CN106191902A - A kind of method preparing hydrogen doping oxide ceramics micro Nano material - Google Patents
A kind of method preparing hydrogen doping oxide ceramics micro Nano material Download PDFInfo
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- CN106191902A CN106191902A CN201610615695.3A CN201610615695A CN106191902A CN 106191902 A CN106191902 A CN 106191902A CN 201610615695 A CN201610615695 A CN 201610615695A CN 106191902 A CN106191902 A CN 106191902A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
A kind of method preparing hydrogen doping oxide ceramics micro Nano material, belongs to field of inorganic nonmetallic material.The present invention uses cathode plasma electrolysis tech, with metal salt solution as electrolyte, adds a certain amount of water soluble polymer and modifying agent；The metal or alloy of inert electrode or corresponding slaine is anode material, with the single metals such as titanium, aluminum, ferrum or titanium, aluminum, ferrum combination alloy as cathode material；Apply certain voltage make cathode surface and plasma discharge around occurs, afterwards product cathode surface and around deposit, portion of product is splashed in electrolyte through effects such as bombardments, purified, dry etc. process obtains having even particle size distribution, the nanometer of the features such as specific surface area is big and the ceramic oxide particle of micro-meter scale.Compared with other conventional powder technologies of preparing, preparation method of the present invention is simple, and disposable input cost is low, and will prepare the multi-step integrated steps of reaction such as hydroxide, high temperature sintering and hydrogenation treatment, shorten preparation flow, prepare the micro Nano material that hydrogen doping is modified efficiently.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, refer to one and utilize liquid phase cathode plasma electrolysis tech system
The method of standby hydrogen doping oxide ceramics micro Nano material.
Background technology
Oxide structure pottery is that development is compared early and a widely used class ceramic material, have high intensity, high temperature resistant,
Antioxidation and the performance such as good chemical stability and electrical insulating property.Oxide ceramics is various in style, and purposes is extremely wide, can make
For structural material, functional material and high grade refractory.And there is the oxide ceramics of micro nano structure due to its specific surface area
Greatly, surface activity high, be more widely used in electronics, information, laser, infrared, computer, aerospace, atomic energy, change
Many fields such as work, metallurgy.
Doping is performance control measures conventional in oxide ceramics research, the research work that hydrogen adulterates in oxide material
Make seldom.Traditionally, material is acted on and typically mainly studies the hydrogen embrittlement in metal material, hydrogen induced cracking and fracture by hydrogen
Deng harm.And in recent years, atomic hydrogen doped oxide material is modified as an emerging research field, in the world by more
Carry out the most academic concerns.Some that oxide material prepared by conventional method do not has can be obtained by atomic hydrogen modification
Peculiar performance, such as TiO2Deng the change of device for Optical Properties of Materials, and Al2O3, the significantly changing of the material electric property such as ZnO.
Hydrogen and isotope thereof, to the physical chemistry combined process that the doping process of solid material is a kind of complexity, comprise and are
Arrange the independent of one another and physic-chemical changes that is mutually related.The processing mode realizing hydrogen doping typically has two kinds: at high temperature gas phase hydrogen
Reason and electrochemical hydrogen process.During high temperature gas phase hydrogen processes, it is generally required to first carry out application of vacuum, it is passed through the hydrogen of certain pressure intensity afterwards
Gas, carries out a few hours even days of heat treatment at relatively high temperatures；During electrochemical hydrogen processes, it is generally required to first sample is made
Electrode, if the poorly conductive of material also needs to carry out pretreatment, puts into the electrochemical hydrogen carrying out a couple of days in solution afterwards by sample
Process.Both the above method is all on the basis of preparing pottery, then carries out long period and more complicated hydrogenation treatment.
