CN108863355A - A kind of preparation method for the modified Nano zirconium oxide being used to prepare high-strength ceramic - Google Patents
A kind of preparation method for the modified Nano zirconium oxide being used to prepare high-strength ceramic Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of modified Nano zirconium oxide for being used to prepare high-strength ceramic, include the following steps：It prepares and contains zirconium solution；B, preparation pretreatment carbon nanotube；C, zirconium dioxide matrix is prepared；D, zirconium dioxide matrix is heat-treated under nitrogen protection, obtains modified Nano zirconium oxide.The preparation method of nano zircite provided by the invention is raw material using zirconium chloride, and the carbon nanotube being modified in preparation process can be obviously improved the stability of zirconium oxide, when being used to prepare ceramics, has very high mechanical strength and dimensional stability.
Description
Technical field
The invention belongs to field of nanometer material technology, belong to nano modified inorganic field of non-metallic materials, and in particular to Yi Zhongyong
In the preparation method for the modified Nano zirconium oxide for preparing high-strength ceramic.
Background technique
Nano zircite has the characteristics that thermal shock resistance is strong, high temperature resistant, chemical stability are good, Material cladding is prominent.It will
Nano zircite and other materials（Al2O3 、SiO2）It is compound, the performance parameter of material can be greatlyd improve, its fracture is improved
Toughness, bending strength etc..Therefore, nano zirconium dioxide is not only applicable to structural ceramics and function ceramics field, is also applied to mention
The surface characteristic of highly metallic material（Heat conductivity, thermal shock resistance, high temperature oxidation resistance etc.）.
Currently, zirconium oxide, used also as ceramic additive, still, there are three types of crystal habits for zirconium oxide：Monocline, is stood at four directions
Prismatic crystal phase, there is also differences, directly addition will cause product or glaze paint for volume in the conversion process for the zirconium oxide of different shape
Cracking, influence the quality of product, now, promoted when aoxidizing modified zirconia often through metal oxide etc. is added wherein
The stability of zirconium oxide often adds yttrium nitrate as stabilizer during the preparation process now, and dosage is larger, yttrium nitrate tool
There is extremely strong toxicity, easily occur harmful by-products during processing and in by-product, there is harmfulness to environment and operator.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of modified Nano zirconium oxide for being used to prepare high-strength ceramic, lead to
The adjustment to nano zircite preparation method is crossed, the stability of zirconium oxide is improved, meanwhile, improve the dispersion of nano zircite
Property, it ensure that intensity and high temperature resistance.
The invention is realized by the following technical scheme：
A kind of preparation method for the modified Nano zirconium oxide being used to prepare high-strength ceramic, includes the following steps：
A, take by weight 100 parts of zirconium chloride, 400 parts of dehydrated alcohol, 20 parts of anhydrous acetic acid be put into container, use magnetic stirring apparatus
Stir 30-60min；
B, treatment fluid is prepared, treatment fluid is made of following component by weight：0.8 part of silane coupling agent, 0.05 part of lanthanum nitrate, ten
0.7 part of dialkyl sulfonates, 1 part of oxalic acid, 30 parts of water are mixed 20min, obtain treatment fluid, take 8 parts of carbon nanotube to be added
It states in treatment fluid, using ultrasonication 60-81min, then mixed liquor is evaporated using vacuum rotary evaporator, obtains pre- place
Manage carbon nanotube；The application handles carbon nanotubes using coupling agent, lanthanum nitrate etc., utilizes the good stability of carbon nanotubes and huge
Big specific surface area and adsorptivity can have preferably complexing and suction-operated to zirconia base, rise in subsequent processing
To stabilized zirconia structure, meanwhile, it can be used as skeleton, nano zircite enable to be dispersed in the frame week of carbon nanotube composition
Side promotes the intensity of material, still, and can keep the laxity of nano zircite.
