CN102189406A - Processing method and anti-corrosion technology for magnetic refrigeration material - Google Patents
Processing method and anti-corrosion technology for magnetic refrigeration material Download PDFInfo
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- CN102189406A CN102189406A CN2010101198647A CN201010119864A CN102189406A CN 102189406 A CN102189406 A CN 102189406A CN 2010101198647 A CN2010101198647 A CN 2010101198647A CN 201010119864 A CN201010119864 A CN 201010119864A CN 102189406 A CN102189406 A CN 102189406A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
- H01F1/015—Metals or alloys
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Abstract
The invention relates to a method for processing a magnetic refrigeration material by taking rare earth metal Gd and a multicomponent alloy thereof as raw materials. The magnetic refrigeration material taking Gd as a main body mainly comprises a pure Gd piece, pure Gd particles, a rolled Gd piece, a Gd-based alloy and a Gd-based alloy rolled piece. The processing method comprises the following steps of: firstly, processing a Gd metal or Gd-based alloy ingot; secondly, carrying cold rolling and vacuum heat treatment; thirdly, treating the surface of the rolled piece; fourthly, precisely dividing the rolled piece; and fifthly, plating the surface of the rolled piece.
Description
Technical field:
The present invention relates to a kind of processing method of magnetic refrigerating material, referring specifically to rare earth metal gadolinium and multicomponent alloy thereof is the processing method of the magnetic refrigerating material of raw material.
Technical background:
The refrigerating material of people's employing at present is a lot, chemical materials such as liquefied ammonia, liquid helium, freon, lithium bromide are arranged, these refrigerating materials all are to freeze by the principle of gasification heat absorption and liquefaction heat radiation, and they not only cost an arm and a leg, and its making and use all to bring to environment and pollute and destroy.
This century the '20s end, scientist has found the magnetothermal effect principle, emit heat to the external world when being the magnetic refrigerating material isothermal magnetization, absorb heat from the external world during adiabatic demagnetization, thereby reach the purpose of refrigeration, many subsequently scientists and engineers have carried out a large amount of research and developments to material, magnetic Refrigeration Technique and the device with magnetothermal effect, up to the present, the following low temperature magnetic refrigeration apparatus of 20K is in some field practicability, but its making must carry out at low temperatures, cost is too big.
Room temperature magnetic refrigerating is meant with the magnetic material to be a kind of novel Refrigeration Technique of working medium, its principle is to utilize the magnetothermal effect of magnetic refrigerating material (Magnetocaloric efffect, MCE), emit heat to the external world when being the magnetic refrigerating material isothermal magnetization, absorb the principle of heat during adiabatic demagnetization from the external world, thereby reach the purpose of refrigeration.The magnetic refrigeration is the Refrigeration Technique of an environmental protection.Compare with tradition refrigeration, atmospheric ozone layer is not had destruction, no room temperature effect, unit duty height, energy consumption, moving component are few, so mechanical oscillation and noise are little, and operating frequency is low, the reliability height.Aspect the thermal efficiency, the magnetic refrigeration can reach 30%～60% of Carnot cycle, and relies on the kind of refrigeration cycle of gas compression-expansion generally can only reach 5%～10%.The magnetic refrigeration application is in extensive range, from μ K, mK and to all applicable more than the room temperature.In the low temperature field, the magnetic Refrigeration Technique has application promise in clinical practice aspect liquid nitrogen, liquid helium, especially the green energy resource liquid hydrogen producing; In the particularly near room temperature field of high temperature, the magnetic refrigeration has broad application prospects at refrigerator, air-conditioning and supermarket food product refrigeration system aspects, so the improvement of the production method of magnetic refrigerating material seems very urgent.
Summary of the invention:
At present, magnetic refrigerating material is mainly based on the material of gadolinium: pure gadolinium sheet (Gd), pure gadolinium particle, rolling gadolinium sheet, gadolinium base alloy, gadolinium base alloy rolls sheet.