Patent of invention " method (the ZL of a kind of liquid phase cathode plasma electrolytic preparation aluminum oxide micro-sphere powder
201510587893.9) " propose to utilize cathode plasma technology to prepare aluminum oxide micro-sphere, but this kind of method is for aluminum oxide micro-sphere
Preparation time, be only applicable to prepare the relatively simple microsphere of 26S Proteasome Structure and Function, and the oxide ceramics that can not expand to other be micro-
Nano material, more without reference to the hydrogen doping impact on oxide ceramics micro Nano material.
Summary of the invention
The purpose of the present invention is to propose to a kind of collect that ceramic is standby and hydrogenation treatment prepares hydrogen doping oxidation in the method for a step
Thing pottery micro Nano material.The method uses cathode plasma electrolysis tech, is possible not only to prepare the modification of multiple hydrogen doping
Oxide ceramics micro Nano material, and have and prepare simple, cost-effective feature.
The present invention, with metal salt solution as electrolyte, adds a certain amount of water soluble polymer, heats electrolyte
Process；The metal or alloy of inert electrode or corresponding slaine is anode material, with the single metals such as titanium, aluminum, ferrum or titanium, aluminum,
The alloy of ferrum combination is cathode material；Apply certain voltage make cathode surface and plasma discharge around occur, the most instead
Answer product cathode surface and around deposit, portion of product is splashed in electrolyte through the effect such as bombardment, purified, be dried etc.
Reason obtains the micro-nano product of oxide ceramics.
The concrete grammar of the present invention is as follows:
Select one or more metal salt solutions as electrolyte, including titanium sulfate, zirconium nitrate, Yttrium trinitrate, ferric nitrate or sulphuric acid
Ferrum, aluminum nitrate, nitric acid stannum, Lanthanum (III) nitrate, zinc nitrate or zinc sulfate etc., and the mixing of above-mentioned several slaine, control slaine
Solution concentration is 5～500g/L；Control the cathode material area ratio with anode material less than 1:1；During cathode plasma electrolysis, adopt
With the pulse power or DC source, controlling voltage is 50～300V, when using the pulse power, and frequency 100～1000Hz, dutycycle
10%～90%；Control the response time in 2min and above time.
Described water soluble polymer is polyvinyl alcohol, or Polyethylene Glycol, or polyethylene glycol oxide, or polyvinylpyrrolidone,
Addition is between 2g/L～50g/L.
The temperature range of described electrolyte heat treated is 20 ~ 100 DEG C, and the process time is 0.5 ~ 10 hour.
Described inert electrode selects graphite or platinized platinum.
Described purification, be dried be by cathode plasma electrolysis process after electrolyte, through standing obtain bottom turbid solution
Or direct centrifugal treating, through water and alcohol washes for several times, it is dried in drying baker afterwards and collects, obtain the oxide doped with hydrogen
Pottery micro Nano material.
It is an advantage of the current invention that:
(1) cathode hydrogen evolution reaction and energy of plasma are made full use of, under conditions of being not required to extra hydrogenation treatment, in the solution
Prepare even particle size distribution, the hydrogen doping oxide ceramics that specific surface area is big and the physical and chemical performance such as optics, electricity is excellent
Micro Nano material.
(2) electrolyte carries out heating etc. process, or add water soluble polymer, or through above two-step pretreatment, can drop
Electric current density in low cathode plasma electrolytic process, it is achieved prepared by low-power consumption.
(3) the method preparation is simple, and disposable input cost is low, and will prepare hydroxide, sintering and hydrogenation treatment
React an integrated step Deng multi-step, shorten preparation flow, prepare the micro Nano material that hydrogen doping is modified efficiently.
Accompanying drawing explanation
Fig. 1 is the pattern of hydrogen doping titanium dioxide micro-nano material in embodiment 1.
Fig. 2 is the pattern of hydrogen doping zirconium dioxide micro Nano material in embodiment 2.
Specific embodiment
Below in conjunction with embodiment, technical scheme is further illustrated.
