阅读说明：本技术 一种高耐蚀性稀土磁制冷材料以及在制冷机中的使用方法 (A kind of highly anticorrosive rare earth magnetic refrigerating material and the application method in refrigeration machine ) 是由 龙毅 薛佳宁 张虎 叶荣昌 于 2019-08-26 设计创作，主要内容包括：本发明属于磁制冷领域。本发明所述的高耐蚀性稀土磁制冷材料在PH值为7-8的液体热交换介质中浸泡12小时,腐蚀速率不超过0.15g/m<Sup>2</Sup>.h。上述高耐蚀性稀土磁制冷材料的化学分子式为(La<Sub>1-x</Sub>R<Sub>x</Sub>)(Fe<Sub>13-a-b-c</Sub>M<Sub>y</Sub>Co<Sub>t</Sub>Si<Sub>z</Sub>)C<Sub>α</Sub>+zX(X：Fe<Sub>2</Sub>Nb、Fe<Sub>2</Sub>Ti、La<Sub>5</Sub>Si<Sub>3</Sub>+Ni),由基体相1:13相以及单一的特殊杂相组成,特殊杂相有：含有Ni元素的La-rich相、Fe<Sub>2</Sub>Nb相、Fe<Sub>2</Sub>Ti相等。本发明的高耐蚀性稀土磁制冷材料中,添加Ni、Nb、Ti等元素主要形成提高耐蚀性的特殊杂相,而不会进入具有磁热效应的基体1:13相中,使得上述材料在具有高耐蚀性的同时保持了大的磁热效应,可以作为实用材料用于磁制冷技术中。高耐蚀性稀土磁制冷材料在磁制冷机中工作时,材料工作面与水流方向成70度到110度夹角,能够进一步增加耐蚀效果。(The invention belongs to magnetic refrigerating fields.Highly anticorrosive rare earth magnetic refrigerating material of the present invention impregnates 12 hours in the liquid heat exchange medium that pH value is 7-8, and corrosion rate is no more than 0.15g/m 2 .h.The chemical molecular formula of above-mentioned highly anticorrosive rare earth magnetic refrigerating material is (La 1‑x R x )(Fe 13‑a‑b‑c M y Co t Si z )C α + zX (X:Fe 2 Nb、Fe 2 Ti、La 5 Si 3 + Ni), it is made of matrix phase 1:13 phase and single special miscellaneous phase, special miscellaneous phase has: the La-rich phase containing Ni element, Fe 2 Nb phase, Fe 2 Ti is equal.In highly anticorrosive rare earth magnetic refrigerating material of the invention, the elements such as addition Ni, Nb, Ti, which primarily form, improves corrosion proof special miscellaneous phase, without entering in the matrix 1:13 phase with magnetothermal effect, so that above-mentioned material maintains big magnetothermal effect while with high corrosion-resistant, Applied Materials can be used as in magnetic Refrigeration Technique.When highly anticorrosive rare earth magnetic refrigerating material works in magnetic refrigerator, material working face and water (flow) direction can further increase anti-corrosion effect at 70 degree to 110 degree angles.)

1. a kind of highly anticorrosive rare earth magnetic refrigerating material has special miscellaneous phase, it is characterised in that: simultaneously by addition Ni, Nb element Non-equilibrium proportion is carried out, is formed in highly anticorrosive rare earth magnetic refrigerating material single special miscellaneous other than matrix 1:13 phase Phase significantly reduces the galvanic corrosion current density of material by the electrochemical properties between the special miscellaneous phase of control and matrix phase, into And improve material entirety corrosion resistance；

The highly anticorrosive rare earth magnetic refrigerating material impregnates 12 hours in the liquid heat exchange medium that pH value is 7-8, corrosion speed Rate is no more than 0.15g/m².h；The material is impregnated in distilled water after keeping its electrode potential basicly stable, carries out polarization curve Measurement, corrosion electric current density is less than 5 μ A/cm²。

