CN107180910B - A kind of preparation method of Nano silver grain load aluminic acid magnesium material and material obtained - Google Patents
A kind of preparation method of Nano silver grain load aluminic acid magnesium material and material obtained Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of Nano silver grain load aluminic acid magnesium material and materials obtained, described method includes following steps: 1) mixing sea grass shape magnesium aluminate powder and soluble silver salt solution, 10~60min of ultrasonic disperse, it is stirred for 10~60min, is uniformly mixed and obtains mixed solution；The mass fraction of the soluble silver salt is 0.1~20%；2) mixed solution of step 1) is mixed with reducing agent, stirs 10~60min, be uniformly mixed；Moisture is dried and removed, MgAl is obtained2O4/ Ag nano-powder；3) MgAl for obtaining step 2)2O4/ Ag nano-powder carries out discharge plasma sintering, obtains the Nano silver grain load aluminic acid magnesium material；The present invention utilizes high conductivity, the one-dimensional transmission structure of sea grass shape of magnesium aluminate and the high Seebeck coefficient of magnesium aluminate of Ag, has prepared high performance ceramic thermoelectric material.
Description
Technical field
The invention belongs to technical field of composite preparation more particularly to a kind of Nano silver grain to load aluminic acid magnesium material
Preparation method and material obtained.
Background technique
In recent years, the gradually increasing, to waste heat (waste incineration, petrochemical industry, automobile to environmental protection consciousness with people
Etc. industries waste heat) recycle pay attention to again and the very big improvement of pyroelectric material performance so that research and development of thermoelectric material and in energy
Application in terms of source is widely paid close attention to and is studied.Thermoelectric material is to realize thermal energy and electricity using solid interior carrier transport
The functional material that directly can mutually convert has wide practical use in terms of waste-heat power generation and free-floride.Traditional
Bi2Se3, Bi2Te3, the inorganic thermoelectric material such as PbSe ZT figure of merit with higher shows the application potential in terms of thermoelectricity, but
It is that the features such as element contained by these materials is toxic, expensive, rare limit its scope of application.Therefore, high property is researched and developed
Energy, the thermoelectric new material that environmental-friendly, thermal stability is high, resistant to chemical etching have positive realistic meaning.
And aluminic acid magnesium material thermal stability is high, chemical stability is good, resistant to chemical etching, and has certain conductivity and height
Seebeck coefficient, low thermal coefficient, and high temperature resistant, high-intensitive ceramic can be prepared into, be a kind of ideal thermoelectricity
Basis material.But the not high feature of conductivity also constrains it in the application in thermoelectricity field, therefore, how to utilize aluminic acid
Ideal thermoelectric material is prepared as matrix in magnesium, has positive research significance.
Summary of the invention
In view of the above-mentioned drawbacks in the prior art, it is negative to be to provide a kind of Nano silver grain for one of main object of the present invention
The Nano silver grain load magnesium aluminate composite wood with good thermoelectricity capability has been prepared in the preparation method for carrying aluminic acid magnesium material
Material.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of Nano silver grain load aluminic acid magnesium material, described method includes following steps:
1) sea grass shape magnesium aluminate powder and soluble silver salt solution are mixed, 10 ~ 60 min of ultrasonic disperse, it is stirred for 10 ~
60 min are uniformly mixed and obtain mixed solution；The mass fraction of the soluble silver salt is 0.1 ~ 20%；
2) mixed solution of step 1) is mixed with reducing agent, stirs 10 ~ 60 min, be uniformly mixed；It dries and removes
Moisture obtains MgAl2O4/ Ag nano-powder；
3) MgAl for obtaining step 22O4/ Ag nano-powder carries out discharge plasma sintering, obtains the nano grain of silver
Son load aluminic acid magnesium material；
The discharge plasma sintering includes: that heating rate is 10 ~ 100 DEG C/min, 20 ~ 80MPa of sintering pressure, heat preservation temperature
1000 ~ 1300 DEG C of degree, 5 ~ 20min of soaking time；
The sea grass shape magnesium aluminate powder include the nanocrystalline mutual gantry of magnesium aluminate of form in the form of sheets together, formed sea
The width of grass-like structure, the sea grass shape magnesium aluminate powder is 250 ~ 400 nm, with a thickness of 50 ~ 80 nm, the length of sea grass shape structure
Degree is 1 ~ 4 μm.
As a further preference, in the step 1), the specific surface area of the sea grass shape magnesium aluminate powder is 170-260
m2/g。
As a further preference, in the step 1), the soluble silver salt in silver nitrate and silver acetate extremely
Few one kind.