C, pretreatment carbon nanotube made from step b is mixed with the obtained mixture of step a, with turning for 1000r/min
Speed stirring 30min, then ultrasonic vibration 20min, is added dropwise the sodium hydroxide solution of 2mol/L thereto, constantly makes during being added dropwise
It is handled with ultrasonic oscillation, until solution PH is that 8.2 stoppings are added dropwise, is filtered, washing obtains zirconium dioxide matrix；
In this step, it by processing, is dispersed in zirconium ion in carbon nanotube, forms stable bonding structure, then carry out
Heat treatment, it is ensured that nano zircite keeps good mechanical property and shatter value after heat treatment, promotes the performance used.By
There is porous structure in carbon nanotube, after adding treatment fluid, the ingredient in treatment fluid can be inhaled with good dispersing agent
Attached effect, solution mesoxalic acid also can be adsorbed on pore surface by the chemical bonds such as hydrogen bond and suction-operated, after being evaporated, also
When containing zirconium solution can then be added with residual fraction oxalate, zirconium ion and oxalate is complexed, can zirconium more uniformly be divided
It is dispersed in around carbon nanotube, lye is then added, wash, the mutually exclusive work of polarity in zirconium oxide nucleation process due to oxalic acid
With playing the role of steric hindrance to reunion, so that nano zircite more refines, dispersibility is more preferable, when preparation ceramics, pottery can be improved
The consistency of ceramic material.
D, zirconium dioxide matrix is heat-treated under nitrogen protection, obtains modified Nano zirconium oxide.
In step d, heat treatment temperature is 380-420 DEG C, heat treatment time 2h.
In step d in heat treatment step, zirconium dioxide matrix is first heated to 150 DEG C, increasing extent of temperature is 3 DEG C/min,
20min is kept the temperature, is then ground into fine powder using airflow milling, 400 DEG C is being continuously heating to, is keeping the temperature 2h.It further avoids sintered
It agglomerates in journey, promotes treatment effect.
The carbon nanotube passes through modification, and processing step is as follows（1）, prepare modification liquid, modification liquid is methyl-silicone oil
With ethylene glycol by weight 1:6 are made；
（2）, by carbon nanotube be added modification liquid in, be ultrasonically treated 2h, be then evaporated under reduced pressure, remove solvent, then at 50-60 DEG C
Lower drying；
（3）, by step（2）The raw material handled well is placed in high temperature process furnances, is warming up to 460 DEG C, isothermal holding 30min, then
490 DEG C are warming up to the speed of 3 DEG C/min, 60min is kept the temperature, obtains surface-modified carbon nanotubes；It can guarantee at this temperature
The structure of carbon nanotube, meanwhile, the speed that Si oxide is deposited in carbon nano tube surface is able to ascend by the way of gradually heating up
Degree and uniformity.Processing is modified to carbon nanotube in the application, it is fully dispersed rear high using methyl-silicone oil and carbon nanotube
Temperature processing, makes carbon nanotube surface layer generate the oxide of silicon, under the premise of guaranteeing that carbon nanotube is porous, improves material
Intensity and heat resistance.
System pressure is 0.02MPa in the step d.
Silane coupling agent is KH550 in the step b.
A kind of ceramic preparation is as follows：It uses the zirconium oxide in each embodiment as basis material respectively, is then added
The colorant of the binder of zirconium oxide weight 4%, zirconium oxide weight 0.5%, the binder be paraffin and polyvinyl alcohol by weight
Than 2：3 are mixed, and ceramic idiosome is then made, and are then sintered molding to idiosome, when sintering, are first warming up to 230 DEG C of guarantors
Temperature processing 1h, is then warming up to 580 DEG C with the heating rate of 6 DEG C/min, keeps the temperature 20min, then be warming up to 780 DEG C with 8 DEG C/min,
30min is kept the temperature, is then warming up to 1200 DEG C with the speed of 2.5 DEG C/min, keeps the temperature 2h, then be warming up to the speed of 2 DEG C/min
1460 DEG C, 20min is kept the temperature, then be warming up to 1650 DEG C, keeps the temperature 50min, obtain ceramics.The colorant is coloured using Vanadium zirconium blue
Agent.
