CN107200585A - Long bar-shaped hafnium boride powder of one kind and preparation method thereof - Google Patents
Long bar-shaped hafnium boride powder of one kind and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to long bar-shaped hafnium boride powder of one kind and preparation method thereof.Its technical scheme is：27 ~ 42wt% hafnium oxide powder, 8 ~ 18wt% boron carbide powder, 3 ~ 9wt% carbon black powder, 10 ~ 27wt% chlorination powder for lithium and 22 ~ 34wt% potassium chloride powder is well mixed, obtain mixed reactant.The crucible that will be equipped with mixed reactant is put into saggar, it is placed in again in microwave oven, vacuum is evacuated to for 10 ~ 50Pa, then 10 ~ 60min is incubated under the conditions of circulation argon gas atmosphere and 1100 ~ 1300 °C, natural cooling, cleaned repeatedly with deionized water, 6 ~ 12h is finally dried under the conditions of 65 ~ 80 °C, produce long bar-shaped hafnium boride powder.The present invention has that cost is low, technique is simple, reaction temperature is low, reaction rate is high, be adapted to industrialized production and the characteristics of environmental protection, and prepared product purity is high, possess that uniform club shaped structure, size are controllable, specific surface area is big and sintering character is good.
Description
Technical field
The invention belongs to hafnium boride powder technical field.Specifically related to a kind of long bar-shaped hafnium boride powder and its preparation side
Method.
Background technology
Hafnium boride based ultra-high temperature ceramics have high-melting-point because of it, excellent high temperature resistance erosion performance, outstanding high-temperature mechanics
Performance and good conduction, heat conductivility, are widely used in the engine thermal protection department of spaceship and reentry vehicle
Part, the end cap of navaho, Advanced Nuclear Energy Systems radiation pretective hood and metallic high temperature melting and continuous casting electricity consumption
The important high-temperature structural material field such as pole.It is current prepare boronation hafnium ceramic main method be by hafnium boride powder in high temperature and
It is sintered under condition of high voltage.Therefore, new method that is extensive, preparing high-quality hafnium boride powder at low cost is developed, is
Further expand and deepen the key of its application field.
In addition, it is mutually to promote that the enhancing with anisotropic structure and hydrodynamics potentiality is introduced in hafnium boride ceramic matrix
Enter the effective way of its performance optimization.However, the harsh service condition of hafnium boride base ceramics not only significantly limit its enhancing
The range of choice of phase material, and cause preparation technology to complicate, cost increase and the ill effect such as product structure is uneven.Mirror
In this, the hafnium boride powder with uniform club shaped structure is prepared by developing new technology, will be expected to by " self-reinforcing " mechanism
The combination property of sintered products is significantly lifted, and effectively simplification of flowsheet and reduction prepare cost.
The existing hafnium boride powder method for preparing mainly includes thermal reduction, chemical method and simple substance reaction synthesis method.Compare
Chemical method and simple substance reaction synthesis method, thermal reduction have the advantages that preparation efficiency is higher and controllability is preferable.But existing heat
Reducing process stills need to use expensive or virose raw material and high synthesis temperature and the contour energy consumption condition of soaking time length,
And be difficult to form uniform club shaped structure：" preparation method that hafnium boride powder material is synthesized using organic matter precursor containing hafnium "
（CN102557642A）Patented technology, using the higher organic matter precursor containing hafnium of price, glucose and boric acid as raw material,
Hafnium boride powder is thermally treated resulting in through 1300 ~ 1700 °C of insulations within 1 ~ 5 hour, but does not report that it has club shaped structure；" one kind system
The standby method with Rod-like shape hafnium boride powder "（CN201210506176.5）Patented technology, with hafnium oxide, boron carbide and
Graphite is raw material, first passes through ball milling and the preprocessing process such as compressing, then carries out 1200 ~ 1800 °C of insulations 0.5 ~ 5 hour
Heat treatment, the content for having obtained rod-shpaed particle is only 90wt% hafnium boride powder；" preparation technology of bar-shaped hafnium boride powder "
（CN201410116048.9）Patented technology, bar-shaped hafnium oxide is prepared by raw material of virose hafnium tetrachloride, passes through phenolic aldehyde tree
Fat is cracked and crushing prepares carbon dust, then 1600 ~ 1800 °C of progress is incubated 0.5 after above-mentioned hafnium oxide and carbon dust mixs with boron carbide
The heat treatment of ~ 2 hours, has obtained micron footpath than being only more than 2 times of hafnium boride powder.