As a further preference, in the step 1), the quality of the sea grass shape magnesium aluminate powder and soluble silver salt
Number ratio is 1:2 ~ 2:1.
As a further preference, in step 2, the reducing agent is selected from glucose, ethylene glycol, formaldehyde, hydrazine hydrate and boron
At least one of sodium hydride；The mass ratio of the material of silver ion is 1:1 ~ 2:1 in the reducing agent and step 1).
As a further preference, in the step 1), the sea grass shape magnesium aluminate powder is obtained by following preparation method
, this method comprises:
(1) urea being mixed with water, heating stirring to urea dissolves to obtain solution, and the concentration of the urea is 0.15 ~
1mol/l；
(2) pattern controlling agent is added in the solution that step (1) obtains, and makes the pattern controlling agent molten under stiring
Solution, the thermostatic before continuing to keep after dissolution stir 30 ~ 80 min, obtain mixed solution；The pattern controlling agent and institute
The molar ratio for stating urea is 10:1 ~ 3:1；
(3) aluminum soluble salt and soluble magnesium salt are added in the mixed solution that step (2) obtains, it is molten to form presoma
The precursor solution is placed in 2 ~ 5 h of water bath with thermostatic control by liquid；
(4) by step (3), treated that the precursor solution is transferred in autoclave, in 1 ~ 10 MPa pressure and
After reacting 2 ~ 5h under the conditions of 130 ~ 180 DEG C of temperature, after products therefrom washing, being separated by solid-liquid separation and be dry, then through 700 ~ 1200
It is roasted at DEG C, obtains the sea grass shape magnesium aluminate powder.
As a further preference, in step (3), the soluble magnesium salt is in magnesium chloride, magnesium nitrate and magnesium acetate
At least one；The aluminum soluble salt is selected from least one of aluminum nitrate, aluminium chloride and aluminum acetate.
As a further preference, the range of the molar ratio x of the aluminum soluble salt and magnesium salts are as follows: 1≤x≤3, it is described can
Dissolubility aluminium salt and the molar ratio of urea are in 1:5 ~ 1:50.
As a further preference, the pattern controlling agent is selected from neopelex, oleic acid, polyvinyl alcohol and ten
At least one of sodium dialkyl sulfate.
Another object of the present invention is to provide one kind Nano silver grains as made from above-mentioned preparation method to load magnesium aluminate
The conductivity of material, the Nano silver grain load aluminic acid magnesium material is 106S/m, Seebeck coefficient S are 200 ~ 700 μ V/K, heat
0.5 ~ 1.0 W/mK of conductance.
The beneficial effects of the present invention are: the present invention is using sea grass shape magnesium aluminate as matrix, by itself and the metal that conducts electricity very well
Ag nano-particles reinforcement, the absorption using sea grass shape magnesium aluminate powder to Ag ion, by Ag ionic anchors in sea grass shape structure,
Again by in-situ reducing, by Ag nanometer particle load on the surface of magnesium aluminate sea grass shape structure.Through discharge plasma sintering, obtain
The high MgAl of consistency2O4/ Ag ceramic composite.Ag nano particle has high electric conductivity, and electronics is fast along sea grass shape structure
Speed transmission, effectively improves the conductivity of magnesium aluminate ceramic matrix；And the energy dispersive effect of Ag nanoparticle effectively guarantees
Magnesium aluminate ceramic matrix high Seebeck coefficient.The phonon of the low thermal conductivity of aluminic acid magnesium matrix and Ag nanoparticle in the base
Scattering effect assigns material low thermal coefficient, so as to improve the thermoelectricity capability of material.
Preparation process of the present invention is simple, operate conveniently, is high-efficient, at low cost, it can be achieved that industrialized mass production, and sufficiently
Using aluminic acid magnesium matrix high thermal stability, environment friendly, chemical corrosion resistance the advantages that, have in industrial waste heat power field
Very big application potential.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of 1 sea grass shape structure magnesium aluminate nano-powder of the embodiment of the present invention.
Specific embodiment
The present invention as provide a kind of Nano silver grain load aluminic acid magnesium material preparation method and made from material, solve
Existing magnesium aluminate thermoelectricity matrix conductivity low insufficient defect, has been prepared the nano grain of silver with good thermoelectricity capability
Son load aluminic acid magnesium base composite material.
