CN103952581B - A kind of method of adding pore-forming material and preparing high porosity molybdenum silicon boron porous material - Google Patents
A kind of method of adding pore-forming material and preparing high porosity molybdenum silicon boron porous material Download PDFInfo
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- CN103952581B CN103952581B CN201410166718.8A CN201410166718A CN103952581B CN 103952581 B CN103952581 B CN 103952581B CN 201410166718 A CN201410166718 A CN 201410166718A CN 103952581 B CN103952581 B CN 103952581B
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Abstract
Add the method that pore-forming material prepares high porosity molybdenum silicon boron porous material, belong to refractory metal porous material preparation field.Pore-forming material used is bicarbonate of ammonia.Use commercial Mo powder, Si powder, B powder, prepare burden by the volume percent of required three kinds of phases, add dehydrated alcohol, use omnidirectional planetary ball mill batch mixing 12 ~ 36h, paraffin gasoline binder is added in the Mo-Si-B element powders mixed, paraffin gasoline forming aid present accounts for 5 ~ 13wt.% of Mo-Si-B element powders and paraffin gasoline binder total amount, bicarbonate of ammonia pore-forming material is added again evenly, bicarbonate of ammonia Content of Pore-forming Agents accounts for Mo-Si-B element powders, 30 ~ 75vol.% of paraffin gasoline binder and bicarbonate of ammonia pore-forming material total amount, through coldmoulding after mixing, be placed in high-temperature atmosphere sintering oven and normal pressure-sinteredly prepare high porosity Mo under argon gas atmosphere protection
5siB
2-Mo
3si-Mo
5si
3triple-phase alloys.Prepared material porosity and pore structure adjustable, working condition requirements different in industrial production can be met.This technical process is simple, and economy is good.
Description
Technical field
The invention belongs to refractory metal porous material preparation field, the preparation method of compound molybdenum silicon boron porous material between the high porosity metal relating generally to high-melting-point, infusibility.
Background technology
The features such as porous material is the material comprising a large amount of hole, and different from dense material, it is low that it has density, and specific surface area is large, and high and damping capacity is good than mechanical property are a kind of functional structure materials with huge applications potentiality.Current porous material has been widely used in the numerous areas such as aerospace, petrochemical complex, nuclear power, environmental protection, medical treatment, metallurgy, building and electrochemistry, play in national economy and act on day by day significantly (Liu Peisheng. porous material draws opinion [M]. Beijing: press of Tsing-Hua University, 2004.).
Be at present porous ceramics and porous metal material at filtration, purification, the most popular porous material of catalytic field, the mechanical property of porous metal material, thermal conductivity, electroconductibility and thermal shock resistance are fine, but corrosion resistance and high temperature oxidation drag not enough.The corrosion resistance of porous ceramic film material, high temperature oxidation drag, thermotolerance and excellent in abrasion resistance, but its fragility is large, toughness, poor ductility and heat-shock resistance is poor.Porous ceramics and porous metal deficiency separately limits its application as high temperature filtration, purification, catalytic material, therefore necessary exploitation can filter in conjunction with a new generation of porous ceramics and porous metal advantage, purification, catalysis porous material.
Mo-Si-B series intermetallic compound has the chemical property between metal and pottery, Mo wherein
5siB
2-Mo
3si-Mo
5si
3outstanding advantages (the LembergJA that triple-phase alloys has that hot strength is high, creep resistance good, toughness and heat-shock resistance are better than pottery, corrosion resistance nature and antioxidant property and ceramic phase is worked as, RitchieRO.Mo-Si-BAlloysforUltrahigh-TemperatureStructura lApplications [J] .AdvancedMaterials, 2012,24 (26): 3445-3480.), be the excellent selection of porous material.There is no the relevant report of preparation porous Mo-Si-B alloy at present.
