CN1249261C - Noncrystalline alloy based composite material containing boride particles - Google Patents
Noncrystalline alloy based composite material containing boride particles Download PDFInfo
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- CN1249261C CN1249261C CN 03111569 CN03111569A CN1249261C CN 1249261 C CN1249261 C CN 1249261C CN 03111569 CN03111569 CN 03111569 CN 03111569 A CN03111569 A CN 03111569A CN 1249261 C CN1249261 C CN 1249261C
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims description 105
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- 229910008423 Si—B Inorganic materials 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
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- 229910017876 Cu—Ni—Si Inorganic materials 0.000 claims description 2
- 229910017945 Cu—Ti Inorganic materials 0.000 claims description 2
- 229910017985 Cu—Zr Inorganic materials 0.000 claims description 2
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- 229910018532 Ni—Sn Inorganic materials 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 17
- 229910016459 AlB2 Inorganic materials 0.000 abstract 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 abstract 1
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- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 abstract 1
- 229910001325 element alloy Inorganic materials 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 66
- 239000010949 copper Substances 0.000 description 60
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- 230000002950 deficient Effects 0.000 description 2
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- 235000006708 antioxidants Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 238000000498 ball milling Methods 0.000 description 1
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Abstract
The present invention provides a composite material of boride particles and a basal body of an amorphous alloy. Materials can be selected and designed according to different use requirements, such as the type of boride particles, the relative quantity of volumes, average particle size, particle shape and type of the amorphous alloy forming the basal body. The boride particles can be selected from common CrB, TiB2, ZrB2, AlB2, etc., the average particle size of the particles is within a range between 10 nanometers and 200 micrometers, and the amorphous alloy is a poly-element alloy at least containing more than two metal elements in transition group. The volume content of the boride particles is from 5 to 40%, and the basal body of the amorphous alloy accounts for the rest volume. Compared with a single amorphous alloy without boride particles, the amorphous alloy base composite material reinforced with the boride particles has the advantages of better comprehensive mechanical property and thermal stability.
Description
Technical field:
The present invention relates to a kind of matrix material, the matrix material that boride particle and amorphous alloy matrix constitute.
Background technology:
Compare with conventional polycrystalline metal material, amorphous alloy (also claiming metallic glass) is because the long-range of its atomic arrangement is unordered and do not have crystal boundary, has characteristics such as high strength, corrosion-resistant and isotropy.Some amorphous alloy showed tangible glass transition (promptly change supercooled liquid into by amorphous solid, this is attended by the sudden change of viscosity and specific heat usually) before crystallization change takes place, form the supercooled liquid temperature range Δ T of broad
x(Δ T
xBe defined as the starting temperature T that crystallization change takes place in the continuous heat-processed of non-crystalline solids
xWith glass transformation temperature T
gDifference, i.e. Δ T
x=T
x-T
g).Have now found that the nearly tens of kinds of alloy systems that can form non-crystal structure have These characteristics, Δ T
xValue can surpass 30 ℃, even can surpass 100 ℃, as Mg-Ln-TM, Ln-Al-TM, Zr-Al-TM, Ti-Zr-TM, Ti-Ni-Cu-Sn, Zr-(Ti, Nb, Pd)-Al-TM, Zr-Ti-TM-Be, Fe-(Al, Ga)-(P, C, B, Si), Ni-Cu-Nb-Mo-P-B, Ni-Cr-Nb-Mo-P-B, (Cu, Ni)-(Ti, Zr)-(Sn, Si), Co-Zr-Nb-B, Pd-Cu-Ni-P, (Fe, Co)-(Zr, Hf, Nb, Ta)-(Ln=lanthanide series metal, TM=magnesium-yttrium-transition metals) such as Bo.One of characteristics of this class amorphous alloy are sharply to descend in supercooled liquid temperature range viscosity, can show " class superplasticity " behavior, and unit elongation can surpass 200%.Utilize this characteristic can be implemented in the small-sized component that the supercooled liquid temperature range is processed into the nearly clean shape of amorphous alloy the shape complexity.The supercooled liquid temperature range Δ T of broad
xWith at Δ T
x" class superplasticity " behavior in the temperature range also can be with amorphous alloy powder or strip by fixed block materials that becomes of powder metallurgy technology such as hot pressing, hot-extrudable, impulse of current heating, plasma sinterings.