In order to solve drawbacks described above, the main thought of the embodiment of the present invention is:
Nano silver grain of the embodiment of the present invention loads the preparation method of aluminic acid magnesium material, and described method includes following steps:
1) sea grass shape magnesium aluminate powder and soluble silver salt solution are mixed, 10 ~ 60 min of ultrasonic disperse, then magnetic agitation
10 ~ 60 min are uniformly mixed and obtain mixed solution；The mass fraction of the soluble silver salt is 0.1 ~ 20%；
2) mixed solution of step 1) is mixed, 10 ~ 60 min of magnetic agitation with reducing agent, is uniformly mixed；It is dry
Moisture is removed, MgAl is obtained2O4/ Ag nano-powder；
3) MgAl for obtaining step 22O4/ Ag nano-powder carries out discharge plasma sintering, obtains the nano grain of silver
Son load aluminic acid magnesium material；
The discharge plasma sintering includes: that heating rate is 10 ~ 100 DEG C/min, 20 ~ 80MPa of sintering pressure, heat preservation temperature
1000 ~ 1300 DEG C of degree, 5 ~ 20min of soaking time；
The sea grass shape magnesium aluminate powder include the nanocrystalline mutual gantry of magnesium aluminate of form in the form of sheets together, formed sea
The width of grass-like structure, the sea grass shape magnesium aluminate powder is 250 ~ 400 nm, with a thickness of 50 ~ 80 nm, the length of sea grass shape structure
Degree is 1 ~ 4 μm.
The embodiment of the present invention makes full use of the chemical stability and thermal stability of magnesium aluminate, can make in different environment
With.Pass through the techniques such as the load capacity of regulation Ag nanoparticle and discharge plasma sintering, i.e., the thermoelectricity of controllable composite material
Performance, regulation is convenient, technique is practical, it is easy to accomplish mass production.Composite material prepared by the present invention, thermoelectricity capability table
It is existing are as follows: conductivity is up to 106S/m, Seebeck coefficient S are 200 ~ 700 μ V/K, and 0.5 ~ 1.0 W/mK of thermal conductivity can be applied to heat
Electrical domain.
Magnesium aluminate raw powder's production technology is more at this stage, such as solid reaction process, coprecipitation, sol-gel method, is sprayed
Seasoning, hydro-thermal method, micro emulsion method etc..Wherein hydro-thermal method have the advantages that it is environmental-friendly, easy to operate, controllable to particle size and
It is widely adopted.For example, using hydro-thermal method and surfactant that can prepare sheet, micropore shape, spherical, layer for template at present
The magnesium aluminate powder body material of shape or the patterns such as rodlike.
In the step 1), the sea grass shape magnesium aluminate powder can be obtained by following preparation method, this method comprises:
(1) urea being mixed with water, heating stirring to urea dissolves to obtain solution, and the concentration of the urea is 0.15 ~
1mol/l；
(2) pattern controlling agent is added in the solution that step (1) obtains, and makes the pattern controlling agent molten under stiring
Solution, the thermostatic before continuing to keep after dissolution stir 30 ~ 80 min, obtain mixed solution；The pattern controlling agent and institute
The molar ratio for stating urea is 10:1 ~ 3:1；
(3) aluminum soluble salt and soluble magnesium salt are added in the mixed solution that step (2) obtains, it is molten to form presoma
The precursor solution is placed in 2 ~ 5 h of water bath with thermostatic control by liquid；
(4) by step (3), treated that the precursor solution is transferred in autoclave, in 1 ~ 10 MPa pressure and
After reacting 2 ~ 5h under the conditions of 130 ~ 180 DEG C of temperature, after products therefrom washing, being separated by solid-liquid separation and be dry, then through 700 ~ 1200
It is roasted at DEG C, obtains the sea grass shape magnesium aluminate powder.
The sea grass shape magnesium aluminate raw powder's production technology is the content of the concentration and urea by control pattern controlling agent,
Using the interaction between pattern controlling agent and urea, pattern controlling agent is made to form the stratiform liquid of size uniformity, stable structure
Crystalline substance adsorbs presoma, and controls the direction of final crystal growth；It is acted on simultaneously using the precipitating reagent of urea, finally in stratiform liquid
Crystal phase symplastic growth is prepared for sea grass shape aluminic acid magnesium crystal.
The sea grass shape magnesium aluminate raw powder's production technology utilizes the interaction of urea and pattern controlling agent, obtains uniform
Molten cause type layered liquid crystal micro-structure；Crystal structure regulation only needs the concentration and urea and pattern controlling agent of each component
Size uniformity, sea grass shape structure nano-powder can be prepared in ratio.The process conditions of experiment are convenient, easy to operate,
Mass production easy to accomplish.The sea grass shape magnesium aluminate powder of preparation has high specific surface area and high porosity, energy
Enough as good catalyst, perhaps catalyst carrier is applied in inorganic, organic or light-catalyzed reaction.The sea grass shape aluminium
Sour magnesium raw powder's production technology can overcome the problems, such as that the hard aggregation between powder granule, powder dispersity are good.
