CN103468226B - A kind of lanthanum ferrum silica-based room temperature magnetic refrigerating composite and preparation method - Google Patents
A kind of lanthanum ferrum silica-based room temperature magnetic refrigerating composite and preparation method Download PDFInfo
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Abstract
A kind of lanthanum ferrum silica-based room temperature magnetic refrigerating composite, it is for uniformly to be mixed with macromolecular material and auxiliary agent by lanthanum ferrum silicon base compound, after through the composite of mold pressing with hot briquetting；Lanthanum ferrum silicon base compound is 10～500: 10: 0.1～1 with the weight of macromolecular material and auxiliary agent；Its preparation method: 1) silica-based for lanthanum ferrum powder, macromolecular material and auxiliary agent are the most uniformly mixed；Load grinding tool afterwards, use moulding press cold moudling；Heat up bond vitrified curing molding again；Have an advantage in that: on the basis of original preparation LaFeSi based compound, solve that LaFeSi base magnetic refrigerating material hardness is big, fragility big, be difficult to the problems such as machine-shaping；This room temperature magnetic refrigerating composite can completely cut off with heat exchanging fluid, prevents magnetic refrigeration working substance oxidation in use；The method utilizing compression molding is the most compressing by composite, it is simple to form high-specific surface area and low channel of resistance to flow magnetic refrigeration part after assembling.
Description
Technical field
The present invention relates to a kind of metallicl magnetic material, particularly to a kind of lanthanum ferrum silica-based room temperature magnetic refrigerating composite and
Its preparation method.
Background technology
Along with the development of modern society, Refrigeration Technique is to improving human lives and working environment serves vital
Effect, provides new research and uses platform the most also to modern science and technology.Refrigeration Technique mainly has at present
Liquid gasification refrigeration, absorption refrigeration, gas expansion refrigeration, thermoelectric cooling, thermoacoustic refrigeration, pulse tube refrigeration etc. are many
The mode of kind.Wherein, the most frequently used Refrigeration Technique be liquid gasification refrigeration, this technology use cold-producing medium be based on
The halogenated materials of the lighter hydrocarbons such as freon, not only has greenhouse effect, and energy resource consumption is big, additionally these cold-producing mediums
Also have strong ozone-depleting effect, huge to the destruction of environment.Therefore, a kind of not only environmental protection is found but also energy-efficient
New Refrigerating technology has become as problem demanding prompt solution in world wide.The magnetothermal effect utilizing material grows up
Magnetic Refrigeration Technique be in recent years by the new technique with important application prospect paid attention to both at home and abroad extensively.By
In room temperature magnetic refrigerating technology, there is environmental protection and energy-efficient feature, paid much attention to by countries in the world, high
Effect magnetic refrigerating material and relevant issues research thereof the most just cause the great interest of people.
As far back as 1881, Warburg just reported in the document of Ann.Phys.13 (1881) 141, is put into by ferrum
During magnetic field can outside heat release, here it is the magnetothermal effect being widely studied later (Magnetocaloric effect, MCE)
Phenomenon.Magnetothermal effect is the intrinsic properties of magnetic material, at present magnetothermal effect is commonly defined as magnetic material and exists
Magnetic field strengthens or heat release or the physical phenomenon of heat absorption when weakening, or perhaps material is produced during magnetization or demagnetization
Raw isothermal Entropy Changes or adiabatic heating phenomenon.Magnetic refrigeration modes is a kind of new refrigeration with magnetic material as working medium
Technology, its ultimate principle is made by the reversible magnetothermal effect of magnetic refrigerating material, i.e. during magnetic refrigerating material isothermal magnetization,
Outwardly release heat, and reduce because of temperature during adiabatic demagnetization, from extraneous draw heat, reach purpose of freezing.Profit
The magnetic Refrigeration Technique got up with magnetothermal effect phenomenon development, compared with traditional liquid gasification Refrigeration Technique, tool
Have three clear advantages: (1) environmental protection: magnetic refrigeration uses solid coolant working medium, solve gas poisonous,
Easily leakage, inflammable and to problems such as the destruction of ozone layer and greenhouse effect；(2) energy-efficient: magnetic refrigeration produces magnetic
The thermal procession of heat effect is high reversible, and its intrinsic thermodynamic efficiency can reach Carnot efficiency, and actual energy
The efficiency realized also can reach the 60%-70% of Carnot's cycle efficiency, the highest；(3) reliable and stable: magnetic freezes
Without gas compressor, vibration and noise is little, and the life-span is long, and reliability is high.