Although amorphous alloy has high yield strength, elastic strain limit and higher fracture toughness property, lack stretching plastic, its application is restricted.One of approach that addresses this problem is to suppress the germinating of local shear zone by the introducing of the second phase crystal grain, promotes the formation of multiple shear bands, further strengthens the amorphous alloy matrix, improves its toughness and plasticity.At present, be used as the enhancing body second phase particle and comprise following a few class: refractory metals such as (1) tantalum, niobium, hafnium, molybdenum, tungsten; (2) MgO, CeO, Al
2O
3, Zr
2O
3, Y
2O
3Deng oxide ceramics; (3) carbide ceramics such as WC, TiC, SiC, ZrC; (4) Si
3N
4, nitride ceramics such as AlN, TiN and TaN, the second phase particle particulate is of a size of tens to 100 microns.The method that strengthens body introducing amorphous alloy is had: (1) directly is added into the second phase particle in the alloy melt, promptly forms matrix material after the melt cooling.Its defective is to be difficult for realizing the uniform distribution of the second phase particle on matrix; (2) the second phase particle and amorphous alloy powder machinery is mixed, realize the uniform distribution of the second phase particle on matrix.This method is used for the oxide compound second phase particle dispersion in early days in the superalloy matrix, improves the hot strength of superalloy.Its defective is the impurity element that is easy to introduce from ball milling instrument and atmosphere, as iron, oxygen, carbon etc.
The metal boride pottery has high-melting-point, high rigidity, has high specific conductivity under all temperature, and is all highly stable in various aggressive chemistry media, metal melt and steam, and has high electricity and lead and positive temperature coefficient of resistance.More than 1300 ℃ or 1300 ℃, performance has plasticity; The reflectivity height of boride, volatility is low, is extraordinary shielding material; Its room temperature hardness is fine, and can keep higher hardness at high temperature, is the ideal high-temperature and wear-proof.Because the ultrahigh hardness and the wear resistance of boride, and high-modulus (rigidity) and excellent high-temperature performance combine anti-oxidant and corrodibility, obviously are better than oxide ceramics and Wimet.Boride particle has obtained successful application as the enhancing body of many crystalline structure metal-base composites.For example, as tool material, it has enough wear resistancies, hardness and relative high toughness, as cutting tool (bronze, brass, aluminium alloy) and drilling tool (rock and concrete).Some boride is used for high conductivity and opposing melt, is widely used in the industrial production, and as the electrode of electrolyzer, structure units such as bearing, nozzle and injection molding, valve and sealing member.
Summary of the invention:
The invention provides the matrix material of a kind of boride particle/amorphous alloy matrix, is the matrix material that boride particle and amorphous alloy matrix constitute, and it is characterized in that boride particle is CrB, TiB
2, ZrB
2, AlB
2In the particle any, amorphous alloy are the multicomponent alloy that contains two or more transiting group metal elements at least, and the volume content of boride particle is 5～40%, and the amorphous alloy matrix is a surplus.
In the matrix material of boride particle of the present invention/amorphous alloy matrix, the transiting group metal elements of the matrix material of described boride particle/amorphous alloy matrix is preferably Ag, Ce, Co, Cu, Fe, Gd, Hf, La, Mo, Nb, Nd, Ni, Pd, Ta, Ti, V, W, Y, Zn, Zr.
In the matrix material of boride particle of the present invention/amorphous alloy matrix, the matrix amorphous alloy of the matrix material of described boride particle/amorphous alloy matrix is preferably Cu-Zr, Cu-Ti, Ni-Zr, Fe-Zr, Co-Zr, Ti-Fe, NI-Zr-Ti, Ti-Ni-Cu, Ti-Ni-Cu-Co, Ti-Zr-Ni-Cu-Co, Cu-Hf-Zr, Cu-Ti-Zr, Ni-Co-Zr-Ti, Cu-Ni-Ti-Zr, Cu-Ni-Ti-Zr-Y, Zr-Ti-Nb-Ni-Cu alloy.
In the matrix material of boride particle of the present invention/amorphous alloy matrix, the amorphous alloy of the matrix material of described boride particle/amorphous alloy matrix contains Al, B, Be, C, Ca, Ga, Ge, Mg, P, Si, Sn element.