In order to which the objectives, technical solutions, and advantages of the present invention are more clearly understood, with reference to embodiments, to the present invention
It is further elaborated.Specific data are only to explain the present invention involved in specific example described herein, not
For limiting the present invention.
Embodiment 1
By 100 parts of sea grass shape magnesium aluminate powders and 100 parts, the AgNO of 0.1% mass fraction3Solution mixing, ultrasonic disperse
10 min, then 10 min of magnetic agitation keep its mixing full and uniform；The glucose equal with the amount of nitric acid silver material, magnetic is added
Power stirs 10 min, keeps its mixing full and uniform；It is placed in 80 DEG C of dry 6h in baking oven again moisture is evaporated off, obtains MgAl2O4/
Ag nano-powder；Gained powder is placed in graphite jig and carries out discharge plasma sintering, heating rate is 10 DEG C/min, is protected
Temperature is 1000 DEG C, sintering pressure 20MPa, and the sintered heat insulating time is 5min.It is negative that Nano silver grain is obtained after the completion of sintering
Carry aluminic acid magnesium base composite material.
The sea grass shape magnesium aluminate raw powder's production technology includes:
10 mmol urea are dissolved into the deionized water of 10 mL, are warming up to 60 DEG C, and water bath with thermostatic control under stiring
30min dissolves urea sufficiently.Then neopelex is added thereto, and makes pattern control under constant temperature stirring
Agent, which is sufficiently dissolved, forms homogeneous solution, and wherein the molar ratio of neopelex and urea is 10:1；Again to above-mentioned solution
The molar ratio of middle addition magnesium nitrate and aluminum nitrate, magnesium nitrate and aluminum nitrate is 1:2, and the molar ratio of aluminum nitrate and urea is 1:5, and
The deionized water that certain volume is added forms the mixed solution of 20 mL, urea concentration 0.5mol/l.To dissolve raw material sufficiently
With contact with each other, the solution is in 60 DEG C of 3 h of heat preservation.The stainless steel that above-mentioned solution is finally transferred to polytetrafluoroethyllining lining is high
It presses in reaction kettle.At 130 DEG C, operating pressure is 5 MPa, after 2 h of reaction, and products therefrom is washed through deionized water and dehydrated alcohol
After washing, filtering, 80 DEG C of 6 h of drying in baking oven are placed in, presoma is obtained, it is placed in again in Muffle furnace through 700 DEG C of roasting 2h,
Obtain the magnesium aluminate nano-powder of sea grass shape structure.
Magnesium aluminate nano-powder of the embodiment of the present invention is sea grass shape structure, and nanocrystalline single magnesium aluminate is strip, sheet
The mutual gantry of object, forms sea grass shape structure, and the width of sea grass shape magnesium aluminate powder is 250 ~ 280 nm, with a thickness of 50 ~ 60 nm,
Between about 1 ~ 2 μm of length of sea grass shape structure.Specific surface area is 260 m2/g。
After tested, Nano silver grain manufactured in the present embodiment loads magnesium aluminate Electrical Conductivity of Composites 106S/m, thermal conductivity
It is 700 μ V/K for 0.5 W/mK, Seebeck coefficient S.
Embodiment 2
100 parts of sea grass shape magnesium aluminate powders and 100 parts of 20% AgNO3Solution mixing, 60 min of ultrasonic disperse, then magnetic force
60 min are stirred, keep its mixing full and uniform；The hydrazine hydrate equal with the amount of the substance of silver nitrate, magnetic agitation 60 is added
Min keeps its mixing full and uniform；It is placed in 80 DEG C of dry 6h in baking oven again moisture is evaporated off, obtains MgAl2O4/ Ag nano powder
Body；Gained powder is placed in graphite jig and carries out discharge plasma sintering, heating rate is 100 DEG C/min, and holding temperature is
1300 DEG C, sintering pressure 80MPa, the sintered heat insulating time is 20 min.Nano silver grain load aluminic acid is obtained after the completion of sintering
Magnesium base composite material.