NaZn13The LaFe of structure13-xSixCompound is one of the most valued current magnetothermal effect material.
The applicant is one of domestic researcher carrying out LaFeSi based compound magnetic hystersis loss the earliest, from theoretical and experimental
LaFeSi compound magnetic entropy is become and the impact of magnetic loss by systematic study interstitial atom carbon.Research finds, magnetic field lures
The itinerant-electron metamagnetic sent out has a significant impact to magnetothermal effect and magnetic hystersis loss, and with the change of phase transition temperature
Change closely related.In LaFeSi based compound, substitute La with other rare earths (R) or all can with Si replacement Fe
The magnetic entropy making LaFeSi based compound becomes the rapid decrease with the increase of Curie temperature, introduces gap hydrogen and carbon makes magnetic entropy
Become less with the fall of Curie temperature, and substitute Fe with Co and be between the two；Rare earth R substitutes La meeting
The change magnetic transition causing Magnetic Field-Induced strengthens, although magnetic hystersis loss has risen but magnetic entropy change dramatically increases, and part
Co substitutes Fe can slow down the speed that magnetic entropy change reduces with Curie temperature rising, and magnetic hystersis loss disappears the most completely simultaneously
Losing, gap hydrogen and carbon are also to suppressing the delayed important function that risen, and the heat that the introducing of carbon makes LaFeSi compound is steady
Qualitative significantly improve.Therefore, in LaFeSi interstitial compound, by the appropriate replacement of R and Co, control magnetic
Field induction becomes the magnetic transition impact on material magnetothermal effect, can suppress again heat stagnation while ensureing to obtain great magnetic entropy variation
And magnetic hysteresis, and easily dimmable Curie temperature, it is to obtain the big magnetothermal effect of room temperature and low magnetic hystersis loss magnetic refrigerating material
Effective way.
LaFeSi based compound has the big magnetothermal effect of room temperature and low magnetic hystersis loss as novel magnetic refrigerating material, but
These materials, when using as magnetic refrigeration working substance, need to be processed into certain shape；Due to LaFeSi based compound
Being a kind of metal gap compound, fragility is big, poor impact resistance, and traditional processing technique is difficult to add these materials
Work becomes the shape needed for Magnetic refrigerator, greatly limit its application at magnetic refrigerator.As far back as 1999
Year, the K.A.Gschneidner of U.S.'s Arm ' s laboratory just points out, the development of magnetic Refrigeration Technique not only needs to send out
Now novel with sign magnetic refrigerating material, is also required to these materials processing to become to be suitable to the porous of magnetic refrigeration process simultaneously
Medium (includes parallel plate, spherical, sandwich structure, linear structure etc.).The processing of current room temperature magnetic refrigerating material
Forming method and technique mainly include the methods such as composite algorithm, powder metallurgy and vacuum diffusion welding；By selecting fusing point
The metal that heat conductivity is higher than refrigeration working medium less than refrigeration working medium, heating and melting aftershaping, the limitation of this method
Property be it is difficult to ensure that bi-material fusing time do not generate intermetallic compound.Diffusion in vacuum Welding is in vacuum
Or pressurize under inert gas shielding, make mother metal be in close contact, but this method is unsuitable for the sample that fragility is bigger；
These forming methods based on the magnetic refrigerating material on the basis of high-temperature fusion or hot pressing, processing temperature is high, and energy disappears
Consumption is big, is difficult to finely modulate the pattern of magnetic refrigerating material, it more difficult to realize the magnetic refrigerating material of preparation porous.
Summary of the invention
Present invention aim on the basis of original preparation LaFeSi base compound material, for LaFeSi base magnetic system
The hardness of cold material is big, fragility big, be difficult to the problems such as machine-shaping, and provides a kind of and be prone to based on macromolecular material
Lanthanum ferrum silica-based room temperature magnetic refrigerating composite of machine-shaping and preparation method thereof, improves LaFeSi base magnetic refrigerating material
Processing characteristics, and improve the mechanical property of magnetic refrigerating material, for the application of a kind of applicable magnetic refrigerator compact structure,
The LaFeSi base magnetic refrigeration composite material that intensity is high.