Embodiment 1
Selection titanium sulfate solution is electrolyte, and controlled concentration is at 150g/L；Add 20g/L Polyethylene Glycol, electrolyte is carried out 20
DEG C, the process of 0.5 hour.With titanium alloy as negative electrode, platinized platinum is anode, and ratio of cathodic to anodic area is 1:3.Use the pulse power, control
Voltage 60 ~ 120V processed, frequency 500Hz, dutycycle 60%.The control response time is 10min, carries out cathode plasma cell reaction.
By reacted electrolyte, obtain bottom turbid solution through standing, process (4000 revs/min) by centrifugation, and with water and ethanol
Clean for several times, product be dried in drying baker collect afterwards, obtain titanium dioxide ceramic micro Nano material doped with hydrogen (as
Shown in Fig. 1).After testing, the hydrogen content in product is about 1.89ppm.
Embodiment 2
Selecting five nitric hydrate zirconium solutions is electrolyte, and controlled concentration is at 300g/L；Add 20g/L Polyethylene Glycol, to electrolyte
Carry out 80 DEG C, the process of 4 hours.With titanium alloy as negative electrode, platinized platinum is anode, and ratio of cathodic to anodic area is 1:4.Employing pulse electricity
Source, controls voltage 70 ~ 140V, frequency 500Hz, dutycycle 60%.The control response time is 30min, carries out cathode plasma electrolysis
Reaction.By reacted electrolyte, obtain bottom turbid solution through standing, process (4000 revs/min) by centrifugation, and with water and
Product for several times, is dried in drying baker and collects, obtain the micro-nano material of the zirconia ceramic doped with hydrogen by alcohol washes afterwards
Material (as shown in Figure 2).After testing, the hydrogen content in product is about 52.54ppm.
Embodiment 3
Selecting Fe(NO3)39H2O solution is electrolyte, and controlled concentration is at 300g/L；Add 15g/L polyvinylpyrrolidone, right
Electrolyte carries out 20 DEG C, the process of 0.5 hour.With rustless steel as negative electrode, platinized platinum is anode, and ratio of cathodic to anodic area is 1:2.Use
The pulse power, controls voltage 60 ~ 120V, frequency 500Hz, dutycycle 40%.The control response time is 10min, carry out negative electrode etc. from
Sub-cell reaction.By reacted electrolyte, obtain bottom turbid solution through standing, process (4000 revs/min) by centrifugation, and
With water and alcohol washes for several times, product is dried in drying baker collects afterwards, obtain the iron oxide ceramics micro-nano doped with hydrogen
Rice material.
Embodiment 4
Selecting zinc nitrate hexahydrate solution is electrolyte, and controlled concentration is at 300g/L；Add 20g/L Polyethylene Glycol, to electrolyte
Carry out 20 DEG C, the process of 0.5 hour.With titanium alloy as negative electrode, platinized platinum is anode, and ratio of cathodic to anodic area is 1:4.Employing pulse electricity
Source, controls voltage 70 ~ 120V, frequency 500Hz, dutycycle 80%.The control response time is 10min, carries out cathode plasma electrolysis
Reaction.By reacted electrolyte, obtain bottom turbid solution through standing, process (4000 revs/min) by centrifugation, and with water and
Product for several times, is dried in drying baker and collects, obtain the zinc oxide ceramics micro Nano material doped with hydrogen by alcohol washes afterwards.
Embodiment 5
Selecting five nitric hydrate zirconiums and six nitric hydrate samarium mixed solutions is electrolyte, controlled concentration be respectively 257.6g/L and
266.7g/L；Add 20g/L polyvinylpyrrolidone, electrolyte is carried out 60 DEG C, the process of 4 hours.With titanium alloy as negative electrode,
Platinized platinum is anode, and ratio of cathodic to anodic area is 1:4.Use the pulse power, control voltage 100 ~ 170V, frequency 500Hz, dutycycle
60%.The control response time is 20min, carries out cathode plasma cell reaction.By reacted electrolyte, obtain through standing
Bottom turbid solution, processes (4000 revs/min) by centrifugation, and with water and alcohol washes for several times, afterwards by product in drying baker
It is dried and collects, obtain the samarium zirconate pottery micro Nano material doped with hydrogen.