In the matrix material of boride particle of the present invention/amorphous alloy matrix, the amorphous alloy of the matrix material of described boride particle/amorphous alloy matrix is preferably Al-Ni-La, Al-Ni-Co-Y, Al-Ni-Fe-Ce, Al-Fe-Gd, Al-Ni-Gd, Mg-Cu-Y, Mg-Cu-Ag-Y, Mg-Cu-Y-Ca, Mg-Cu-Zn-Y, Mg-Cu-Ag-Pd-Y, Mg-Ni-Nd, Ti-Cu-Ni-Sn, Ti-Cu-Ni-Si, Ti-Cu-Ni-Si-B, Ti-Zr-Cu-Ni-Si-B, Ti-Zr-Cu-Ni-Si-B-Sn, Ti-Cu-Ni-Al-Sn, Ti-Cu-Ni-Be, Zr-Al-Cu, Zr-Al-Cu-Ni, Zr-Al-Co-Ni, Zr-Al-Co-Ni-Y, Zr-Ti-Cu-Ni-Be, Zr-Ti-Cu-Ni-B, Zr-Al-Cu-Ni-Ta, Ht-Al-Cu-Ni, La-Al-Ni, La-Al-Cu, La-Al-Cu-Ni, La-Al-Cu-Ni-Co, Ni-Si-B, Ni-Fe-P, Ni-Zr-Ti-Si, Ni-Cu-Co-Zr-Ti-Nb, Ni-Cu-Nb-Mo-P-B, Ni-Nb-Cr-Mo-P-B, Ni-Nb-Fe-Cr-Mo-P-B, Cu-Ti-Zr-Sn, Cu-Ni-Ti-Zr-Sn, Cu-Ni-Ti-Zr-Si, Nd-Fe-Al, Nd-Fe-Co-Al, Pd-Ni-P, Pd-Ni-Cu-P, Pd-Ni-Fe-Cu-P, Pd-Cu-Si, Pd-Ag-Cu-Si, Fe-Nb-B, Fe-Zr-B, Fe-Zr-Nb-B, Fe-Al-Si-B, Fe-P-Si-B, Fe-P-C-B, Fe-Al-P-C-B, Fe-Al-P-Si-B, Fe-Al-P-C-B-Ge, Fe-Al-Ga-P-B-Ge, Fe-Al-Ga-P-B-Si, Fe-Al-Ga-P-C-Si, Fe-Al-Ga-P-C-B-Si, Fe-Al-Ga-P-C-B-Nb, Fe-Nb-Al-Ga-P-C-B-Si, Fe-Co-Ni-Zr-B, Fe-Co-Ni-Nb-Zr-B, Fe-Co-Ni-Zr-Nb-B, Fe-Co-Ni-Zr-Ta-Bo, Fe-Co-Zr-Mo-W-B, Fe-Co-Ni-Hf-Nb-B, Fe-Co-Ni-Hf-Ta-B, Fe-Cu-Nb-Si-B, Co-Fe-Zr-W-B, Co-Fe-Zr-Ta-B, Co-Cr-Al-Ga-P-B-C, Co-V-Al-Ga-P-B-Co, the Co-Fe-Cr-Al-Ga-P-B-C alloy.
In the matrix material of boride particle of the present invention/amorphous alloy matrix, CrB, the TiB of the matrix material of described boride particle/amorphous alloy matrix
2, ZrB
2, AlB
2The particulate size range is 10 nanometers to 200 micron, form matrix material after, these ceramic second phase particle dispersions are distributed on the amorphous alloy matrix.
The matrix material of this class boride particle/amorphous alloy matrix provided by the invention, can carry out material according to different service requirementss and select and design, comprise type, volume relative quantity, mean particle size, the particle shape of boride particle and the type that constitutes the amorphous alloy of matrix.
The present invention as matrix, introduces boride particle as strengthening body with amorphous alloy with obvious glass transition, forms the matrix material of boride particle/amorphous alloy matrix.The introducing of an amount of boride helps improving the thermostability and the mechanical property of single-phase amorphous alloy.Simultaneously, but the introducing of boride does not significantly destroy the processing characteristics of matrix amorphous alloy in the supercooled liquid temperature range.The matrix material that contains the boronation composition granule can be prepared into block materials by technology such as melt casting, powder metallurgy.Utilize its " class superplasticity " behavior, can realize the near clean formation type processing of complicated shape component in the supercooled liquid temperature range.