Show through professional person's result of the test for many years, the material of relative other several proterties, rolling developing direction with rare earth metal gadolinium or gadolinium base alloy for having superiority, rolling densification, corrosion resistance is higher relatively, therefore reduces cost under the situation of guaranteed quality, is beneficial to the industrialization of magnetic Refrigeration Technique, be the technology research project of pendulum in face of global people, the present invention just provides a kind of comparatively production technology of economic magnetic refrigerating material.The gadolinium metal of commonsense method melting or gadolinium base alloy are because the restriction of its density, often can't obtain big skill upgrading, therefore in order to reach higher unit magnetic refrigerating capacity, all be to be principal direction to increase surface area in the past, the gadolinium sheet metal of cold rolling preparation or gadolinium base alloy sheet are because material is fine and close more, in unit volume, more magnetic refrigeration working substance is arranged, can more direct lifting magnetic refrigerating capacity.
Be the production gadolinium base magnetic refrigerating material of high efficiency, low cost more, the present invention proposes following technical solution.
Technological process:
Be prepared as the main technological principle of describing with the gadolinium metal, the processing technology of gadolinium base binary or multicomponent alloy roughly the same:
One, the processing and fabricating of gadolinium metal or gadolinium base alloy material ingot:
1, gadolinium metal charge ingot adopts the vacuum intermediate frequency furnace to carry out melting by the reduction reaction method, makes technical grade gadolinium ingot (purity is greater than 99.9% relatively, and total amount is greater than 99.5%), and for removing calcium class light impurities, regulation must be used vacuum medium frequency remelting one time.
Technology is described: the gadolinium fluoride and the calcium metal that adopt wet method to fluoridize adopt hydraulic press to be pressed into ingot in proportion respectively, and the tungsten crucible of packing into vacuumizes that (vacuum is higher than 1*10
-1Handkerchief) temperature (1400-1600 degree) that raises melts and carries out reduction reaction, casts after reaction is finished, adopt the quick cool metal of water cooled copper mould, temperature near room temperature after blow-on take out the gadolinium ingot, thereafter the gadolinium ingot is carried out shove charge melting casting again again after the fragmentation, carry out the remelting program.
If 2 need preparation gadolinium base alloy material ingot, then the gadolinium metal does not then need remelting again, can be directly adopt the vacuum intermediate frequency furnace directly to be smelted into the material ingot by the proportioning back of weighing on gadolinium metal and required other metals, this process can directly realize alloying and remove light weight calcium class impurity.Alloy ratio is Gd
xB
yM
z, X=(0.6-0.85) wherein, Y=(0.4-0.15), Z=surplus), can be any of other metals of terres rares about other alloy B, M.
3, cooling off the material ingot surface of coming out of the stove adopts the method for polishing grinding to remove top layer impurity.
4, use lathe, milling machine and line cutting kind equipment will expect that ingot is divided into the material embryo that presets specification, to meet the roughing requirement.
5, the material embryo with well cutting carries out cleaning polishing, removes oxide layer and top layer impurity that processing stays.
Two, cold rolling and vacuum heat:
The specification material embryo that cutting and polishing is good carries out cold rolling, requiring to be rolled the technology passage according to rolling final thickness determines, the rolling thickness that uses at present is the master as the 0.5-1.2 millimeter, and (vacuum heat temperature empirical equation is: (melting point metal+273)/2-273 to eliminate rolling stress and to alleviate the phenomenon that rolling back material hardens to be aided with vacuum heat according to rolling mill practice in cold-rolled process.
Three, rolling surface treatment:
Be worked into rolling of suitable dimension, after vacuum heat, select whether to carry out surface grinding processing (for example can adopt twin grinder to carry out lappingout) according to the fineness of customer requirement.
Four, rolling precision cut apart:
The technology that rolling precision cut apart has several, selects or is used in combination according to customer requirement precision and processing quantity, specifically describes as follows:
1, the mould punching press is cut apart: relatively low as the customer requirement dimensional accuracy, and can make diel and carry out burst processing, above method is fit to more large batch of processing, and cost is lower, and speed is very fast, but tolerance is bigger.
2, for satisfying the required precision height, little in batches requirement can be made suitable frock, anchor clamps, and the mode that adopts laser cutting, high-pressure water knife cutting or line to cut is carried out rough segmentation, reserve that suitable allowance finish grindes or CNC milling machine processing, to reach the tolerance of customer requirement.
3, in actual production process, can be according to client's required precision, use can combine above-mentioned a few class processing methods.