Summary of the invention
The object of this invention is to provide one and prepare high porosity Mo
5siB
2-Mo
3si-Mo
5si
3the method of triple-phase alloys porous material.The Mo-Si-B porous material prepared has the resistance to corrosion suitable with porous ceramic film material, and its toughness is better than pottery, and its porosity and pore structure can be regulated by the content of pore-forming material and granularity, make it be applicable to working condition requirements different in industrial production.This method technical process is simple, good economy performance.
The present invention adopts bicarbonate of ammonia as pore-forming material, and use high-temperature atmosphere sintering oven is normal pressure-sintered under argon gas atmosphere protection prepares high porosity Mo-Si-B porous material.In Mo-Si-B porous alloy, the volume percent content scope of three kinds of phases is: 0.4%-99.8%Mo
5siB
2, 0.1%-99%Mo
3si, 0.1%-99%Mo
5si
3(volume percent range of three kinds of phases meets Mo
5siB
2+ Mo
3si+Mo
5si
3=100%).Use that raw material powder is commercial Mo powder (2 ~ 150 μm, >=99.9wt.%), Si powder (2 ~ 150 μm, >=99.9wt.%), B powder (2 ~ 150 μm, >=99.9wt.%) mixture.After the mixed powder of preparation being added dehydrated alcohol, batch mixing is also dry, adds paraffin gasoline binder and bicarbonate of ammonia pore-forming material, mix rear coldmoulding in powder after the drying.Powder compact prepares high porosity porous material by normal pressure-sintered, and its concrete technology flow process is as follows:
(1) by required Mo
5siB
2-Mo
3si-Mo
5si
3the volume percent content of three kinds of phases, calculate the weight percent of Mo powder, Si powder and B powder, make required mixed powder, add dehydrated alcohol as batch mixing medium, be placed in omnidirectional planetary ball mill batch mixing 12 ~ 36h, then in vacuum drying oven in 30-80 DEG C of drying 4 ~ 8h;
(2) in the Mo-Si-B element powders mixed after the drying, add paraffin gasoline binder (paraffinicity is 20wt.%), paraffin gasoline forming aid present accounts for 5 ~ 13wt.% of Mo-Si-B element powders and paraffin gasoline binder total amount, bicarbonate of ammonia pore-forming material is added again evenly, bicarbonate of ammonia Content of Pore-forming Agents accounts for 30 ~ 75vol.% of Mo-Si-B element powders, paraffin gasoline binder and bicarbonate of ammonia pore-forming material total amount, through coldmoulding after mixing, be placed in high-temperature atmosphere sintering oven and carry out normal pressure-sintered under argon gas atmosphere protection; Sintering process is: rise to 300 ~ 400 DEG C with 5 ~ 10 DEG C/min from room temperature, and insulation 1 ~ 2h removes binder and pore-forming material, then rises to 1500 ~ 1650 DEG C with 5 ~ 20 DEG C/min, and insulation 1 ~ 3h, then stove is chilled to room temperature.
The invention has the advantages that Mo
5siB
2-Mo
3si-Mo
5si
3the resistance to corrosion of triple-phase alloys porous material is better than metal polyporous material, and toughness is better than ceramic porous material.By adding bicarbonate of ammonia pore-forming material, and adjusting its content and granularity, porosity and the pore size of porous material can be controlled, obtain high porosity Mo-Si-B triple-phase alloys porous material, different industrial requirements can be met.Further, the fabricated in situ of material and the generation of hole are that a step completes, and technical process is simple, and economy is good.
