CN101817675B - Preparation method of boron nitride nanotube-intensified silicon oxide ceramic - Google Patents
Preparation method of boron nitride nanotube-intensified silicon oxide ceramic Download PDFInfo
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Abstract
The present invention relates to a preparation method of a boron nitride nanotube-intensified silicon oxide ceramic, which comprises the following steps of: A. pre-treating boron nitride nanotubes; B. weighing the boron nitride nanotubes and nano-grade and micron-grade silicon oxides; C. treating with different surface active agents; D. adding to a ball-milling pot, and compounding; E. drying, and screening; F. carrying out the hot pressed sintering in a multifunctional high-temperature sintering furnace in the shielding gas atmosphere; G. maintaining the temperature, then stopping heating, and naturally cooling to the room temperature; and H. machining the sintered ceramic block, and then testing the performance. The present invention is a method which effectively improves the mechanical property of the silicon oxide, and greatly improves the mechanical property of the silicon oxide. The bend strength of the boron nitride nanotube-intensified silicon oxide ceramic is up to 130MPa, and is 6.5 times higher than that of the pure silicon oxide ceramic (19.6MPa).The process improves the mechanical property of the silicon oxide ceramic, and has the advantages of simple process, stability, high safety, easy operation and large scale production.
Description
Technical field
The present invention relates to a kind of preparation method of SiO 2-ceramic, especially a kind of preparation method of boron nitride nanotube-intensified silicon oxide ceramic.
Background technology
Boron nitride nano-tube is stable on energy, has the wide energy gap of constant (being about 5.5eV), has high chemical stability and antioxidant property, and energy gap do not change with the change of the chirality and the pipe number of plies, and simultaneously its oxidizing temperature is up to 900 ℃.These advantages make it at aspects such as high temperature, high strength fibre, semiconductor materials, are especially obtaining application widely aspect the highly malleablized of stupalith.
Common ceramic toughening method comprises: phase toughness, whisker and particle malleableize, fiber malleableize, nano wire and nanotube malleableize etc.But phase transformation, whisker and particle malleableize effect are not obvious especially; The operation engineering of fiber malleableize is comparatively complicated, is not easy to operation, and the density of product is relatively poor simultaneously; At present a lot of people use carbon nanotube to come toughening ceramic, but the high temperature oxidation of carbon nanotube and at high temperature easily and body material its application that drawbacks limit such as reacted.
The mixing procedure of traditional ceramics is difficult to guarantee dispersed uniform, make the unstable properties of pottery, experiment conclusion repeatability is relatively poor, the utilization tensio-active agent disperses material, it is more even that boron nitride nano-tube is disperseed, silicon-dioxide powdery is difficult for reuniting, thereby makes the various performances of pottery more stable.
Application number is the following technology that discloses in 200910015758.1 Chinese patent application, its preparation method comprises and takes by weighing raw material, ball milling, sintering, insulation cooling and preparation finished product, but its mechanical milling process utilization is dry mixing process, and the mixed powder homogeneity is poor, influences the quality of product; Do not adopt protective atmosphere in the sintering process, influence the quality of product; And in the process of preparation finished product, efficient is low, and is of poor quality.
Summary of the invention
The objective of the invention is provides a kind of technological process simple for overcoming above-mentioned the deficiencies in the prior art, process stabilizing, and the process security is good, and the equipment easy handling is convenient to the preparation method of the boron nitride nanotube-intensified silicon oxide ceramic of scale operation.