Beneficial effects of the present invention：The preparation method of nano zircite provided by the invention is raw material, system using zirconium chloride
Modified carbon nanotube, can be obviously improved the stability of zirconium oxide, not need that other stabilizers are additionally added during standby, and
And modified carbon nano-tube has good intensity and dispersibility, when being used to prepare ceramics, has very high mechanical strength and ruler
Very little stability, meanwhile, the dispersion performance of the nano zircite of the application preparation is good, and it is higher with the compatibility of other materials, it can
Suitable for ceramics, the intensity and consistency of ceramics can be obviously improved.Due to carbon nanotube therein have it is good dispersibility and
Hydrotropy, the compound several functions composition of zirconium oxide energy of preparation, is further improved, significantly conducive to the performance to zirconium oxide
Improve the use scope of material.
Specific embodiment
Embodiment 1
A kind of preparation method for the modified Nano zirconium oxide being used to prepare high-strength ceramic, includes the following steps：
A, take by weight 100 parts of zirconium chloride, 400 parts of dehydrated alcohol, 20 parts of anhydrous acetic acid be put into container, use magnetic stirring apparatus
Stir 30-60min；
B, treatment fluid is prepared, treatment fluid is made of following component by weight：0.8 part of silane coupling agent, 0.05 part of lanthanum nitrate, ten
0.7 part of dialkyl sulfonates, 1 part of oxalic acid, 30 parts of water are mixed 20min, obtain treatment fluid, take 8 parts of carbon nanotube to be added
It states in treatment fluid, using ultrasonication 60-81min, then mixed liquor is evaporated using vacuum rotary evaporator, obtains pre- place
Manage carbon nanotube；
C, pretreatment carbon nanotube made from step b is mixed with the obtained mixture of step a, is stirred with the revolving speed of 1000r/min
30min is mixed, then ultrasonic vibration 20min, the sodium hydroxide solution of 2mol/L is added dropwise thereto, continued on during being added dropwise super
Sound wave shock processing filters, washing obtains zirconium dioxide matrix until solution PH is that 8.2 stoppings are added dropwise；
D, zirconium dioxide matrix is heat-treated under nitrogen protection, obtains modified Nano zirconium oxide.
In step d in heat treatment step, zirconium dioxide matrix is first heated to 150 DEG C, increasing extent of temperature is 3 DEG C/min,
20min is kept the temperature, is then ground into fine powder using airflow milling, 400 DEG C is being continuously heating to, is keeping the temperature 2h.
The carbon nanotube passes through modification, and processing step is as follows（1）, prepare modification liquid, modification liquid is methyl-silicone oil
With ethylene glycol by weight 1:6 are made；
（2）, by carbon nanotube be added modification liquid in, be ultrasonically treated 2h, be then evaporated under reduced pressure, remove solvent, then at 50-60 DEG C
Lower drying；
（3）, by step（2）The raw material handled well is placed in high temperature process furnances, is warming up to 460 DEG C, isothermal holding 30min, then
490 DEG C are warming up to the speed of 3 DEG C/min, 60min is kept the temperature, obtains surface-modified carbon nanotubes.
Embodiment 2
A kind of preparation method for the modified Nano zirconium oxide being used to prepare high-strength ceramic, includes the following steps：
A, take by weight 100 parts of zirconium chloride, 400 parts of dehydrated alcohol, 20 parts of anhydrous acetic acid be put into container, use magnetic stirring apparatus
Stir 30-60min；
B, treatment fluid is prepared, treatment fluid is made of following component by weight：0.8 part of silane coupling agent, 0.05 part of lanthanum nitrate, ten
0.7 part of dialkyl sulfonates, 1 part of oxalic acid, 30 parts of water are mixed 20min, obtain treatment fluid, take 8 parts of carbon nanotube to be added
It states in treatment fluid, using ultrasonication 60-81min, then mixed liquor is evaporated using vacuum rotary evaporator, obtains pre- place
Manage carbon nanotube；
C, pretreatment carbon nanotube made from step b is mixed with the obtained mixture of step a, is stirred with the revolving speed of 1000r/min
30min is mixed, then ultrasonic vibration 20min, the sodium hydroxide solution of 2mol/L is added dropwise thereto, continued on during being added dropwise super
Sound wave shock processing filters, washing obtains zirconium dioxide matrix until solution PH is that 8.2 stoppings are added dropwise；
D, zirconium dioxide matrix is heat-treated under nitrogen protection, obtains modified Nano zirconium oxide.