Technical solution of the present invention is as follows for achieving the above object:
The lanthanum ferrum silica-based room temperature magnetic refrigerating composite that the present invention provides, its be by powder lanthanum ferrum silicon base compound and
Graininess macromolecular material and granular auxiliary agent uniformly mix, after through molding and the straight flap-type of hot briquetting, straight
The composite of ripple glaze flap-type or in a zigzag ripple glaze flap-type；
Described macromolecular material is selected from polyethylene, polrvinyl chloride, polypropylene, polybutene, polystyrene, polymethyl
Acid methyl ester, Kynoar, politef, polyamide, polyimides, polyethylene terephthalate, polyethylene
One in naphthoic acid ester, polyether sulfone, Merlon, phenolic resin and epoxy resin, two or more；
Described auxiliary agent one in antioxidant, plasticizer and heat stabilizer, two or three；
Described lanthanum ferrum silicon base compound is 10～500: 10: 0.1～1 with the weight of macromolecular material and auxiliary agent.
Described lanthanum ferrum silicon base compound is La (FeSi)13、La(FeSi)13R1、La(FeCoSi)13、
La(FeCoSi)13R1、LaR(FeSi)13、LaR(FeSi)13R1、LaR(FeCoSi)13Or LaR (FeCoSi)13R1；
Wherein, R1 is C, H or CH；R is Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho,
Er, Tm, Yb or Lu.
The particle diameter of described powdered lanthanum ferrum silicon base compound is 0.005～0.5 millimeter.
Described antioxidant be diphenylamines, p-phenylenediamine, dihydroquinoline, 2, tri-grades of butyl-4-methyl of 6-Phenol, double
(3,5-tri-grades of butyl-4-hydroxy phenyls) thioether or four (β-(3,5-tri-grades of butyl-4-hydroxy phenyls) propanoic acid) seasons penta
Four alcohol esters；
Described plasticizer is dibutyl phthalate, makes phthalic acid di-isooctyl, phthalic acid two isodecyl
Ester, phthalic acid two (2-Octyl Nitrite), dioctyl sebacate, adipic acid dibutyl ester, Azelaic Acid dibutyl ester,
Trioctyl phosphate, tricresyl phosphate, diphenylisooctyl phosphate, epoxidised fatty acid glyceride, epoxyfatty acid
Monoesters, epoxy tetrahydrophthalic acid ester, chlorinated paraffin or chlorination stearate；
Described heat stabilizer be dibasic lead stearate, hydration lead sulfate tribasic, Dythal,
Dibasic lead phosphite, normal-butyl sulfur are for tin salt, dialkyltin mercaptides or carboxylic acid organotin.
Described straight flap-type, straight ripple glaze flap-type or zigzag ripple glaze flap-type lanthanum ferrum silica-based room temperature magnetic refrigerating composite wood
The thickness of material is 0.1～2.0 millimeter.
The preparation method of the lanthanum ferrum silica-based room temperature magnetic refrigerating composite that the present invention provides, its step is as follows:
1) lanthanum ferrum silicon base compound is become 0.005～0.5 milli by pulverizing, ball milling, plasma spraying or machine tooling
The powder of rice；
2) under normal temperature condition, respectively macromolecular material and auxiliary agent are ground to the granule of 100～250 mesh at grinder
Shape, afterwards, joins by weight by powder lanthanum ferrum silicon base compound, graininess macromolecular material and granular auxiliary agent
Than being the ratio mixing of 10～500: 10: 0.1～1 and being uniformly dispersed with dispersion machine；
3) mixed material of mix homogeneously is loaded in grinding tool, under 1～10MPa pressure with moulding press cold pressing 10～
Molding in 30 minutes；It is shaped as straight flap-type, straight ripple glaze flap-type or zigzag ripple glaze flap-type；
4) again in 1～10MPa pressure limit, it is warming up to 100-300 DEG C with the heating rate of 1～5 DEG C/min,
Constant temperature 5～be cooled to room temperature after 30 minutes, unloads grinding tool and obtains lanthanum ferrum silica-based room temperature magnetic refrigerating composite；
Described macromolecular material is selected from polyethylene, polrvinyl chloride, polypropylene, polybutene, polystyrene, polymethyl
Acid methyl ester, Kynoar, politef, polyamide, polyimides, polyethylene terephthalate, polyethylene
One in naphthoic acid ester, polyether sulfone, Merlon, phenolic resin and epoxy resin, two or more；
Described auxiliary agent one in antioxidant, plasticizer and heat stabilizer, two or three.
Described lanthanum ferrum silicon base compound is La (FeSi)13、La(FeSi)13R1、La(FeCoSi)13、
La(FeCoSi)13R1、LaR(FeSi)13、LaR(FeSi)13R1、LaR(FeCoSi)13Or LaR (FeCoSi)13R1；
Wherein, R1 is C, H or CH；R is Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho,
Er, Tm, Yb or Lu；
Described straight flap-type, straight ripple glaze flap-type or zigzag ripple glaze flap-type lanthanum ferrum silica-based room temperature magnetic refrigerating composite wood
The thickness of material is 0.1～2.0 millimeter.