In summary, the existing method generally existing cost of material height for preparing hafnium boride powder, complex process, preparation temperature
Degree is high, preparation efficiency is low, do not possess uniform anisotropy（It is bar-shaped）Structure, it is difficult to industrialized production and pollution environment etc. lacks
Point.
The content of the invention
It is contemplated that overcoming the defect of prior art, it is therefore an objective to provide that a kind of cost of material is low, technique simple, prepare temperature
Spend the bar-shaped hafnium boride powder preparation method of high, the suitable length of industrialized production and environmental protection of low, preparation efficiency；Using this method
The bar-shaped hafnium boride powder purity of the length of preparation is high, the controllable, specific surface area that possesses uniform club shaped structure, size is big and sintering character
Well.Product has the reinforcing potentiality of uniform anisotropic structure and material property.
To achieve the above object, the technical solution adopted by the present invention is comprised the concrete steps that：
(1) by 27 ~ 42wt% hafnium oxide powder, 8 ~ 18wt% boron carbide powder, 3 ~ 9wt% carbon black powder, 10 ~ 27wt%
Chlorination powder for lithium and 22 ~ 34wt% potassium chloride powder are well mixed, and obtain mixture.
(2) mixture is loaded into crucible, then the crucible is loaded in saggar, then filled using silicon carbide powder
Gap between the saggar and the crucible.
(3) saggar filled behind gap is placed in microwave oven, vacuum is first evacuated to for 10 ~ 50Pa, then in stream
Under the conditions of dynamic argon gas atmosphere, 1100 ~ 1300 °C are warming up to 5 ~ 50 °C/min heating rate, 10 ~ 60min is incubated, it is natural
Cooling, obtains the hafnium boride powder of bulk processing.
(4) hafnium boride powder of the bulk processing is cleaned 3 ~ 5 times with deionized water, in 65 ~ 80 ° in vacuum drying chamber
6 ~ 12h is incubated under the conditions of C, long bar-shaped hafnium boride powder is produced.
The purity of the hafnium oxide powder is technical grade or is analysis level, average particle size particle size≤10mm.
The purity of the boron carbide powder is technical grade or is analysis level, average particle size particle size≤30mm.
The purity of the carbon black powder is technical grade or is analysis level, average particle size particle size≤30mm.
The purity of the chlorination powder for lithium is technical grade or is analysis level, average particle size particle size≤100mm.
The purity of the potassium chloride powder is technical grade or is analysis level, average particle size particle size≤100mm.
The purity of the silicon carbide powder is technical grade or is analysis level, average particle size particle size≤5mm.
Due to using above-mentioned technical proposal, the present invention has following good effect and outstanding feature compared with prior art：
1. raw material resources of the present invention are abundant and cheap, not using expensive and poisonous and hazardous raw material, into
This is low, and technical process is simple, the requirement of mass production can be met, with considerable industrialization prospect.
2. the microwave heating condition that the present invention is used can make reactant produce microwave effects such as " spontaneous heatings ", with conventional heat also
Former method is compared, and significantly reduces the synthesis temperature (being reduced to 1100 ~ 1300 °C by >=1600 °C) of long bar-shaped hafnium boride powder, and
And it has been significantly increased preparation efficiency, 10 are foreshortened to by existing a few hours the time required to preparing pure phase hafnium boride powder ~
60min。
3. the crystal growth from flux condition that the present invention is used has following both sides good effect：On the one hand, fused-salt medium can have
Effect ground reduces the average atom diffusion length of reactant and can improve diffusion rate, further speeds up the long bar-shaped hafnium boride powder of synthesis
The reaction rate of body；On the other hand, fused-salt medium not only contributes to prepare the bar-shaped hafnium boride powder of the length of pattern and size uniform,
And hafnium boride powder formation and the long club shaped structure with high-specific surface area are may advantageously facilitate, so as to strengthen the bar-shaped hafnium boride of the length
The sintering activity of powder.