In step d in heat treatment step, zirconium dioxide matrix is first heated to 150 DEG C, increasing extent of temperature is 3 DEG C/min,
20min is kept the temperature, is then ground into fine powder using airflow milling, 400 DEG C is being continuously heating to, is keeping the temperature 2h.
Embodiment 3
A kind of preparation method for the modified Nano zirconium oxide being used to prepare high-strength ceramic, includes the following steps：
A, take by weight 100 parts of zirconium chloride, 400 parts of dehydrated alcohol, 20 parts of anhydrous acetic acid be put into container, use magnetic stirring apparatus
Stir 30-60min；
B, treatment fluid is prepared, treatment fluid is made of following component by weight：0.8 part of silane coupling agent, 0.05 part of lanthanum nitrate, ten
0.7 part of dialkyl sulfonates, 1 part of oxalic acid, 30 parts of water are mixed 20min, obtain treatment fluid, take 8 parts of carbon nanotube to be added
It states in treatment fluid, using ultrasonication 60-81min, then mixed liquor is evaporated using vacuum rotary evaporator, obtains pre- place
Manage carbon nanotube；The application handles carbon nanotubes using coupling agent, lanthanum nitrate etc., utilizes the good stability of carbon nanotubes and huge
Big specific surface area and adsorptivity can have preferably complexing and suction-operated to zirconia base, rise in subsequent processing
To stabilized zirconia structure, meanwhile, it can be used as skeleton, nano zircite enable to be dispersed in the frame week of carbon nanotube composition
Side promotes the intensity of material, still, and can keep the laxity of nano zircite.
C, pretreatment carbon nanotube made from step b is mixed with the obtained mixture of step a, with turning for 1000r/min
Speed stirring 30min, then ultrasonic vibration 20min, is added dropwise the sodium hydroxide solution of 2mol/L thereto, constantly makes during being added dropwise
It is handled with ultrasonic oscillation, until solution PH is that 8.2 stoppings are added dropwise, is filtered, washing obtains zirconium dioxide matrix；
D, zirconium dioxide matrix is heat-treated under nitrogen protection, treatment temperature is 400 DEG C, obtains modified Nano zirconium oxide.
The carbon nanotube passes through modification, and processing step is as follows（1）, prepare modification liquid, modification liquid is methyl-silicone oil
With ethylene glycol by weight 1:6 are made；
（2）, by carbon nanotube be added modification liquid in, be ultrasonically treated 2h, be then evaporated under reduced pressure, remove solvent, then at 50-60 DEG C
Lower drying；
（3）, by step（2）The raw material handled well is placed in high temperature process furnances, is warming up to 460 DEG C, isothermal holding 30min, then
490 DEG C are warming up to the speed of 3 DEG C/min, 60min is kept the temperature, obtains surface-modified carbon nanotubes.
