length relation;
Fig. 4 is the data of multi-component heat resistance alloy Embodiment B 1 to B9 of the present invention and hardness value thereof, fracture length measurement;
Fig. 5 is the X-ray diffraction chart of multi-component heat resistance alloy Embodiment B 1 to B9 of the present invention;
Fig. 6 a is each the element mol ratio of multi-component heat resistance alloy embodiment A 1 to A8 of the present invention and the factor response diagram of hardness relation;
Fig. 6 b is each the element mol ratio of multi-component heat resistance alloy Embodiment B 1 to B9 of the present invention and the factor response diagram of fracture length relation;
Fig. 7 only changes the data of chromium and hardness value thereof, fracture length measurement for multi-component heat resistance alloy Embodiment C 1 to C4 of the present invention;
Fig. 8 is the X-ray diffraction chart of multi-component heat resistance alloy Embodiment C 1 to C4 of the present invention;
Fig. 9 is the hardness value and the fracture length of multi-component heat resistance alloy Embodiment C 1 of the present invention, C3 and three kinds of compositions of B8;
Figure 10 sprays on metal base as thermal barrier coatings material experiment schema for multi-component heat resistance alloy embodiment of the present invention;
Figure 11 sprays plasma spray parameter on metal base for multi-component heat resistance alloy embodiment of the present invention with plasma spray;
Figure 12 is not passing through vacuum heat treatment and the X-ray diffraction chart after Overheating Treatment for multi-component heat resistance alloy Embodiment B 8 alloy powders of the present invention and coating;
Figure 13 is the character of the multi-component alloy coat of multi-component heat resistance alloy Embodiment B 8 of the present invention;
Figure 14 is the material composition of multi-component heat resistance alloy embodiment D1 of the present invention;
Figure 15 is not passing through vacuum heat treatment and the X-ray diffraction chart after Overheating Treatment for multi-component heat resistance alloy embodiment D1 multi-component alloy powder of the present invention and coating;
Figure 16 is the character of multi-component heat resistance alloy embodiment D1 multi-component alloy coat of the present invention;
Figure 17 is that the character of multi-component heat resistance alloy Embodiment B 8 of the present invention, D1 and SKD61 hot-work die steel compares; And
Figure 18 is the metal filled property test of multi-component heat resistance alloy of the present invention as the coating of low thermally conductive dies.
Embodiment
Below enumerate specific embodiment describing content of the present invention in detail, and with icon as aid illustration.The symbol of mentioning in the explanation is with reference to diagrammatical symbol.
The present invention proposes a kind of mould with multi-component heat resistance alloy layer, comprises metal base, and coating multi-component heat resistance alloy layer thereon.
Above-mentioned metal base for example is the metal base of thin ancient piece of jade, round, flat and with a hole in its centre casing die casting and the metal base of semi-solid shaping die.
The present invention proposes a kind of multi-component heat resistance alloy, includes cobalt element, and its weight percent is the total a% that forms of alloy, 6%≤a%≤41%; Chromium element, its weight percent are the total b% that forms of alloy, 5%≤b%≤36%; Ferro element, its weight percent are the total c% that forms of alloy, 4%≤c%≤38%; Nickel element, its weight percent are the total d% that forms of alloy, 5%≤d%≤44%; Element silicon, its weight percent are the total e% that forms of alloy, 2%≤e%≤20%; And titanium elements, its weight percent is the total f% that forms of alloy, 3%≤f%≤29%; And a%+b%+c%+d%+e%+f%≤100%.
Above-mentioned multi-component heat resistance alloy can comprise aluminium element or zr element.Weight percent when wherein comprising aluminium element is the total g% that forms of alloy, 2%≤g%≤25%, and a%+b%+c%+d%+e%+f%+g%≤100%.And be alloy total h% that forms, 6%≤h%≤43%, and a%+b%+c%+d%+e%+f%+h%≤100% of the weight percent when comprising zr element.
