CN102730689B - Surface treatment method of boron carbide powder - Google Patents
Surface treatment method of boron carbide powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 135
- 229910052580 B4C Inorganic materials 0.000 title claims abstract description 74
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000004381 surface treatment Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 31
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- 230000032683 aging Effects 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 22
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
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- 238000001035 drying Methods 0.000 claims description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 15
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000015895 biscuits Nutrition 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000008698 shear stress Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
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- 238000011010 flushing procedure Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 238000009768 microwave sintering Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a surface treatment method of boron carbide powder. The surface treatment method comprises the following steps of: an acid treatment process of sufficiently mixing the boron carbide powder, water and acid, wherein the using amount of the acid is configured to enable a pH value of a mixture to be within 0.5-3; a process of aging the mixture at a ruled temperature within aging ruled time; and a process of filtering and washing obtained filter cake or powder with water until a pH (Potential of Hydrogen) value of a filtrate is 3-6.
Description
Technical field
The invention belongs to inorganic materials forming field, be specifically related to the surface treatment method of boron carbide powder, to remove the impurity of powder surface, improve the dispersion stabilization of boron carbide powder in water, be conducive to the wet moulding of boron carbide powder.
Background technology
The outstanding feature of boron carbide ceramics is hardness high (being only second to cubic boron nitride and diamond), low (the theoretical density 2.52g/cm of density
3) and neutron-absorption cross-section large.These outstanding advantages make boron carbide ceramics aspect the neutron absorber material of high-abrasive material, lightweight armor material and nuclear industry, have very important application.
In above-mentioned application, conventionally need to prepare large size or complex-shaped goods.And the outstanding feature of wet moulding is to prepare the biscuit of ceramics of complicated shape, and then the boron carbide ceramics of acquisition complicated shape, but wet moulding is very high to the dispersiveness requirement of powder, so it is particularly important to strengthen the dispersiveness of boron carbide powder.Particularly commercial boron carbide powder foreign matter content is high, and composition is more complicated, is difficult to realize good distribution in the aqueous solution.Therefore need boron carbide powder to carry out surface treatment, to improve the dispersion stabilization of powder.
At present, have in the groundwork aspect the surface treatment of boron carbide powder: Holcombe etc. (referring to patent documentation 1) are by a large amount of excessive nitric acid treatment boron carbide powders, by removing impurity Ca main in boron carbide powder, strengthen the microwave sintering activity of boron carbide powder.Pujari etc. (referring to patent documentation 2) adopt the water of higher degree (>95%) and comparatively high temps (>20 DEG C) to clean boron carbide powder, remove the oxide compound of boron carbide powder surface, object is also to improve the sintering activity of boron carbide powder.Bar-viz etc. (referring to patent documentation 3) process boron carbide powder by alcoholic solution as aqueous isopropanol, wash away the boron oxide of powder surface, and object is also to improve the sintering activity of boron carbide powder.Fetterley etc. (referring to patent documentation 4) are ground to the Fe in boron carbide powder while removing ball milling by pickling boron carbide powder, and purifying boron carbide powder obtains the boron carbide powder for hot pressed sintering.
Existing other documents (referring to non-patent literature 1,2,3,4,5) also show, are the boron oxides in order to remove boron carbide powder surface at present, to strengthen the sintering activity of boron carbide powder to boron carbide powder surface treatment object.
Pickling norbide is for the homemade boron carbide powder of purifying on the other hand, Liu Pixian etc. (referring to patent documentation 5) adopt the homemade boron carbide powder of vitriol oil pickling, then wash boron carbide powder with water, in the time that the pH of filtrate is between 6.5-7.5, stop washing, the object of pickling is to improve the purity of homemade boron carbide powder.Gu Yunle etc. (referring to patent documentation 6) adopt concentrated hydrochloric acid to remove the impurity in synthetic powder, adopt distilled water flushing boron carbide powder, until the pH of powder is neutral, stop cleaning, and the object of its pickling is also to improve the purity of self-control boron carbide powder.