4. new thermal reduction of the present invention can realize the long bar-shaped boron of synthesis in the case of reducing agent not excess
Change the complete progress of hafnium powder reaction, so that the not reactant and accessory substance of remained unreacted in product.On this condition, lead to
The separation of high-purity hafnium boride powder and fused-salt medium can efficiently be realized by crossing simple washing process, be conducive to water resource
Save using the recovery and recycling with fused-salt medium, meet environment protection requirement.
5. the bar-shaped hafnium boride powder of length obtained by the present invention has long rodlike single-crystal structure after testing：Specific surface area be 100 ~
200m2/g；A diameter of 100 ~ 300nm, length is 500 ~ 2000nm.
Therefore, the present invention have cost is low, technique is simple, reaction temperature is low, reaction rate is high, be adapted to industrialized production and
The characteristics of environmental protection, the bar-shaped hafnium boride powder purity of prepared length is high, it is controllable to possess uniform club shaped structure, size, ratio
Surface area is big and sintering character is good.
Brief description of the drawings
Fig. 1 is a kind of XRD spectrum for growing bar-shaped hafnium boride powder prepared by the present invention；
Fig. 2 is the micro-structure diagram of the bar-shaped hafnium boride powder of another length prepared by the present invention.
Embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description, not to the limit of its protection domain
System.
It is first that the raw material Unify legislation involved by present embodiment is as follows to avoid repeating, no longer gone to live in the household of one's in-laws on getting married in embodiment
State：
The purity of the hafnium oxide powder is technical grade or is analysis level, average grain diameter≤10mm.
The purity of the boron carbide powder is technical grade or is analysis level, average particle size particle size≤30mm.
The purity of the carbon black powder is technical grade or is analysis level, average particle size particle size≤30mm.
The purity of the chlorination powder for lithium is technical grade or is analysis level, average particle size particle size≤100mm.
The purity of the potassium chloride powder is technical grade or is analysis level, average particle size particle size≤100mm.
The purity of the silicon carbide powder is technical grade or is analysis level, average particle size particle size≤5mm.
Embodiment 1
Long bar-shaped hafnium boride powder of one kind and preparation method thereof.The preparation method is comprised the concrete steps that：
(1) by 27 ~ 30wt% hafnium oxide powder, 9 ~ 13wt% boron carbide powder, 5 ~ 7wt% carbon black powder, 14 ~ 20wt%
Chlorination powder for lithium and 30 ~ 32wt% potassium chloride powder are well mixed, and obtain mixed reactant.
(2) mixture is loaded into crucible, then the crucible is loaded in saggar, then filled using silicon carbide powder
Gap between saggar and crucible.
(3) saggar filled behind gap is placed in microwave oven, vacuum is first evacuated to for 10 ~ 50Pa, then in stream
Under the conditions of dynamic argon gas atmosphere, 1150 ~ 1200 °C are warming up to 20 ~ 40 °C/min heating rate, 15 ~ 40min is incubated, it is natural
Cooling, obtains the hafnium boride powder of bulk processing.
(4) hafnium boride powder of the bulk processing is cleaned 3 ~ 5 times with deionized water, dry 6 under the conditions of 65 ~ 80 °C ~
12h, produces long bar-shaped hafnium boride powder.
The bar-shaped hafnium boride powder of length manufactured in the present embodiment is after testing：Specific surface area is 190 ~ 200m2/g；With uniform
Long bar-shaped microstructure, a diameter of 120 ~ 180nm of long bar-shaped hafnium boride powder, length is 600 ~ 1400nm.
Embodiment 2
Long bar-shaped hafnium boride powder of one kind and preparation method thereof.The preparation method is comprised the concrete steps that：
(1) by 29 ~ 33wt% hafnium oxide powder, 8 ~ 11wt% boron carbide powder, 3 ~ 5wt% carbon black powder, 20 ~ 27wt%
Chlorination powder for lithium and 31 ~ 34wt% potassium chloride powder are well mixed, and obtain mixed reactant.