The applied theory of the present invention is as described below:
Heat conduction property involves the transport property of complicated phonon, and closely related with microstructure, the lattice defect of material.Multi-component heat resistance alloy of the present invention is because of having the amorphousness microstructure, and the mean free path of its carrier and phonon will significantly shorten, and heat-conduction coefficient also declines to a great extent thereupon.Therefore, multi-component heat resistance alloy of the present invention has following ideal thermal barrier coatings (thermal-barrier coating; TBC) all material characteristic:
(1) has low heat conduction coefficient (k).
(2) have and thermal expansivity (coefficientof thermal expansion that for example magnesium alloy pressure-casting mould (SKD61) is close; CTE).
(3) with base material for example SKD61 can form good bonding (bonding), metallic bond (metallic bond) preferably.
(4) reduce the unrelieved stress (residual stress) that coating and base material produce during fabrication.
(5) do not produce fragility Jie metallographic phase (brittle intermetallicphases) between coating and the base material as far as possible.
(6) coating has relative thermostability (about 600 ℃).
(7) coated material tool machinability is for example ground (grinding) or polishing (polishing), to form slick surface.
(8) the some ductility of material tool of coating and toughness and thermal fatigue that can reduce (thermal fatigue) or thermal shocking (thermal shock).
(9) coating tool heat resistanceheat resistant cyclic oxidation (cyclic oxidation) character (about 600 ℃).
(10) coated material has the above hardness of about Rc40.
Simultaneously, multi-component heat resistance alloy of the present invention is that metallic substance has workability, and the phonon thermal conduction of amorphous structure (phonon thermal conductivity) coefficient is essentially low.Therefore multi-component heat resistance alloy of the present invention is suitable as the coated material on thermal barrier coatings material, especially the magnesium alloy pressure-casting mould of low melting point sheet metal sheet and semi-solid-state shaping spare very much.
Multi-component heat resistance alloy of the present invention is when being coated on the thermal barrier coatings material of for example low melting point sheet metal sheet and semi-solid-state shaping spare, its applied coating method is for example earlier made the multi-component heat resistance alloy bulk with multi-component heat resistance alloy with the vacuum arc melting furnace melting, utilize water to dust bulk then and ball milling method is made the multi-component heat resistance alloy powder of 74～125 μ m, again with for example plasma spray, the high-speed flame thermospray, plasma transferred arc formula fusion method, physical vaporous deposition, chemical Vapor deposition process ... or the like method, the multi-component heat resistance alloy powder is sprayed on the metal base of low melting point sheet metal sheet or semi-solid-state shaping spare.
Coating is being coated on the SKD61 magnesium alloy pressure-casting mould, suppose to produce enough thermal resistances (thermal barrier) effect and need the coating of 0.5mm (millimeter), and mould can not be in high temperature (if temperature 〉=500 ℃ when implementing, mould may be out of shape), also or when mould is big need big body of heater, cause problems such as equipment volume increase.The present invention sprays multi-component alloy of the present invention on the SKD61 base material with plasma spray (plasma spray) technology through selection behind the experimental study and forms thermal barrier coatings, is better suited method.
The following example of the present invention is with multiple common pure metal material, comprise cobalt, chromium, iron, nickel, silicon, titanium and aluminium or zirconium, utilize the alloy system of field mouth laboratory method preparation different mol ratio, utilize vacuum arc melting furnace (Vacuum-Arc Furnace) dissolving melting to make the multi-component alloy cube matherial again.And the multi-component alloy cube matherial can utilize ball milling method to make the multi-component alloy powder.The multi-component alloy powder then can plasma spray (Plasma Spray) mode be sprayed on metal base as the thermal barrier coatings material.
Emphasis of the present invention mainly is the multi-component alloy thermal resistance material of tool low heat conduction coefficient and the exploitation of coating thereof.This laboratory on the multi-component alloy research cumulative experimental data and in advance result of study learn: aluminium, cobalt, iron, nickel and silicon have and help the alloy rigidity value (Hardness value Hv) maintains Hv about 900; The influence of chromium and titanium is uncertain.The experiment fs is carried out L with seven elements such as aluminium, chromium, cobalt, iron, nickel, silicon and titaniums
82
7The field cause for gossip of orthogonal table is tested and is obtained embodiment A 1 to A8.