But patent documentation 5 and 6 disclosed schemes are all to adopt greatly excessive acid directly to process powder, for example, in the disclosed scheme of patent documentation 5, the amount of the vitriol oil used is 10～15wt% of butt weight in slurry, and acid amount used is large; Adopt the concentrated hydrochloric acid of 35 excessive～38wt% in the disclosed scheme of patent documentation 6 again.Visible acid amount used is large, the powder surface of wherethrough reason may residual a large amount of acid, follow-up with a large amount of water repeatedly repeatedly clean could remove residual acid, and existing these schemes also require to be washed to filtrate to neutral left and right, with the water yield larger, in the time of large-scale application, not only can increase like this cost, but also pollute the environment.The disclosed pickling of above-mentioned document and/or washing are all the impurity in order to remove boron carbide powder.Therefore, be badly in need of the low and environmental friendliness of a kind of cost, can effectively remove impurity, can also improve the surface treatment method of powder dispersity.
About the method for improving powder dispersity, the people such as William (referring to non-patent literature 6) disclose water or washed with methanol powder, the dispersiveness of washing rear powder has improved, and adopt the density of biscuit of washing rear powder injection forming also to increase than originally, think that the raising of dispersed raising and biscuit density is after cleaning due to the minimizing of boron carbide powder surface oxidation boron content.
Prior art:
Patent documentation 1:US 5252267;
Patent documentation 2:US 7919040 B2;
Patent documentation 3:US 2008/0279747 A1;
Patent documentation 4:US 3137584;
Patent documentation 5:CN 102161586A;
Patent documentation 6:CN 101786625A;
Non-patent literature 1:Dole, S.; Prochazka, S.; Doremus, R., Microstructural coarsening during sintering of boron carbide.
j Am Ceram Soc 1989,
72 (6), 958-966.
Non-patent literature 2:Lee, H.; Speyer, R. F., Pressureless sintering of boron carbide.
j Am Ceram Soc 2003,
86 (9), 1468-1473.
Non-patent literature 3:Speyer, R. F.; Lee, H.; Bao, Z., Processes and methods of making boron carbide. Google Patents:2009.
Non-patent literature 4:Pujari, V. K.; Hennessey, J. T.; Reilly, C. J., METHODS OF FORMING SINTERED BORON CARBIDE. US Patent No.2011/0227259:2010.
Non-patent literature 5:Sigl, L. S., Processing and mechanical properties of boron carbide sintered with TiC.
j. European Ceram. Soc. 1998,
18 (11), 1521-1529.
Non-patent literature 6:Williams, P. D.; Hawn, D. D., AQUEOUS DISPERSION AND SLIP CASTING OF BORON-CARBIDE POWDER-EFFECT OF PH AND OXYGEN-CONTENT.
j. Am. Ceram. Soc. 1991,
74 (7), 1614-1618..
Summary of the invention
In the face of the problems referred to above that prior art exists, the inventor has recognized the need to provide a kind of cost low and environmental friendliness, can effectively remove impurity, can also improve the surface treatment method of powder dispersity.To this, the present invention has done further improvement research in existing scheme, after deliberation, contriver finds when with acid treatment boron carbide powder, can can ensure more fully to remove impurity and can improve dispersed time and can remainingly not cross again polyacid by controlling sour consumption, can reduce thus the water consumption of follow-up water washing process.Again, the powder of large-scale application is all to adopt the mode of boron oxide or boric acid reduction to prepare boron carbide powder at present.In powder after preparation, have remaining boric acid or boron oxide, and also can there is oxidation and generate boron oxide or boric acid in norbide surface in air, thus, although through treating processes repeatedly, the pH of boron carbide powder liquid suspension still shows slightly acidic, and the pH of the filtrate after cleaning is also slightly acidic.If filtrate will reach the neutrality of reporting in existing document or make pH at 6.5-7.5, need to repeatedly carry out water washing process with a large amount of water.And the inventor finds after deliberation, even do not arrive neutrality through several times washing filtrate pH, but while being slightly acidic, gained powder still can present good dispersiveness.