2. highly anticorrosive rare earth magnetic refrigerating material according to claim 1, it is characterised in that: the height with special miscellaneous phase Anticorrosive rare earth magnetic refrigerating material is (La in chemical molecular formula by non-equilibrium proportion_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_α's La, Si, Ni, Nb, Fe, Ti element are added in matrix alloy, preparing chemical molecular formula is (La_1-xR_x)(Fe_{13-a-b- c}M_aCo_bSi_c)C_α+ zX (X:Fe₂Nb、Fe₂Ti、La₅Si₃+ Ni) alloy；Wherein, R be rare earth element ce, it is any in Pr, Nd The content of one or any two or more combination, R meets the range of x；M is any one in Mn, Cr or two kinds any Above combination, M content meet y range；The range that the range that the range of x is 0~0.3, a is 0~0.4, b is 0~1.2, c's The range that the range that range is 1.2~1.6, α is 0~0.2, z is 0.04~0.12；

The highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase is by matrix phase 1:13 phase and single special miscellaneous phase Composition, special miscellaneous phase have: the La-rich phase containing Ni element, Fe₂Nb phase, Fe₂Ti phase；The content of matrix 1:13 phase is with volume hundred Point than meter, 85% or more, the content of single special miscellaneous phase with volume percentage, 15% hereinafter, above two chemistry at The content adduction divided should be 100%.

3. highly anticorrosive rare earth magnetic refrigerating material according to claim 2, it is characterised in that: chemical molecular formula be (La_{1- x}R_x)(Fe_13-a-b-cM_aCo_bSi_c)C_αMatrix alloy in add La, Si, Ni element, prepare chemical molecular formula be (La_1-xR_x) (Fe_13-a-b-cM_aCo_bSi_c)C_α+zLa₅Si₃The alloy of+zNi；Wherein, R be rare earth element ce, in Pr, Nd any one or Any two or more combination, the content of R meet the range of x；M is any one in Mn, Cr or any two or more group It closes, M content meets the range of a；The range that the range that the range that the range of x is 0~0.3, a is 0~0.4, b is 0~1.2, c is The range that the range of 1.2~1.6, α are 0~0.2, z is 0.04~0.12；

The obtained highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase, by phase 1:13 phase and single special miscellaneous phase Composition, special miscellaneous phase are the La-rich phase containing Ni element；The content of matrix 1:13 phase with volume percentage, 85% with On, the content matrix of single special miscellaneous phase is with volume percentage, 15% hereinafter, the content of above two chemical component sums it up It should be 100%.

4. highly anticorrosive rare earth magnetic refrigerating material according to claim 2, it is characterised in that: chemical molecular formula be (La_{1- x}R_x)(Fe_13-a-b-cM_aCo_bSi_c)C_αMatrix alloy in add Fe, Nb element, preparing chemical molecular formula is (La_1-xR_x) (Fe_13-a-b-cM_aCo_bSi_c)C_α+zFe₂The alloy of Nb；Wherein, R be rare earth element ce, in Pr, Nd any one or it is any The content of two or more combinations, R meets the range of x；M is any one in Mn, Cr or any two or more combination, M Content meets y range；The range that the range that the range that the range of x is 0~0.3, a is 0~0.4, b is 0~1.2, c is 1.2~ The range that 1.6, α range is 0~0.2, z is 0.04~0.12；

The obtained highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase, by matrix phase 1:13 phase and single special Miscellaneous phase Fe₂Nb composition；The content of matrix 1:13 phase is with volume percentage, 85% or more, the content of single special miscellaneous phase with Volume percentage, 15% hereinafter, the content adduction of above two chemical component should be 100%.

5. highly anticorrosive rare earth magnetic refrigerating material according to claim 2, it is characterised in that: chemical molecular formula be (La_{1- x}R_x)(Fe_13-a-b-cM_aCo_bSi_c)C_αMatrix alloy in add Fe, Ti element, preparing chemical molecular formula is (La_1-xR_x) (Fe_13-a-b-cM_yCo_tSi_z)C_α+zFe₂The alloy of Ti；Wherein, R be rare earth element ce, in Pr, Nd any one or it is any The content of two or more combinations, R meets the range of x；M is any one in Mn, Cr or any two or more combination, M Content meets y range；The range that the range that the range that the range of x is 0~0.3, a is 0~0.4, b is 0~1.2, c is 1.2~ The range that 1.6, α range is 0~0.2, z is 0.04~0.12；

The obtained highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase, by matrix phase 1:13 phase and single special Miscellaneous phase Fe₂Ti composition；The content of matrix 1:13 phase is with volume percentage, 85% or more；The content of single special miscellaneous phase with Volume percentage, below 15%；The content adduction of above two chemical component should be 100%.