Fig. 1 is the data of multi-component heat resistance alloy embodiment A 1 to A8 of the present invention and hardness value thereof, fracture length measurement, as shown in Figure 1, the alloy rigidity value and the fracture length of embodiment A 1 to A8, its hardness value is minimum to be Hv 319 (A2), reaches as high as Hv 1089 (A3).
Fig. 2 is the X-ray diffraction chart of multi-component heat resistance alloy embodiment A 1 to A8 of the present invention.As shown in Figure 2, embodiment A 2 is main with FCC (face-centered cubic, face-centered cubic) crystallization phases, and embodiment A 3 and A5 are with BCC (body-centred cubic, body-centered cubic) crystallization phases and Cr
3The Si crystallization phases is main, and all the other embodiment alloys all form the structure based on the BCC crystallization phases.
Fig. 3 a is each the element mol ratio of multi-component heat resistance alloy embodiment A 1 to A8 of the present invention and the factor response diagram of hardness relation.Fig. 3 b is each the element mol ratio of multi-component heat resistance alloy embodiment A 1 to A8 of the present invention and the factor response diagram of fracture length relation.Shown in the factor response diagram of Fig. 3 a and each element mol ratio of Fig. 3 b and hardness, fracture length relation, chromium can reduce slight crack length when increasing hardness, and iron, aluminium, titanium influence are less.According to The above results, fixing iron: aluminium: the ratio of titanium=0.2: 1: 0.2 is that variable is got three level mol ratios and cooperated L with nickel, cobalt, chromium and silicon
93
4The orthogonal table is done the alloy configuration and is obtained Embodiment B 1 to B9.
Fig. 4 is the data of multi-component heat resistance alloy Embodiment B 1 to B9 of the present invention and hardness value thereof, fracture length measurement.As shown in Figure 4, the alloy rigidity value and the fracture length of Embodiment B 1 to B9, its hardness value is minimum to be Hv 741 (Embodiment B 3), reaches as high as Hv 1017 (Embodiment B 9).
Fig. 5 is the X-ray diffraction chart of multi-component heat resistance alloy Embodiment B 1 to B9 of the present invention.As shown in Figure 5, the alloy of Embodiment B 1 to B9 is mainly based on the BCC crystallization phases, and the B8 alloy has tangible Cr
3Si phase diffraction peak.
Fig. 6 a is each the element mol ratio of multi-component heat resistance alloy embodiment A 1 to A8 of the present invention and the factor response diagram of hardness relation.Fig. 6 b is each the element mol ratio of multi-component heat resistance alloy Embodiment B 1 to B9 of the present invention and the factor response diagram of fracture length relation.Shown in the graph of a relation of Fig. 6 a and each element mol ratio of Fig. 6 b and hardness, fracture length, in Embodiment B 1 to B9 alloy, chromium can reduce fracture length when increasing hardness.In embodiment A 1 to A8 alloy experimental data, confirm iron: aluminium: titanium=0.2: 1: 0.2; In Embodiment B 1 to B9 alloy experimental data, confirm nickel: cobalt: silicon=1: 0.6: 1.Comprehensive embodiment A 1 to A8 alloy data and Embodiment B 1 to B9 alloy data, obtaining taking into account the preferable alloy combination of hardness and flexible is AlCo
0.6CrFe
0.2Ni
0.2Si
0.2Ti
0.2With AlCo
0.6Cr
xFe
0.2NiSiTi
0.2
Again with the above-mentioned AlCo that is determined
0.6Cr
xFe
0.2NiSiTi
0.2The multi-component alloy only changes the chromium mol ratio and carries out the alloy configuration, obtains Embodiment C 1 to C4.Fig. 7 only changes the data of chromium and hardness value thereof, fracture length measurement for multi-component heat resistance alloy Embodiment C 1 to C4 of the present invention.As shown in Figure 7, the hardness value and the fracture length of Embodiment C 1 to C4, hardness value is minimum to be Hv 888 (Embodiment C 1), reaches as high as Hv 1045 (Embodiment C 3 and Embodiment C 4), learn that with hardness and fracture length general performance two kinds of composition performances of Embodiment C 1 and C3 are preferable.