The sea grass shape magnesium aluminate raw powder's production technology includes:
30 mmol urea are dissolved into the deionized water of 50 mL, are warming up to 80 DEG C, and water bath with thermostatic control under stiring
30min dissolves urea sufficiently.Then neopelex is added thereto, and makes pattern control under constant temperature stirring
Agent, which is sufficiently dissolved, forms homogeneous solution, and wherein the molar ratio of neopelex and urea is 7:1；Again into above-mentioned solution
It is added magnesium nitrate and aluminum nitrate, the molar ratio of magnesium nitrate and aluminum nitrate is 1:2, and the molar ratio of aluminum nitrate and urea is 1:10, and
The deionized water that certain volume is added forms the mixed solution of 200 mL, urea concentration 0.15mol/l.To keep raw material sufficiently molten
It solves and contacts with each other, the solution is in 60 DEG C of 3 h of heat preservation.Above-mentioned solution is finally transferred to the stainless steel of polytetrafluoroethyllining lining
In autoclave.At 140 DEG C, operating pressure is 5 MPa, after reaction 6h, by products therefrom through deionized water and dehydrated alcohol
Washing after filtering, is placed in 80 DEG C of 6 h of drying in baking oven, obtains presoma, it is placed in Muffle furnace again and is roasted through 800 DEG C
2h is to get the magnesium aluminate nano-powder for arriving sea grass shape structure.
Magnesium aluminate nano-powder is sea grass shape structure, and nanocrystalline single magnesium aluminate is strip, the mutual gantry of tablet, shape
At sea grass shape structure, the width of sea grass shape magnesium aluminate powder is 300 ~ 320 nm, with a thickness of 60 ~ 70 nm, the length of sea grass shape structure
Between about 2 ~ 3 μm of degree.Specific surface area is 190 m2/g。
After tested, Nano silver grain manufactured in the present embodiment loads 5.2 * 10 of magnesium aluminate Electrical Conductivity of Composites6S/m, heat
Conductance is 1.0 W/mK, and Seebeck coefficient S is 200 μ V/K.
Embodiment 3
100 parts of sea grass shape magnesium aluminate powders and the mixing of 100 parts of 10% silver acetate solution, 30 min of ultrasonic disperse, then magnetic
Power stirs 30 min, keeps its mixing full and uniform；The sodium borohydride of the amount of the substance of 2 times of silver acetates, magnetic agitation 30 is added
Min keeps its mixing full and uniform；It is placed in 80 DEG C of dry 6h in baking oven again moisture is evaporated off, obtains MgAl2O4/ Ag nano powder
Body；Gained powder is placed in graphite jig and carries out discharge plasma sintering, heating rate is 50 DEG C/min, and holding temperature is
1200 DEG C, sintering pressure 50MPa, the sintered heat insulating time is 10 min.Nano silver grain load aluminic acid is obtained after the completion of sintering
Magnesium base composite material.
The sea grass shape magnesium aluminate raw powder's production technology includes:
50 mmol urea are dissolved into the deionized water of 100 mL, are warming up to 60 DEG C, and water bath with thermostatic control under stiring
30min dissolves urea sufficiently.Then oleic acid is added thereto, and so that pattern controlling agent is sufficiently dissolved shape under constant temperature stirring
At homogeneous solution, the molar ratio of oleic acid and urea is 6:1；Magnesium acetate and aluminum acetate, magnesium acetate is added into above-mentioned solution again
It is 1:2 with the molar ratio of aluminum acetate, the molar ratio of aluminum acetate and urea is 1:15, and the deionized water that certain volume is added is formed
The mixed solution of 250 mL, urea concentration 0.2mol/l.To make raw material sufficiently dissolve and contact with each other, which protects at 60 DEG C
3 h of temperature.Finally above-mentioned solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining.At 170 DEG C, work pressure
Power is 5 MPa, after reaction 4h, by products therefrom after deionized water and dehydrated alcohol washing, filtering, is placed in baking oven and does for 80 DEG C
Dry 6 h, obtains presoma, it is placed in Muffle furnace again and roasts 2h through 700 DEG C to get the magnesium aluminate of sea grass shape structure is arrived
Nano-powder.
Magnesium aluminate nano-powder is sea grass shape structure, and nanocrystalline single magnesium aluminate is strip, the mutual gantry of tablet, shape
At sea grass shape structure, the width of sea grass shape magnesium aluminate powder is 320 ~ 340 nm, with a thickness of 50 ~ 60 nm, the length of sea grass shape structure
Between about 1 ~ 2 μm of degree.Specific surface area is 210m2In the range of/g.
After tested, Nano silver grain manufactured in the present embodiment loads 1.8 * 10 of magnesium aluminate Electrical Conductivity of Composites6S/m, heat
Conductance is 0.9 W/mK, and Seebeck coefficient S is 300 μ V/K.
