CN103060692B - High corrosion resistance rare earth-iron chromium silicon carbon magnetocaloric material and preparation method thereof - Google Patents
High corrosion resistance rare earth-iron chromium silicon carbon magnetocaloric material and preparation method thereof Download PDFInfo
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- CN103060692B CN103060692B CN201310014932.7A CN201310014932A CN103060692B CN 103060692 B CN103060692 B CN 103060692B CN 201310014932 A CN201310014932 A CN 201310014932A CN 103060692 B CN103060692 B CN 103060692B
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Abstract
The invention belongs to the technical field of magnetic refrigeration materials, and provides a high corrosion resistance rare earth-iron chromium silicon carbon magnetocaloric material, which comprises part of chromium atoms substituting for iron atoms as well as carbon atoms as interstitial atoms. After the high corrosion resistance rare earth-iron chromium silicon carbon magnetocaloric material is soaked in tap water of 25 DEG C for 12 hours, the corrosion rate is less than 0.2g/m<2>.h. The high corrosion resistance rare earth-iron chromium silicon carbon magnetocaloric material has two chemical molecular formulas, one is La1-xRx(Fe1-y-mCryMm)13-zSizCa, and the other is LaFeSi. The corrosion rate of the high corrosion resistance rare earth-iron chromium silicon carbon magnetocaloric material is less than half that of ordinary rare earth-iron silicon magnetocaloric material; and the high corrosion resistance rare earth-iron chromium silicon carbon magnetocaloric cast ingot has high magnetic entropy change value after short-time annealing, thus being used in magnetic refrigeration technology as a practical material.
Description
Technical field
The invention belongs to technical field of magnetic, provide the rare-earth-iron chrome-silicon carbon compound that a kind of solidity to corrosion is very strong, particularly relate to a kind of rare-earth-iron chrome-silicon carbon compound and preparation thereof of solidity to corrosion NaZn13 structure.
Background technology
In recent years, because magnetic Refrigeration Technique is considered to one of a kind of environmental protection, the new Refrigeration Technique of the energy-efficient next generation, the magnetic refrigerating material exploratory development with the change of huge magnetic entropy arouses great concern.Particularly there is NaZn
13the rare-earth-iron cobalt and silicon compound of phase, because the prices of raw and semifnished materials are cheap, magnetic entropy change is large, is acknowledged as the magnetic cooling material having practical prospect most.There are many articles and patent reports NaZn
13the rare-earth-iron cobalt and silicon compound of phase.Patent 03121051.1 proposes and adds the La of C as interstitial atom
1-xr
x(Fe
1-ym
y)
13-zs
izc
αcompound, R is rare earth metal, and M is single or more than one Al, Co, Be, Ga, the B of trace, Ti, V, Cr, Mn, Ni, Zr, Nb, Ml, Hf, Ta, W element, its content y changes to 0.1 from 0, obtains a kind of Curie temperature adjustable near room temperature on a large scale, and magnetic entropy becomes the compound being better than Gd.Patent CN101567240 proposes entirety and has the La with NaZn13 type
1-xr
x(Fe
zsi
ytM
1-z-y)
13the material of identical composition and preparation technology thereof, R is rare earth metal, and TM is single or more than one trace of Al, Co, Cr, Mn, Ni element.Patent CN101477864 proposes a kind of Rare-Earth Magnetic refrigerating material and the preparation technology thereof with large magnetothermal effect, and the chemical general formula of magnetic refrigerating material is: [La
1-xr
x] (Fe
1-zm
z)
13-αa
αd
β, R is rare earth metal, and M is single or more than one Al, Co, Be, Ga, B, Ti, V, Cr, Mn, Ni, Zr, Nb, Ml, Hf, Ta, W unit prime element, and A is single or more than one Si or Al; D is single or more than one C, H, N, B, and preparation technology uses single element ball milling to obtain method to obtain molecular formula for [La
1-xr
x] (Fe
1-zm
z)
13-αa
αd
βmaterial.But because this method can not make single element complete reaction generate [La
1-xr
x] (Fe
1-zm
z)
13-αa
αd
βmaterial, can leave a lot of α-Fe, and Ball-milling Time is long, there is problem of oxidation.US Patent No. 2010/0143178A1 proposes the great magnetic entropy variation material and preparation method that molecular formula is RrTtAa.Here R is rare earth metal, and T is Fe, and the Some substitute element of Fe: Co, Mn, Ni, Pt and Pd, and A is Si, Ga, Ge, Mn, Sn, Sb.This preparation method can suitability for industrialized production.