Fig. 8 is the X-ray diffraction chart of multi-component heat resistance alloy Embodiment C 1 to C4 of the present invention.As shown in Figure 8, the alloy of Embodiment C 1 to C4 is mainly by BCC and Cr
3Two kinds of crystallization phasess of Si are formed.Along with the chromium mol ratio increases, orderly BCC diffraction peak (100) dies down.Wait to homogenize handle after, Cr
3Si phase diffraction peak is more clearly.
Learn that by Embodiment C 1 to C4 alloy rigidity and fracture length general performance result two kinds of composition performances of Embodiment C 1 and C3 are preferable.Comprehensive again embodiment A 1 to A8 and two groups of experimental datas of Embodiment B 1 to B9 alloy find that B8 also has high rigidity and a minimum fracture length of tool.
Fig. 9 is the hardness value and the fracture length of multi-component heat resistance alloy Embodiment C 1 of the present invention, C3 and three kinds of compositions of B8.As shown in Figure 9, though Embodiment B 8 alloy rigidity values do not have Embodiment C 1 alloy and Embodiment C 3 hardness of alloy value height, still have the level of Hv 880.The fracture length of Embodiment B 8 alloys behind impression test has only 48 μ m (micron), much smaller than the fracture length of Embodiment C 1 alloy and Embodiment C 3 alloys.Therefore, choose Embodiment B 8 alloy A lCo
0.6CrFe
0.2Ni
0.2Si
0.2Ti
0.2As coated material, Embodiment B 8 alloys are sprayed on magnesium alloy pressure-casting moulding stock (SDK61) surface with plasma spray.
Figure 10 sprays on metal base as thermal barrier coatings material experiment schema for multi-component heat resistance alloy embodiment of the present invention.As shown in figure 10, in the preparation of SKD61 magnesium alloy pressure-casting mould base material, earlier mechanical workout 102 is made on SKD61 magnesium alloy pressure-casting mould base material 100 surfaces, and made blast 104 on SKD61 magnesium alloy pressure-casting mould base material 100 surfaces and handle (Ra=7.5).With the die steel standard thermal treatment 106 of 100 do quenchings of the SKD61 magnesium alloy pressure-casting mould base material behind the blast 104 and double tempering, do again after the end and replenish blast 108 (Ra=7.0).On the other hand, the multi-component alloy cube matherial 101 usefulness Stainless Steel Crucibles of Embodiment B 8 are smashed to 700 μ m particles, insert in the ball milling (ball miller) and do ball milling powder process 103, multi-component alloy cube matherial 101 is ground to form the powder that particle diameter is 74～125 μ m with the dry type ball milling method.The employed little ball material of wherein used container inside lining and ball milling all is to adopt zirconium white.
Figure 11 sprays plasma spray parameter on metal base for multi-component heat resistance alloy embodiment of the present invention with plasma spray, as the flow process of Figure 10 and with the plasma spray parameter of Figure 11, with the powder that the multi-component alloy cube matherial 101 of Embodiment B 8 is ground to form, utilize plasma spray 110 technology that powder is sprayed on the SKD61 magnesium alloy pressure-casting mould base material 100 blast surfaces after surface treatment is intact.With spraying SKD61 magnesium alloy pressure-casting mould base material 100 behind the multi-component alloy,, do follow-up coating performance and analyze 130 with the emulation working conditions through 600 ℃ of excess temperatures and the vacuum heat treatment 120 of 2 hours time.
Figure 12 is not passing through vacuum heat treatment and the X-ray diffraction chart after Overheating Treatment for multi-component heat resistance alloy Embodiment B 8 alloy powders of the present invention and coating.As Figure 12 and learn that via calculating Embodiment B 8 alloy degree of crystallinity have descended 34%, degree of crystallinity becomes 66%.After showing that powder is via plasma spray, coating is tending towards amorphous phase (amorphous phase).After Overheating Treatment, the degree of crystallinity of Embodiment B 8 alloys rises 8%, and degree of crystallinity becomes 74%.The multi-component alloy coat of Embodiment B 8 is behind 600 ℃ of annealed of Overheating Treatment, and structure does not produce obvious crystallization phenomenon, and the coating after the thermal treatment still has phase stability.