Embodiment 4
100 parts of sea grass shape magnesium aluminate powders and 100 parts of 5% AgNO3Solution mixing, 20 min of ultrasonic disperse, then magnetic force
20 min are stirred, keep its mixing full and uniform;The addition formaldehyde equal with the amount of the substance of silver nitrate, 30 min of magnetic agitation,
Keep its mixing full and uniform；It is placed in 60 DEG C of dry 8h in baking oven again moisture is evaporated off, obtains MgAl2O4/ Ag nano-powder；It will
Gained powder, which is placed in graphite jig, carries out discharge plasma sintering, and heating rate is 20 DEG C/min, holding temperature 1100
DEG C, sintering pressure 40MPa, the sintered heat insulating time is 15 min.It is multiple that Nano silver grain load magnesium aluminate is obtained after the completion of sintering
Condensation material.
The sea grass shape magnesium aluminate raw powder's production technology includes:
100 mmol urea are dissolved into the deionized water of 300 mL, are warming up to 60 DEG C, and water bath with thermostatic control under stiring
30min dissolves urea sufficiently.Then polyvinyl alcohol is added thereto, and keeps pattern controlling agent sufficiently molten under constant temperature stirring
Solution forms homogeneous solution, and wherein the molar ratio of polyvinyl alcohol and urea is 4:1；Magnesium chloride and chlorination is added into above-mentioned solution again
The molar ratio of aluminium, magnesium chloride and aluminium chloride is 1:2, and the molar ratio of aluminum nitrate and urea is 1:35, and going for certain volume is added
Ionized water forms the mixed solution of 125 mL, urea concentration 0.8mol/l.To make raw material sufficiently dissolve and contact with each other, this is molten
Liquid is in 60 DEG C of 3 h of heat preservation.Finally above-mentioned solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining.?
140 DEG C, operating pressure is 5 MPa, after reaction 5h, by products therefrom after deionized water and dehydrated alcohol washing, filtering, is placed in
80 DEG C of 6 h of drying, obtain presoma in baking oven, it are placed in again in Muffle furnace through 1000 DEG C of roasting 2h to get to sea grass shape
The magnesium aluminate nano-powder of structure.
Magnesium aluminate nano-powder is sea grass shape structure, and nanocrystalline single magnesium aluminate is strip, the mutual gantry of tablet, shape
At sea grass shape structure, the width of sea grass shape magnesium aluminate powder is 250 ~ 280 nm, with a thickness of 50 ~ 65 nm, the length of sea grass shape structure
Between about 3 ~ 4 μm of degree.Specific surface area is 170 m2In the range of/g.
After tested, Nano silver grain manufactured in the present embodiment loads 1.8 * 10 of magnesium aluminate Electrical Conductivity of Composites5S/m, heat
Conductance is 0.75 W/mK, and Seebeck coefficient S is 380 μ V/K.
Embodiment 5
100 parts of sea grass shape magnesium aluminate powders and the mixing of 100 parts of 1% silver acetate solution, 20 min of ultrasonic disperse, then magnetic force
20 min are stirred, keep its mixing full and uniform;The ethylene glycol equal with the amount of the substance of silver acetate, magnetic agitation 30 is added
Min keeps its mixing full and uniform；It is placed in 70 DEG C of 7 h of drying in baking oven again moisture is evaporated off, obtains MgAl2O4/ Ag nano powder
Body；Gained powder is placed in graphite jig and carries out discharge plasma sintering, heating rate is 20 DEG C/min, and holding temperature is
1100 DEG C, sintering pressure 40MPa, the sintered heat insulating time is 15 min.Nano silver grain load aluminic acid is obtained after the completion of sintering
Magnesium base composite material.
The sea grass shape magnesium aluminate raw powder's production technology includes:
500 mmol urea are dissolved into the deionized water of 500mL, are warming up to 80 DEG C, and water bath with thermostatic control under stiring
60min dissolves urea sufficiently.Then lauryl sodium sulfate is added thereto, and makes pattern controlling agent under constant temperature stirring
Sufficiently dissolution forms homogeneous solution, and wherein lauryl sodium sulfate and the molar ratio of urea are 3:1；It is added again into above-mentioned solution
Magnesium acetate and aluminium chloride, wherein the molar ratio of magnesium acetate and aluminium chloride is 1:2, and the molar ratio of aluminium chloride and urea is 1:50, and
The deionized water that certain volume is added forms the mixed solution of 500 mL, urea concentration 1mol/l.To dissolve raw material sufficiently
With contact with each other, the solution is in 80 DEG C of 3 h of heat preservation.The stainless steel that above-mentioned solution is finally transferred to polytetrafluoroethyllining lining is high
It presses in reaction kettle.At 180 DEG C, operating pressure is 5 MPa, after reaction 3h, and products therefrom is washed through deionized water and dehydrated alcohol
After washing, filtering, 80 DEG C of 6 h of drying in baking oven are placed in, presoma is obtained, it is placed in Muffle furnace again and roasted through 1200 DEG C
2h is to get the magnesium aluminate nano-powder for arriving sea grass shape structure.
