CN106191902B - A method of preparing hydrogen doping oxide ceramics micro Nano material - Google Patents
A method of preparing hydrogen doping oxide ceramics micro Nano material Download PDFInfo
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- CN106191902B CN106191902B CN201610615695.3A CN201610615695A CN106191902B CN 106191902 B CN106191902 B CN 106191902B CN 201610615695 A CN201610615695 A CN 201610615695A CN 106191902 B CN106191902 B CN 106191902B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
Abstract
A method of hydrogen doping oxide ceramics micro Nano material is prepared, field of inorganic nonmetallic material is belonged to.A certain amount of water soluble polymer and modifying agent is added using metal salt solution as electrolyte using cathode plasma electrolysis tech in the present invention；The metal or alloy of inert electrode or corresponding metal salt is anode material, and the alloy combined using the single metal such as titanium, aluminium, iron or titanium, aluminium, iron is cathode material；Applying certain voltage makes cathode surface and surrounding that plasma discharge occur, later reaction product cathode surface and around deposit, the effects of portion of product is through bombarding is splashed in electrolyte, the processing such as purified, dry obtain, the ceramic oxide particle of nanometer and micro-meter scale large specific surface area the features such as uniform with particle diameter distribution.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-steps such as hydroxide, high temperature sintering and hydrogenation treatment and react an integrated step, preparation flow is shortened, the modified micro Nano material of hydrogen doping is efficiently prepared.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, utilize liquid phase cathode plasma electrolysis tech system what is involved is a kind of
The method of standby hydrogen doping oxide ceramics micro Nano material.
Background technique
Oxide structure ceramics are to develop more early and widely used a kind of ceramic material, have high intensity, high temperature resistant,
The performances such as anti-oxidant and 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 the oxide ceramics with micro nano structure is due to its specific surface area
Greatly, the features such as high surface activity, more it is widely used in electronics, information, laser, infrared, computer, aerospace, atomic energy, change
Many fields such as work, metallurgy.
Doping is common performance control measures, the research work that hydrogen adulterates in oxide material in oxide ceramics research
Make also seldom at present.Traditionally, hydrogen main research general to the effect of material is in the hydrogen embrittlement, hydrogen induced cracking and fracture of metal material
Deng harm.And in recent years, the modified research field emerging as one of atomic hydrogen doped oxide material, in the world by more
Carry out more academic concerns.Do not have by the oxide material that atomic hydrogen modification can obtain conventional method preparation some
Peculiar performance, such as TiO2The variation of equal device for Optical Properties of Materials and Al2O3, the materials electric property such as ZnO significantly changes.
Hydrogen and its isotope are a kind of physical chemistry combined process of complexity to the doping process of solid material, include-are
Arrange the independent of one another and physic-chemical changes that are mutually related.There are two types of the processing mode of realization hydrogen doping is general：At high temperature gas phase hydrogen
Reason and electrochemical hydrogen processing.In the processing of high temperature gas phase hydrogen, generally requires and be first vacuum-treated, be passed through the hydrogen of certain pressure intensity later
Gas carries out a few hours even days of heat treatment at relatively high temperatures；In electrochemical hydrogen processing, generally requires and first sample is made
Sample is put into the electrochemical hydrogen that a couple of days is carried out in solution if the poorly conductive of material is also pre-processed by electrode later
Processing.Both the above method is then to carry out the long period and more complex hydrogenation treatment on the basis of preparing ceramics.
Patent of invention a kind of " method of liquid phase cathode plasma electrolytic preparation aluminum oxide micro-sphere powder（ZL
201510587893.9）" propose to prepare aluminum oxide micro-sphere using cathode plasma technology, but such method is used for aluminum oxide micro-sphere
Preparation when, be only applicable to preparation structure and the relatively simple microballoon of function, and it is micro- to expand to other oxide ceramics
Nano material, the more influence without reference to hydrogen doping to oxide ceramics micro Nano material.
Summary of the invention
Collect that ceramic system is standby and hydrogenation treatment in the method for a step prepares hydrogen doping oxidation the purpose of the present invention is to propose to a kind of
Object ceramics micro Nano material.This method uses cathode plasma electrolysis tech, can not only prepare what a variety of hydrogen dopings were modified
Oxide ceramics micro Nano material, and have the characteristics that prepare simple, save the cost.