In addition, notice that the composition of above-mentioned patent etc. just pays close attention to the possibility that material has the preparation of industrialization of great magnetic entropy variation performance and material.If needed NaZn
13the rare-earth-iron cobalt and silicon compound of phase is used for, in magnetic cooling technology, needing the water using rare-earth-iron cobalt and silicon compound is put into as heat exchange medium to work.That is, the Working environment of great magnetic entropy variation material is in water.Therefore, the corrosive nature of material in water is just extremely important.Propose and reduced the corrosion of water to rare-earth-iron cobalt and silicon compound, such as CN101514458A by the method for inhibiter; Also have and coating is carried out to increase the solidity to corrosion of rare-earth-iron cobalt and silicon compound to material, such as Japanese Patent Te Open 2005-113209.But inhibiter is all generally meta-alkalescence, how much can damage other parts of refrigerator, and the rare-earth-iron cobalt and silicon compound size majority used as refrigeration working medium in refrigerator is below 1mm, brings difficulty to coating.
Summary of the invention
In order to solve the problem, the present invention uses chromium element as an alternative, proposes highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material and preparation method thereof.
The invention provides a kind of highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material and preparation method thereof.
Described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material is when temperature is 10 to 40 degrees Celsius, and be soak 12 hours in the liquid heat exchange medium of 7-8 at pH value, erosion rate is less than 0.2g/m
2.h; After described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material soaks and makes its electropotential basicly stable in distilled water, carry out polarization curve measurement, its corrosion potential is greater than-0.7V;
Described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material is made up of two kinds of chemical molecular formulas, and a kind of chemical molecular formula is La
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
α, another kind of chemical molecular formula LaFeSi, La
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
αcontent with volume percentage, more than 92%, LaFeSi content is with volume percentage, and more than 1%, the content of above-mentioned two kinds of chemical compositions adds and should be 100%; Chromium atom containing Some substitute iron atom in above-mentioned highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material, the C atom existed as interstitial atom.
Further, the La in described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
α, wherein R is the arbitrary combination that one or more than one meets Ce, Pr, Nd, Sm rare earth element of x scope; The scope of x is 0 ~ 0.5; M is that one or more meet the arbitrary combination of the following element of m scope: Co, Mn, Cu, Nb; The scope of m is: 0 ~ 0.1; The scope of y is 0.009 ~ 0.04; The scope of z is 1.0 ~ 1.7; The scope of α is 0.10 ~ 0.2.
Further, the preparation method of highly anticorrosive rare earth as above-siderochrome silicon-carbon magneto-caloric material, comprise step: use metal La, R, Fe, Cr, M element, and Si, C element as raw material, respectively by two kinds of chemical molecular formula weighings in above-mentioned highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material; By the raw material of above-mentioned two kinds of chemical molecular formulas, put into vacuum induction furnace, after vacuumizing, in argon gas atmosphere, melting obtains ingot casting, then is annealed 1 day to 10 days in 1000 degree to 1200 degree by above-mentioned ingot casting, obtains highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material.
Preferably, the preparation method of highly anticorrosive rare earth as above-siderochrome silicon-carbon magneto-caloric material, comprise step: use metal La, R, Fe, Cr, M element, and Si, C element is as raw material, respectively by two kinds of chemical formula weighings of above-mentioned highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material, put into centrifugal atomizing balling head, controlled cooling model speed makes a dendrite width at below 5mm, chilling ball is carried out under argon shield, prepare the bead that diameter is 0.1mm ~ 2mm, then above-mentioned bead ingot casting is annealed 2 hours to 2 days in 1000 degree to 1200 degree, obtain highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material.Described bead is the bead including two kinds of chemical molecular formulas, and above-mentioned highly anticorrosive rare earth-hot bead of siderochrome silicon-carbon magnetic, in annealing process, owing to there is LaFeSi phase, can promote that the α-Fe after smelting generates 1 mutually; 13 phases.