Described antioxidant be diphenylamines, p-phenylenediamine, dihydroquinoline, 2, tri-grades of butyl-4-methyl of 6-Phenol, double
(3,5-tri-grades of butyl-4-hydroxy phenyls) thioether or four (β-(3,5-tri-grades of butyl-4-hydroxy phenyls) propanoic acid) seasons penta
Four alcohol esters；
Described plasticizer is dibutyl phthalate, makes phthalic acid di-isooctyl, phthalic acid two isodecyl
Ester, phthalic acid two (2-Octyl Nitrite), dioctyl sebacate, adipic acid dibutyl ester, Azelaic Acid dibutyl ester,
Trioctyl phosphate, tricresyl phosphate, diphenylisooctyl phosphate, epoxidised fatty acid glyceride, epoxyfatty acid
Monoesters, epoxy tetrahydrophthalic acid ester, chlorinated paraffin or chlorination stearate；
Described heat stabilizer be dibasic lead stearate, hydration lead sulfate tribasic, Dythal,
Dibasic lead phosphite, normal-butyl sulfur are for tin salt, dialkyltin mercaptides or carboxylic acid organotin.
Lanthanum ferrum silica-based room temperature magnetic refrigerating composite that the present invention provides and preparation method thereof has the advantages that
How lanthanum ferrum silica-based room temperature magnetic refrigerating composite of the present invention and preparation method thereof solves by oxidizable, easy
The silica-based magnetic refrigerating material of lanthanum ferrum of efflorescence is in the technical application of room temperature magnetic refrigerating；The room temperature magnetic refrigerating material of preparation can
Completely cut off with heat exchanging fluid, can effectively prevent magnetic refrigeration working substance oxidation in use；Utilize the side of compression molding
Composite is once pressed into flat sheet, straight ripple glaze sheet or zigzag ripple glaze sheet by method, it is simple to formed after assembling
High-specific surface area and low channel of resistance to flow magnetic refrigeration part.
Accompanying drawing explanation
Fig. 1 is straight flap-type lanthanum ferrum silica-based room temperature magnetic refrigerating composite schematic diagram；
Fig. 2 is straight ripple glaze flap-type lanthanum ferrum silica-based room temperature magnetic refrigerating composite schematic diagram；
Fig. 3 is zigzag ripple glaze flap-type lanthanum ferrum silica-based room temperature magnetic refrigerating composite schematic diagram.
Detailed description of the invention
Hereinafter with reference to the description present invention that specific embodiment is detailed.
Embodiment 1
By the 97.5 weight portion particle diameters La (FeSi) less than 0.05 millimeter13Compound powder, 2.25 weight portion 150 mesh
The hexamethylenetetramine that phenolic resin (macromolecular material) powder sieved and 0.25 weight portion 150 mesh sieve (helps
Agent) mixing, disperses 15 minutes on high speed dispersor, after material to be mixed is dispersed, is loaded by appropriate material
In the mould of preparation straight foil (thickness is 0.1 millimeter), and mould is placed on moulding press, at room temperature pressurizes
To 10MPa, upper and lower module, after 5 minutes, is warming up to 150 DEG C with the speed of 3 DEG C/min by constant voltage, continues at 10MPa
Keep under the conditions of pressure and 150 DEG C 15 minutes, then stop heating；Lay down after upper and lower mould deblocking temperature is down to room temperature
Pressure, takes off mould from moulding press, and the demoulding i.e. can get the La (FeSi) that thickness is 0.1 milli13Room temperature magnetic refrigerating
The straight foil of composite.
After tested, the thermal conductivity of prepared composite is not less than 3.0 ± 0.2W/ (m K), by the lanthanum ferrum silicon of molding
Basal cell's temperature magnetic refrigerating composite does according to use requirement and suitably cuts out, and i.e. can be used for the word refrigeration of room-temperature magnetic refrigerator
Parts.
