CN103643201B - Mo base Mo+Si+Cr+Fe coating composite material and preparation method - Google Patents
Mo base Mo+Si+Cr+Fe coating composite material and preparation method Download PDFInfo
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- CN103643201B CN103643201B CN201310512164.8A CN201310512164A CN103643201B CN 103643201 B CN103643201 B CN 103643201B CN 201310512164 A CN201310512164 A CN 201310512164A CN 103643201 B CN103643201 B CN 103643201B
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Abstract
The present invention relates to a kind of metal-ceramic composite material preparation method, particularly Mo base Mo+Si+Cr+Fe coating composite material and preparation method.Powdered mixture is made up 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.Apply recommended formula and the preparation technology of this inventive method, with Si for mainly to ooze source, introduce Cr and Fe and ooze source, under the effect of the penetration-assisting agents such as NHCl4 for auxiliary, the Mo base Mo+Si+Cr+Fe gradient cladding thickness prepared reaches as high as 1100um, than Mo base MoSi prepared by general method
2alloying layer thickness is much larger.The sample gradient cladding compactness extent prepared is high, and hardness is large, and Vickers' hardness can reach HV=422.36.Material of the present invention is in 1600 DEG C of environments for use, and high temperature creep, thermal shock resistance are excellent.
Description
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 to be a kind of fusing point the be refractory metal of 2622 DEG C, under high temperature, it has very strong tensile strength and creep strength, good thermotolerance, thermal expansivity is low, thermal conductivity and electric conductivity 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 exothermic body and high-temperature structural material are applied to the energising melt electrode etc. of the high-temperature component of aerospace and nuclear energy, electric furnace heating element and glass industry.
But the high-temperature oxidation resistance of molybdenum is poor, top coat solves one of anti-oxidation effective way of Mo sill in atmosphere, and when 400 degrees Celsius, Mo starts oxidation, generates three kinds of oxidation productss MoO, MoO
2, MoO
3serious volatilization is all there is in it more than 725 DEG C, the oxidation of further acceleration Mo, this just greatly limit the use of molybdenum base material under high temperature aerobic environment, and along with the rising of temperature, degree of oxidation aggravates, the oxide compound of generation makes the microtexture of molybdenum loosen, cause embrittlement and the structural failure of molybdenum when applied at elevated temperature of molybdenum, significantly limit the use of molybdenum as high-temperature material; And oxide compound volatilization can form a large amount of white dense smoke, contaminate environment, causes certain harm to HUMAN HEALTH.Therefore, the high temperature oxidation problem of molybdenum is material supplier author, a molybdenum producer and application person difficult problem urgently to be resolved hurrily always.
In sum, be 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 high-temperature field application extremely this problem limited, by technological development and improvement, provides a kind of Mo base Mo+Si+Cr+Fe gradient cladding matrix material and preparation method thereof.
For solving prior art Problems existing, the present invention adopts technical scheme as follows:
With Si, Cr, Fe nanometer powder of purity>=99.9% for oozing source, with Al
2o
3-NHCl
4for penetration-assisting agent, generate Mo-Mo+Si+Cr+Fe gradient cladding matrix material through high temperature in the diffusion of Mo matrix surface generation chemical reaction, its preparation process is as follows:
1. by Si, Cr, Fe nanometer powder and Al
2o
3-NHCl
4powder weighs mixing by proportioning, and adopts the abundant batch mixing of ball milling method, makes it dispersed; Powdered mixture is made up 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 order is: 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 block surface finish, remove surface oxidation black layer;
3. get the 50%(volume percent of 1. mixed powder) load in vessels crucible, use corresponding tool compacting, then by packaged for the Mo that handles well in 2. enter, finally will 1. in remaining mixed powder add and cover Mo block, and use instrument compacting;
4. 3. obtained sample is placed in the box-type high-temperature furnace of pressure-fired argon shield; set temperature system on request; actual temp system is: rise to 950 DEG C-1300 DEG C with the temperature rise rate of 8 DEG C-15 DEG C, be then incubated 90min-180min, naturally cooling in finally sealed burner hearth and obtained finished product.
The inventive method has the following advantages:
1, recommended formula and the preparation technology of this inventive method is applied, with pure metal molybdenum for matrix is according to diffusion basic theories and molybdenum base material high temperature resistance to oxidation mechanism, with Si for mainly to ooze source, introduce Cr and Fe and ooze source for auxiliary, under the effect of the penetration-assisting agents such as NHCl4, the Mo base Mo+Si+Cr+Fe gradient cladding thickness prepared reaches as high as 1100um, than Mo base MoSi prepared by general method
2alloying layer thickness is much larger.
2, owing to adopting rational temperature schedule, the sample gradient cladding compactness extent prepared is high, and hardness is large, and Vickers' hardness can reach HV=422.36.
3, material of the present invention is in 1600 DEG C of environments for use, and the inspection of high temperature creep, thermal shock resistance is all better than MoSi
2bar material.
4, after high temperature air environment uses, surface of test piece is as before smooth, does not occur tiny crack or skin effect phenomenon.
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
Fig. 1, the SEM pattern photo of 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 Mo base Mo+Si+Cr+Fe gradient cladding matrix material prepared by the inventive method.
Embodiment
Below in conjunction with specific embodiment, introduction detailed is further done to technical scheme of the present invention, but protection scope of the present invention is not limited thereto.