Magnesium aluminate nano-powder is sea grass shape structure, and nanocrystalline single magnesium aluminate is strip, the mutual gantry of tablet, shape
At sea grass shape structure, the width of sea grass shape magnesium aluminate powder is 380 ~ 400 nm, with a thickness of 60 ~ 70 nm, the length of sea grass shape structure
Between about 3 ~ 4 μm of degree.Specific surface area is 250 m2In the range of/g.
After tested, Nano silver grain manufactured in the present embodiment loads 6.8 * 10 of magnesium aluminate Electrical Conductivity of Composites5S/m, heat
Conductance is 0.85 W/mK, and Seebeck coefficient S is 500 μ V/K.
Technical solution in above-mentioned the embodiment of the present application, at least have the following technical effects or advantages:
The present invention, by itself and the metal Ag nano-particles reinforcement to conduct electricity very well, is utilized using sea grass shape magnesium aluminate as matrix
Absorption of the sea grass shape magnesium aluminate powder to Ag ion, by Ag ionic anchors in sea grass shape structure, then through in-situ reducing, by Ag
Nanometer particle load is on the surface of magnesium aluminate sea grass shape structure.Through discharge plasma sintering, the high MgAl of consistency is obtained2O4/Ag
Ceramic composite.Ag nano particle has high electric conductivity, and electronics is quickly transmitted along sea grass shape structure, effectively improves aluminium
The conductivity of sour magnesium ceramic matrix；And that magnesium aluminate ceramic matrix is effectively guaranteed is high for the energy dispersive effect of Ag nanoparticle
Seebeck coefficient.It is low to assign material for the phon scattering effect of the low thermal conductivity of aluminic acid magnesium matrix and Ag nanoparticle in the base
Thermal coefficient, so as to improve the thermoelectricity capability of material.
Preparation process of the present invention is simple, operate conveniently, is high-efficient, at low cost, it can be achieved that industrialized mass production, and sufficiently
Using aluminic acid magnesium matrix high thermal stability, environment friendly, chemical corrosion resistance the advantages that, have in industrial waste heat power field
Very big application potential.
Although preferred embodiments of the present invention have been described, it is created once a person skilled in the art knows basic
Property concept, then additional changes and modifications may be made to these embodiments.So it includes excellent that the following claims are intended to be interpreted as
It selects embodiment and falls into all change and modification of the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various modification and variations without departing from the spirit and scope of the present invention.If in this way, these modifications and changes of the present invention
Within the scope of the claims of the present invention and its equivalent technology, then the present invention is also intended to encompass these modification and variations and exists
It is interior.
Claims (10)
1. a kind of preparation method of Nano silver grain load aluminic acid magnesium material, it is characterised in that: described method includes following steps:
1) sea grass shape magnesium aluminate powder and soluble silver salt solution are mixed, 10 ~ 60 min of ultrasonic disperse is stirred for 10 ~ 60
Min is uniformly mixed and obtains mixed solution；The mass fraction of the soluble silver salt is 0.1 ~ 20%；
2) mixed solution of step 1) is mixed with reducing agent, stirs 10 ~ 60 min, be uniformly mixed；Moisture is dried and removed,
Obtain MgAl2O4/ Ag nano-powder；
3) MgAl for obtaining step 22O4/ Ag nano-powder carries out discharge plasma sintering, and it is negative to obtain the Nano silver grain
Carry aluminic acid magnesium material；
The discharge plasma sintering includes: that heating rate is 10 ~ 100 DEG C/min, 20 ~ 80MPa of sintering pressure, holding temperature
1000 ~ 1300 DEG C, 5 ~ 20min of soaking time；
The sea grass shape magnesium aluminate powder include the nanocrystalline mutual gantry of magnesium aluminate of form in the form of sheets together, formed sea grass shape
The width of structure, the sea grass shape magnesium aluminate powder is 250 ~ 400 nm, and with a thickness of 50 ~ 80 nm, the length of sea grass shape structure is
1~4 μm。
2. the preparation method of Nano silver grain load aluminic acid magnesium material according to claim 1, it is characterised in that: the step
1) in, the specific surface area of the sea grass shape magnesium aluminate powder is 170-260 m2/g。
3. the preparation method of Nano silver grain load aluminic acid magnesium material according to claim 1, it is characterised in that: the step
1) in, the soluble silver salt is selected from least one of silver nitrate and silver acetate.