At this, the invention provides a kind of surface treatment method of boron carbide powder, it is characterized in that, comprising: by boron carbide powder, water and sour well-mixed acid treatment operation, the consumption of wherein said acid is configured to make the pH value of mixture to be controlled at 0.5～3; The ageing operation of described mixture under specified temperature and in the ageing specified time; And filtration, the gained filter cake washing step that to wash with water to filtrate pH value be 3～6.
The present invention controls acid amount used by pH value to 0.5～3 of controlling mixture, then ageing certain hour in the aqueous solution of this pH value, can remove the impurity in boron carbide powder, acid amount used is few, and follow-up washing times is less, the water yield of use is also corresponding less, for scale operation, can significantly reduce costs, and also less to the pollution of environment.
In addition, the present invention only makes filtrate pH value to 3～6 can realize the dispersiveness of improving powder by washing several times in water washing process, without repeatedly rinsing to filtrate pH to neutral with large water gaging as prior art, thereby, can further reduce water consumption, cost-saving and environmentally friendly.
In the present invention, boron carbide powder, water and acid can be mixed in random order.But be preferably, in described acid treatment operation, first mix described boron carbide powder and water, then drip pH value to 0.5～3 of described acid to mixture.Before adding acid, adopt the first dispersion powder of water of suitable amount, be conducive to carrying out smoothly of acid cleaning process.
Again, in the present invention, can adopt conventional acid, for example sulfuric acid, nitric acid, hydrochloric acid or its mixing acid forming arbitrarily.All more common, easy acquisitions of acid used, cost are low, are conducive to large-scale production.
Preferably, in the present invention, water used is deionized water.Adopt deionized water, the possibility that washing environment may be able to be introduced to impurity drops to minimum, further improves the purity of processing the powder obtaining.
Again, in the present invention, in described acid treatment operation, the mass ratio of described boron carbide powder and water can be 6:1～1:7.5, and the volume fraction of corresponding boron carbide powder is between 70%-5%.
Preferably, above-mentioned ageing can be carried out 1～168 hour at 0～100 DEG C, that is, and and in described ageing operation: the temperature of described regulation can be 0～100 DEG C, and described specific time can be 1～168 hour.Take such ageing condition, be conducive to acid and fully contact with norbide, effectively remove impurity.
Again, method of the present invention also can comprise lyophilize or at 80～200 DEG C dry through washing after filter cake or the drying process of powder.
The present invention adopts a kind of method simple, easily control to get final product purifying norbide, can improve the dispersiveness of powder simultaneously.Method cost of the present invention is low, environmental friendliness, be easy to scale production, and prepared powder purity is high, good dispersity, be conducive to the wet moulding of boron carbide powder, such as injection forming, gel casting forming and injection molding etc., can be made into thus the boron carbide ceramics of different shape, thereby having broad application prospects aspect the neutron absorber material of high-abrasive material, lightweight armor material and nuclear industry.
Brief description of the drawings
Fig. 1 illustrates that the viscosity of the powder that obtains by exemplary method processing of the present invention and comparative example powder is with the curve of shear rate change;
Fig. 2 illustrates that the shear-stress of the powder that obtains by exemplary method processing of the present invention and comparative example powder is with the curve of shear rate change.
Embodiment
With reference to Figure of description, and further illustrate with the following embodiments the present invention, should be understood that following embodiment is only for the present invention is described, and unrestricted the present invention.
First, by the business boron carbide powder of buying on market, or homemade boron carbide powder is dispersed in water formation mixture, for example, form suspension/suspension liquid.Homemade powder can by prior art disclosed method prepare.At this, about the consumption of water, be preferably, the mass ratio of boron carbide powder weight and water is between 6:1～1:7.5, but this is only preferred consumption, is not essential.Preferably, adopt deionized water to disperse boron carbide powder, like this, can reduce bringing into of ambient impurities.
Then, acid is added into said mixture to regulate the pH value (herein and herein the pH value of indication all refer to be converted into the pH value at 25 DEG C) of mixture in the scope of 0.5-3.Acid used can adopt common hydrochloric acid (HCl), sulfuric acid (H
2sO
4), nitric acid (HNO
3) or the solution of its different concns, can be also the mixing acid/mixing solutions of their any composition.