Embodiment 2
95 parts of particle diameters are not more than the La (FeSi) of 0.1 millimeter13It is poly-that C compound powder, 4.5 part of 100 mesh sieve
The polyvinyl-chloride use dispersion heat that plasticizer that vinyl chloride powder, 0.25 part of 100 mesh sieve, 0.25 part of 100 mesh sieve
Stabilizer mixes, and disperses 15 minutes, after thing to be mixed is uniformly dispersed, loaded by appropriate material on high speed dispersor
Prepare in the grinding tool of straight ripple glaze sheet (thickness is 1 millimeter), and be placed on moulding press, at room temperature pressurize
To 5MPa, after constant voltage keeps 15 minutes, with the speed of 5 DEG C/min, bolster is warming up to 140 DEG C, Jin Er
Keep at a temperature of 5MPa pressure and 140 DEG C 10 minutes, then stop heating.Treat that bolster temperature is down to room temperature
After lay down pressure, grinding tool is taken off from flat board moulding press, it is 1 millimeter that the sample demoulding i.e. can get thickness
La(FeSi)13The straight ripple glaze thin slice of C powder/polrvinyl chloride room temperature magnetic refrigerating composite.
After tested, the thermal conductivity of this composite is not less than 2.8 ± 0.2W/ (m K), by silated for the lanthanum ferrum of such molding
Compound/polrvinyl chloride room temperature magnetic refrigerating composite uses requirement to do suitable cutting according to refrigeration machine, i.e. can be used for room temperature
Magnetic refrigerator.
Embodiment 3
93 parts of particle diameters are not more than the La (FeCoSi) of 0.5 millimeter13The poly-first that compound powder, 7 part of 200 mesh sieve
Base methacrylate powder mixes, and disperses 15 minutes on high speed dispersor, after thing to be mixed is uniformly dispersed, and will be suitable
Amount material loads in the grinding tool of preparation straight foil (thickness is 0.6 millimeter), and is placed on moulding press, in room
It is forced into 8MPa under temperature, after constant voltage keeps 15 minutes, with the speed of 5 DEG C/min, bolster is warming up to 160 DEG C,
And then keep at a temperature of 8MPa pressure and 160 DEG C 10 minutes, then stop heating.Treat that bolster temperature drops
Laying down pressure to room temperature, taken off by grinding tool from flat board moulding press, it is 0.6 millimeter that the sample demoulding i.e. can get thickness
Thick La (FeCoSi)13The straight foil of powder/polymethyl methacrylate room temperature magnetic refrigerating composite.
After tested, the thermal conductivity of this composite is 2.2 ± 0.2W/ (m K), by the silica-based chemical combination of lanthanum ferrum of such molding
Thing/polymethyl methacrylate room temperature magnetic refrigerating composite uses requirement to do suitable cutting according to refrigeration machine, the most available
In room-temperature magnetic refrigerator.
Embodiment 4
90 parts of particle diameters are not more than the La (FeCoSi) of 0.3 millimeter13H compound powder, 10 part of 150 mesh sieve
Polyamic acid performed polymer powder mixes, and disperses 15 minutes on high speed dispersor, after thing to be mixed is uniformly dispersed, and will
Appropriate material loads in the grinding tool of preparation ripple glaze sheet (thickness is 1.5 millimeters) in a zigzag, and is placed on moulding press
On, at room temperature it is forced into 5MPa, after constant voltage keeps 15 minutes, with the speed of 5 DEG C/min by bolster liter
Temperature is to 150 DEG C, and then keeps 15 minutes at a temperature of 5MPa pressure and 150 DEG C；Continue the speed with 5 DEG C/min
It is warming up to 200 DEG C, then keeps 15 minutes at 5MPa and 200 DEG C；It is further continued for the ramp of 5 DEG C/min
To 250 DEG C, then keep 15 minutes at 5MPa and 250 DEG C；Continue with the ramp of 5 DEG C/min to 300 DEG C,
Then keep having completed hot pressing amidation process in 15 minutes at 5MPa and 300 DEG C.Treat that bolster temperature is down to
Laying down pressure after room temperature, taken off by grinding tool from flat board moulding press, it is 1.5 millimeters thick that the sample demoulding i.e. can get thickness
La (FeCoSi)13The zigzag ripple glaze sheet of H powder/polyimides room temperature magnetic refrigerating composite.
After tested, the thermal conductivity of this composite is 2.0 ± 0.2W/ (m K), by the silica-based chemical combination of lanthanum ferrum of such molding
Thing/polyimides room temperature magnetic refrigerating composite uses requirement to do suitable cutting according to refrigeration machine, i.e. can be used for room temperature magnetic
Refrigeration machine.