The matrix material of boride particle provided by the invention/amorphous alloy matrix can by in multiple material preparation and the synthetic method any or several mix to make be used for obtaining, depend on required material forms, as powder, strip, ingot casting, plate etc.(1) can be prepared into the gram level to feather weight thin band material (30～900 microns of thickness) in batches by single roller melt-spun method, can be by any acquisition gram level in the methods such as gas atomization, mechanical alloying to feather weight composite material powder in batches.If as body material, can directly be prepared into the block materials of thickness in the millimeter magnitude by conventional melt casting process with the stronger alloy of some intrinsic amorphous formation ability.(2) can adopt following method to realize the evenly mixed of boride particle and matrix alloy: (1) is added into boride particle in the alloy melt, after (electromagnetism or machinery) stirs melt is cooled off rapidly, boride particle is freezed in matrix, and alloy melt forms amorphous alloy simultaneously; (2) boride particle and powdered alloy (or chip, fragment) is mixed through mechanical mill, powdered alloy (or chip, fragment) can be pre-amorphous powder (or chip, fragment), after the presmelting alloying broken powder (or chip, fragment), with have the element powders mixture of the alloy phase of obvious glass transition feature with chemical composition.(3) utilize high-octane mechanical mill (being mechanical alloying) uniform distribution of the decrystallized and boride particle of matrix alloy can be finished simultaneously, and can make initial boride particle further broken, reach nanoscale, form boride nano particle/amorphous alloy base composite material.Compare with the single amorphous alloy that does not contain the boronation composition granule, boride particle enhanced amorphous alloy base composite material has improved comprehensive mechanical performance and thermostability.
Description of drawings:
Fig. 1 is the Ti that mechanical mill formed after 32 hours
50Cu
18Ni
22Al
4Sn
6Amorphous alloy and contain 10% (volume) respectively and the CrB/Ti of 15% (volume) CrB
50Cu
18Ni
22Al
4Sn
6The X of the matrix material of amorphous alloy matrix and initial state CrB ceramic particle penetrates the line that spreads out and penetrates collection of illustrative plates (Cu target);
Fig. 2 is the Ti that mechanical mill formed after 32 hours
50Cu
18Ni
22Al
4Sn
6Amorphous alloy and contain 10% (volume) respectively and the CrB/Ti of 15% (volume) CrB
50Cu
18Ni
22Al
4Sn
6The differential scanning calorimeter analytical results of the matrix material of amorphous alloy matrix (heating rate is 40K/min, among the figure be the starting temperature of glass transition to upward arrow indication place);
Fig. 3 is the Ti that mechanical mill formed after 32 hours
50Cu
18Ni
22Al
4Sn
6Amorphous alloy and contain 10% (volume) respectively and 30% (volume) TiB
2TiB
2/ Ti
50Cu
18Ni
22Al
4Sn
6The matrix material of amorphous alloy matrix and initial state TiB
2The X of ceramic particle penetrates the line that spreads out and penetrates collection of illustrative plates (Cu target);
Fig. 4 is the Ti that mechanical mill formed after 32 hours
50Cu
18Ni
22Al
4Sn
6Amorphous alloy and contain 10% (volume) respectively and 15% (volume) TiB
2TiB
2/ Ti
50Cu
18Ni
22Al
4Sn
6The differential scanning calorimeter analytical results of the matrix material of amorphous alloy matrix (heating rate is 40K/min, among the figure be the starting temperature of glass transition to upward arrow indication place);
Fig. 5 is that the X of the different composite material powder that forms of mechanical mill penetrates the line that spreads out and penetrates collection of illustrative plates (Cu target):
A) Ti
50Cu
35Ni
12Sn
3Alloy+10% (volume) nanometer TiB
2
B) Zr
65Al
7.5Cu