Five, rolling overlay coating handled:
1, the activity of gadolinium metal or gadolinium base binary or multicomponent alloy is all bigger, than being easier to oxidation, needs coating processing is carried out on its surface.
2, must consider that the thermal conductivity factor of coating and thickness of coating can meet the material operating mode, so need satisfy following two requirements:
(1) coating layer thickness is controlled at 6-10 μ m as far as possible.
(2) and select for use thermal conductivity factor near or equal the coating or the coating of base material thermal conductivity factor, such as: the thermal conductivity factor of metal gadolinium is: W/ (m.k)=10.6, the thermal conductivity factor of binary and multicomponent alloy can be measured by the thermal conductivity factor tester of specialty.
3, for example: poly-tetrafluoro type coating, Parylene conformal coating class methods are done suitable adjustment and can also be selected as coating.
4, in the common electrical depositing process pickling process is arranged all, pickling process can cause material surface oxidation blackout, the compact oxidation layer that forms also is not easy to remove synchronously, operations such as the pickling that all need adopt in the electroplating processes process, electrolytic degreasing, electro-deposition, all more can cause the workpiece hydrogen embrittlement, so get rid of the common anticorrosion mode of water plating class in principle.
5, coating for example: through test of many times, can determine that zinc-chromium coating is more suitable a kind of selection! Now anticorrosion mechanism is described below:
1., wall effect: because sheet zinc, aluminium lamination shape are overlapping, hindered the process that corrosive mediums such as water, oxygen arrive matrix, can play a kind of shielding action of isolation.
2., passivation: in the processing procedure of zinc-chromium coating, chromic acid and zinc, aluminium powder and parent metal generation chemical reaction generate fine and close passivating film, and this passivating film has good decay resistance.
3., cathodic protection effect: the topmost protective effect of zinc-aluminium chrome coating is the same with zinc coat, is that matrix is carried out cathodic protection.
6, the working procedure of zinc-chromium coating:
Solvent degreasing---mechanical ball blast (sandblast)---spraying---baking---secondary spraying---baking---drying.
The selection of anti-corrosion method is not limited only to zinc-chromium coating, allly can not cause hydrogen embrittlement and top layer oxidation, meets the thermal conductivity factor requirement and meets the coating or the coating of thickness requirement, all can be used as the surface anticorrosion method of material.
Showing through for many years result of the test, is rolling developing direction for having superiority of magnetic refrigeration of raw material with rare earth metal gadolinium or gadolinium base alloy, because through the rolling rare earth metal gadolinium that forms or the sheet material of gadolinium base alloy, its compactness height, good corrosion resistance.The processing method of rolling magnetic refrigerating material has been improved production procedure, has reduced working condition, has saved production cost, has strengthened the antiseptic property of product, and being known as by people is a kind of very promising novel magnetic refrigerating material technology of preparing.
Description of drawings:
Fig. 1 is a process flow diagram of the present invention.
The specific embodiment:
The Rare-Earth Magnetic refrigerating material is free of contamination refrigerating working material, replace refrigerator, refrigerator, refrigerator-freezer and the air-conditioner that uses freon refrigerant at present with magnetic refrigerating material, can eliminate and be used to produce and use environmental pollution that freon class refrigeration caused and the destruction of atmospheric ozone layer.The magnetic refrigeration is by the magnetothermal effect principle, utilize externally-applied magnetic field and make the magnetic moment of magnetic working medium that orderly, unordered variation (phase transformation) take place to cause magnet heat absorption and exothermic effects and the kind of refrigeration cycle of carrying out, compare characteristics such as magnetic refrigeration has the close height of entropy, volume is little, simple in structure, noise is little, efficient is high and low in energy consumption with gas compression refrigeration.Current, the magnetic refrigeration is used widely at low-temperature space.At present, because the forbidding of Freon gas, the research of room temperature magnetic refrigerating has become international forward position research topic.China will completely forbid chloro-fluorocarbon and hydrogen chloro-fluorocarbon compounds cold-producing mediums such as production and use freon in 2010, therefore, need quickening to study the research of magnetic Refrigeration Technique and application, will develop paces.
It is raw material that the present invention adopts gadolinium metal and gadolinium based multicomponent alloy, frequently produce the material ingot through twice melting in the stove in a vacuum, after cold rolling and vacuum heat, make rolled sheet again, rolled sheet is carried out overlay coating or coating and can be obtained cold rolling magnetic refrigerating material after surface treatment and precision are cut apart.