Accompanying drawing explanation
Fig. 1 is 32.37vol%Mo
5siB
2-4.5vol%Mo
3si-63.13vol%Mo
5si
3the XRD figure spectrum of high porosity porous material (1600 DEG C, 2h);
Fig. 2 is 32.37vol%Mo prepared by interpolation 30 ~ 60vol% bicarbonate of ammonia pore-forming material
5siB
2-4.5vol%Mo
3si-63.13vol%Mo
5si
3the porosity of high porosity porous material and percentage of open area curve;
Fig. 3 is 32.37vol%Mo
5siB
2-4.5vol%Mo
3si-63.13vol%Mo
5si
3the scanning electron microscope pattern of high porosity porous material (50vol% bicarbonate of ammonia, pore-forming material granularity :-80+100 order);
Fig. 4 is 32.37vol%Mo
5siB
2-4.5vol%Mo
3si-63.13vol%Mo
5si
3the graph of pore diameter distribution of high porosity porous material (40 ~ 60vol% bicarbonate of ammonia, pore-forming material granularity :-80+100 order);
Fig. 5 is 32.37vol%Mo
5siB
2-4.5vol%Mo
3si-63.13vol%Mo
5si
3high porosity porous material (50vol% bicarbonate of ammonia, pore-forming material granularity: (a)-50+80 order; (b)-100+150 order; (c)-150+200 order; (d)-200 order) scanning electron microscope pattern;
Fig. 6 is 32.37vol%Mo
5siB
2-4.5vol%Mo
3si-63.13vol%Mo
5si
3the graph of pore diameter distribution of high porosity porous material (50vol% bicarbonate of ammonia, pore-forming material granularity :-50+80 order ,-200 orders).
Specific examples
Embodiment 1:
By thing phase volume ratio 32.37vol%Mo
5siB
2-4.5vol%Mo
3si-63.13vol%Mo
5si
3make required mixed powder, use (4 μm commercial, Mo powder, 99.9wt.%), (6 μm, Si powder, 99.999wt.%), (3.96 μm, B powder, 99.99wt.%), add dehydrated alcohol as batch mixing medium, be placed in omnidirectional planetary ball mill batch mixing 24h, then in vacuum drying oven in 50 DEG C of dry 6h; In the Mo-Si-B element powders mixed after the drying, add paraffin gasoline binder (paraffinicity is 20wt.%), paraffin gasoline forming aid present accounts for the 9wt.% of Mo-Si-B element powders and paraffin gasoline binder total amount, bicarbonate of ammonia pore-forming material is added again evenly, bicarbonate of ammonia Content of Pore-forming Agents accounts for 30 ~ 60vol.% of Mo-Si-B element powders, paraffin gasoline binder and bicarbonate of ammonia pore-forming material total amount, take appropriate mixed powder after mixing, be cold-pressed into Φ 13mm cylinder pressed compact.Pressed compact is placed in high-temperature atmosphere sintering oven and rises to 350 DEG C with 5 DEG C/min from room temperature under an argon atmosphere, insulation 1h, then rises to 1600 DEG C with 10 DEG C/min, and insulation 2h, then stove is chilled to room temperature, obtains the cylindrical sample of Φ 13 × 8mm.Its XRD figure spectrum is as Fig. 1, and can find out, material prepared by reaction sintering is desired triple-phase alloys, does not have the diffraction peak of other thing phases.It is 56 ~ 73% that drainage records its porosity, and open porosity is 46 ~ 65%, and its porosity and percentage of open area curve are as shown in Figure 2.Fig. 3 is porous material scanning electron microscope secondary electron pattern prepared by 50vol% bicarbonate of ammonia, can find out that its pore structure is the composite pore structural of 1 ~ 3 μm of reacting hole and 100 μm of level creating holes.Fig. 4 is the pore size distribution curve that mercury injection apparatus records, and the hole that Y value represents a certain aperture accounts for porose volume percent, and pore size distribution is two peak structure, mainly concentrates on 1 ~ 4 μm and 5 ~ 45 μm.The specific surface area that mercury injection apparatus records is 0.168 ~ 0.18m
2/ g.Its compressive strength at room temperature is 15 ~ 66MPa.
