CN103643201A - Mo-based Mo+Si+Cr+Fe coating layer composite material and preparation method thereof - Google Patents

Mo-based Mo+Si+Cr+Fe coating layer composite material and preparation method thereof Download PDF

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CN103643201A
CN103643201A CN201310512164.8A CN201310512164A CN103643201A CN 103643201 A CN103643201 A CN 103643201A CN 201310512164 A CN201310512164 A CN 201310512164A CN 103643201 A CN103643201 A CN 103643201A
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burner hearth
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CN103643201B (en
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潘文浩
许峰
牛晚扬
于保阳
谢辰星
孙小巍
陈彦文
王华栋
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Shenyang Jianzhu University
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Shenyang Jianzhu University
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Abstract

The invention relates to a preparation method of a metal-ceramic composite material, and especially relates to a Mo-based Mo+Si+Cr+Fe coating layer composite material and a preparation method thereof. A powder mixture comprises the following components in parts by weight: 50-80 parts of Si, 5-15 parts of Cr, 5-10 parts of Fe, 5-10 parts of Al2O3, and 5-15 parts of NHCl4. With application of the recommended formula and the preparation process of the method, with Si as a main penetration source and induction of Cr and Fe as auxiliary penetration sources, and under the action of NHCl4 and other co-penetration agents, the thickness of a prepared Mo-based Mo+Si+Cr+Fe gradient coating layer can reach a maximum value of 1100 [mu]m and is much larger than the thickness of a Mo-based MoSi2 penetration layer. The prepared sample gradient coating layer has high densification degree and large hardness, and has the Vickers hardness of up to 422.36. The material has excellent high temperature creep property and excellent thermal shock stability in a 1600 DEG C using environment.