For achieving the above object, the present invention adopts following technical proposals:
A kind of preparation method of boron nitride nanotube-intensified silicon oxide ceramic may further comprise the steps:
A. remove the impurity in the boron nitride nano-tube;
B. take by weighing material, take by weighing boron nitride nano-tube, nanometer grade silica and micron silica respectively with balance;
C. disperse, in load weighted boron nitride nano-tube, nanometer grade silica and micron silica, add different tensio-active agents respectively and carry out dispersion treatment, dispersion agent is ethanol, boron nitride nano-tube utilization ultra-sonic dispersion, nanometer grade silica and micron silica utilization dispersed with stirring;
D. batch mixing, boron nitride nano-tube, nanometer grade silica and micron silica after disperseing among the step C packed in the lump to add dehydrated alcohol in the planetary type ball-milling jar and carries out ball milling;
E. dry, sieve after the mixed powder that ball milling is good among the step D put into the loft drier drying;
F. hot pressed sintering places graphite jig with the mixed powder that sieves after the drying in the step e, and graphite jig is positioned in the multifunctional high-temperature sintering oven hot pressed sintering becomes ceramic block under protective atmosphere;
G. insulation cooling, mixed powder stops heating in the step F after hot pressed sintering becomes ceramic block, and graphite jig is incubated in the multifunctional high-temperature sintering oven, naturally cools to room temperature;
H. processing is surveyed its performance with the ceramic block of cool to room temperature among the step G after grinding machine and cutting machine processing.
In the described steps A in the boron nitride nano-tube removal of impurity be earlier the effective hydrochloric acid of boron nitride nanometer to be cleaned three times, use washed with de-ionized water then three times, put into loft drier again at 50 ℃ ± 5 ℃ dry 24h ± 1h down.
Boron nitride nano-tube, nanometer grade silica and micron silica mass ratio are among the described step B: 4 ~ 5:14 ~ 15:80 ~ 82.
The effective ultra-sonic dispersion of boron nitride nanometer among the described step C, its tensio-active agent is a cetyl trimethylammonium bromide, and the mass ratio of cetyl trimethylammonium bromide and boron nitride nano-tube is 4 ~ 4.5:95.5 ~ 96, dispersion medium ethanol volume is 100 ± 10ml;
Described nanometer grade silica and micron silica dispersed with stirring, its tensio-active agent is a sodium laurylsulfonate, and the mass ratio of sodium laurylsulfonate and nanometer grade silica and micron silica is 4 ~ 4.5:95.5 ~ 96, and dispersion medium ethanol volume is 100 ± 10ml.
The processing parameter of batch mixing is among the described step D: room temperature lower planet formula ball grinder rotating speed is 350 ± 5 r/min, and ball milling 10 ± 1 hours, alcoholic acid volume are 100 ± 10ml;
The drying process parameter is that drying temperature is 120 ± 5 ℃ in the described step e, and dry 120 ± 5min crosses 200 mesh sieves;
The processing parameter of hot pressed sintering is in the described step F: under argon gas atmosphere, be warming up to 1350 ± 10 ℃ with 25 ± 1 ℃/min, pressurization 25 ± 1MPa;
Soaking time is 90 ± 5min among the described step G.
Graphite jig in the step F of the present invention and multifunctional high-temperature sintering oven all are existing installations, the FVPHP-R-5 that produces of Japanese fuji electric wave company for example, specification FRET-20.
Beneficial effect of the present invention is: technological process is simple, stable, and the process security is good, and the equipment easy handling is convenient to scale operation.Because boron nitride nano-tube is easy to reunite, the present invention has adopted tensio-active agent to carry out dispersion treatment in order to overcome this shortcoming, and it is more even that mixed powder is mixed, and has given full play to the toughening effect of boron nitride nano-tube.
Compared with prior art, the present invention adopts the technology of ball milling wet mixing to carry out batch mixing, and it is more abundant that two kinds of powders are mixed.The present invention adopts protective atmosphere, can prevent the oxidation of boron nitride nano-tube, makes it remain tubular structure, has played good toughening effect.The present invention uses the multifunctional high-temperature sintering oven to carry out hot pressed sintering, has improved ceramic density, thereby has improved its flexural strength.Finally, the present invention makes the flexural strength of boron nitride nanotube-intensified silicon oxide ceramic reach 130MPa, improves 6.5 times more than than the pure silicon dioxide pottery.