Embodiment 2:
By thing phase volume ratio 32.37vol%Mo
5siB
2-4.5vol%Mo
3si-63.13vol%Mo
5si
3make required mixed powder, use (4 μm commercial, Mo powder, 99.9wt.%), (6 μm, Si powder, 99.999wt.%), (3.96 μm, B powder, 99.99wt.%), add dehydrated alcohol as batch mixing medium, be placed in omnidirectional planetary ball mill batch mixing 24h, then in vacuum drying oven in 50 DEG C of dry 6h.In the Mo-Si-B element powders mixed after the drying, add paraffin gasoline binder (paraffinicity is 20wt.%), paraffin gasoline forming aid present accounts for the 9wt.% of Mo-Si-B element powders and paraffin gasoline binder total amount, add again evenly and account for Mo-Si-B element powders, paraffin gasoline binder and bicarbonate of ammonia pore-forming material total amount 50vol.%, granularity is-50+80 order ,-100+150 order ,-150+200 order ,-200 object bicarbonate of ammonia pore-forming materials, take appropriate mixed powder after mixing, be cold-pressed into Φ 13mm cylinder pressed compact.Pressed compact is placed in high-temperature atmosphere sintering oven and rises to 350 DEG C with 5 DEG C/min from room temperature under an argon atmosphere, insulation 1h, then is warming up to 1600 DEG C with 10 DEG C/min, and insulation 2h, then stove is chilled to room temperature, obtains the cylindrical sample of Φ 13 × 8mm.Fig. 5 is its scanning electron microscope secondary electron pattern, can find out that the aperture along with the reduction porous material of pore-forming material granularity reduces.Fig. 6 is the pore size distribution curve of porous material prepared by-50+80 order ,-200 order pore-forming materials that mercury injection apparatus records.
Claims (2)
1. add the method that pore-forming material prepares high porosity molybdenum silicon boron porous material, it is characterized in that pore-forming material used is bicarbonate of ammonia, in Mo-Si-B porous alloy, the scope of the volume percent content of three kinds of phases is 0.4%-99.8%Mo
5siB
2, 0.1%-99%Mo
3si, 0.1%-99%Mo
5si
3; The volume percent range of three kinds of phases meets Mo
5siB
2+ Mo
3si+Mo
5si
3=100%; Its concrete technology flow process is as follows:
(1) commercial Mo powder, Si powder, B powder is used, by required Mo
5siB
2-Mo
3si-Mo
5si
3the volume percent content of three kinds of phases, calculate the weight percent of Mo powder, Si powder and B powder, make required mixed powder, add dehydrated alcohol as batch mixing medium, be placed in omnidirectional planetary ball mill batch mixing 12 ~ 36h, then in vacuum drying oven in 30-80 DEG C of drying 4 ~ 8h;
(2) in the Mo-Si-B element powders mixed after the drying, interpolation paraffin gasoline binder, paraffinicity are 20wt.%, paraffin gasoline forming aid present accounts for 5 ~ 13wt.% of Mo-Si-B element powders and paraffin gasoline binder total amount, bicarbonate of ammonia pore-forming material is added again evenly, bicarbonate of ammonia Content of Pore-forming Agents accounts for 30 ~ 75vol.% of Mo-Si-B element powders, paraffin gasoline binder and bicarbonate of ammonia pore-forming material total amount, through coldmoulding after mixing, be placed in high-temperature atmosphere sintering oven and carry out normal pressure-sintered under argon gas atmosphere protection; Sintering process is: rise to 300 ~ 400 DEG C with 5 ~ 10 DEG C/min from room temperature, and insulation 1 ~ 2h removes binder and pore-forming material, then rises to 1500 ~ 1650 DEG C with 5 ~ 20 DEG C/min, and insulation 1 ~ 3h, then stove is chilled to room temperature.
2. a kind of method of adding pore-forming material and preparing high porosity molybdenum silicon boron porous material according to claim 1, it is characterized in that raw material uses commercial 2 ~ 150 μm, >=99.9wt.%Mo powder, 2 ~ 150 μm, >=99.9wt.%Si powder, 2 ~ 150 μm, >=99.9wt.%B powder.
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