Figure 13 is the character of the multi-component alloy coat of multi-component heat resistance alloy Embodiment B 8 of the present invention.By Figure 13 and cooperate in the X-ray diffraction chart of Figure 12 as can be known, the plasma spray technology can make Embodiment B 8 multi-component alloy coats trend towards forming amorphous structure, makes heat-conduction coefficient low to about 3.24W/mK.
Multi-component heat resistance alloy of the present invention can vacuum arc melting furnace dissolving melting be made the multi-component alloy cube matherial.And the multi-component alloy cube matherial can utilize ball milling method to make the multi-component alloy powder.The multi-component alloy powder then can plasma spray (Plasma Spray) mode be sprayed on metal base as the thermal barrier coatings material.Multi-component heat resistance alloy of the present invention, still trends towards forming amorphous structure, and has low heat-conduction coefficient after the plasma spray technology as the thermal barrier coatings material.
Figure 14 is the material composition of multi-component heat resistance alloy embodiment D1 of the present invention.Multi-component heat resistance alloy of the present invention can comprise aluminium element or zr element, now the aluminium element in the multi-component alloying constituent of Embodiment B 8 is replaced as zr element, can obtain the multi-component heat resistance alloy of embodiment D1 as shown in figure 14.The applied theory of embodiment D1 is the radius (r of zr element
Zr=1.45 ) a little more than the radius (r of aluminium element
Al=1.43 ), material may be easier to form the amorphousness attitude in theory, and the heat of zirconium biography coefficient is little than aluminium.
Figure 15 is not passing through vacuum heat treatment and the X-ray diffraction chart after Overheating Treatment for multi-component heat resistance alloy embodiment D1 multi-component alloy powder of the present invention and coating.As Figure 15 and learnt that by calculating embodiment D1 material degree of crystallinity has descended 85%, degree of crystallinity becomes 15%.Show embodiment D1 powder via after the plasma spray, the coating strong tendency forms the amorphousness attitude.After Overheating Treatment, embodiment D1 material degree of crystallinity rises 9%, and degree of crystallinity becomes 24%.Embodiment D1 multi-component alloy coat is identical with Embodiment B 8 multi-component alloy coats, and after 600 ℃ of annealing of Overheating Treatment, structure does not produce obvious crystallization phenomenon equally again, and coating also has phase stability.And embodiment D1 material is through there being the phenomenon of oxidation behind the plasma spray, makes zr element in the powder behind high temperature oxidation, zirconium dioxide (ZrO
2) the apparition of diffraction peak.
Figure 16 is the character of multi-component heat resistance alloy embodiment D1 multi-component alloy coat of the present invention, by Figure 16 and cooperate in the X-ray diffraction chart of Figure 15 as can be known, the plasma spray technology can make embodiment D1 multi-component alloy coat trend towards forming amorphous structure equally, and amorphous tendency is stronger, make heat-conduction coefficient low to about 3.14W/mK, lower than Embodiment B 8 (3.24W/mK) multi-component alloy coat.
Multi-component heat resistance alloy of the present invention, when replacing aluminium element with zr element, except the heat of zirconium in theory pass coefficient than aluminium little, in reality as the thermal barrier coatings material, after the plasma spray technology, still trend towards forming amorphous structure, and have low heat-conduction coefficient, coating also has phase stability.
Figure 17 is that the character of multi-component heat resistance alloy Embodiment B 8 of the present invention, D1 and SKD61 hot-work die steel compares.As shown in figure 17, the hardness mean value of Embodiment B 8 coatings is Hv 580, and the hardness mean value of embodiment D1 coating is Hv 722, all is higher than the hardness Hv 450 of SKD61 die steel base material.And the interface unrelieved stress of Embodiment B 8 coatings is+17.99 Mpa, less than the bond strength at interface.The heat-conduction coefficient of Embodiment B 8, embodiment D1 multi-component alloy coat is than low approximately progression of heat-conduction coefficient of SKD61 die steel.
