CN103624491A - Forming process of magnetic refrigeration material - Google Patents
Forming process of magnetic refrigeration material Download PDFInfo
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- CN103624491A CN103624491A CN201310591204.2A CN201310591204A CN103624491A CN 103624491 A CN103624491 A CN 103624491A CN 201310591204 A CN201310591204 A CN 201310591204A CN 103624491 A CN103624491 A CN 103624491A
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- Prior art keywords
- magnetic refrigeration
- magnetic
- working substance
- refrigeration working
- forming method
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a forming process of a magnetic refrigeration material. The forming process comprises the following steps that the magnetic refrigeration material is ground into powder, a foam metal material of a three-dimensional network structure is filled with the magnetic refrigeration material powder, and the foam metal material filled with the magnetic refrigeration material powder is solidified and pressed into a lamelliform material. The forming process of the magnetic refrigeration material has the advantages of solving the problem that the magnetic refrigeration material is difficult to form, and improving the heat transfer capacity of the magnetic refrigeration material.
Description
Technical field
The present invention relates to a kind of magnetic refrigerating material moulding process, particularly relate to the preparation method of high-melting-point fragility magnetic refrigerating material sheet moulding.
Background technology
Room temperature magnetic refrigerating technology, as a kind of novel Refrigeration Technique, due to advantages such as high-efficiency environment friendlies, is more and more subject to people's attention.And room temperature magnetic refrigerating material is as one of room temperature magnetic refrigerating key technology, extremely the researcher of various countries payes attention to, and current developed room temperature magnetic refrigerating material mainly contains Gd base alloy, Mn base alloy and rare earth-transition group alloy, LaFe
13-xsi
xbe associated gold.
In practical application due to the needs of magnetic refrigerator (system) structural design and solid-liquid heat exchange, magnetic refrigerating material is wanted the processed various shapes that are prepared into conventionally, thereby improve the solid-liquid heat exchange efficiency in magnetic refrigerator (system), and magnetic cooling material mostly is the magneto-caloric materials such as intermetallic compound and oxide, because its fragility is large, moulding is very difficult.Magnetic refrigerating material is applied in magnetic refrigerator as magnetic working medium, not only needs large magnetic heating performance, also should possess certain intensity and toughness simultaneously, and the difform working medium that meets solid-liquid heat exchange needs.So preparation has certain toughness, and the practical magnetic refrigerating material with higher heat exchange efficiency becomes particularly important.At present, the moulding of relevant fragility magnetic refrigerating material is reported to some extent, as directly used graininess (the coated thin metal of one deck in surface), sheet (high temperature sintering moulding), but far can not meet the needs of magnetic refrigeration, in addition, the material of sinter molding is still more crisp, and heat conductivility is poor.The present invention can effectively prepare toughness and the good sheet magnetic refrigerating material of thermal conductivity.
Summary of the invention
The object of the invention is to overcome the shortcoming that fragility magnetic refrigeration alloy is difficult to moulding, provide a kind of laminar magnetic refrigerating material moulding process with higher heat exchange efficiency, for technological reserve is carried out in the application of magnetic refrigerating material on room temperature magnetic refrigerating.
The present invention's magnetic refrigerating material used is mainly high-melting-point fragility magnetic refrigeration alloy, and its concrete moulding process is as follows:
1) magnetic refrigeration alloy used is ground to 100 order-200 orders, the different particle size interval of 200 order-300 order;
2) powder in different-grain diameter interval after grinding is mixed according to certain mass ratio, in interpolation weight ratio, be no more than 10 bonding agent, after fully stirring, be filled in the foam metal with tridimensional network;
3) low-temperature evaporation moisture and solidify, utilizes laminar below roll squeezer compacting 0.8mm, the shape material of laminating.
Preferably, the step 2) weight ratio optional (100 order-200 order) in described different-grain diameter interval: (200 order-300 order)=0:1,1:4,1:3,1:2,1:1,2:1,3:1,4:1, object is for increasing the loading of magnetic refrigerating material.
Preferably, step 2) described bonding agent can be selected carboxymethyl cellulose (CMC)+polytetrafluoroethylene (PTFE), epoxy resin, heat conductive silica gel, metallic tin (Sn).
Preferably, step 2) object of described use foam metal is to utilize it to do skeleton to be convenient to moulding, reduce the fragility of material, and the thermal conductivity factor that had of selected foam metal, porosity > 90%, the surface density 650-7000g/m of foam metal
2, hole density (ppi) 20-90, thickness < 5mm.
Preferably, the selection of step 3) bake out temperature: above organic binder bond bake out temperature is between 100-200 ℃; The bake out temperature of low-melting-point metal is at T
moltento T
moltenbetween+50 ℃.Drying time is chosen as 2-6 hour.