The present invention realizes by controlling the pH value of mixture, and particularly, if pH value, higher than 0.5, will be passed through more water washing process after pickling, removing powder surface can adsorbable acid, in the time of large-scale application, can increase cost; If pH is lower than 3, acid can not be removed the impurity in powder completely, thereby affects the dispersiveness of boron carbide powder.Should be understood that sour addition manner can adopt the mode of dropping, can be again that stir so that powder fully contacts with acid on dropping limit, limit.
Add after acid, ageing for some time in this pH value (, 0.5-3) scope, can remove the impurity in boron carbide powder.Ideally, ageing 1-168h under 0-100 DEG C of condition.Should understand in the time adopting lower Aging Temperature, adaptability extends digestion time, and in the time adopting higher Aging Temperature, adaptability shortens digestion time.
After ageing, washed with de-ionized water, repeatedly suction filtration or filtration, when filtering or the pH value of the filtrate of suction filtration (is converted into pH at 25 DEG C) within the scope of 3-6, stops cleaning.Dry filter powder under 80-200 DEG C of temperature condition, or adopt cryodesiccated way to be dried powder, after being dried, powder being ground and sieve, obtain the boron carbide powder of favorable dispersity.
After ageing, filter, gained filter cake can adopt water, and preferably washed with de-ionized water is until filtrate pH value is 3～6.The mode of washing can be, adopt water repeatedly repeatedly flush cake until filtrate pH is 3～6, but preferably, after each washing, filter cake is dispersed in water again, refilters, repeatedly combined filtering and redispersion step, until filtrate pH is 3～6, so each washing can ensure that water fully contacts with powder, can reduce washing times and water consumption.Filter the mode that preferably adopts suction filtration, to improve the efficiency of filtration here.
After washing, then dry filter powder under 80-200 DEG C of temperature condition, or adopt cryodesiccated way to be dried powder, and after being dried, powder being ground and sieve, can obtain the boron carbide powder of favorable dispersity.
The solution of the present invention is passed through boron carbide powder ageing in the aqueous solution of pH value 0.5-3, thereby removes the impurity of powder surface.By repeatedly cleaning and filtering, remove acid and the impurity cationic of powder surface absorption again.Until the pH value of filtrate is in the scope of 3-6.After dry, can obtain dispersed higher powder.Method simply, easily control, cost is low, environmental friendliness.
Further exemplify embodiment and comparative example below to describe the present invention in detail.Should be understood that following embodiment and/or comparative example are also for the present invention is described better, and unrestricted the present invention.
Be averaged the norbide business powder 0.5kg that particle diameter is about 0.5 μ m, the deionized water of quality 3kg, both are mixed, then drip nitric acid, constantly stir and the pH value of test suspension liquid, pH reaches at 3 o'clock and stops adding nitric acid.Under 50 DEG C of conditions, by suspension ageing 48h.Said mixture is filtered, after filtration, the powder leaching is used to washed with de-ionized water again, repeat washed with de-ionized water process.The pH of last test filtrate approaches 5, stops washing.By the powder leaching, under 120 DEG C of conditions, dry.Dried powder is ground and sieved, obtain boron carbide powder.
Being averaged particle diameter is the norbide business powder 1.5kg of 3.5 μ m left and right, the deionized water of quality 3kg, and both are mixed, and then drips sulfuric acid, constantly stirs the also pH value of test suspension liquid, waits pH to reach 1, stops adding sulfuric acid.Under 100 DEG C of conditions, by suspension ageing 1h.Said mixture is carried out to suction filtration.After suction filtration, the powder redispersion leaching in deionized water and stir, then is carried out to suction filtration, repeat said process.The pH of last test filtrate is 4, stops washing.By the powder leaching, under 200 DEG C of conditions, dry.After dried powder is ground, sieve, obtain the boron carbide powder for wet moulding.