Embodiment 5
50 parts of particle diameters are not more than the LaPr (FeSi) of 0.3 millimeter13It is poly-that compound powder, 48 part of 150 mesh sieve
Polycarbonate powder, 2 parts of normal-butyl sulfur mix for tin salt (heat stabilizer), disperse 15 minutes on high speed dispersor,
After thing to be mixed is uniformly dispersed, appropriate said mixture material is loaded preparation straight foil (thickness is 2 millimeters)
In grinding tool, and it is placed on moulding press, is at room temperature forced into 1MPa, after constant voltage keeps 15 minutes, with 5 DEG C/min
Speed bolster is warming up to 250 DEG C, and then at a temperature of 1MPa pressure and 250 DEG C keep 15 minutes,
Then heating is stopped.After bolster temperature be down to room temperature, lay down pressure, grinding tool taken off from flat board moulding press,
The sample demoulding i.e. can get the LaPr (FeSi) that thickness is 2 millimeters thick13Powder/Merlon room temperature magnetic refrigerating composite
Straight foil.
After tested, the thermal conductivity of this composite is 0.8 ± 0.2W/ (m K), by the silica-based chemical combination of lanthanum ferrum of such molding
Thing/Merlon room temperature magnetic refrigerating composite uses requirement to do suitable cutting according to refrigeration machine, i.e. can be used for room temperature magnetic
Refrigeration machine.
Embodiment 6
By the 97.5 weight portion particle diameters LaCe (FeSi) less than 0.05 millimeter13CH compound powder, 2.5 weight portions 150
The Kynoar powder mixing that mesh sieves, disperses 15 minutes on high speed dispersor, and material to be mixed is dispersed
After, appropriate material is loaded in the mould of preparation ripple glaze sheet (thickness is 0.2 millimeter) in a zigzag, and mould is put
On moulding press, being at room temperature forced into 10MPa, constant voltage is after 5 minutes, with the speed of 3 DEG C/min by upper and lower mould
Block is warming up to 180 DEG C, continues to keep under the conditions of 10MPa pressure and 180 DEG C 15 minutes, then stops heating；
Laying down pressure after upper and lower mould deblocking temperature is down to room temperature, taken off by mould from moulding press, the demoulding i.e. can get thickness
It is the LaCe (FeSi) of 0.2 milli13The zigzag ripple glaze sheet of CH room temperature magnetic refrigerating composite.
After tested, the thermal conductivity of prepared composite is not less than 2.9 ± 0.2W/ (m K), by the lanthanum ferrum silicon of molding
Basal cell's temperature magnetic refrigerating composite does according to use requirement and suitably cuts out, and i.e. can be used for the word refrigeration of room-temperature magnetic refrigerator
Parts.
Embodiment 7
93 parts of particle diameters are not more than the LaGd (FeCoSi) of 0.4 millimeter13Compound powder, 6.9 part of 200 mesh sieve
Polypropylene powder, 0.1 part of dihydroquinoline powder (antioxidant) mixing, disperse 15 minutes on high speed dispersor,
After thing to be mixed is uniformly dispersed, appropriate material is loaded in the grinding tool of preparation straight foil (thickness is 0.8 millimeter),
And be placed on moulding press, at room temperature it is forced into 8MPa, after constant voltage keeps 15 minutes, with 5 DEG C/min's
Bolster is warming up to 200 DEG C by speed, and then holding 10 minutes at a temperature of 8MPa pressure and 200 DEG C, so
Rear stopping is heated.After bolster temperature be down to room temperature, lay down pressure, grinding tool taken off from flat board moulding press,
The sample demoulding i.e. can get the LaGd (FeCoSi) that thickness is 0.8 millimeters thick13Powder/polymethyl methacrylate room temperature
The straight foil of magnetic refrigeration composite material.
After tested, the thermal conductivity of this composite is 2.3 ± 0.2W/ (m K), by the silica-based chemical combination of lanthanum ferrum of such molding
Thing/polymethyl methacrylate room temperature magnetic refrigerating composite uses requirement to do suitable cutting according to refrigeration machine, the most available
In room-temperature magnetic refrigerator.
Embodiment 8
94 parts of particle diameters are not more than the LaEr (FeCoSi) of 0.2 millimeter13C compound powder, 5.9 part of 200 mesh sieve
Polybutene powder, 2, the mixing of tri-grades of butyl-4-methylphenol (antioxidant) of 6-, high speed dispersor disperses 15
Minute, after thing to be mixed is uniformly dispersed, appropriate material is loaded and prepares straight ripple glaze thin slice (thickness is 0.4 millimeter)
Grinding tool in, and be placed on moulding press, be at room temperature forced into 8MPa, after constant voltage keeps 15 minutes, with
Bolster is warming up to 200 DEG C by the speed of 5 DEG C/min, and then keeps 10 at a temperature of 8MPa pressure and 200 DEG C
Minute, then stop heating.Pressure is laid down, by grinding tool from flat board moulding press after bolster temperature is down to room temperature
On take off, the sample demoulding i.e. can get the LaEr (FeCoSi) that thickness is 0.4 millimeters thick13C powder/polymethylacrylic acid
The straight ripple glaze thin slice of methyl ester room temperature magnetic refrigerating composite.