17.5Ni
10Alloy+15% (volume) TiB
2
C) Ni
65Nb
5Cr
5Mo
5P
14B
6Alloy+20% (volume) CrB;
D) La
55Al
25Cu
10Ni
5Co
5Alloy+10% (volume) TiB
2
Fig. 6 is the differential scanning calorimeter analytical results (heating rate is 40K/min, among the figure be the starting temperature of glass transition to upward arrow indication place) of the different composite material powder that forms of mechanical mill:
A) Ti
50Cu
35Ni
12Sn
3Alloy+10% (volume) nanometer TiB
2
B) Zr
65Al
7.5Cu
17.5Ni
10Alloy+15% (volume) TiB
2
C) Ni
65Nb
5Cr
5Mo
5P
14B
6Alloy+20% (volume) CrB;
D) La
55Al
25Cu
10Ni
5Co
5Alloy+10% (volume) TiB
2
Fig. 7 is that the X of the different composite material amorphous alloy band that forms of quench penetrates the line that spreads out and penetrates collection of illustrative plates (Cu target):
A) Ti
50Cu
18Ni
22Al
4Sn
6Alloy+20% (volume) TiB
2
B) Zr
65Al
7.5Cu
17.5Ni
10Alloy+10% (volume) ZrB
2
Fig. 8 is the differential scanning calorimeter analytical results (heating rate is 40K/min, among the figure be the starting temperature of glass transition to upward arrow indication place) of the different composite material amorphous alloy band that forms of quench:
A) Ti
50Cu
18Ni
22A
L4Sn
6Alloy+20% (volume) TiB
2
B) Zr
65Al
7.5Cu
17.5Ni
10Alloy+10% (volume) ZrB
2
Embodiment:
Select Ti
50Cu
18Ni
22Al
4Sn
6Alloy is matrix (alloying constituent is an atomic percent), and the CrB particle is for strengthening body.Form CrB particle/Ti by mechanical alloying
50Cu
18Ni
22Al
4Sn
6Amorphous alloy is the composite powder of matrix.With commercially available purity be 99.9% titanium, copper, nickel, aluminium and tin element bar or particle as parent material, be mixed with nominal alloy Ti by atomic percent
50Cu
18Ni
22Al
4Sn
6, in electric arc furnace, become mother alloy button ingot through melt back for several times, then its Mechanical Crushing being become granularity is 200 or 325 purpose master alloy powders.The addition of CrB ceramic particle is 10～20% (volumes), and CrB purity is 99.5%, granularity 200 orders.Powder mixture and GCr15 steel ball fill in the quenching stainless steel jar mill under high-purity Ar atmosphere (99.99%) than 5: 1 by ball and weight of material.Airtight ball grinder is installed on the SPEX 8000 high energy vibration formula ball mills grinds.Ti
50Cu
18Ni
22Al
4Sn
6Powdered mixture and the X-ray diffraction spectrum of powdered mixture after mechanical alloying in 32 hours and the heat of adding the CrB ceramic particle of 10～20.% (volumes) therein analyze (differential scanning calorimeter, DS C, down with) as depicted in figs. 1 and 2.The result shows: powdered mixture has formed CrB/Ti
50Cu
18Ni
22Al
4Sn
6Amorphous alloy base composite material.Glass transformation temperature (the T of this matrix material
g), crystallization starting temperature (T
x) and supercooled liquid temperature range width (Δ T
x) list in table 1.
Embodiment 2
Select Ti
50Cu
18Ni
22Al
4Sn
6Alloy is matrix (alloying constituent is an atomic percent), TiB
2Particle is for strengthening body.The preparation of matrix alloy is identical with embodiment 1.At Ti
50Cu
18Ni
22Al
4Sn
6Add 10%～30% (volume) TiB in the alloy
2Particle is with commercially available TiB
2Powder is a parent material, granularity 200 orders, and purity is 99.0%, forms TiB through mechanical alloying
2Particle/Ti
50Cu
18Ni
22Al
4Sn
6Amorphous alloy base composite material.The mechanical mill process is identical with embodiment 1.Ti
50Cu
18Ni
22Al
4Sn
6Powdered mixture and the TiB that adds 10～30.% (volumes) therein
2The X-ray diffraction spectrum of the powdered mixture of ceramic particle after mechanical alloying in 32 hours and heat are analyzed (DSC) as shown in Figure 3 and Figure 4.Glass transformation temperature (the T of this matrix material
g), crystallization starting temperature (T
x) and supercooled liquid temperature range width (Δ T
x) list in table 1.