Description of drawings
Fig. 1 strengthens the x-ray diffraction pattern of silicon dioxide base pottery and pure silicon dioxide ceramics sample for boron nitride nano-tube;
Fig. 2, Fig. 3 are respectively scanning electron microscope (SEM) shape appearance figure of sample.
Embodiment
The present invention is further described below in conjunction with drawings and Examples.
(a) is the 1g boron nitride nano-tube among Fig. 1, and 3g nanometer grade silica and 16g micron silica are ball-milling medium ball milling 10 hours with alumina balls, under argon gas atmosphere, 1350 ℃, pressurization 25MPa carries out hot pressed sintering, is incubated the x-ray diffraction pattern of the matrix material that makes after 1.5 hours.(b) is 3g nanometer grade silica and 16g micron silica among Fig. 1, with alumina balls is ball-milling medium ball milling 10 hours, under argon gas atmosphere, and 1350 ℃, pressurization 25MPa carries out hot pressed sintering, is incubated the x-ray diffraction pattern of the matrix material that makes after 1.5 hours.As can be seen from the figure silicon-dioxide all exists mutually with two kinds of things in two kinds of samples, be respectively quartzy mutually with cristobalite mutually, and pure SiO
2The mix height of boron nitride nano-tube of crystallization degree.
Fig. 2, Fig. 3 are the SEM photos of two kinds of sample fractures.From Fig. 2 is under argon gas atmosphere, and 1350 ℃, pressurization 25MPa carries out hot pressed sintering, and the SEM that be incubated the matrix material fracture that makes after 1.5 hours schemes, from photo as can be seen, pure SiO
2Crystal grain is more and do not have the obvious characteristics pattern, and the connection of intergranule only depends on bonding strength each other, so its intensity is very low.Fig. 3 is adding 5% boron nitride nano-tube, and under argon gas atmosphere, 1350 ℃, pressurization 25MPa carries out hot pressed sintering, is incubated the SEM figure of the matrix material fracture that makes after 1.5 hours.As can be seen from the figure boron nitride nano-tube is dispersed in the silica substrate uniformly, and can significantly find out nanotube extracting and distribution on crystal boundary in fracture place.In crack propagation process, boron nitride nano-tube since its preferably mechanical property can stop the continuation expansion of crackle, the deflection that perhaps cracks, nanotube extract and in the bridging of fracture place.These distribution modes all can consume the energy of crack propagation, thus the performance that effectively improved material.BN has inhibition SiO
2The effect of growing up of crystal grain, thus add massfraction be the SiO 2-ceramic of 5% boron nitride nano-tube under the same process condition, mechanical property has had raising by a relatively large margin than pure silicon dioxide pottery.
Embodiment 1: make wild phase, make matrix with nanometer grade silica and micron silica and prepare SiO 2-ceramic through hot pressed sintering with boron nitride nano-tube.
At first the effective analytically pure hydrochloric acid of boron nitride nanometer is cleaned three times, use washed with de-ionized water then three times, put into loft drier dry 23h under 45 ℃ again.
Take by weighing the 1g boron nitride nano-tube with electronic balance again, 3g nanometer grade silica and 16g micron silica, to adopt ultra-sonic dispersion after the boron nitride nano-tube pre-treatment, tensio-active agent is a cetyl trimethylammonium bromide, and the cetyl trimethylammonium bromide quality is 0.0416g, dispersion medium is an ethanol, and volume is 100ml.Silicon-dioxide dispersed with stirring, tensio-active agent are sodium laurylsulfonate, and the sodium laurylsulfonate quality is 0.7917g, and dispersion medium is an ethanol, and volume is 100ml; To disperse the back material to pack into to add dehydrated alcohol in the planetary type ball-milling jar to carry out ball mill mixing, the ball milling parameter is 350r/min under the room temperature, ball milling 10 hours.And scattered material put into loft drier at 120 ℃ of dry 120min of environment, cross 200 mesh sieves; Then mixed powder being placed diameter is the graphite jig of 42mm; adopt argon gas as protective atmosphere in multi-functional hot pressing sintering oven, be warming up to 1350 ℃ with 25 ℃/min, pressurization 25MPa carries out hot pressed sintering; stop heating behind the insulation 90min, make it in stove, naturally cool to room temperature.The pottery that sinters is obtained finished product after grinding machine and cutting machine processing.