Preferably, the preparation method of described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material, comprise step: use metal La, R, Fe, Cr, M element, and Si, C element is as raw material, respectively by two kinds of chemical formula weighings of above-mentioned highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material, then preparing chemical molecular formula with quick quenching furnace is respectively La
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
αstrip and chemical molecular formula be the strip of LaFeSi, controlled cooling model speed makes a dendrite width at below 5mm, be mixed in proportion powder process again, sinter between 1200 degree at 800 degree, anneal 2 hours to 2 days in 1000 degree to 1200 degree after sintering, obtain highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material.Sintering method can be normal sintering, and at this moment sintering temperature with 1000 degree to 1200 degree as well, also can sinter with SPS, and at this moment sintering temperature with 800 degree to 950 degree as well.Because two kinds of compositions are prepared separately into band, so the composition of highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material can control more accurately.
Preferably, described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material, heat-treats in hydrogen, obtains highly anticorrosive rare earth-siderochrome silicon hydrocarbon compound.Like this, anticorrosive rare earth of the present invention-siderochrome silicon-carbon magneto-caloric material can any inhibiter, and on-line operation is as in the tap water of heat exchange medium.If use the water medium being added with inhibiter, then further increase the preservative effect of anticorrosive rare earth-siderochrome silicon magneto-caloric material.
Highly anticorrosive rare earth of the present invention-siderochrome silicon-carbon magneto-caloric material is made up of two kinds of chemical molecular formulas, and wherein one is La
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
α, another kind is LaFeSi, La
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
αcontent is with volume percentage, and more than 92%, LaFeSi content is with volume percentage, and more than 1%, both add and are 100%.Chemical formula La
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
α1:13 phase required in highly anticorrosive rare earth of the present invention-siderochrome silicon-carbon magneto-caloric material is mainly provided.Corrosion experiment shows, if go back balance α-Fe phase in material, then the corrosion of rare-earth-iron chrome-silicon magneto-caloric material in water is around α-Fe phase, occurs from 1:13 phase.Therefore corrosion proof magneto-caloric material to be obtained, α-Fe phase will be reduced as far as possible. there is the LaFeSi of trace in highly anticorrosive rare earth of the present invention-siderochrome silicon-carbon magneto-caloric material, can promote during annealing that in described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material, 1:13 phase is formed, under same annealing conditions, substantially increase the 1:13 phase content generated in anticorrosive rare earth-siderochrome silicon magneto-caloric material, eliminate α-Fe phase, like this, can reach and prevent from corroding the object occurred.
And, the mechanism of corrosion research of rare-earth-iron silicon magneto-caloric material is shown, and general rareearth magnetic material, such as Nd
2fe
14b is different, the current potential of LaFeSi material higher than the current potential of 1:13 phase, even if therefore in highly anticorrosive rare earth of the present invention-siderochrome silicon-carbon magneto-caloric material containing a small amount of LaFeSi, also can not aggravate material and corrode in water, not form the center that corrosion occurs.Therefore anticorrosive rare earth of the present invention-siderochrome silicon-carbon magneto-caloric material, because of the 1:13 phase having more than 92%, so both can have great magnetic entropy variation, can have very strong resistance to corrosion again, is best magnetic refrigerating material.
Containing high density Cr element in highly anticorrosive rare earth of the present invention-siderochrome silicon-carbon magneto-caloric material.Add rare-earth-iron chrome-silicon carbon magneto-caloric material resistance to corrosion in water that Cr can increase substantially.Electrochemical test shows, had both reduced anodic current density and the cathode current density of material, and in turn increased the impedance of material after adding high density Cr element.Along with the increase of Cr content, current density reduces, and resistance increases.In tap water, anticorrosive rare earth of the present invention-siderochrome silicon-carbon magneto-caloric material erosion rate is much smaller than the material not adding Cr element and carbon simultaneously.
Experiment of the present invention shows, Cr content in 0.15 ~ 0.4 scope, La
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
αthere is good corrosion resistance, when Cr content is more than 0.4, the resistance to corrosion that material has still had, but La
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
αthe magnetic entropy change of material can significantly reduce, and can not get the heat absorption required for magnetic Refrigeration Technique and exothermal effect.And Cr content is less than 0.15, then the resistance to corrosion of material reduces, and is corroded very soon in water.