Figure 18 is the metal filled property test of multi-component heat resistance alloy of the present invention as the coating of low thermally conductive dies.As shown in figure 18, the mould that sprays multi-component heat resistance alloy of the present invention is arranged, its filling ratio all is higher than the mould that does not spray multi-component heat resistance alloy of the present invention, especially has the effect that significantly promotes especially in lower its filling ratio of die casting casting plug speed (0.1m/s, 0.2m/s).
Therefore multi-component heat resistance alloy of the present invention has better heat insulation effect as the thermal barrier coatings material than SKD61 die steel.Multi-component heat resistance alloy of the present invention is still metallic substance during as thermal barrier coatings, so comparable pottery has better processability, and its heat-conduction coefficient also can reach the level of stupalith.
Multi-component heat resistance alloy of the present invention, thermal resistance material for multi-component alloy with low heat conduction coefficient, be different from the thermal resistance material of prior art based on oxide compound and carbide, the present invention makes with the pure metal element fully, do not add to appoint yet and close rare elements, can reduce the manufacturing cost of thermal resistance material.
The amorphous structure of multi-component heat resistance alloy utilization of the present invention itself, and because the lattice distortion that atomic size difference is caused, making phonon and carrier move is hindered, reduce the mean free path of phonon and carrier greatly, allow multi-component heat resistance alloy of the present invention have the heat-conduction coefficient close with pottery.
The present invention can apply on the thin part casting forming mould of low melting point metal, for example magnesium alloy casing casting forming.At present, the casting forming mould is based on the SKD61 hot-work die steel, and multi-component heat resistance alloy of the present invention is a metallic substance, has the thermal expansivity close with SKD61, and the unrelieved stress between mould base material and alloy coat is extremely low, can not cause the phenomenon of peeling off.
Multi-component heat resistance alloy of the present invention also has more the favorable mechanical processibility because metallic substance has more preferable ductility and toughness compared with ceramic thermal resistance material.
The present invention is coated in multi-component heat resistance alloy on the metal base, when being coated on the metal base than stupalith, thermal cycling process in the time of more resisting casting forming and semi-solid-state shaping, the shaping qualification rate and the die life of increase low melting point sheet metal sheet and solid molding spare.
Except avoiding the problems referred to above, the present invention is because can be applied to plasma spray technical, therefore also avoided when mould is big need big body of heater problem, can lower the cost of process apparatus.
The present invention is different from the coating of oxide coating, spray in the process at plasma spray, base material does not need heating, carry gas with quite high acceleration with multi-component alloy molten particles hit base material, mutually high kinetic energy and thermal power transfer are arranged in the knockout process, produce localized hyperthermia at substrate surface, make coating and base material between have goodish bonding (bonding), coating has more quite high density.
Multi-component heat resistance alloy of the present invention can be used in NB, PC, mobile phone, digital camera ... or the like the thin ancient piece of jade, round, flat and with a hole in its centre casing die casting of 3C commodity and the heat insulating coat of semi-solid shaping die.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (10)
1, a kind of multi-component heat resistance alloy is characterized in that, includes:
Cobalt element, its weight percent are the total a% that forms of alloy, 6%≤a%≤41%;
Chromium element, its weight percent are the total b% that forms of alloy, 5%≤b%≤36%;
Ferro element, its weight percent are the total c% that forms of alloy, 4%≤c%≤38%;
Nickel element, its weight percent are the total d% that forms of alloy, 5%≤d%≤44%;
Element silicon, its weight percent are the total e% that forms of alloy, 2%≤e%≤20%; And
Titanium elements, its weight percent are the total f% that forms of alloy, 3%≤f%≤29%;
A%+b%+c%+d%+e%+f%≤100% wherein.
2, multi-component heat resistance alloy according to claim 1 is characterized in that, comprises an aluminium element or a zr element.