Embodiment 2: make wild phase, make matrix with nanometer grade silica and micron silica and prepare SiO 2-ceramic through hot pressed sintering with boron nitride nano-tube.
At first the effective analytically pure hydrochloric acid of boron nitride nanometer is cleaned three times, use washed with de-ionized water then three times, put into loft drier dry 24h under 50 ℃ again.
Take by weighing the 0.8g boron nitride nano-tube with electronic balance again, 2.8g nanometer grade silica and 16.4g micron silica, to adopt ultra-sonic dispersion after the boron nitride nano-tube pre-treatment, tensio-active agent is a cetyl trimethylammonium bromide, and the mass ratio of cetyl trimethylammonium bromide and boron nitride nano-tube is 0.0333g, dispersion medium is an ethanol, and volume is 90ml.Silicon-dioxide dispersed with stirring, tensio-active agent are sodium laurylsulfonate, and the sodium laurylsulfonate quality is 0.8g, and dispersion medium is an ethanol, and volume is 90ml; To disperse the back material to pack into to add dehydrated alcohol in the planetary type ball-milling jar to carry out ball mill mixing, the ball milling parameter is 345r/min under the room temperature, ball milling 9 hours.And scattered material put into 115 ℃ of dry 115min of loft drier, cross 200 mesh sieves; Then mixed powder being placed diameter is the graphite jig of 42mm; adopt argon gas as protective atmosphere in multi-functional hot pressing sintering oven, be warming up to 1340 ℃ with 24 ℃/min, pressurization 24MPa carries out hot pressed sintering; stop heating behind the insulation 85min, make it in stove, naturally cool to room temperature.The pottery that sinters is obtained finished product after grinding machine and cutting machine processing.
Embodiment 3: make wild phase, make matrix with nanometer grade silica and micron silica and prepare SiO 2-ceramic through hot pressed sintering with boron nitride nano-tube.
At first the effective analytically pure hydrochloric acid of boron nitride nanometer is cleaned three times, use washed with de-ionized water then three times, put into loft drier dry 25h under 55 ℃ again.
Take by weighing the 0.9g boron nitride nano-tube with electronic balance again, 3g nanometer grade silica and 16.1g micron silica, to adopt ultra-sonic dispersion after the boron nitride nano-tube pre-treatment, tensio-active agent is a cetyl trimethylammonium bromide, and the mass ratio of cetyl trimethylammonium bromide and boron nitride nano-tube is 0.0625g, dispersion medium is an ethanol, and volume is 110ml.Silicon-dioxide dispersed with stirring, tensio-active agent are sodium laurylsulfonate, and the sodium laurylsulfonate quality is 1.1875g, and dispersion medium is an ethanol, and volume is 110ml; To disperse the back material to pack into to add dehydrated alcohol in the planetary type ball-milling jar to carry out ball mill mixing, the ball milling parameter is 355r/min under the room temperature, ball milling 11 hours.And scattered material put into 125 ℃ of dry 125min of loft drier, cross 200 mesh sieves; Then mixed powder being placed diameter is the graphite jig of 42mm; adopt argon gas as protective atmosphere in multi-functional hot pressing sintering oven, be warming up to 1360 ℃ with 26 ℃/min, pressurization 26MPa carries out hot pressed sintering; stop heating behind the insulation 95min, make it in stove, naturally cool to room temperature.The pottery that sinters is obtained finished product after grinding machine and cutting machine processing.