Preferably, step 3) utilizes the roll squeezer can multi-pass roll-in, avoids being out of shape excessive material cracking.
Compared with prior art, the invention has the advantages that and utilize the reticulated polymer foam metal with better toughness to do skeleton, the magneto-caloric materials such as metalwork compound and oxide are filled wherein, and the material after moulding has certain toughness, and heat exchange efficiency improves greatly; Technique is simple, with low cost, is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1. the sheet LaFe after moulding
11.6si
1.4material outline drawing.
Fig. 2. three-dimensional netted foam copper matrix outline drawing.
Fig. 3. the LaFe after moulding
11.6si
1.4flaky material toughness exploded view directly perceived.
Fig. 4. the optical microscopy map of three-dimensional netted foam copper matrix.
Fig. 5. LaFe
11.6si
1.4the microstructure figure of alloy sheet moulding sample.
Fig. 6. the XRD diffracting spectrum of powder and the XRD diffracting spectrum of sheet specimens before moulding.
the specific embodiment
Below in conjunction with drawings and Examples, the present invention is described in further details; given embodiment can not be interpreted as limiting the scope of the invention, and the nonessential improvement that those skilled in the art have done the present invention according to the invention described above content and adjustment should belong to protection scope of the present invention.
Embodiment 1
According to weight ratio preparation 2%CMC solution, after 48h, solution has certain viscosity; Getting hole density PPI is 90, and surface density is 650g/m
2, porosity is 97%, the foam copper that thickness is 2mm (as Fig. 2), and sheet foam copper has tridimensional network (as Fig. 4), will have NaZn
13the LaFe of phase
11.6si
1.4alloy grinds to form 100 order-200 orders and two interval particles of 200 order-300 orders, and mixes with weight ratio 1:4; By mixed LaFe
11.6si
1.4particle mixes with weight ratio 85:15 with CMC solution, stirs 30min; To pasty liquid, add PTFE, weight is about LaFe
11.6si
1.41.5% of particle, formation pasty liquid stirs; Immediately this pasty liquid is painted into sheet foam copper with hairbrush, has filled the hole of foam copper as far as possible; Put into 110 ℃ of 3h of drying box and dry, evaporate its moisture, then can multi-pass roll-in, just formation sheet LaFe as shown in Figure 1 at roll squeezer
11.6si
1.4alloy, and there is certain toughness (Fig. 3).Adopt light microscope to carry out tissue topography's analysis, LaFe
11.6si
1.4in the hole of the evengranular foam copper that is filled in tridimensional network (as Fig. 5); Carry out XRD diffraction analysis (as Fig. 6), there is NaZn
13the LaFe of phase
11.6si
1.4alloy phase does not change, and has just added the diffraction maximum of a Cu more, and the magnetic heating performance of this illustrative material does not change.
Embodiment 2
According to weight ratio preparation 2%CMC solution, after 48h, solution has certain viscosity; Getting hole density PPI is 90, and surface density is 650g/m
2, porosity is 97%, the sheet foam copper (as Fig. 2) that thickness is 2mm, has tridimensional network (as Fig. 4), will have the LaFe of NaZn13 phase
11.6si
1.4alloy grinds to form 100 order-200 orders and two interval particles of 200 order-300 orders, and mixes with weight ratio 1:4; The LaFe that 200 order-400 order Sn particles is added to mixing
11.6si
1.4in particle, LaFe
11.6si
1.4particle mixes than 85:5 is even with Sn particle weight, and hybrid particles is mixed with weight ratio 85:15 with CMC solution, stirs 30min and forms pasty liquid; Immediately this pasty liquid is painted into sheet foam copper with hairbrush, has filled the hole of foam copper as far as possible; Put into 230 ℃ of 4h of drying box and dry, evaporate its moisture, then can multi-pass roll-in at roll squeezer, the sheet LaFe that thickness is 0.6mm just formed
11.6si
1.4alloy.
[0021] embodiment 3
According to weight ratio preparation 2%CMC solution, after 48h, solution has certain viscosity; Getting hole density PPI is 40, and surface density is 1100g/m
2, porosity is 95%, the sheet foam copper (as Fig. 2) that thickness is 2mm, has tridimensional network (as Fig. 4), will have the LaFe of NaZn13 phase
11.6si
1.4alloy grinds to form 100 order-200 orders and two interval particles of 200 order-300 orders, and mixes with weight ratio 1:2; The LaFe that 200 order-400 order Sn particles is added to mixing
11.6si
1.4in particle, LaFe
11.6si
1.4particle mixes than 85:5 is even with Sn particle weight, and hybrid particles is mixed with weight ratio 85:15 with CMC solution, stirs 30min and forms pasty liquid; Immediately this pasty liquid is painted into sheet foam copper with hairbrush, has filled the hole of foam copper as far as possible; Put into 230 ℃ of 5h of drying box and dry, evaporate its moisture, then can multi-pass roll-in at roll squeezer, the sheet LaFe that thickness is 0.66mm just formed
11.6si
1.4alloy.