The present invention adds C element and carrys out collaborative micro-Cr, improves the resistance to corrosion of rare-earth-iron chrome-silicon magneto-caloric material in water.In addition, C element also can shorten annealing time.Experiment shows, the C element of 0.1 ~ 0.2 atom is added in the gap of the principal phase NaZn13 phase structure of rare-earth-iron chrome-silicon magneto-caloric material, can be good at collaborative Cr, increases the resistance to corrosion of material.The more important thing is, the bulk La obtained with method meltings such as common induction furnace or electric arc furnace
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zingot casting, generally need annealing to obtain for more than 5 days 1:13 principal phase that volume ratio is more than 90%, research of the present invention finds, if add the C element of more than 0.10 atom in the material, effectively can shorten annealing time.Same material, if add C element, can shorten over half by annealing time.Like this, add Cr and C simultaneously, both can ensure very high corrosion resistance nature, also can anneal at short notice and obtain the 1:13 phase that volume ratio is more than 92%, material of the present invention has very high practicality.If but C atom content is higher than 0.2, then can not ensure that C is all arranged in the gap of principal phase NaZn13 phase structure, at this moment α-Fe is had to separate out mutually in material, along with the further increase of C atom, to a large amount of α-Fe be had to separate out mutually in material, 1:13 phase principal phase content in final material is difficult to reach and is greater than 92%, thus reduces magnetic entropy change value; And the content of C element increases, and can destroy the character of the first-order phase transition of rare-earth-iron chrome-silicon carbon magneto-caloric material, C atom content is higher than after 0.2, and the magnetic phase transition of rare-earth-iron chrome-silicon magneto-caloric material is second-order phase transition.
The present invention's arbitrary combination of a small amount of one or more Co, Mn, Cu, Nb substitutes Fe element, regulates Curie temperature.Experiment of the present invention shows, Co element also can be worked in coordination with Cr and be improved the resistance to corrosion of rare-earth-iron chrome-silicon magneto-caloric material in water, and in annealing process, promote that 1:13 phase is formed, but, other regulate the element of Curie temperature, and such as Cu etc., can reduce the resistance to corrosion of material.Such as, when adding Cu to regulate Curie temperature, its corrosion resistance reduces greatly.At this moment, in order to obtain that there is high anti-corrosion magneto-caloric material, the Cr adding 0.3 ~ 0.4 atom is needed.
Highly anticorrosive rare earth of the present invention-siderochrome silicon-carbon magneto-caloric material, employs and puts into vacuum induction furnace melting by after two kinds of chemical formulas respectively weighing, obtains the highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material including two kinds of chemical molecular formulas.Above-mentioned highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material, in annealing process, owing to there is LaFeSi, can promote that the α-Fe after smelting generates 1 mutually; 13 phases.In addition, the present invention directly uses C element to put into induction furnace melting, eliminates the general Fe-C of use alloy and smelts to the master alloy carried out when C adds, and can ensure the even of C content, provide cost savings.
In sum, the invention has the advantages that:
1, highly anticorrosive rare earth of the present invention-siderochrome silicon-carbon magneto-caloric material has strong resistance to corrosion in water, can on-line operation as in the water of heat exchange medium.
2, bulk anticorrosive rare earth-siderochrome silicon carbon compound of the present invention can form the 1:13 phase of more than 92% at short notice, reduces preparation cost.
3, solidity to corrosion of the present invention is compared with general rare-earth-iron silicon magneto-caloric material containing the rare-earth-iron silicon magneto-caloric material of chromium carbon, only with the addition of Cr and C, does not obviously change the magnetic entropy performance of material monolithic, is that a kind of huge magnetic entropy with practical value becomes magnetic refrigerating working medium.