4. according to claim 1 or the preparation method of 3 Nano silver grains load aluminic acid magnesium materials, it is characterised in that: described
In step 1), the mass fraction ratio of the sea grass shape magnesium aluminate powder and soluble silver salt is 1:2 ~ 2:1.
5. the preparation method of Nano silver grain load aluminic acid magnesium material according to claim 1, it is characterised in that: the step
2) in, the reducing agent is selected from least one of glucose, ethylene glycol, formaldehyde, hydrazine hydrate and sodium borohydride；The reducing agent
The mass ratio of the material with silver ion in step 1) is 1:1 ~ 2:1.
6. the preparation method of Nano silver grain load aluminic acid magnesium material according to claim 1, it is characterised in that: the step
1) in, the sea grass shape magnesium aluminate powder is obtained by following preparation method, this method comprises:
(1) urea is mixed with water, heating stirring to urea dissolves to obtain solution, and the concentration of the urea is 0.15 ~ 1mol/
l；
(2) pattern controlling agent is added in the solution that step (1) obtains, and under stiring dissolves the pattern controlling agent, it is molten
Thermostatic before continuing to keep after solution stirs 30 ~ 80 min, obtains mixed solution；The pattern controlling agent and the urea
Molar ratio be 10:1 ~ 3:1；
(3) aluminum soluble salt and soluble magnesium salt are added in the mixed solution that step (2) obtains, forms precursor solution, it will
The precursor solution is placed in 2 ~ 5 h of water bath with thermostatic control；
(4) by step (3), treated that the precursor solution is transferred in autoclave, 1 ~ 10 MPa pressure and 130 ~
After reacting 2 ~ 5h under the conditions of 180 DEG C of temperature, after products therefrom washing, being separated by solid-liquid separation and be dry, then through at 700 ~ 1200 DEG C
Roasting, obtains the sea grass shape magnesium aluminate powder.
7. the preparation method of Nano silver grain load aluminic acid magnesium material according to claim 6, it is characterised in that: step (3)
In, the soluble magnesium salt is selected from least one of magnesium chloride, magnesium nitrate and magnesium acetate；The aluminum soluble salt is selected from nitric acid
At least one of aluminium, aluminium chloride and aluminum acetate.
8. the preparation method of Nano silver grain load aluminic acid magnesium material according to claim 6, it is characterised in that: described solvable
The range of the molar ratio x of property aluminium salt and soluble magnesium salt are as follows: the molar ratio of 1≤x≤3, the aluminum soluble salt and urea is in 1:5
Between ~ 1:50.
9. the preparation method of Nano silver grain load aluminic acid magnesium material according to claim 6, it is characterised in that: the pattern
Controlling agent is selected from least one of neopelex, oleic acid, polyvinyl alcohol and lauryl sodium sulfate.
10. material made from the preparation method of Nano silver grain load aluminic acid magnesium material as described in claim any one of 1-9,
Be characterized in that: the conductivity of the Nano silver grain load aluminic acid magnesium material is 106S/m, Seebeck coefficient S are 200 ~ 700 μ V/
K, 0.5 ~ 1.0 W/mK of thermal conductivity.
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| CN102181855A (en) * | 2011-03-29 | 2011-09-14 | 北京化工大学 | Spinel film with controllable feature and preparation method thereof |
| CN102839010A (en) * | 2011-06-23 | 2012-12-26 | 中国石油天然气集团公司 | Preparation method for modified magnesium aluminum spinel having acidity and alkality |
| CN106346016A (en) * | 2016-08-30 | 2017-01-25 | 电子科技大学 | Preparation method of silver/graphene composite films and application of preparation method in ultraviolet detectors |
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| CN102181855A (en) * | 2011-03-29 | 2011-09-14 | 北京化工大学 | Spinel film with controllable feature and preparation method thereof |
| CN102839010A (en) * | 2011-06-23 | 2012-12-26 | 中国石油天然气集团公司 | Preparation method for modified magnesium aluminum spinel having acidity and alkality |
| CN106346016A (en) * | 2016-08-30 | 2017-01-25 | 电子科技大学 | Preparation method of silver/graphene composite films and application of preparation method in ultraviolet detectors |
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