3, multi-component heat resistance alloy according to claim 2 is characterized in that, the weight percent of this aluminium element is the total g% that forms of alloy, 2%≤g%≤25%, and a%+b%+c%+d%+e%+f%+g%≤100%.
4, multi-component heat resistance alloy according to claim 2 is characterized in that, the weight percent of this zr element is the total h% that forms of alloy, 6%≤h%≤43%, and a%+b%+c%+d%+e%+f%+h%≤100%.
5, a kind of mould with multi-component heat resistance alloy layer is characterized in that, includes:
One metal base; And
One multi-component heat resistance alloy layer is coated on this metal base.
6, the mould with multi-component heat resistance alloy layer according to claim 5 is characterized in that, this metal base is included as the metal base of thin ancient piece of jade, round, flat and with a hole in its centre casing die casting and the metal base of semi-solid shaping die.
7, the mould with multi-component heat resistance alloy layer according to claim 5 is characterized in that, the material of this multi-component heat resistance alloy layer includes:
Cobalt element, its weight percent are the total a% that forms of alloy, 6%≤a%≤41%;
Chromium element, its weight percent are the total b% that forms of alloy, 5%≤b%≤36%;
Ferro element, its weight percent are the total c% that forms of alloy, 4%≤c%≤38%;
Nickel element, its weight percent are the total d% that forms of alloy, 5%≤d%≤44%;
Element silicon, its weight percent are the total e% that forms of alloy, 2%≤e%≤20%; And
Titanium elements, its weight percent are the total f% that forms of alloy, 3%≤f%≤29%;
A%+b%+c%+d%+e%+f%≤100% wherein.
8, the mould with multi-component heat resistance alloy layer according to claim 7 is characterized in that, the material of this multi-component heat resistance alloy layer comprises an aluminium element or a zr element.
9, the mould with multi-component heat resistance alloy layer according to claim 8 is characterized in that, the weight percent of this aluminium element is the total g% that forms of alloy, 2%≤g%≤25%, and a%+b%+c%+d%+e%+f%+g%≤100%.
10, the mould with multi-component heat resistance alloy layer according to claim 8 is characterized in that, the weight percent of this zr element is the total h% that forms of alloy, 6%≤h%≤43%, and a%+b%+c%+d%+e%+f%+h%≤100%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106660110A (en) * | 2014-08-20 | 2017-05-10 | 日立金属株式会社 | Method for manufacturing coated mold for die casting |
| CN109913771A (en) * | 2019-04-02 | 2019-06-21 | 中国科学院宁波材料技术与工程研究所 | A kind of VAlTiCrSi high-entropy alloy film and its application under briny environment |
| CN114657438A (en) * | 2022-04-11 | 2022-06-24 | 大连理工大学 | Si-containing eutectic high-entropy alloy and preparation method thereof |
| CN116121619A (en) * | 2023-02-10 | 2023-05-16 | 西北工业大学 | Liquid quenched complex phase alloy based on electrostatic suspension and preparation method thereof |
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2005
- 2005-12-31 CN CNB2005101376893A patent/CN100489135C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106660110A (en) * | 2014-08-20 | 2017-05-10 | 日立金属株式会社 | Method for manufacturing coated mold for die casting |
| CN109913771A (en) * | 2019-04-02 | 2019-06-21 | 中国科学院宁波材料技术与工程研究所 | A kind of VAlTiCrSi high-entropy alloy film and its application under briny environment |
| CN114657438A (en) * | 2022-04-11 | 2022-06-24 | 大连理工大学 | Si-containing eutectic high-entropy alloy and preparation method thereof |
| CN114657438B (en) * | 2022-04-11 | 2022-09-20 | 大连理工大学 | Si-containing eutectic high-entropy alloy and preparation method thereof |
| CN116121619A (en) * | 2023-02-10 | 2023-05-16 | 西北工业大学 | Liquid quenched complex phase alloy based on electrostatic suspension and preparation method thereof |
| CN116121619B (en) * | 2023-02-10 | 2023-08-29 | 西北工业大学 | Liquid quenched complex phase alloy based on electrostatic suspension and preparation method thereof |
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| CN100489135C (en) | 2009-05-20 |
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