(2) mixture is loaded into crucible, then the crucible is loaded in saggar, then filled using silicon carbide powder
Gap between saggar and crucible.
(3) saggar filled behind gap is placed in microwave oven, vacuum is first evacuated to for 10 ~ 50Pa, then in stream
Under the conditions of dynamic argon gas atmosphere, 1100 ~ 1150 °C are warming up to 30 ~ 50 °C/min heating rate, 25 ~ 50min is incubated, it is natural
Cooling, obtains the hafnium boride powder of bulk processing.
(4) hafnium boride powder of the bulk processing is cleaned 3 ~ 5 times with deionized water, dry 6 under the conditions of 65 ~ 80 °C ~
12h, produces long bar-shaped hafnium boride powder.
The bar-shaped hafnium boride powder of length manufactured in the present embodiment is after testing：Specific surface area is 165 ~ 190m2/g；With uniform
Long bar-shaped microstructure, a diameter of 160 ~ 280nm of long bar-shaped hafnium boride powder, length is 500 ~ 1200nm.
Embodiment 3
Long bar-shaped hafnium boride powder of one kind and preparation method thereof.The preparation method is comprised the concrete steps that：
(1) by 36 ~ 39wt% hafnium oxide powder, 14 ~ 16wt% boron carbide powder, 7 ~ 9wt% carbon black powder, 10 ~ 14wt%
Chlorination powder for lithium and 24 ~ 30wt% potassium chloride powder be well mixed, obtain mixed reactant.
(2) mixture is loaded into crucible, then the crucible is loaded in saggar, then filled using silicon carbide powder
Gap between saggar and crucible.
(3) saggar filled behind gap is placed in microwave oven, vacuum is first evacuated to for 10 ~ 50Pa, then in stream
Under the conditions of dynamic argon gas atmosphere, 1100 ~ 1250 °C are warming up to 5 ~ 20 °C/min heating rate, 20 ~ 60min is incubated, it is natural
Cooling, obtains the hafnium boride powder of bulk processing.
(4) hafnium boride powder of the bulk processing is cleaned 3 ~ 5 times with deionized water, dry 6 under the conditions of 65 ~ 80 °C ~
12h, produces long bar-shaped hafnium boride powder.
The bar-shaped hafnium boride powder of length manufactured in the present embodiment is after testing：Specific surface area is 150 ~ 180m2/g；With uniform
Long bar-shaped microstructure, a diameter of 100 ~ 170nm of long bar-shaped hafnium boride powder, length is 1400 ~ 2000nm.
Embodiment 4
Long bar-shaped hafnium boride powder of one kind and preparation method thereof.The preparation method is comprised the concrete steps that：
(1) by 33 ~ 38wt% hafnium oxide powder, 9 ~ 15wt% boron carbide powder, 3 ~ 7wt% carbon black powder, 16 ~ 20wt%
Chlorination powder for lithium and 22 ~ 28wt% potassium chloride powder are well mixed, and obtain mixed reactant.
(2) mixture is loaded into crucible, then the crucible is loaded in saggar, then filled using silicon carbide powder
Gap between saggar and crucible；
(3) saggar filled behind gap is placed in microwave oven, vacuum is first evacuated to for 10 ~ 50Pa, then in flowing
Under the conditions of argon gas atmosphere, 1250 ~ 1300 °C are warming up to 20 ~ 40 °C/min heating rate, 10 ~ 40min is incubated, it is naturally cold
But, the hafnium boride powder of bulk processing is obtained.
(4) hafnium boride powder of the bulk processing is cleaned 3 ~ 5 times with deionized water, temperature 6 is dried under the conditions of 65 ~ 80 °C
~ 12h, produces long bar-shaped hafnium boride powder.
The bar-shaped hafnium boride powder of length manufactured in the present embodiment is after testing：Specific surface area is 190 ~ 200m2/g；With uniform
Long bar-shaped microstructure, a diameter of 220 ~ 300nm of long bar-shaped hafnium boride powder, length is 1200 ~ 1700nm.