Claims (6)
1. the preparation method of a boron nitride nanotube-intensified silicon oxide ceramic is characterized in that, may further comprise the steps:
A. remove the impurity in the boron nitride nano-tube;
B. take by weighing material, take by weighing boron nitride nano-tube, nanometer grade silica and micron silica respectively with balance, described boron nitride nano-tube, nanometer grade silica and micron silica mass ratio are: 4 ~ 5:14 ~ 15:80 ~ 82;
C. disperse, in load weighted boron nitride nano-tube, add cetyl trimethylammonium bromide and carry out dispersion treatment, the mass ratio of described cetyl trimethylammonium bromide and boron nitride nano-tube is 4 ~ 4.5:95.5 ~ 96, in nanometer grade silica and micron silica, add sodium laurylsulfonate and carry out dispersion treatment, the mass ratio of described sodium laurylsulfonate and nanometer grade silica or micron silica is 4 ~ 4.5:95.5 ~ 96, dispersion agent is ethanol, the ethanol volume is 100 ± 10mL, boron nitride nano-tube utilization ultra-sonic dispersion, nanometer grade silica and micron silica utilization dispersed with stirring;
D. batch mixing, boron nitride nano-tube, nanometer grade silica and micron silica after disperseing among the step C packed in the lump to add dehydrated alcohol in the planetary type ball-milling jar and carries out ball milling;
E. dry, sieve after the mixed powder that ball milling is good among the step D put into the loft drier drying;
F. hot pressed sintering places graphite jig with the mixed powder that sieves after the drying in the step e, and graphite jig is positioned in the multifunctional high-temperature sintering oven hot pressed sintering becomes ceramic block under protective atmosphere;
G. insulation cooling, mixed powder stops heating in the step F after hot pressed sintering becomes ceramic block, and graphite jig is incubated in the multifunctional high-temperature sintering oven, naturally cools to room temperature;
H. processing is surveyed its performance with the ceramic block of cool to room temperature among the step G after grinding machine and cutting machine processing.
2. the preparation method of boron nitride nanotube-intensified silicon oxide ceramic according to claim 1 is characterized in that:
In the described steps A in the boron nitride nano-tube removal of impurity be earlier the effective hydrochloric acid of boron nitride nanometer to be cleaned three times, use washed with de-ionized water then three times, put into loft drier again at 50 ℃ ± 5 ℃ dry 24h ± 1h down.
3. the preparation method of boron nitride nanotube-intensified silicon oxide ceramic according to claim 1, it is characterized in that: the processing parameter of batch mixing is among the described step D: room temperature lower planet formula ball grinder rotating speed is 350 ± 5 r/min, ball milling 10 ± 1h, alcoholic acid volume are 100 ± 10mL.
4. the preparation method of boron nitride nanotube-intensified silicon oxide ceramic according to claim 1, it is characterized in that: the drying process parameter is that drying temperature is 120 ± 5 ℃ in the described step e, dry 120 ± 5min crosses 200 mesh sieves.
5. the preparation method of boron nitride nanotube-intensified silicon oxide ceramic according to claim 1 is characterized in that:
The processing parameter of hot pressed sintering is in the described step F: under argon gas atmosphere, be warming up to 1350 ± 10 ℃ with 25 ± 1 ℃/min, pressurization 25 ± 1MPa.
6. the preparation method of boron nitride nanotube-intensified silicon oxide ceramic according to claim 1, it is characterized in that: soaking time is 90 ± 5min among the described step G.
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| CN104984401B (en) * | 2015-07-22 | 2018-05-29 | 成都大学 | A kind of preparation method of temperature-sensitive hydrogel/tricalcium phosphate material |
| JP6683485B2 (en) * | 2016-01-28 | 2020-04-22 | 積水化学工業株式会社 | Boron nitride nanotube material and thermosetting material |
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