Description

Mo base Mo+Si+Cr+Fe coating composite material and preparation method
Technical field
The present invention relates to a kind of metal-ceramic composite material preparation method, particularly Mo base Mo-Mo+Si+Cr+Fe gradient cladding matrix material and preparation method, belong to ceramic powder metallurgical material technical field.
Background technology
Molybdenum is that a kind of fusing point is the refractory metal of 2622 ℃, under high temperature, it has very strong tensile strength and creep strength, good thermotolerance, thermal expansivity is low, thermal conductivity and electric conductivity are high, liquid towards metal, potassium, calcium, bismuth and caesium etc. have good corrosion stability simultaneously, are widely used in the numerous areas such as machinery, metallurgy, national defence, chemical industry, electronics.Metal molybdenum Chang Zuowei high temperature heating element and high-temperature structural material are applied to the energising melt electrode etc. of high-temperature component, electric furnace heating element and the glass industry of aerospace and nuclear energy.
But the high-temperature oxidation resistance of molybdenum is poor, top coat is to solve one of anti-oxidation effective way of Mo sill in air, and in the time of 400 degrees Celsius, Mo starts oxidation, generates three kinds of oxidation products MoO, MoO 2, MoO 3at 725 ℃, all there is above serious volatilization in it, further accelerate the oxidation of Mo, this has just limited the use of molybdenum base material under high temperature aerobic environment greatly, and along with the rising of temperature, degree of oxidation aggravation, the oxide compound of generation makes the microtexture of molybdenum loose, cause embrittlement and the structural failure of molybdenum when applied at elevated temperature of molybdenum, greatly limited the use of molybdenum as high-temperature material; And oxide compound volatilization can form a large amount of white dense smoke, and contaminate environment, causes certain harm to HUMAN HEALTH.Therefore, the high temperature oxidation problem of molybdenum is material supplier author, the molybdenum producer and application person's difficult problem urgently to be resolved hurrily always.
In sum, be to solve the high temperature oxidation problem of molybdenum, research and develop that a kind of to have that density is high, high temperature oxidation resistent susceptibility is good, temperature sharply changes gradient cladding matrix material not easy to crack extremely urgent.
summary of the invention
The object of the invention is to solve current pure metal Mo in limited this problem of high-temperature field application extreme, by technological development and improvement, provides a kind of Mo base Mo+Si+Cr+Fe gradient cladding matrix material and preparation method thereof.
The problem existing for solving prior art, the present invention adopts technical scheme as follows:
With Si, the Cr of purity>=99.9%, Fe nanometer powder for oozing source, with Al 2o 3-NHCl 4for penetration-assisting agent, through high temperature, in the diffusion of Mo matrix surface generation chemical reaction, generate Mo-Mo+Si+Cr+Fe gradient cladding matrix material, its preparation process is as follows:
1. by Si, Cr, Fe nanometer powder and Al 2o 3-NHCl 4powder weighs and mixes by proportioning, and adopts the abundant batch mixing of ball milling method, makes it dispersed; Powdered mixture is comprised of following weight proportion:
Si:50-80 weight part, Cr:5-15 weight part, Fe:5-10 weight part, Al 2o 3: 5-10 weight part, NHCl 4: 5-15 weight part.
Batch mixing is sequentially: first add Si powder, then mix Cr powder, Fe powder, Al 2o 3powder, is mixed; Finally mix NHCl 4mixed again.
2. apply 1200# sand paper by the polishing of pure Mo piece surface finish, remove the black layer of surface oxidation;
3. get the 1. 50%(volume percent of mixed powder) pack in vessels crucible, use corresponding tool compacting, then enter the Mo handling well in is 2. packaged, finally will be 1. in remaining mixed powder add and cover Mo piece, and use instrument compacting;
4. 3. prepared sample is placed in to the box-type high-temperature furnace of pressure-fired argon shield; set temperature system on request; actual temp system is: with the temperature rise rates of 8 ℃-15 ℃, rise to 950 ℃-1300 ℃, be then incubated 90min-180min, naturally cooling in finally sealed burner hearth and make finished product.
The inventive method has the following advantages:
1, apply recommended formula and the preparation technology of this inventive method, take pure metal molybdenum as matrix is according to diffusion basic theories and molybdenum base material high temperature resistance to oxidation mechanism, with Si for mainly oozing source, introduce Cr and Fe for the auxiliary source of oozing, under the effect of the penetration-assisting agents such as NHCl4, the Mo base Mo+Si+Cr+Fe gradient cladding thickness of preparing reaches as high as 1100um, the Mo base MoSi preparing than general method 2alloying layer thickness is much larger.
2, owing to adopting rational temperature schedule, the sample gradient cladding compactness extent of preparing is high, and hardness is large, and Vickers' hardness can reach HV=422.36.
3, material of the present invention is in 1600 ℃ of environments for use, and high temperature creep, thermal shock resistance check are all better than MoSi 2bar material.
4, after high temperature air environment is used, as before, there is not tiny crack or skin effect phenomenon in test specimen smooth surface.
5, the inventive method also has the advantages such as raw materials cost is low, simple to operate, preparation time is short.
Accompanying drawing explanation
 