After tested, the thermal conductivity of this composite is 2.3 ± 0.2W/ (m K), by the silica-based chemical combination of lanthanum ferrum of such molding
Thing/polymethyl methacrylate room temperature magnetic refrigerating composite uses requirement to do suitable cutting according to refrigeration machine, the most available
In room-temperature magnetic refrigerator.
Embodiment 9
92 parts of particle diameters are not more than the LaNd (FeCoSi) of 0.5 millimeter13CH compound powder, 7.5 part of 200 mesh mistake
Polyethylene terephthalate's powder of sieve, 0.25 part of double (3,5-tri-grades of butyl-4-hydroxy phenyls) thioether powder are (anti-
Oxygen agent), the mixing of 0.25 part of dialkyltin mercaptides (heat stabilizer), high speed dispersor disperses 15 minutes,
After thing to be mixed is uniformly dispersed, appropriate material is loaded in the grinding tool of preparation straight foil (thickness is 1.2 millimeters),
And be placed on moulding press, at room temperature it is forced into 8MPa, after constant voltage keeps 15 minutes, with 5 DEG C/min's
Bolster is warming up to 200 DEG C by speed, and then holding 10 minutes at a temperature of 8MPa pressure and 200 DEG C, so
Rear stopping is heated.After bolster temperature be down to room temperature, lay down pressure, grinding tool taken off from flat board moulding press,
The sample demoulding i.e. can get the LaNd (FeCoSi) that thickness is 1.2 millimeters thick13CH powder/polymethyl methacrylate room
The straight foil of temperature magnetic refrigerating composite.
After tested, the thermal conductivity of this composite is 2.0 ± 0.2W/ (m K), by the silica-based chemical combination of lanthanum ferrum of such molding
Thing/polymethyl methacrylate room temperature magnetic refrigerating composite uses requirement to do suitable cutting according to refrigeration machine, the most available
In room-temperature magnetic refrigerator.
Claims (7)
1. a lanthanum ferrum silica-based room temperature magnetic refrigerating composite, it is characterized in that, it is for uniformly to be mixed with graininess macromolecular material and granular auxiliary agent by powder lanthanum ferrum silicon base compound, after through molding and the composite of the straight flap-type of hot briquetting, straight ripple glaze flap-type or in a zigzag ripple glaze flap-type；
Described lanthanum ferrum silicon base compound is La (FeSi)13、La(FeSi)13R1、La(FeCoSi)13、La(FeCoSi)13R1、LaR(FeSi)13、LaR(FeSi)13R1、LaR(FeCoSi)13Or LaR (FeCoSi)13R1；Wherein, R1 is C, H or CH；R is Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu；
Described macromolecular material one in polyethylene, polrvinyl chloride, polypropylene, polybutene, polystyrene, polymethyl methacrylate, Kynoar, politef, polyamide, polyimides, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, Merlon, phenolic resin and epoxy resin, two or more；
Described auxiliary agent one in antioxidant, plasticizer and heat stabilizer, two or three；Wherein,
Described antioxidant be diphenylamines, p-phenylenediamine, dihydroquinoline, 2, tri-grades of butyl-4-methylphenols of 6-, double (3, tri-grades of butyl-4-hydroxy phenyls of 5-) thioether or four (β-(3,5-tri-grades of butyl-4-hydroxy phenyls) propanoic acid) pentaerythritol ester；
Described plasticizer is dibutyl phthalate, diisooctyl phthalate, diisooctyl phthalate, phthalic acid two (2-Octyl Nitrite), dioctyl sebacate, adipic acid dibutyl ester, Azelaic Acid dibutyl ester, trioctyl phosphate, tricresyl phosphate, diphenylisooctyl phosphate, epoxidised fatty acid glyceride, epoxy fatty acid monoester, epoxy tetrahydrophthalic acid ester, chlorinated paraffin or chlorination stearate；
Described heat stabilizer is that dibasic lead stearate, hydration lead sulfate tribasic, Dythal, dibasic lead phosphite, normal-butyl sulfur are for tin salt, dialkyltin mercaptides or carboxylic acid organotin；
Described lanthanum ferrum silicon base compound is 10～500:10:0.1～1 with the weight of macromolecular material and auxiliary agent.