Claims (6)
1. the method preparing hydrogen doping oxide ceramics micro Nano material, it is characterised in that: with metal salt solution for electrolysis
Liquid, adds a certain amount of water soluble polymer, and electrolyte is carried out heat treated；Inert electrode or the metal of corresponding slaine or
Alloy is anode material, with titanium, aluminum, the single metal of ferrum or titanium, aluminum, ferrum combination alloy as cathode material；Apply certain electricity
Pressure makes cathode surface and plasma discharge around occurs, and product is at cathode surface and around deposition, portion of product afterwards
Being splashed in electrolyte through the effect such as bombardment, the process such as purified, dry obtains the micro-nano product of oxide ceramics.
The method preparing hydrogen doping oxide ceramics micro Nano material the most as claimed in claim 1, it is characterised in that: specifically side
Method be select one or more metal salt solutions as electrolyte, including titanium sulfate, zirconium nitrate, Yttrium trinitrate, ferric nitrate or sulphuric acid
Ferrum, aluminum nitrate, nitric acid stannum, Lanthanum (III) nitrate, zinc nitrate or zinc sulfate, and the mixing of above-mentioned several slaine, control slaine molten
Liquid concentration is 5～500g/L；Control the cathode material area ratio with anode material less than 1:1；During cathode plasma electrolysis, use
The pulse power or DC source, controlling voltage is 50～300V, when using the pulse power, frequency 100～1000Hz, dutycycle
10%～90%；Control the response time in 2min and above time.
The method preparing hydrogen doping oxide ceramics micro Nano material the most as claimed in claim 1, it is characterised in that: described water
Soluble macromolecular is polyvinyl alcohol, or Polyethylene Glycol, or polyethylene glycol oxide, or polyvinylpyrrolidone, addition at 2g/L～
Between 50g/L.
The method preparing hydrogen doping oxide ceramics micro Nano material the most as claimed in claim 1, it is characterised in that: described electricity
The temperature range solving liquid heat treated is 20 ~ 100 DEG C, and the process time is 0.5 ~ 10 hour.
The method preparing hydrogen doping oxide ceramics micro Nano material the most as claimed in claim 1, it is characterised in that: described lazy
Property electrode select graphite or platinized platinum.
The method preparing hydrogen doping oxide ceramics micro Nano material the most as claimed in claim 1, it is characterised in that carry described in:
Pure, dry is the electrolyte after cathode plasma electrolysis being processed, and obtains bottom turbid solution or direct centrifugal treating through standing,
Through water and alcohol washes for several times, it is dried in drying baker afterwards and collects, obtain the oxide ceramics micro Nano material doped with hydrogen.
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| CN106929876A (en) * | 2017-05-02 | 2017-07-07 | 福建省建筑科学研究院 | The preparation method of metal oxide nano ball |
| CN107385485A (en) * | 2017-07-11 | 2017-11-24 | 北京科技大学 | Large area successive sedimentation coating and surface modifying method |
| CN110453259A (en) * | 2019-08-13 | 2019-11-15 | 北京理工大学 | A kind of preparation method for fiber woven material refractory coating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744676A (en) * | 2017-01-23 | 2017-05-31 | 上海朗研光电科技有限公司 | The device and its synthetic method of glow discharge synthesizing nano-particle |
| CN106929876A (en) * | 2017-05-02 | 2017-07-07 | 福建省建筑科学研究院 | The preparation method of metal oxide nano ball |
| CN107385485A (en) * | 2017-07-11 | 2017-11-24 | 北京科技大学 | Large area successive sedimentation coating and surface modifying method |
| CN107385485B (en) * | 2017-07-11 | 2019-03-15 | 北京科技大学 | Large area successive sedimentation coating and surface modifying method |
| CN110453259A (en) * | 2019-08-13 | 2019-11-15 | 北京理工大学 | A kind of preparation method for fiber woven material refractory coating |
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