The SEM pattern photo of Fig. 1, the Mo base Mo+Si+Cr+Fe gradient cladding matrix material prepared for the inventive method.
The SEM pattern photo of the Mo base Mo+Si+Cr+Fe gradient cladding matrix material that Fig. 2 is also prepared for the inventive method.
Fig. 3 is the micro-hardness testing result photo of the Mo base Mo+Si+Cr+Fe gradient cladding matrix material prepared of the inventive method.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is done to further detailed introduction, but protection scope of the present invention is not limited to this.
Embodiment 1
The Si powder 15g that gets purity>=99.9% packs in mixing container, is weighing respectively Fe powder, the 1g Al of the Cr powder of 1g, 1g 2o 3mix in mixing container by after ball mill mixing 15min, by load weighted 2g NHCl 4mix mixing container, continue after ball mill mixing 10min, by the 50%(percent by volume of this mixture) pack in clean corundum crucible, with instrument by its compacting, by the purity that grinding process is good more than 99.9%, be of a size of 10mm * 10mm * 5mm metal molybdenum piece and be placed on the powder of compacting, then add remaining 50% mixture compacting.Then, the sample having installed is put into the box atmospheric resistance furnace that passes into high-purity argon gas, mix up gas flow, open cooling water valve, temperature rise rate with 10 ℃/min, through 120min, temperature is risen to 1200 ℃, under this temperature condition, be incubated 180min, in whole insulating process, in burner hearth, be slight positive pressure state.Finally, after reaching soaking time, make sample naturally cool to room temperature in the burner hearth of sealing.Through product section is carried out XRD, SEM and energy spectrum analysis and product surface is carried out to micro-hardness testing result showing, gradient cladding thickness is about 600um, coating even compact, hardness HV=399.4.
Embodiment 2
The Si powder 12g that gets purity>=99.9% packs in mixing container, is weighing respectively Fe powder, the 1g Al of the Cr powder of 3g, 2g 2o 3mix in mixing container by after ball mill mixing 15min, by load weighted 2g NHCl 4mix mixing container, continue after ball mill mixing 10min, by the 50%(percent by volume of this mixture) pack in clean corundum crucible, with instrument by its compacting, by the purity that grinding process is good more than 99.9%, be of a size of 10mm * 10mm * 5mm metal molybdenum piece and be placed on the powder of compacting, then add remaining 50% mixture compacting.Then, the sample having installed is put into the box atmospheric resistance furnace that passes into high-purity argon gas, mix up gas flow, open cooling water valve, temperature rise rate with 10.8 ℃/min, through 120min, temperature is risen to 1300 ℃, under this temperature condition, be incubated 180min, in whole insulating process, in burner hearth, be slight positive pressure state.Finally, after reaching soaking time, make sample naturally cool to room temperature in the burner hearth of sealing.Through product section is carried out XRD, SEM and energy spectrum analysis and micro-hardness testing result is carried out in product gradient cladding surface showing, gradient cladding thickness is about 1100um, coating even compact, hardness HV=422.36.
Embodiment 3
The Si powder 10g that gets purity>=99.9% packs in mixing container, is weighing respectively Fe powder, the 2g Al of the Cr powder of 3g, 2g 2o 3mix in mixing container by after ball mill mixing 15min, by load weighted 3g NHCl 4mix mixing container, continue after ball mill mixing 10min, by the 50%(percent by volume of this mixture) pack in clean corundum crucible, with instrument by its compacting, by the purity that grinding process is good more than 99.9%, be of a size of 10mm * 10mm * 5mm metal molybdenum piece and be placed on the powder of compacting, then add remaining 50% mixture compacting.Then, the sample having installed is put into the box atmospheric resistance furnace that passes into high-purity argon gas, mix up gas flow, open cooling water valve, temperature rise rate with 9.5 ℃/min, through 100min, temperature is risen to 950 ℃, under this temperature condition, be incubated 180min, in whole insulating process, in burner hearth, be slight positive pressure state.Finally, after reaching soaking time, make sample naturally cool to room temperature in the burner hearth of sealing.Through product section is carried out XRD, SEM and energy spectrum analysis and product surface is carried out to micro-hardness testing result showing, gradient cladding thickness is about 350um, coating even compact, hardness HV=239.64.

Claims (3)