Claims (4)
1. the processing method of a magnetic refrigerating material and anti-corrosion method thereof, it is characterized in that adopting gadolinium or gadolinium base alloy is raw material, has adopted following technological process: the processing and fabricating of gadolinium metal or gadolinium base alloy material ingot, and--cold rolling and vacuum heat--handle by-rolling overlay coating of rolling surface treatment--rolling precision cut apart--.
2. by the processing method and the anti-corrosion method thereof of the described magnetic refrigerating material of claim 1, it is characterized in that the gadolinium metal through the vacuum intermediate frequency furnace is smelted into the material ingot by reduction reaction after,, the material ingot be pulverized into stove melting again, and gadolinium base alloy only carries out melting once and gets final product.
3. by the processing method and the anti-corrosion method thereof of the described magnetic refrigerating material of claim 1, it is characterized in that selecting for use rolling mode to process.
4. by the processing method and the anti-corrosion method thereof of the described magnetic refrigerating material of claim 1, it is characterized in that selecting for use gadolinium metal or gadolinium base alloy as the making raw material of expecting ingot.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101198647A CN102189406A (en) | 2010-03-08 | 2010-03-08 | Processing method and anti-corrosion technology for magnetic refrigeration material |
| PCT/CN2010/000619 WO2011109923A1 (en) | 2010-03-08 | 2010-05-04 | Processing procedure and corrosion protection method for magnetic refrigeration material |
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| CN2010101198647A CN102189406A (en) | 2010-03-08 | 2010-03-08 | Processing method and anti-corrosion technology for magnetic refrigeration material |
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| WO (1) | WO2011109923A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103624491A (en) * | 2013-11-22 | 2014-03-12 | 四川大学 | Forming process of magnetic refrigeration material |
| GB2539010A (en) * | 2015-06-03 | 2016-12-07 | Vacuumschmelze Gmbh & Co Kg | Method of fabricating an article for magnetic heat exchange |
| CN108026613A (en) * | 2016-05-30 | 2018-05-11 | 株式会社藤仓 | Gadolinium wire rod and its manufacture method, metal covering gadolinium wire rod, heat exchanger and magnetic refrigeration apparatus using gadolinium wire rod |
| US10472694B2 (en) | 2015-06-03 | 2019-11-12 | Vacuumschmelze Gmbh & Co. Kg. | Method of fabricating an article for magnetic heat exchanger |
| CN113277545A (en) * | 2021-05-12 | 2021-08-20 | 厦门大学 | Gadolinium fluorocarbonate, and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104499056B (en) * | 2015-01-14 | 2017-01-18 | 厦门大学 | Tetrahydroxy gadolinium oxide dihydrate and preparation and applications thereof |
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- 2010-05-04 WO PCT/CN2010/000619 patent/WO2011109923A1/en active Application Filing
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| CN101463443A (en) * | 2007-12-18 | 2009-06-24 | 比亚迪股份有限公司 | Alloy material containing gadolinium, bismuth and stibium and preparation thereof |
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Non-Patent Citations (1)
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| FREDERICK MILSTEIN等: "Influence of plastic deformation and recrystallization upon permeability anomalies in gadolinium metal", 《APPLIED PHYSICS》, vol. 43, no. 10, 31 October 1972 (1972-10-31), pages 4217 - 4225 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103624491A (en) * | 2013-11-22 | 2014-03-12 | 四川大学 | Forming process of magnetic refrigeration material |
| 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 |
| US11118241B2 (en) | 2015-06-03 | 2021-09-14 | Vacuumschmelze Gmbh & Co. Kg | Method of fabricating an article for magnetic heat exchange |
| CN108026613A (en) * | 2016-05-30 | 2018-05-11 | 株式会社藤仓 | Gadolinium wire rod and its manufacture method, metal covering gadolinium wire rod, heat exchanger and magnetic refrigeration apparatus using gadolinium wire rod |
| CN113277545A (en) * | 2021-05-12 | 2021-08-20 | 厦门大学 | Gadolinium fluorocarbonate, and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| WO2011109923A1 (en) | 2011-09-15 |
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Application publication date: 20110921 |