The present invention is added a certain amount of water soluble polymer, heats to electrolyte using metal salt solution as electrolyte
Processing；The metal or alloy of inert electrode or corresponding metal salt is anode material, with the single metal such as titanium, aluminium, iron or titanium, aluminium,
The alloy of iron combination is cathode material；Applying certain voltage makes cathode surface and surrounding that plasma discharge occur, later instead
Answer product cathode surface and around deposit, the effects of portion of product is through bombarding, is splashed in electrolyte, purified, dry etc.
Reason obtains the micro-nano product of oxide ceramics.
It is of the invention that the specific method is as follows：
Select one or more metal salt solutions as electrolyte, including titanium sulfate, zirconium nitrate, yttrium nitrate, ferric nitrate or
The mixing of ferric sulfate, aluminum nitrate, nitric acid tin, lanthanum nitrate, zinc nitrate or zinc sulfate etc. and above-mentioned several metal salts, control gold
Belong to concentration of salt solution in 5~500g/L；The area ratio of cathode material and anode material is controlled less than 1：1；Cathode plasma electrolysis
When, using the pulse power or DC power supply, control voltage is 50~300V, when using the pulse power, 100~1000Hz of frequency,
Duty ratio 10%~90%；The reaction time is controlled in 2min and the above time.
The water soluble polymer is polyvinyl alcohol or polyethylene glycol or polyethylene glycol oxide or polyvinylpyrrolidone,
Additional amount is between 2g/L~50g/L.
The temperature range of the electrolyte heat treatment is 20 ~ 100 DEG C, and the processing time is 0.5 ~ 10 hour.
The inert electrode selects graphite or platinized platinum.
The purification, drying are that cathode plasma is electrolysed treated electrolyte, obtain bottom turbid solution by standing
Or direct centrifugal treating, it is for several times through water and alcohol washes, dry in drying box later to collect to get the oxide doped with hydrogen
Ceramic micro Nano material.
The advantage of the invention is that：
（1）Cathode hydrogen evolution reaction and energy of plasma are made full use of, under conditions of being not required to additional hydrogenation treatment, molten
Prepare that particle diameter distribution is uniform in liquid, the excellent hydrogen doping oxide of the physical and chemical performances such as large specific surface area and optics, electricity
Ceramic micro Nano material.
（2）Electrolyte is carried out the processing such as to heat, or water soluble polymer is added, or through the above two-step pretreatment, can drop
Current density in low cathode plasma electrolytic process realizes low-power consumption preparation.
（3）This method preparation is simple, and disposable input cost is low, and will prepare hydroxide, sintering and hydrogenation treatment
Equal multi-steps react an integrated step, shorten preparation flow, efficiently prepare the modified micro Nano material of hydrogen doping.
Detailed description of the invention
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
Technical solution of the present invention is further illustrated below with reference to embodiment.
Embodiment 1
Selection titanium sulfate solution is electrolyte, and controlled concentration is in 150g/L；Be added 20g/L polyethylene glycol, to electrolyte into
20 DEG C of row, processing in 0.5 hour.Using titanium alloy as cathode, platinized platinum is anode, and anode and cathode area ratio is 1:3.Using pulse electricity
Source controls 60 ~ 120V of voltage, frequency 500Hz, duty ratio 60%.The control reaction time is 10min, carries out cathode plasma electrolysis
Reaction.By the electrolyte after reaction, bottom turbid solution is obtained by standing, through centrifugal treating（4000 revs/min）, and with water and
Alcohol washes are for several times, dry in drying box by product later to collect, and obtain the micro-nano material of titanium dioxide ceramic doped with hydrogen
Material（As shown in Figure 1）.Through detecting, the hydrogen content in product is about 1.89ppm.
Embodiment 2
Selecting five nitric hydrate zirconium solutions is electrolyte, and controlled concentration is in 300g/L；20g/L polyethylene glycol is added, to electricity
It solves liquid and carries out 80 DEG C, processing in 4 hours.Using titanium alloy as cathode, platinized platinum is anode, and anode and cathode area ratio is 1:4.Using pulse
Power supply controls 70 ~ 140V of voltage, frequency 500Hz, duty ratio 60%.The control reaction time is 30min, carries out cathode plasma electricity
Solution reaction.By the electrolyte after reaction, bottom turbid solution is obtained by standing, through centrifugal treating（4000 revs/min）, and use water
And alcohol washes are for several times, later that product is dry in drying box to collect, the zirconia ceramic obtained doped with hydrogen is micro-nano
Material（As shown in Figure 2）.Through detecting, the hydrogen content in product is about 52.54ppm.