Embodiment 4
A kind of preparation method for the modified Nano zirconium oxide being used to prepare high-strength ceramic, includes the following steps：
A, take by weight 100 parts of zirconium chloride, 400 parts of dehydrated alcohol, 20 parts of anhydrous acetic acid be put into container, use magnetic stirring apparatus
Stir 30-60min；
B, treatment fluid is prepared, treatment fluid is made of following component by weight：0.8 part of silane coupling agent, 0.05 part of lanthanum nitrate, ten
0.7 part of dialkyl sulfonates, 1 part of oxalic acid, 30 parts of water are mixed 20min, obtain treatment fluid, take 8 parts of carbon nanotube to be added
It states in treatment fluid, using ultrasonication 60-81min, then mixed liquor is evaporated using vacuum rotary evaporator, obtains pre- place
Manage carbon nanotube；The application handles carbon nanotubes using coupling agent, lanthanum nitrate etc., utilizes the good stability of carbon nanotubes and huge
Big specific surface area and adsorptivity can have preferably complexing and suction-operated to zirconia base, rise in subsequent processing
To stabilized zirconia structure, meanwhile, it can be used as skeleton, nano zircite enable to be dispersed in the frame week of carbon nanotube composition
Side promotes the intensity of material, still, and can keep the laxity of nano zircite.
C, pretreatment carbon nanotube made from step b is mixed with the obtained mixture of step a, with turning for 1000r/min
Speed stirring 30min, then ultrasonic vibration 20min, is added dropwise the sodium hydroxide solution of 2mol/L thereto, constantly makes during being added dropwise
It is handled with ultrasonic oscillation, until solution PH is that 8.2 stoppings are added dropwise, is filtered, washing obtains zirconium dioxide matrix；
D, zirconium dioxide matrix is heat-treated under nitrogen protection, treatment temperature is 400 DEG C, obtains modified Nano zirconium oxide.
Comparative example 1
Compared with Example 1, carbon nanotube is not used.
Comparative example 2
Compared with Example 1, carbon nanotube is handled without using the treatment fluid in step b.
Comparative example 3
Compared with Example 1, oxalic acid is added without in the treatment fluid in step b.
Comparative example 4
The stabilization tetragonal zirconium dioxide containing yttrium oxide of conventional method preparation.
In order to verify influence of the nano zircite to manufactured ceramic performance in each embodiment, the application is each using the present invention
The nano zircite prepared in embodiment and comparative example is prepared into ceramics.
Experiment 1
Ceramics are prepared using the method recorded in description of the invention, then test the performance of the ceramics of each group raw material preparation, respectively
Group sample structure such as table 1；
Table 1
Note：Color uniformity degree is indicated using the quantity of * in table 1, and * quantity illustrates that color is more uniform.
As shown in Table 1, there is better intensity and hardness using ceramics prepared by the application method, moreover, ceramic dense
Degree is high, and surface is flawless, and quality is obviously improved.
Experiment 2
In order to verify in the application respectively implement in influence of the modified Nano zirconium oxide to ceramic color stability is prepared, design with
Lower experiment sprays quality in processing environment by the ceramics of preparation respectively using 36h is handled respectively at 200 DEG C, 500 DEG C, 800 DEG C
The light salt brine of score 0.5%, statistics ceramic color variation, as a result such as table 2：
Note：With +++ ++ it indicates initial color, is indicated after color is thin out or discoloration with reduction+quantity ,+illustrate color more
Conservation rate is higher.
There is table 2 it is found that the ceramics of the present processes preparation have better face with ceramics prepared by nano zirconium dioxide
Color keeps effect.
Experiment 3
In order to verify the influence in the application to heat resistance after carbon nano-tube modification, tested as follows, statistics each group is weightless
Rate, as a result such as table 3：
Experimental group 1
Use the scheme of modified carbon nano-tube in embodiment 1.
Experimental group 2
The carbon nanotube passes through modification, and processing step is as follows（1）, prepare modification liquid, modification liquid is methyl-silicone oil and second
Glycol is by weight 1:6 are made；
（2）, by carbon nanotube be added modification liquid in, be ultrasonically treated 2h, be then evaporated under reduced pressure, remove solvent, then at 50-60 DEG C
Lower drying；
（3）, by step（2）The raw material handled well is placed in high temperature process furnances, is handled 120min at 490 DEG C, is obtained to surface and change
Property carbon nanotube.Other steps are the same as embodiment 1.
Experimental group 3
Carbon nanotube is without processing, other steps are the same as embodiment 1.