Accompanying drawing explanation
Fig. 1 is the 1# solidity to corrosion magneto-caloric material of the present invention in embodiment, at the X ray diffracting spectrum of 1080 degree of annealing after 3 days under room temperature.Wherein, X-coordinate is diffraction angle, and ordinate zou is diffracted intensity;
Fig. 2 is 1# solidity to corrosion magneto-caloric material and control sample LaFe in embodiment 1
10.87co
0.63si
1.5, LaFe
10.87co
0.63si
1.5c
0.12the erosion rate after 12 hours is soaked in tap water;
Fig. 3 is polarization curve.Wherein, a curve is the comparative material LaFe in the embodiment of the present invention 1
11.4si
1.5c
0.12polarization curve, b curve be comparative material LaFe in the embodiment of the present invention 1
10.87co
0.63si
1.5polarization curve, c curve represent the polarization curve of the 1# solidity to corrosion magneto-caloric material in the embodiment of the present invention 1, d curve is the polarization curve of the 3# solidity to corrosion magneto-caloric material in the present embodiment 3;
Fig. 4 is the back scattering figure of 1# solidity to corrosion magneto-caloric material of the present invention in embodiment 1;
Fig. 5 is the magnetic entropy change value of 1# solidity to corrosion magneto-caloric material of the present invention in embodiment 1;
Fig. 6 is the 2# solidity to corrosion magneto-caloric material of the present invention of embodiment 2, and at the X ray diffracting spectrum of 1100 degree of annealing after 2 days under room temperature, wherein, X-coordinate is diffraction angle, and ordinate zou is diffracted intensity;
In Fig. 7 embodiment 2,2# solidity to corrosion magneto-caloric material of the present invention is going the erosion rate in tap water.Wherein, X-coordinate is etching time, and ordinate zou is rate of weight loss;
The magnetic entropy change value of 2# solidity to corrosion magneto-caloric material of the present invention under the variation magnetic field of 2T in Fig. 8 embodiment 2;
Fig. 9 is the magnetic entropy change value that in embodiment 3, after 3# solidity to corrosion magneto-caloric material activation of the present invention, hydrogenation obtained after 1 hour under 523K;
Figure 10 is the back scattering figure of 4# solidity to corrosion magneto-caloric material of the present invention in embodiment 4.
Embodiment
Embodiment 1:
The starting material such as La, Fe, Si, Cr, C are made into LaFe respectively by chemical composition
11.3cr
0.2si
1.5c
0.12and LaFeSi, then according to volume ratio 0.97 (LaFe
11.3cr
0.2si
1.5c
0.12): the ratio of 0.3 (LaFeSi) is made into 1# solidity to corrosion magneto-caloric material three kilograms, is made into contrast sample LaFe according to chemical composition simultaneously
10.87co
0.63si
1.5, LaFe
11.4si
1.5c
0.12three kilograms, put into vacuum induction furnace melting, pouring diameter after melting into is in the cylindricality casting mold of 50mm, wall thickness 3mm, base thickness 30mm, obtains the ingot casting of uniform composition.Ingot casting is annealed 3 days at 1080 DEG C, then directly puts into frozen water fast quenching.Fig. 1 represents the X ray diffracting spectrum of 1# solidity to corrosion magneto-caloric material of the present invention, and wherein, X-coordinate is diffraction angle, and ordinate zou is diffracted intensity.As can be seen from Figure 1, under the assistance of LaFeSi, the invention described above 1# solidity to corrosion magneto-caloric material, after annealing in short 3 days, has defined 1:13 phase principal phase, and does not find that there is the diffraction peak of significantly other dephasigns.The formation of 1:13 phase is significantly better than the embodiment in patent CN101477864.Fig. 2 illustrates 1# solidity to corrosion magneto-caloric material of the present invention and contrast sample LaFe
10.87co
0.63si
1.5, LaFe
11.4si
1.5c
0.12erosion rate figure. as can be seen from the figure, in the material adding Cr, the erosion rate of 12 hours is 0.15g/m
2.h, and do not increase the contrast sample LaFe of Cr
10.87co
0.63si
1.5erosion rate be more than a times of embodiment of the present invention 1# sample.Contrast sample LaFe
11.4si
1.5c
0.12erosion rate a little less than contrast sample LaFe
10.87co
0.63si
1.5, confirm that C element also has certain solidity to corrosion, but contrast sample LaFe
11.4si
1.5c
0.12erosion rate be still far longer than 1# sample in the embodiment of the present invention. known, of the present invention have extraordinary corrosion resistance nature containing chromium carbon high anti-corrosion magneto-caloric material.Fig. 3 represents the contrast material LaFe in 1# and 3# solidity to corrosion magneto-caloric material of the present invention and embodiment 1
10.87co
0.63si
1.5, LaFe
11.4si
1.5c
0.12polarization curve, wherein, X-coordinate is corrosion potential, and ordinate zou is corrosion current.As can be seen from Figure 3, the corrosion potential of 1# solidity to corrosion magneto-caloric material of the present invention is obviously than contrast material LaFe
10.87co
0.63si
1.5, LaFe
11.4si
1.5c
0.12high.The interpolation of Cr doping and LaFeSi makes the corrosion potential of the invention described above 1# solidity to corrosion magneto-caloric material be elevated to as-598mV, has very strong resistance to corrosion.Fig. 4 is the back scattering figure of 1# solidity to corrosion magneto-caloric material of the present invention.Known with energy spectrum analysis, be mainly the 1:13 principal phase of grey in Fig. 4, also there is the LaFeSi phase of trace white.Adopt SQUID to measure magnetzation curve, calculate under 2T magnetic field, magnetic entropy becomes 17.0J/kg.K, sees Fig. 5.