6. a kind of application method of highly anticorrosive rare earth magnetic refrigerating material as described in claim 1 in refrigeration machine, feature exist In: when working in the recirculated water of magnetic refrigerator, the working face and water (flow) direction of highly anticorrosive rare earth magnetic refrigerating material are at 70 degree To 110 degree of angles.

Technical field

The invention belongs to technical field of magnetic, and in particular to significantly improve Rare-earth Iron by forming special miscellaneous phase The corrosion resistance of silicon-base alloy, and corrosion proof method is improved in dynamic flowing water.

Background technique

Magnetic Refrigeration Technique is the Refrigeration Technique of a new generation.With a cube NaZn₁₃The La (Fe, Si) of type structure (1:13 phase)₁₃ Base magnetic refrigerating material is magnetic refrigeration due to having many advantages, such as that great magnetic entropy variation, Curie temperature are continuously adjustable, at low cost, green non-poisonous The ideal candidates material of refrigeration working medium in machine.NaZn₁₃The La (Fe, Si) of type structure (1:13 phase)₁₃Base magnetic refrigerating material has been used In Magnetic refrigerator, show there is good refrigeration effect.There are many article and patent report NaZn₁₃The rare-earth-iron of phase Cobalt silicon alloy.Patent CN104694813A proposes a kind of NaZn₁₃The La of type structure_1+aFe_13-b-cCo_bSi_cH_dMatrix body magnetic refrigeration Material and preparation method, the La obtained with the preparation method of patent_1+aFe_13-b-cCo_bSi_cH_dMatrix body magnetic refrigerating material has Big magnetothermal effect and low magnetic lag is ideal nearly room temperature magnetic refrigerating working.Patent CN103649352A, CN103502497A Provide the La with the Curie temperature not less than 250K₁-_fRE_f(Fe_1-a-b-c-d-eSi_aCo_bX_cY_dZ_e)₁₃Magnetic refrigerating material, and mention For when being subjected to reaching as high as the changes of magnetic field of 2 teslas magnetic entropy become maximum value be not less than 5J/Kg.K.Patent CN103814144A It is obtained by spark-plasma sintering method and subsequent hydrogen abstraction reaction by composition formula La (Fe, Si)₁₃The magnetic refrigerating material that H is indicated, The material has multiple holes, can limit physical damage, such as the generation of cracking using this magnetic refrigerating material.Also there is patent The heat treatment process for having studied Rare-earth Iron silicon substrate magnetic refrigerating material influences the performance of material and practicability.Such as patent CN106086738A provides a kind of reduction miscellaneous phase and adjusts NaZn₁₃The method for annealing of structure rare earth ferro-silicium Curie temperature. By adjusting NaZn₁₃Annealing conditions in structure phase rare-earth-iron-silicon alloy preparation process, reaching reduces NaZn₁₃Structure phase rare earth Rich La phase content, fine tuning NaZn in ferro-silicium₁₃The content of Mn element in structure phase rare-earth-iron-silicon alloy obtains Curie temperature A series of NaZn devious₁₃Structure phase rare-earth-iron-silicon alloy.Also patent CN103436664A passes through in block rare earth iron silicon Alloy all surfaces are made annealing treatment in air after densely coating high-temp. antioxidation coatings, simplify the conjunction of Rare-earth Iron silicon The preparation of gold, reduces costs.In addition, in order to improve the heating conduction of Rare-earth Iron silicon-base alloy and mechanical property, patent CN109524190A provides a kind of composite material and preparation method, including function constituent element: Rare-earth Iron silicon substrate magnetic refrigeration alloy Particle and matrix constituent element: aluminum metal simple substance or aluminium alloy.The composite material has simultaneously keeps high magnetothermal effect and mechanical property Can, and molding easy to process.Patent 03121051.1 proposes the La that C is added as interstitial atom_1-xR_x(Fe_1-yM_y)_{13- z}S_izC_αCompound, R are rare earth metal, and M is micro single or more than one Al, Co, Be, Ga, B, Ti, V, Cr, Mn, Ni, Zr, Nb, Ml, Hf, Ta, W element, content y change to 0.1 from 0, have obtained a kind of Curie temperature in the big model of near room temperature Enclose adjustable, compound of the magnetic entropy change better than Gd.Patent CN101567240 proposes the whole La having with NaZn13 type_1-xR_x (Fe_zSi_yTM_1-z-y)₁₃The material and its preparation process of identical composition, R are rare earth metal, and TM is single or more than one Trace of Al, Co, Cr, Mn, Ni element.United States Patent (USP) US2010/0143178A1 proposes the great magnetic entropy variation that molecular formula is RrTtAa Material and preparation method.Here R is rare earth metal, the part substitute element of T Fe and Fe: Co, Mn, Ni, Pt and Pd, A For Si, Ga, Ge, Mn, Sn, Sb.The preparation method can be with industrialized production.