Embodiment 3
Select Ti
50Cu
35Ni
12Sn
3Alloy is matrix (alloying constituent is an atomic percent), TiB
2Particle is for strengthening body.The preparation of matrix alloy is identical with embodiment 1 or 2, at Ti
50Cu
35Ni
12Sn
3The nanometer TiB of 10% (volume) that adds in the alloy
2Particle is with commercially available TiB
2Nanometer powder is a parent material, and granularity is 10～100nm, and purity is 99.0%, forms boride nano particle/amorphous alloy base composite material through mechanical alloying.The mechanical mill process is identical with embodiment 1 or 2.TiB
2/ Ti
50Cu
35Ni
12Sn
3The X-ray diffraction spectrum of amorphous alloy base composite material and heat are analyzed (DSC) result respectively shown in Fig. 5 (a) and Fig. 6 (a).Glass transformation temperature (the T of this matrix material
g), crystallization starting temperature (T
x) and supercooled liquid temperature range width (Δ T
x) list in table 1.
Embodiment 4
Select Zr
65Al
7.5Cu
17.5Ni
10Alloy is matrix (alloying constituent is an atomic percent), TiB
2Particle is for strengthening body.Form TiB by mechanical alloying
2Particle/amorphous Zr
65Al
7.5Cu
17.5Ni
10Alloy is the composite powder of matrix.The preparation of matrix alloy is with embodiment 1.TiB
2The addition of ceramic particle is 15% (volume), and purity is 99.0%, granularity 200 orders.Powdered mixture and GCr15 steel ball filled in than 15: 1 in the quenching stainless steel jar mill by abrading-ball and weight of material, fed high-purity Ar gas (99.999%) after mechanical pump vacuumizes, and ground at NEV-MA8 type high energy vibration formula ball mill.Zr
65Al
7.5Cu
17.5Ni
10With 15% TiB
2Granular powder mixture forms TiB after mechanical alloying in 40 hours
2Particle/amorphous Zr
65Al
7.5Cu
17.5Ni
10Alloy composite powder.The X-ray diffraction spectrum of this matrix material and hot analytical results are seen Fig. 5 (b) and Fig. 6 (b), its glass transformation temperature (T
g), crystallization starting temperature (T
x) and supercooled liquid temperature range width (Δ T
x) list in table 1.
Embodiment 5
Select Ni
65Nb
5Cr
5Mo
5P
14B
6Alloy is matrix (alloying constituent is an atomic percent), and the CrB particle is for strengthening body.Form CrB particle/amorphous Ni by mechanical alloying
65Nb
5Cr
5Mo
5P
14B
6Alloy is the composite powder of matrix.As parent material, purity is all greater than 99.5% with commercially available nickel, niobium, chromium, molybdenum, phosphorus, boron powder, and granularity is 200 or 325 orders, and being mixed with nominal composition by atomic percent is Ni
65Nb
5Cr
5Mo
5P
14B
6Powdered mixture.The addition of CrB ceramic particle is 20% (volume), and purity is 99.5%, granularity 200 orders.The mechanical mill process is identical with embodiment 1 or 2, Ni
65Nb
5Cr
5Mo
5P
14B
6Powdered mixture and 20% CrB particulate powdered mixture form CrB particle/amorphous Ni after mechanical alloying in 48 hours
65Nb
5Cr
5Mo
5P
14B
6Alloy is the composite powder of matrix.The X-ray diffraction spectrum of this matrix material and hot analytical results are seen Fig. 5 (c) and Fig. 6 (c), its glass transformation temperature (T
g), crystallization starting temperature (T
x) and supercooled liquid temperature range width (Δ T
x) list in table 1.
Select La
55Al
25Cu
10Ni
5Co
5Alloy is matrix (alloying constituent is an atomic percent), TiB
2Particle is for strengthening body.At La
55Al
25Cu
10Ni
5Co
5Add 10% (volume) general T iB in the alloy
2Particle.The preparation of matrix alloy is identical with embodiment 1.The mechanical mill process is identical with embodiment 4,10% (volume) TiB of interpolation
2Ceramic particle forms TiB after mechanical alloying in 60 hours
2Particle/La
55Al
25Cu
10Ni
5Co
5The amorphous alloy base composite material powder.The X-ray diffraction spectrum of this matrix material and hot analytical results respectively shown in Fig. 5 (d) and Fig. 6 (d), its glass transformation temperature (T
g), crystallization starting temperature (T
x) and supercooled liquid temperature range width (Δ T
x) list in table 1.