Embodiment 3
Selection Fe(NO3)39H2O solution is electrolyte, and controlled concentration is in 300g/L；15g/L polyvinylpyrrolidine is added
Ketone carries out 20 DEG C to electrolyte, processing in 0.5 hour.Using stainless steel as cathode, platinized platinum is anode, and anode and cathode area ratio is 1:
2.Using the pulse power, 60 ~ 120V of voltage, frequency 500Hz, duty ratio 40% are controlled.The control reaction time is 10min, carries out yin
Pole plasma cell reaction.By the electrolyte after reaction, bottom turbid solution is obtained by standing, through centrifugal treating（4000 revs/min
Clock）, and for several times with water and alcohol washes, it is later that product is dry in drying box to collect, obtain the iron oxide pottery doped with hydrogen
Porcelain micro Nano material.
Embodiment 4
Selection zinc nitrate hexahydrate solution is electrolyte, and controlled concentration is in 300g/L；20g/L polyethylene glycol is added, to electricity
It solves liquid and carries out 20 DEG C, processing in 0.5 hour.Using titanium alloy as cathode, platinized platinum is anode, and anode and cathode area ratio is 1:4.Using arteries and veins
Power supply is rushed, 70 ~ 120V of voltage, frequency 500Hz, duty ratio 80% are controlled.The control reaction time is 10min, carries out cathode plasma
Cell reaction.By the electrolyte after reaction, bottom turbid solution is obtained by standing, through centrifugal treating（4000 revs/min）, it is used in combination
Water and alcohol washes are for several times, dry in drying box by product later to collect, and the zinc oxide ceramics obtained doped with hydrogen is micro-nano
Material.
Embodiment 5
Selecting five nitric hydrate zirconiums and six nitric hydrate samarium mixed solutions is electrolyte, and controlled concentration is respectively 257.6g/L
And 266.7g/L；20g/L polyvinylpyrrolidone is added, 60 DEG C are carried out to electrolyte, processing in 4 hours.It is yin with titanium alloy
Pole, platinized platinum are anode, and anode and cathode area ratio is 1:4.Using the pulse power, 100 ~ 170V of voltage, frequency 500Hz, duty are controlled
Than 60%.The control reaction time is 20min, carries out cathode plasma cell reaction.By the electrolyte after reaction, by standing
To bottom turbid solution, through centrifugal treating（4000 revs/min）, and for several times with water and alcohol washes, later by product in drying box
Middle dry collection, obtains the samarium zirconate ceramics micro Nano material doped with hydrogen.
Claims (3)
1. a kind of method for preparing hydrogen doping oxide ceramics micro Nano material, it is characterised in that：Select one or more metals
Salting liquid is as electrolyte, including titanium sulfate, zirconium nitrate, yttrium nitrate, ferric nitrate or ferric sulfate, nitric acid tin, lanthanum nitrate, zinc nitrate
Or the mixing of zinc sulfate and above-mentioned several metal salts；Metal salt solution concentration is controlled in 5~500g/L；2~50g/L is added
Water soluble polymer heats electrolyte, and temperature range is 20~100 DEG C, and the processing time is 0.5~10 hour；
The metal or alloy of inert electrode or corresponding metal salt is anode material, is combined with titanium, aluminium, the single metal of iron or titanium, aluminium, iron
Alloy is cathode material；Applying certain voltage makes cathode surface and surrounding that plasma discharge occur, and reaction product exists later
Cathode surface and surrounding deposit, and portion of product is splashed in electrolyte through bombardment effect, control the reaction time in 2min or more
Time；Purified again, drying process obtains the micro-nano product of oxide ceramics of hydrogen doping.
2. the method for preparing hydrogen doping oxide ceramics micro Nano material as described in claim 1, it is characterised in that：The water
Soluble macromolecular is polyvinyl alcohol or polyethylene glycol or polyvinylpyrrolidone.
3. the method for preparing hydrogen doping oxide ceramics micro Nano material as described in claim 1, it is characterised in that：It is described lazy
Property electrode select graphite or platinized platinum.
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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 |
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