The application of Rare-earth Iron silicon substrate magnetic refrigerating material under practical circumstances is had ignored in above-mentioned patent one very heavy The factor wanted, the i.e. Service Environment of material.It is different from the fluorine-containing refrigeration working medium of tradition based on compression-expansion refrigeration cycle principle, magnetic Refrigeration working medium is to cause magnet heat absorption and heat release to be made using the variation for making the magnetic moment of working medium that order-disorder occur by externally-applied magnetic field With and carry out refrigeration cycle.Therefore magnetic refrigerating material exists in refrigeration machine with solid-state, it is necessary to just by means of liquid heat transfer medium The heat exchange being able to achieve between magnetic refrigeration working substance and load.At present in room temperature magnetic refrigerating prototyping, mainly all be selection water or Person's water fluid is as heat-conduction medium.If by NaZn₁₃The Rare-earth Iron silicon substrate magnetic refrigerating material of phase is used in magnetic Refrigeration Technique, It needs for Rare-earth Iron silicon substrate magnetic refrigerating material to be put into the water as heat exchange medium and work.If not taking guarantor in practical application Shield measure, corrosion will seriously affect the performance and its service life of magnetic refrigeration working substance.Have been presented for the method for corrosion inhibiter come Reduce corrosion of the water to room temperature magnetic refrigerating material, for example, patent CN03127022.0 provide a kind of pH value preferred scope 8~ Rust inhibition heat-exchange fluid between 10 can significantly delay the corrosiveness to magnetic refrigeration working substance Gd and Gd alloy；Specially It includes 0.1~10wt% molybdate, 0~5wt% bichromate, 0~8wt% that sharp CN101514458A, which then proposes a kind of form, Nitrite, 0.5~3wt% orthophosphates, 0.05~2wt% silicate, 0~1wt% borate, 0~3wt% benzoic acid Sodium, 0~0.1wt% zinc sulfate, 0~0.5wt% sodium carbonate and 0~10wt% triethanolamine, are suitable for La-Fe-Si system The water soluble rust inhibitor of column magnetic refrigerating material.Also there is to material progress coating the corrosion resistance for increasing rare-earth-iron cobalt and silicon compound, Such as Japanese Patent Laid-Open 2005-113209.But corrosion inhibiter is typically all meta-alkalescence, how much can damage the other of refrigeration machine Component, and the rare-earth-iron cobalt and silicon compound size majority used in refrigeration machine as refrigeration working medium is 1mm hereinafter, to coating Bring difficulty.There are also use Cr to substitute NaZn₁₃Fe element in the rare-earth-iron cobalt and silicon compound of phase, improves the corrosion of material Performance, such as CN103060692A.But this method is corrosion proof simultaneously in improvement material, again such that doped chemical enters In 1:13 phase with magnetothermal effect, causing the magnetic entropy of material to become is reduced.