Embodiment 3
Being averaged particle diameter is the norbide business powder 5.5kg of 7 μ m, the deionized water of quality 1kg, and both are mixed, and then drips nitric acid and hydrochloric acid, constantly stirs and the pH value of test suspension liquid, stops adding after waiting pH to reach 2.5.Under 30 DEG C of conditions, by suspension ageing 168h.Said mixture is carried out to suction filtration.After suction filtration, the powder redispersion leaching in deionized water and stir, then is carried out to suction filtration, repeat said process.The pH of last test filtrate reaches 6.0, stops washing.By the powder leaching, lyophilize.After dried powder is ground, sieve, obtain the boron carbide powder for wet moulding.
Embodiment 4
Being averaged particle diameter is the norbide self-control powder 110g of 350nm and the deionized water of 200g, and both are mixed, and then drips hydrochloric acid, constantly stirs the also pH value of test suspension liquid, waits pH to reach 0.5, stops adding.At ambient temperature, by suspension ageing 36h.Said mixture is carried out to suction filtration.After suction filtration, the powder redispersion leaching in deionized water and stir, then is carried out to suction filtration, repeat said process.The pH of last filtrate reaches 3.7, stops washing.By the powder leaching, 80 DEG C of oven dry.After dried powder is ground, sieve, obtain the boron carbide powder for wet moulding.
Comparative example
Being averaged particle diameter is the norbide self-control powder 110g of 350nm and the deionized water of 200g, by both mixing, suction filtration.After suction filtration, the powder redispersion leaching in deionized water and stir, then is carried out to suction filtration, repeat said process.The pH of last filtrate reaches 4.39, stops washing.By the powder leaching, 80 DEG C of oven dry.
It is 30vol% slurry that the powder of embodiment 4 and the powder of comparative example form respectively solid content, contrast both viscosity and shear-stress with the curve of shear rate change, referring to attached 1 and Fig. 2, wherein 1# powder is that (pH of final filtrate is 3.65 for the powder of example 4, specific conductivity κ=67.5 μ S/cm), 2# powder is the boron carbide powder (pH=4.39 of final filtrate, specific conductivity κ=29.5 μ S/cm) of comparative example.From Fig. 1 and Fig. 2, can find out, within the scope of whole shearing, the viscosity of the powder after pickling and shear-stress, all lower than the powder without pickling, illustrate that pickling contributes to improve the dispersiveness of powder.
Industrial applicability: method technique of the present invention is simply controlled, cost is low, environmental friendliness, be applicable to commercial scale production, and the powder purity obtaining by this law processing is high, good dispersity, can make by wet moulding the boron carbide ceramics of different shape, thereby have broad application prospects on aspect the neutron absorber material of high-abrasive material, lightweight armor material and nuclear industry.
Claims (7)
1. a surface treatment method for boron carbide powder, is characterized in that, comprising:
By boron carbide powder, water and sour well-mixed acid treatment operation, the consumption of wherein said acid is configured to make the pH value of mixture to be controlled at 0.5～3; The ageing operation of described mixture under specified temperature and in the ageing specified time; And filtration, gained filter cake or powder are washed to the washing step that filtrate pH value is 3～6;
Wherein, in described acid treatment operation, the mass ratio of described boron carbide powder and water is 6:1～1:7.5.
2. surface treatment method according to claim 1, is characterized in that, in described acid treatment operation, powder, acid and water mix in any way.
3. surface treatment method according to claim 2, is characterized in that, first mixes described boron carbide powder and water, then drips pH value to 0.5～3 of described acid to mixture.
4. surface treatment method according to claim 1, is characterized in that, described acid is sulfuric acid, nitric acid, hydrochloric acid or its any composition mixing acid.
5. surface treatment method according to claim 1, is characterized in that, described water is deionized water.
6. surface treatment method according to claim 1, is characterized in that, in described ageing: described specified temperature is 0～100 DEG C, the described specified time is 1～168 hour.
7. according to the surface treatment method described in any one in claim 1～6, it is characterized in that, also comprise lyophilize or at 80～200 DEG C, dry the drying process of filter cake after washing.
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|---|---|---|---|---|
| CN105466915B (en) * | 2014-08-21 | 2018-07-13 | 湖北航天化学技术研究所 | Boron carbide content assaying method in boron-propellant primary combustion product |
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