Claims (5)
1. a magnetic refrigeration working substance forming method, the method is that Powdered magnetic refrigerating material is inserted in the foam metal material with tridimensional network, and be pressed into laminarly, it is characterized in that solving the problem that magnetic refrigerating material is difficult to moulding, and improve magnetic refrigerating material heat transfer potential.
2. magnetic refrigeration working substance forming method according to claim 1, is characterized in that adopted magnetic refrigeration working substance comprises intermetallic compound and oxide magneto-caloric material.
3. magnetic refrigeration working substance forming method according to claim 1, is characterized in that adopted foam metal has good toughness and good heat conductivility, comprises copper, aluminium, nickel etc.
4. magnetic refrigeration working substance forming method according to claim 1, is characterized in that Powdered magnetic refrigeration working substance inserts the method for foam metal and relate to that dry method is inserted, wet method is inserted, and adopts the mode such as roll to make its densified moulding.
5. according to magnetic refrigeration working substance forming method described in claim 1 and 4, it is characterized in that dry method is inserted with wet method inserts and contains binding agent or containing binding agent, the solvent that wet method adopts can be the mixed solvent of organic solvent or organic and water etc., and bonding agent can be organic adhesive and low-melting-point metal bonding agent etc.
Priority Applications (1)
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|---|---|---|---|
| CN201310591204.2A CN103624491A (en) | 2013-11-22 | 2013-11-22 | Forming process of magnetic refrigeration material |
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|---|---|---|---|
| CN201310591204.2A CN103624491A (en) | 2013-11-22 | 2013-11-22 | Forming process of magnetic refrigeration material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105469916A (en) * | 2015-11-23 | 2016-04-06 | 四川大学 | Lanthanum-iron-silicon-based room-temperature magnetic refrigerant molding material and preparation method thereof |
| GB2539010A (en) * | 2015-06-03 | 2016-12-07 | Vacuumschmelze Gmbh & Co Kg | Method of fabricating an article for magnetic heat exchange |
| CN106381133A (en) * | 2016-08-25 | 2017-02-08 | 华南理工大学 | La-Fe based magnetic refrigeration composite material and preparation method thereof |
| CN106906408A (en) * | 2015-12-22 | 2017-06-30 | 中国科学院宁波材料技术与工程研究所 | LaFeSi base magnetic refrigeration composite materials and preparation method and application |
| WO2018188262A1 (en) * | 2017-04-14 | 2018-10-18 | 北京科技大学 | Magnetic refrigeration composite material, preparation method therefor and use thereof |
| US10472694B2 (en) | 2015-06-03 | 2019-11-12 | Vacuumschmelze Gmbh & Co. Kg. | Method of fabricating an article for magnetic heat exchanger |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2539010A (en) * | 2015-06-03 | 2016-12-07 | Vacuumschmelze Gmbh & Co Kg | Method of fabricating an article for magnetic heat exchange |
| US10213834B2 (en) | 2015-06-03 | 2019-02-26 | Vacuumschmelze Gmbh & Co. Kg | Method of fabricating an article for magnetic heat exchanger |
| US10472694B2 (en) | 2015-06-03 | 2019-11-12 | Vacuumschmelze Gmbh & Co. Kg. | Method of fabricating an article for magnetic heat exchanger |
| GB2539010B (en) * | 2015-06-03 | 2019-12-18 | Vacuumschmelze Gmbh & Co Kg | Method of fabricating an article for magnetic heat exchange |
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| CN105469916A (en) * | 2015-11-23 | 2016-04-06 | 四川大学 | Lanthanum-iron-silicon-based room-temperature magnetic refrigerant molding material and preparation method thereof |
| CN105469916B (en) * | 2015-11-23 | 2017-12-19 | 四川大学 | A kind of lanthanum iron silicon substrate room-temperature magnetic refrigeration moulding material and preparation method thereof |
| CN106906408A (en) * | 2015-12-22 | 2017-06-30 | 中国科学院宁波材料技术与工程研究所 | LaFeSi base magnetic refrigeration composite materials and preparation method and application |
| CN106381133A (en) * | 2016-08-25 | 2017-02-08 | 华南理工大学 | La-Fe based magnetic refrigeration composite material and preparation method thereof |
| CN106381133B (en) * | 2016-08-25 | 2019-07-12 | 华南理工大学 | A kind of La-Fe base magnetic refrigeration composite material and preparation method thereof |
| WO2018188262A1 (en) * | 2017-04-14 | 2018-10-18 | 北京科技大学 | Magnetic refrigeration composite material, preparation method therefor and use thereof |
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Application publication date: 20140312 |