Embodiment 5
Long bar-shaped hafnium boride powder of one kind and preparation method thereof.The preparation method is comprised the concrete steps that：
(1) by 37 ~ 42wt% hafnium oxide powder, 8 ~ 12wt% boron carbide powder, 4 ~ 5wt% carbon black powder, 14 ~ 19wt%
Chlorination powder for lithium and 26 ~ 30wt% potassium chloride powder are well mixed, and obtain mixed reactant.
(2) mixture is loaded into crucible, then the crucible is loaded in saggar, then filled using silicon carbide powder
Gap between saggar and crucible.
(3) saggar filled behind gap is placed in microwave oven, vacuum is first evacuated to for 10 ~ 50Pa, then in stream
Under the conditions of dynamic argon gas atmosphere, 1200 ~ 1300 °C are warming up to 40 ~ 50 °C/min heating rate, 20 ~ 40min is incubated, it is natural
Cooling, obtains the hafnium boride powder of bulk processing.
(4) hafnium boride powder of the bulk processing is cleaned 3 ~ 5 times with deionized water, dry 6 under the conditions of 65 ~ 80 °C ~
12h produces long bar-shaped hafnium boride powder.
The bar-shaped hafnium boride powder of length manufactured in the present embodiment is after testing：Specific surface area is 155 ~ 170m2/g；With uniform
Long bar-shaped microstructure, a diameter of 200 ~ 260nm of long bar-shaped hafnium boride powder, length is 1000 ~ 1600nm.
Embodiment 6
Long bar-shaped hafnium boride powder of one kind and preparation method thereof.The preparation method is comprised the concrete steps that：
(1) by 32 ~ 37wt% hafnium oxide powder, 14 ~ 18wt% boron carbide powder, 6 ~ 8wt% carbon black powder, 13 ~ 18wt%
Chlorination powder for lithium and 25 ~ 33wt% potassium chloride powder be well mixed, obtain mixed reactant.
(2) mixture is loaded into crucible, then the crucible is loaded in saggar, then filled using silicon carbide powder
Gap between saggar and crucible.
(3) saggar filled behind gap is placed in microwave oven, vacuum is first evacuated to for 10 ~ 50Pa, then in stream
Under the conditions of dynamic argon gas atmosphere, 1100 ~ 1200 °C are warming up to 10 ~ 30 °C/min heating rate, 10 ~ 30min is incubated, it is natural
Cooling, obtains the hafnium boride powder of bulk processing.
(4) hafnium boride powder of the bulk processing is cleaned 3 ~ 5 times with deionized water, dry 6 under the conditions of 65 ~ 80 °C ~
12h, produces long bar-shaped hafnium boride powder.
The bar-shaped hafnium boride powder of length manufactured in the present embodiment is after testing：Specific surface area is 160 ~ 175m2/g；There is uniform length
Bar-shaped microstructure, a diameter of 170 ~ 240nm of long bar-shaped hafnium boride powder, length is 900 ~ 1450nm.
Present embodiment has following good effect and outstanding feature compared with prior art：
1. the raw material resources that present embodiment is used are abundant and cheap, not using expensive and poisonous and hazardous
Raw material, cost is low, and technical process is simple, the requirement of mass production can be met, with considerable industrialization prospect.
2. the microwave heating condition that present embodiment is used can make reactant produce microwave effects such as " spontaneous heatings ", with
Conventional thermal reduction is compared, significantly reduce long bar-shaped hafnium boride powder synthesis temperature (be reduced to 1100 by >=1600 °C ~
1300 °C), and reaction rate has been significantly increased, make the time required to preparation pure phase hafnium boride powder by existing a few hours
Foreshorten to 10 ~ 60min.
3. the crystal growth from flux condition that present embodiment is used has following both sides good effect：On the one hand, fused salt
Medium can effectively reduce the average atom diffusion length of reactant and can improve diffusion rate, further speed up synthesis length bar-shaped
The reaction rate of hafnium boride powder；On the other hand, fused-salt medium not only contributes to prepare the hafnium boride powder of pattern and size uniform
Body, and long club shaped structure of the hafnium boride powder formation with high-specific surface area is may advantageously facilitate, so as to strengthen the bar-shaped boronation of the length
The sintering activity of hafnium powder.