Embodiment 1
The Si powder 15g getting purity>=99.9% loads in mixing container, is weighing Cr powder, the Fe powder of 1g, the 1gAl of 1g respectively
2o
3mix by after ball mill mixing 15min in mixing container, by load weighted 2gNHCl
4mix mixing container, after continuing ball mill mixing 10min, 50%(percent by volume by this mixture) load in clean corundum crucible, with instrument by its compacting, by purity more than 99.9% good for grinding process, be of a size of 10mm × 10mm × 5mm metal molybdenum block to be placed on the powder of compacting, then add remaining 50% mixture and compacting.Then, the sample installed is put into the box atmospheric resistance furnace passing into high-purity argon gas, mix up gas flow, open cooling water valve, with the temperature rise rate of 10 DEG C/min, through 120min, temperature is risen to 1200 DEG C, under this temperature condition, be incubated 180min, in whole insulating process, in burner hearth, be slight positive pressure state.Finally, after reaching soaking time, sample is made to naturally cool to room temperature in the burner hearth closed.Through carrying out XRD, SEM and energy spectrum analysis and carry out micro-hardness testing result to product surface showing to product section, gradient cladding thickness is about 600um, and coating uniform is fine and close, hardness HV=399.4.
Embodiment 2
The Si powder 12g getting purity>=99.9% loads in mixing container, is weighing Cr powder, the Fe powder of 2g, the 1gAl of 3g respectively
2o
3mix by after ball mill mixing 15min in mixing container, by load weighted 2gNHCl
4mix mixing container, after continuing ball mill mixing 10min, 50%(percent by volume by this mixture) load in clean corundum crucible, with instrument by its compacting, by purity more than 99.9% good for grinding process, be of a size of 10mm × 10mm × 5mm metal molybdenum block to be placed on the powder of compacting, then add remaining 50% mixture and compacting.Then, the sample installed is put into the box atmospheric resistance furnace passing into high-purity argon gas, mix up gas flow, open cooling water valve, with the temperature rise rate of 10.8 DEG C/min, through 120min, temperature is risen to 1300 DEG C, under this temperature condition, be incubated 180min, in whole insulating process, in burner hearth, be slight positive pressure state.Finally, after reaching soaking time, sample is made to naturally cool to room temperature in the burner hearth closed.Through carrying out XRD, SEM and energy spectrum analysis and carry out micro-hardness testing result to product gradient cladding surface showing to product section, gradient cladding thickness is about 1100um, and coating uniform is fine and close, hardness HV=422.36.
Embodiment 3
The Si powder 10g getting purity>=99.9% loads in mixing container, is weighing Cr powder, the Fe powder of 2g, the 2gAl of 3g respectively
2o
3mix by after ball mill mixing 15min in mixing container, by load weighted 3gNHCl
4mix mixing container, after continuing ball mill mixing 10min, 50%(percent by volume by this mixture) load in clean corundum crucible, with instrument by its compacting, by purity more than 99.9% good for grinding process, be of a size of 10mm × 10mm × 5mm metal molybdenum block to be placed on the powder of compacting, then add remaining 50% mixture and compacting.Then, the sample installed is put into the box atmospheric resistance furnace passing into high-purity argon gas, mix up gas flow, open cooling water valve, with the temperature rise rate of 9.5 DEG C/min, through 100min, temperature is risen to 950 DEG C, under this temperature condition, be incubated 180min, in whole insulating process, in burner hearth, be slight positive pressure state.Finally, after reaching soaking time, sample is made to naturally cool to room temperature in the burner hearth closed.Through carrying out XRD, SEM and energy spectrum analysis and carry out micro-hardness testing result to product surface showing to product section, gradient cladding thickness is about 350um, and coating uniform is fine and close, hardness HV=239.64.
Claims (1)
1. a preparation method for Mo base Mo+Si+Cr+Fe coating composite material, is characterized in that: with Si, Cr, Fe nanometer powder of purity>=99.9% for oozing source, with Al
2o
3+ NHCl
4for penetration-assisting agent, 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, generate Mo base Mo+Si+Cr+Fe coating composite material through high temperature in the diffusion of Mo matrix surface generation chemical reaction, its preparation process is as follows:
1. by Si, Cr, Fe nanometer powder and Al
2o
3+ NHCl
4powder weighs mixing by proportioning, and adopts the abundant batch mixing of ball milling method, makes it dispersed; Batch mixing order is: 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 block surface finish, remove surface oxidation black layer;
3. get the 50%(volume percent of 1. mixed powder) load in vessels crucible, use corresponding tool compacting, then by packaged for the Mo that handles well in 2. enter, finally will 1. in remaining mixed powder add and cover Mo block, and use instrument compacting;
4. 3. obtained sample is placed in the box-type high-temperature furnace of pressure-fired argon shield, set temperature system on request, through heating, insulation, cool and obtained finished product, temperature schedule is:
With the temperature rise rate of 10 DEG C/min, through 120min, temperature is risen to 1200 DEG C, 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 closed, naturally cool to room temperature; Or
With the temperature rise rate of 10.8 DEG C/min, through 120min, temperature is risen to 1300 DEG C, under this temperature condition, be incubated 180min, slight positive pressure state is in burner hearth in whole insulating process, finally, after reaching soaking time, in the burner hearth closed, naturally cool to room temperature.
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|---|---|---|---|
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|---|---|---|---|
| CN201310512164.8A CN103643201B (en) | 2014-01-13 | 2014-01-13 | Mo base Mo+Si+Cr+Fe coating composite material and preparation method |
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| CN103643201B true CN103643201B (en) | 2016-04-13 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
Family Cites Families (4)
| 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 |
| CN1014617B (en) * | 1986-05-16 | 1991-11-06 | 北京材料工艺研究所 | Permeation process of preparation of anti-oxidation coating used for molybdenum or its alloy |
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