Embodiment 7
Select Ti
50Cu
18Ni
22Al
4Sn
6(atomic ratio) alloy is a matrix, adds 20% (volume) TiB
2Particle is prepared into TiB as strengthening body with the melt supercooled method
2Particle/Ti
50Cu
18Ni
22Al
4Sn
6Amorphous alloy is the matrix material strip of matrix.The preparation of matrix alloy is identical with embodiment 1.The alloy pig of presmelting is through the Mechanical Crushing powdered, with TiB
2Ceramic particle through 0.5 hour mechanically mixing, is cold-pressed into the block blank that diameter is Φ 10 * 20mm with mixture in the Spex8000 ball mill.The matrix material blank is positioned in the silica tube, the silica tube nozzle is of a size of 4 * 0.6mm, after the electromagnetic induction fusing, on the copper roller that is injected in high speed rotating under the effect of high-purity argon gas pressure (roller speed 39 meter per seconds), it is that 40 μ m, width are the TiB of 4mm that melt supercooled becomes thickness
2/ Ti
50Cu
18Ni
22Al
4Sn
6The amorphous alloy base composite material strip.The X-ray diffraction spectrum of this matrix material and hot analytical results respectively shown in Fig. 7 (a) and Fig. 8 (a), its glass transformation temperature (T
g), crystallization starting temperature (T
x) and supercooled liquid temperature range width (Δ T
x) list in table 1.
Embodiment 8
Select Zr
65Al
7.5Cu
17.5Ni
10(atomic ratio) alloy is a matrix, adds 10% (volume) ZrB
2Particle is prepared into ZrB as strengthening body with the melt supercooled method
2Particle/amorphous Zr
65Al
7.5Cu
17.5Ni
10Alloy is the matrix material strip of matrix.The preparation method of strip is with embodiment 7.It is the ZrB of 40 μ m that melt supercooled becomes thickness
2Particle/Zr
65Al
7.5Cu
17.5Ni
10The amorphous alloy base composite material band.The X-ray diffraction spectrum of this matrix material and hot analytical results respectively shown in Fig. 7 (b) and Fig. 8 (b), its glass transformation temperature (T
g), crystallization starting temperature (T
x) and supercooled liquid temperature range width (Δ T
x) list in table 1.
Glass transformation temperature (the T of boride/amorphous alloy composite material among each embodiment of table 1
g), crystallization begins temperature (T
x) and supercooled liquid sector width (Δ T
x) (heating rate is 40K/min)
| Numbering | Matrix material | The preparation method | T g (℃) | T x (℃) | ΔT x (℃) |
| 1 | Ti 50Cu 18Ni 22Al 4Sn 6+ 10% (volume) CrB Ti 50Cu 18Ni 22Al 4Sn 6+ 15% (volume) CrB | MM | 432 444 | 499 506 | 67 62 |
| 2 | Ti 50Cu 18Ni 22Al 4Sn 6+ 10% (volume) TiB 2 Ti 50Cu 18Ni 22Al 4Sn 6+ 30% (volume) TiB 2 | MM | 437 455 | 500 510 | 63 55 |
| 3 | Ti 50Cu 35Ni 12Sn 3+ 10% (volume) TiB 2 | MM | 395 | 466 | 71 |
| 4 | Zr 65Al 7.5Cu 17.5Ni 10+ 15% (volume) TiB 2 | MM | 398 | 471 | 73 |
| 5 | Ni 65Nb 5Cr 5Mo 5P 14B 6+ 20% (volume) CrB | MM | 401 | 441 | 40 |
| 6 | La 55Al 25Cu 10Ni 5Co 5+ 10% (volume) TiB 2 | MM | 220 | 292 | 72 |
| 7 | Ti 50Cu 18Ni 22Al 4Sn 6+ 20% (volume) TiB 2 | MS | 443 | 506 | 63 |
| 8 | Zr 65Al 7.5Cu 17.5Ni 10+ 10% (volume) ZrB 2 | MS | 437 | 492 | 55 |
Annotate: MM: mechanical milling method; MS: melt supercooled method.
Claims (5)
1, the matrix material of a kind of boride particle/amorphous alloy matrix is the matrix material that boride particle and amorphous alloy matrix constitute, and it is characterized in that boride particle is CrB, TiB
2, ZrB
2, or AlB
2In the particle any, CrB, TiB
2, ZrB
2Or AlB
2The particulate size range is 10 nanometers to 200 micron, after forming matrix material, these ceramic second phase particle dispersions are distributed on the amorphous alloy matrix, amorphous alloy is the multicomponent alloy that contains two kinds of transiting group metal elements at least, the volume content of boride particle is 5～40%, and the amorphous alloy matrix is a surplus.