4. the new thermal reduction that present embodiment is used can realize synthesis in the case of reducing agent not excess
The complete progress of long bar-shaped hafnium boride powder reaction, so that the not reactant and accessory substance of remained unreacted in product.Herein
Under the conditions of, point of high-purity hafnium boride powder and fused-salt medium can be efficiently realized by simple and highly efficient washing process
From be conducive to water resource saves the recovery and recycling utilized with fused-salt medium, meets environment protection requirement.
5. long bar-shaped hafnium boride powder made from present embodiment is as shown in drawings：Fig. 1 is using side described in embodiment 1
A kind of XRD spectrum for growing bar-shaped hafnium boride powder prepared by method；Fig. 2 is a kind of long rod prepared using the methods described of embodiment 3
The micro-structure diagram of shape hafnium boride powder.It can be seen that from Fig. 1 ~ Fig. 2：The bar-shaped hafnium boride powder of prepared length is by single-phase HfB2
Composition, with long bar-like single crystal HfB2Structure.Long bar-shaped hafnium boride powder made from present embodiment is after testing：Specific surface area
For 150 ~ 200m2/g；A diameter of 100 ~ 300nm of long bar-shaped hafnium boride powder, length is 500 ~ 2000nm.
Therefore, present embodiment has that cost is low, technique is simple, reaction temperature is low, reaction rate is high, is adapted to industry
The characteristics of metaplasia production and environmental protection, the bar-shaped hafnium boride powder purity of prepared length is high, possess uniform club shaped structure, size
Controllable, specific surface area is big and sintering character is good.
Claims (8)
1. a kind of preparation method for growing bar-shaped hafnium boride powder, it is characterised in that be the step of the preparation method：
(1) by 27 ~ 42wt% hafnium oxide powder, 8 ~ 18wt% boron carbide powder, 3 ~ 9wt% carbon black powder, 10 ~ 27wt%
Chlorination powder for lithium and 22 ~ 34wt% potassium chloride powder are well mixed, and obtain mixture；
(2) mixture is loaded into crucible, then the crucible is loaded in saggar, it is then described using silicon carbide powder filling
Gap between saggar and the crucible；
(3) saggar filled behind gap is placed in microwave oven, vacuum is first evacuated to for 10 ~ 50Pa, then in flowing
Under the conditions of argon gas atmosphere, 1100 ~ 1300 °C are warming up to 5 ~ 50 °C/min heating rate, 10 ~ 60min is incubated, natural cooling,
Obtain the hafnium boride powder of bulk processing；
(4) hafnium boride powder of the bulk processing is cleaned 3 ~ 5 times with deionized water, in 65 ~ 80 °C of bars in vacuum drying chamber
6 ~ 12h is incubated under part, long bar-shaped hafnium boride powder is produced.
2. the preparation method of the bar-shaped hafnium boride powder of length according to claim 1, it is characterised in that the hafnium oxide powder
Purity be technical grade or be analysis level, average particle size particle size≤10mm.
3. the preparation method of the bar-shaped hafnium boride powder of length according to claim 1, it is characterised in that the boron carbide powder
Purity be technical grade or be analysis level, average particle size particle size≤30mm.
4. the preparation method of the bar-shaped hafnium boride powder of length according to claim 1, it is characterised in that the carbon black powder
Purity is technical grade or is analysis level, average particle size particle size≤30mm.
5. the preparation method of the bar-shaped hafnium boride powder of length according to claim 1, it is characterised in that the chlorination powder for lithium
Purity be technical grade or be analysis level, average particle size particle size≤100mm.
6. the preparation method of the bar-shaped hafnium boride powder of length according to claim 1, it is characterised in that the potassium chloride powder
Purity be technical grade or be analysis level, average particle size particle size≤100mm.
7. the preparation method of the bar-shaped hafnium boride powder of length according to claim 1, it is characterised in that the silicon carbide powder
Purity be technical grade or be analysis level, average particle size particle size≤5mm.
8. the long bar-shaped hafnium boride powder of one kind, it is characterised in that the bar-shaped hafnium boride powder of length is according to claim 1 ~ 7
Any one of long bar-shaped hafnium boride powder preparation method prepared by the bar-shaped hafnium boride powder of length.
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