Embodiment 2:
By pure La and technical pure mishmetal Re (La/Re:28.27wt.%, Ce/Re:50.46wt.%, Pr/Re:5.55wt.%, Nd/Re:15.66wt.%)), Fe, Si, Cr, C starting material are respectively by chemical composition La
0.8(Ce, Pr, Nd)
0.2fe
11.25mn
0.1cr
0.3si
1.5c
0.2with LaFeSi preparation, then according to volume ratio 0.98 (LaFe
11.3cr
0.2si
1.5c
0.12): the ratio composition 2# solidity to corrosion magneto-caloric material of 0.2 (LaFeSi), put into vacuum induction furnace melting and obtain ingot casting, then ingot casting is annealed 2 days at 1100 DEG C, directly put into frozen water fast quenching, obtain the compound of uniform composition.Fig. 6 represent 2# solidity to corrosion magneto-caloric material X ray diffracting spectrum, wherein, X-coordinate is diffraction angle, and ordinate zou is diffracted intensity.As can be seen from Figure 6, under the assistance of LaFeSi, the invention described above 2# solidity to corrosion magneto-caloric material, after annealing in short 2 days, has defined 1:13 phase principal phase, and does not find that there is the diffraction peak of significantly other dephasigns.The formation of 1:13 phase is significantly better than the embodiment in patent CN101477864.Fig. 7 is that 2# solidity to corrosion magneto-caloric material is going the erosion rate in tap water.Wherein, X-coordinate is etching time, and ordinate zou is rate of weight loss.As can be seen from Figure 7, the erosion rate of 12 hours is 0.17g/m
2.h.Adopt SQUID to measure magnetzation curve, calculate under 2T magnetic field, magnetic entropy becomes 17.0J/kg.K, sees Fig. 8.As shown in the figure, have employed cheap technical pure mishmetal in the present embodiment to prepare solidity to corrosion magneto-caloric material, have also been obtained the material of high anti-corrosion and great magnetic entropy variation.
Embodiment 3:
The starting material such as La, Fe, Si, Cr, Mn, C are made into LaFe respectively by chemical composition
11.1mn
0.1cr
0.3si
1.5c
0.15and LaFeSi, then according to volume ratio 0.99 (LaFe
11.1mn
0.1cr
0.3si
1.5c
0.15): the ratio of 0.1 (LaFeSi) is made into 3# solidity to corrosion magneto-caloric material, puts into and is atomized into the rear chilling balling-up of ball device fusing, obtain the bead of 0.5 ~ 1mm.Bead is annealed 1 day at 1080 DEG C, then directly puts into frozen water fast quenching.Fig. 3 represents the polarization curve of the material in the hot bead of 3# solidity to corrosion magnetic of the present invention and embodiment 1.As can be seen from Figure 3, the corrosion electric current density of 3# solidity to corrosion magneto-caloric material of the present invention is lower than contrast material LaFe
10.87co
0.63si
1.5, LaFe
11.4si
1.5c
0.12, and corrosion potential is apparently higher than contrast material LaFe
10.87co
0.63si
1.5, LaFe
11.4si
1.5c
0.12.The interpolation of Cr doping and LaFeSi makes the corrosion potential of the invention described above 3# solidity to corrosion magneto-caloric material be elevated to as-562mV, has very strong resistance to corrosion.By the hydrogenation 1 hour under 523K of above-mentioned 3# solidity to corrosion magneto-caloric material, the Curie temperature of this material can be adjusted near room temperature, the magnetic entropy change value obtained is as Fig. 9.