2,, it is characterized in that described transiting group metal elements is meant Ag, Ce, Co, Cu, Fe, Gd, Hf, La, Mo, Nb, Nd, Ni, Pd, Ta, Ti, V, W, Y, Zn, Zr according to the matrix material of the described boride particle of claim 1/amorphous alloy matrix.
3,, it is characterized in that described amorphous alloy is Cu-Zr, Cu-Ti, Ni-Zr, Fe-Zr, Co-Zr, Ti-Fe, Ni-Zr-Ti, Ti-Ni-Cu, Ti-Ni-Cu-Co, Ti-Zr-Ni-Cu-Co, Cu-Hf-Zr, Cu-Ti-Zr, Ni-Co-Zr-Ti, Cu-Ni-Ti-Zr, Cu-Ni-Ti-Zr-Y or Zr-Ti-Nb-Ni-Cu alloy according to the matrix material of the described boride particle of claim 2/amorphous alloy matrix.
4,, it is characterized in that described amorphous alloy contains Al, B, Be, C, Ca, Ga, Ge, Mg, P, Si or Sn element according to the matrix material of the described boride particle of claim 2/amorphous alloy matrix.
5, according to the matrix material of the described boride particle of claim 4/amorphous alloy matrix, it is characterized in that described amorphous alloy is Al-Ni-La, Al-Ni-Co-Y, Al-Ni-Fe-Ce, Al-Fe-Gd, Al-Ni-Gd, Mg-Cu-Y, Mg-Cu-Ag-Y, Mg-Cu-Y-Ca, Mg-Cu-Zn-Y, Mg-Cu-Ag-Pd-Y, Mg-Ni-Nd, Ti-Cu-Ni-Sn, Ti-Cu-Ni-Si, Ti-Cu-Ni-Si-B, Ti-Zr-Cu-Ni-Si-B, Ti-Zr-Cu-Ni-Si-B-Sn, Ti-Cu-Ni-Al-Sn, Ti-Cu-Ni-Be, Zr-Al-Cu, Zr-Al-Cu-Ni, Zr-Al-Co-Ni, Zr-Al-Co-Ni-Y, Zr-Ti-Cu-Ni-Be, Zr-Al-Cu-Ni-Ta, Hf-Al-Cu-Ni, La-Al-Ni, La-Al-Cu, La-Al-Cu-Ni, La-Al-Cu-Ni-Co, Ni-Fe-P, Ni-Zr-Ti-Si, Ni-Cu-Nb-Mo-P-B, Ni-Nb-Cr-Mo-P-B, Ni-Nb-Fe-Cr-Mo-P-B, Cu-Ti-Zr-Sn, Cu-Ni-Ti-Zr-Sn, Cu-Ni-Ti-Zr-Si, Nd-Fe-Al, Nd-Fe-Co-Al, Pd-Ni-P, Pd-Ni-Cu-P, Pd-Ni-Fe-Cu-P, Pd-Cu-Si, Pd-Ag-Cu-Si, Fe-Nb-B, Fe-Zr-B, Fe-Zr-Nb-B, Fe-Al-Ga-P-C-B-Nb, Fe-Nb-Al-Ga-P-C-B-Si, Fe-Co-Ni-Zr-B, Fe-Co-Ni-Nb-Zr-B, Fe-Co-Ni-Zr-Nb-B, Fe-Co-Ni-Zr-Ta-B, Fe-Co-Zr-Mo-W-B, Fe-Co-Ni-Hf-Nb-B, Fe-Co-Ni-Hf-Ta-B, Fe-Cu-Nb-Si-B, Co-Fe-Zr-W-B, Co-Fe-Zr-Ta-B, Co-V-Al-Ga-P-B-C, or Co-Fe-Cr-Al-Ga-P-B-C alloy.
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| CN107686931B (en) * | 2017-08-29 | 2019-04-12 | 东莞市联洲知识产权运营管理有限公司 | A kind of zirconium boride niobium molybdenum-base composite material and preparation method thereof that yttrium ceramic whisker surface is modified |
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