Lanthanum ferrum the most according to claim 1 silica-based room temperature magnetic refrigerating composite, it is characterised in that the particle diameter of described powder lanthanum ferrum silicon base compound is 0.005～0.5 millimeter.
Lanthanum ferrum the most according to claim 1 silica-based room temperature magnetic refrigerating composite, it is characterised in that the thickness of described straight flap-type, straight ripple glaze flap-type or zigzag ripple glaze flap-type lanthanum ferrum silica-based room temperature magnetic refrigerating composite is 0.1～2.0 millimeter.
4. a preparation method for lanthanum ferrum silica-based room temperature magnetic refrigerating composite described in claim 1, its step is as follows:
1) lanthanum ferrum silicon base compound is become by pulverizing, ball milling, plasma spraying or machine tooling the powder of 0.005～0.5 millimeter；
2) under normal temperature condition, respectively macromolecular material and auxiliary agent are ground to the graininess of 100～250 mesh at grinder, afterwards, the ratio that powder lanthanum ferrum silicon base compound, graininess macromolecular material and granular auxiliary agent are 10～500:10:0.1～1 by weight ratio is mixed and is uniformly dispersed with dispersion machine；
3) mixed material of mix homogeneously is loaded in grinding tool, cold pressing molding in 10～30 minutes with moulding press under 1～10MPa pressure；It is shaped as straight flap-type, straight ripple glaze flap-type or zigzag ripple glaze flap-type；
4) again in 1～10MPa pressure limit, it is warming up to 100-300 DEG C with the heating rate of 1～5 DEG C/min, constant temperature 5～be cooled to room temperature after 30 minutes, unloads grinding tool and obtains lanthanum ferrum silica-based room temperature magnetic refrigerating composite；
Described macromolecular material one in polyethylene, polrvinyl chloride, polypropylene, polybutene, polystyrene, polymethyl methacrylate, Kynoar, politef, polyamide, polyimides, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, Merlon, phenolic resin and epoxy resin, two or more；
Described auxiliary agent one in antioxidant, plasticizer and heat stabilizer, two or three.
The preparation method of lanthanum ferrum the most according to claim 4 silica-based room temperature magnetic refrigerating composite, it is characterised in that described lanthanum ferrum silicon base compound is La (FeSi)13、La(FeSi)13R1、La(FeCoSi)13、La(FeCoSi)13R1、LaR(FeSi)13、LaR(FeSi)13R1、LaR(FeCoSi)13Or LaR (FeCoSi)13R1；Wherein, R1 is C, H or CH；R is Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.
The preparation method of lanthanum ferrum the most according to claim 5 silica-based room temperature magnetic refrigerating composite, it is characterised in that the thickness of described straight flap-type, straight ripple glaze flap-type or zigzag ripple glaze flap-type lanthanum ferrum silica-based room temperature magnetic refrigerating composite is 0.1～2.0 millimeter.
The preparation method of lanthanum ferrum the most according to claim 5 silica-based room temperature magnetic refrigerating composite, it is characterized in that, described antioxidant be diphenylamines, p-phenylenediamine, dihydroquinoline, 2, tri-grades of butyl-4-methylphenols of 6-, double (3, tri-grades of butyl-4-hydroxy phenyls of 5-) thioether or four (β-(3,5-tri-grades of butyl-4-hydroxy phenyls) propanoic acid) pentaerythritol ester；
Described plasticizer is dibutyl phthalate, diisooctyl phthalate, diisooctyl phthalate, phthalic acid two (2-Octyl Nitrite), dioctyl sebacate, adipic acid dibutyl ester, Azelaic Acid dibutyl ester, trioctyl phosphate, tricresyl phosphate, diphenylisooctyl phosphate, epoxidised fatty acid glyceride, epoxy fatty acid monoester, epoxy tetrahydrophthalic acid ester, chlorinated paraffin or chlorination stearate；
Described heat stabilizer is that dibasic lead stearate, hydration lead sulfate tribasic, Dythal, dibasic lead phosphite, normal-butyl sulfur are for tin salt, dialkyltin mercaptides or carboxylic acid organotin.
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| CN102466364A (en) * | 2010-11-05 | 2012-05-23 | 中国科学院理化技术研究所 | Magnetic refrigeration working medium bed and preparation method |
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