Embodiment 4:
The starting material such as La, Fe, Si, Cr, Mn, C are made into LaFe respectively by chemical composition
11.3mn
0.1cr
0.3si
1.3c
0.2and LaFeSi, then by putting into vacuum induction furnace melting respectively after two kinds of chemical formulas respectively weighing, obtain two kinds of alloy cast ingots.Then preparing chemical molecular formula respectively with quick quenching furnace is LaFe
11.3mn
0.1cr
0.3si
1.3c
0.2with the strip of LaFeSi, Figure 10 is LaFe
11.3mn
0.1cr
0.3si
1.3c
0.2the scanned photograph of strip, because be quick cooling, it once props up about about 3 μm of brilliant width, is conducive to forming 1 fast at heat treatment stages; 13 phases.0.99 (LaFe by volume
11.3mn
0.1cr
0.3si
1.3c
0.2): the ratio of 0.1 (LaFeSi) is made into 4# solidity to corrosion magneto-caloric material, and mixing powder process, sinters by SPS method at 1000 degree, 1100 degree of annealing 1 day after sintering, obtain 4# highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material.Because two kinds of compositions are prepared separately into strip, so the composition of 4# highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material can control more accurately and adjust at any time.
Claims (3)
1. highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material, it is characterized in that: described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material is when temperature is 10 to 40 degrees Celsius, be soak 12 hours in the liquid heat exchange medium of 7-8 at pH value, erosion rate is less than 0.2g/m
2.h; After described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material soaks and makes its electropotential basicly stable in distilled water, carry out polarization curve measurement, its corrosion potential is greater than-0.7V;
Described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material is made up of two kinds of chemical molecular formulas, and a kind of chemical molecular formula is La
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
α, another kind of chemical molecular formula LaFeSi, La
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
αcontent with volume percentage, more than 92%, LaFeSi content is with volume percentage, and more than 1%, the content of above-mentioned two kinds of chemical compositions adds and is 100%; Chromium atom containing Some substitute iron atom in described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material, the C atom existed as interstitial atom; Wherein, the La in described highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material
1-xr
x(Fe
1-y-mcr
ym
m)
13-zsi
zc
α, wherein R is the arbitrary combination that one or more than one meets Ce, Pr, Nd, Sm rare earth element of x scope; The scope of x is 0 ~ 0.5; M is that one or more meet the arbitrary combination of the following element of m scope: Co, Mn, Cu, Nb; The scope of m is: 0 ~ 0.1; The scope of y is 0.009 ~ 0.04; The scope of z is 1.0 ~ 1.7; The scope of α is 0.10 ~ 0.2.
2. the preparation method of highly anticorrosive rare earth according to claim 1-siderochrome silicon-carbon magneto-caloric material, it is characterized in that, use metal La, R, Fe, Cr, M element, and Si, C element as raw material, respectively by two kinds of chemical molecular formula weighings in above-mentioned highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material; By the raw material of above-mentioned two kinds of chemical molecular formulas, put into vacuum induction furnace, after vacuumizing, in argon gas atmosphere, melting obtains ingot casting, then is annealed 1 day to 10 days in 1000 degree to 1200 degree by above-mentioned ingot casting, obtains highly anticorrosive rare earth-siderochrome silicon-carbon magneto-caloric material.
3. the highly anticorrosive rare earth according to any one of claim 1 or 2-siderochrome silicon-carbon magneto-caloric material, characterized by further comprising: the highly anticorrosive rare earth obtained by above-mentioned preparation method-siderochrome silicon magneto-caloric material is heat-treated in hydrogen, thermal treatment temp is no more than the decomposition temperature of this material 1:13 phase, obtains highly anticorrosive rare earth-siderochrome silicon hydrocarbon compound.
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| CN101748326A (en) * | 2009-10-19 | 2010-06-23 | 北京科技大学 | Preparation method of carbonic rare earth-ferrum, cobalt and silicon compound with NaZn1 structure |
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| CN101748326A (en) * | 2009-10-19 | 2010-06-23 | 北京科技大学 | Preparation method of carbonic rare earth-ferrum, cobalt and silicon compound with NaZn1 structure |
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