Table 3
Note：Data are weight-loss ratio at the corresponding temperature in table（%）；It is tested under aerobic conditions when test；
As shown in Table 3, the carbon nanotube high temperature resistance handled using the application mode is more preferable, due to heavy in carbon nano tube surface
The oxide for having accumulated silicon greatly improves the pyrolysis stability of carbon nanotube.
Claims (6)
1. a kind of preparation method for the modified Nano zirconium oxide for being used to prepare high-strength ceramic, which is characterized in that including following step
Suddenly：
A, take by weight 100 parts of zirconium chloride, 400 parts of dehydrated alcohol, 20 parts of anhydrous acetic acid be put into container, use magnetic stirring apparatus
Stir 30-60min；
B, treatment fluid is prepared, treatment fluid is made of following component by weight：0.8 part of silane coupling agent, 0.05 part of lanthanum nitrate, ten
0.7 part of dialkyl sulfonates, 1 part of oxalic acid, 30 parts of water are mixed 20min, obtain treatment fluid, take 8 parts of carbon nanotube to be added
It states in treatment fluid, using ultrasonication 60-81min, then mixed liquor is evaporated using vacuum rotary evaporator, obtains pre- place
Manage carbon nanotube；
C, pretreatment carbon nanotube made from step b is mixed with the obtained mixture of step a, is stirred with the revolving speed of 1000r/min
30min is mixed, then ultrasonic vibration 20min, the sodium hydroxide solution of 2mol/L is added dropwise thereto, continued on during being added dropwise super
Sound wave shock processing filters, washing obtains zirconium dioxide matrix until solution PH is that 8.2 stoppings are added dropwise；
D, zirconium dioxide matrix is heat-treated under nitrogen protection, obtains modified Nano zirconium oxide.
2. a kind of preparation method of modified Nano zirconium oxide for being used to prepare high-strength ceramic according to claim 1,
It is characterized in that：In step d, heat treatment temperature is 380-420 DEG C, heat treatment time 2h.
3. a kind of preparation method of modified Nano zirconium oxide for being used to prepare high-strength ceramic according to claim 1,
It is characterized in that：In step d in heat treatment step, zirconium dioxide matrix is first heated to 150 DEG C, increasing extent of temperature is 3 DEG C/min,
20min is kept the temperature, is then ground into fine powder using airflow milling, 400 DEG C is being continuously heating to, is keeping the temperature 2h.
4. a kind of preparation method of modified Nano zirconium oxide for being used to prepare high-strength ceramic according to claim 1,
It is characterized in that：The carbon nanotube passes through modification, and processing step is as follows（1）, prepare modification liquid, modification liquid is methyl-silicone oil
With ethylene glycol by weight 1:6 are made；
（2）, by carbon nanotube be added modification liquid in, be ultrasonically treated 2h, be then evaporated under reduced pressure, remove solvent, then at 50-60 DEG C
Lower drying；
（3）, by step（2）The raw material handled well is placed in high temperature process furnances, is warming up to 460 DEG C, isothermal holding 30min, then
490 DEG C are warming up to the speed of 3 DEG C/min, 60min is kept the temperature, obtains surface-modified carbon nanotubes.
5. a kind of preparation side for the modified Nano zirconium oxide for being used to prepare high-strength ceramic described in one of -4 according to claim 1
Method, it is characterised in that：System pressure is 0.02MPa in the step d.
6. a kind of preparation method of modified Nano zirconium oxide for being used to prepare high-strength ceramic according to claim 1,
It is characterized in that, silane coupling agent is KH550 in the step b.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149643A (en) * | 2021-03-13 | 2021-07-23 | 珠海美尔晶义齿科技有限公司 | High-strength ceramic false tooth and preparation method thereof |
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| CN114516754A (en) * | 2021-12-27 | 2022-05-20 | 湘潭顺络电子有限公司 | Ultrahigh-strength high-toughness low-density zirconia ceramic and preparation method and application thereof |
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