1.Mo base Mo+Si+Cr+Fe coating composite material and preparation method, is characterized in that: powdered mixture is comprised of following weight proportion:
Si:50-80 weight part, Cr:5-15 weight part, Fe:5-10 weight part, Al 2o 3: 5-10 weight part, NHCl 4: 5-15 weight part, under pressure-fired argon shield environment, adopt powder packets to ooze method, by High temperature diffusion effect, prepare and obtain.
2. Mo base Mo+Si+Cr+Fe coating composite material as claimed in claim 1 and a preparation method, is characterized in that: with Si, the Cr of purity>=99.9%, Fe nanometer powder for oozing source, with Al 2o 3+ NHCl 4for penetration-assisting agent, through high temperature, in the diffusion of Mo matrix surface generation chemical reaction, generate Mo-Mo+Si+Cr+Fe gradient cladding matrix material, its preparation process is as follows:
1. by Si, Cr, Fe nanometer powder and Al 2o 3-NHCl 4powder weighs and mixes by proportioning, and adopts the abundant batch mixing of ball milling method, makes it dispersed; Batch mixing is sequentially: first add Si powder, then mix Cr powder, Fe powder, Al 2o 3powder, is mixed; Finally mix NHCl 4mixed again;
2. apply 1200# sand paper by the polishing of Mo piece surface finish, remove the black layer of surface oxidation;
3. get the 1. 50%(volume percent of mixed powder) pack in vessels crucible, use corresponding tool compacting, then enter the Mo handling well in is 2. packaged, finally will be 1. in remaining mixed powder add and cover Mo piece, and use instrument compacting;
4. 3. prepared sample is placed in to the box-type high-temperature furnace of pressure-fired argon shield, set temperature system on request, through heating, insulation, cooling and make finished product.
3. Mo base Mo+Si+Cr+Fe coating composite material according to claim 2 and preparation method, is characterized in that: temperature schedule is:
With the temperature rise rate of 10 ℃/min, through 120min, temperature is risen to 1200 ℃, under this temperature condition, be incubated 180min, in whole insulating process, in burner hearth, be slight positive pressure state, last, after reaching soaking time, in the burner hearth of sealing, naturally cool to room temperature;
With the temperature rise rate of 10.8 ℃/min, through 120min, temperature is risen to 1300 ℃, under this temperature condition, be incubated 180min, in whole insulating process, in burner hearth, be slight positive pressure state, finally, after reaching soaking time, in the burner hearth of sealing, naturally cool to room temperature;
With the temperature rise rate of 9.5 ℃/min, through 100min, temperature is risen to 950 ℃, under this temperature condition, be incubated 180min, in whole insulating process, in burner hearth, be slight positive pressure state, last, after reaching soaking time, in the burner hearth of sealing, naturally cool to room temperature.
CN201310512164.8A 2014-01-13 2014-01-13 Mo base Mo+Si+Cr+Fe coating composite material and preparation method Expired - Fee Related CN103643201B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104831212A (en) * 2015-05-09 2015-08-12 安徽鼎恒再制造产业技术研究院有限公司 Hard Fe-Al2O3-Mo material and preparation method thereof
CN104962857A (en) * 2015-07-24 2015-10-07 厦门理工学院 Coating molybdenum heating element applicable in atmosphere and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB820649A (en) * 1956-11-23 1959-09-23 Mini Of Supply Improvements in or relating to refractory coatings for molybdenum and molybdenum-base alloys
US3257230A (en) * 1964-03-24 1966-06-21 Chromalloy American Corp Diffusion coating for metals
JPS60190556A (en) * 1984-03-12 1985-09-28 Mazda Motor Corp Surface treatment of molybdenum-base alloy member
CN86103384A (en) * 1986-05-16 1987-11-18 北京材料工艺研究所 Permeation process of molybdenum or molybdenum alloy oxidation resistant coating and products thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB820649A (en) * 1956-11-23 1959-09-23 Mini Of Supply Improvements in or relating to refractory coatings for molybdenum and molybdenum-base alloys
US3257230A (en) * 1964-03-24 1966-06-21 Chromalloy American Corp Diffusion coating for metals
JPS60190556A (en) * 1984-03-12 1985-09-28 Mazda Motor Corp Surface treatment of molybdenum-base alloy member
CN86103384A (en) * 1986-05-16 1987-11-18 北京材料工艺研究所 Permeation process of molybdenum or molybdenum alloy oxidation resistant coating and products thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104831212A (en) * 2015-05-09 2015-08-12 安徽鼎恒再制造产业技术研究院有限公司 Hard Fe-Al2O3-Mo material and preparation method thereof
CN104962857A (en) * 2015-07-24 2015-10-07 厦门理工学院 Coating molybdenum heating element applicable in atmosphere and preparation method thereof
CN104962857B (en) * 2015-07-24 2017-09-29 厦门理工学院 A kind of coating molybdenum heater that can be used in an atmosphere and preparation method thereof

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