Summary of the invention

To solve the above-mentioned problems, the present invention provide one kind in Rare-earth Iron silicon substrate magnetic refrigerating material addition containing Ni, Nb, The special miscellaneous phase of the elements such as Ti, to improve high material integrally corrosion proof method.

A kind of highly anticorrosive rare earth magnetic refrigerating material has special miscellaneous phase, it is characterised in that: by adding Ni, Nb element And non-equilibrium proportion is carried out, it is formed in highly anticorrosive rare earth magnetic refrigerating material single special miscellaneous other than matrix 1:13 phase Phase significantly reduces the galvanic corrosion current density of material by the electrochemical properties between the special miscellaneous phase of control and matrix phase, into And improve material entirety corrosion resistance；

The highly anticorrosive rare earth magnetic refrigerating material impregnates 12 hours in the liquid heat exchange medium that pH value is 7-8, rotten It loses rate and is no more than 0.15g/m².h；The material is impregnated in distilled water after keeping its electrode potential basicly stable, is polarized Curved measurement, corrosion electric current density is less than 5 μ A/cm²。

Further, the highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase is being changed by non-equilibrium proportion Credit minor is (La_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_αMatrix alloy in add the elements such as La, Si, Ni, Nb, Fe, Ti, Preparing chemical molecular formula is (La_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_α+ zX (X:Fe₂Nb、Fe₂Ti、La₅Si₃+ Ni) alloy； Wherein, R is that rare earth element ce, any one or any two or more combination, the content of R in Pr, Nd meet the model of x It encloses；M is that any one in Mn, Cr or any two or more combination, M content meet y range；The range of x is 0~0.3, a Range be 0~0.4, b range be 0~1.2, c range be 1.2~1.6, α range be 0~0.2, z range be 0.04~0.12.

The highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase is by matrix phase 1:13 phase and single special Miscellaneous phase composition, special miscellaneous phase have: the La-rich phase containing Ni element, Fe₂Nb phase, Fe₂Ti is equal；The content of matrix 1:13 phase with Volume percentage, 85% or more, the content of single special miscellaneous phase is 15% hereinafter, above two with volume percentage The content adduction of chemical component should be 100%.

It further, is (La in chemical molecular formula_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_αMatrix alloy in add La, Si, Ni element, preparing chemical molecular formula is (La_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_α+zLa₅Si₃The alloy of+zNi；Wherein, R is that rare earth element ce, any one or any two or more combination, the content of R in Pr, Nd meet the range of x；M is Any one in Mn, Cr or any two or more combination, M content meet the range of a；The range of x is the model of 0~0.3, a Enclose the range that range that the range for being 0~1.2, c for the range of 0~0.4, b is 1.2~1.6, α is 0~0.2, z be 0.04~ 0.12；

The obtained highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase, by matrix phase 1:13 phase and single Special miscellaneous phase composition, special miscellaneous phase are the La-rich phase containing Ni element；The content of matrix 1:13 phase with volume percentage, 85% or more, the content of single special miscellaneous phase is with volume percentage, 15% hereinafter, the content of above two chemical component Adduction should be 100%.

It further, is (La in chemical molecular formula_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_αMatrix alloy in add Fe, Nb element, preparing chemical molecular formula is (La_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_α+zFe₂The alloy of Nb；Wherein, R is rare earth Any one or any two or more combination, the content of R in Elements C e, Pr, Nd meet the range of x；M is in Mn, Cr Any one or any two or more combination, M content meet y range；The range that the range of x is 0~0.3, a is 0~ The range that the range that the range that 0.4, b range is 0~1.2, c is 1.2~1.6, α is 0~0.2, z is 0.04~0.12；

The obtained highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase, by matrix phase 1:13 phase and single Special miscellaneous phase Fe₂Nb composition；The content of matrix 1:13 phase is with volume percentage, and 85% or more, single special miscellaneous phase contains Amount is with volume percentage, 15% hereinafter, the content adduction of above two chemical component should be 100%.

It further, is (La in chemical molecular formula_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_αMatrix alloy in add Fe, Ti element, preparing chemical molecular formula is (La_1-xR_x)(Fe_13-a-b-cM_yCo_tSi_z)C_α+zFe₂The alloy of Ti；Wherein, R is rare earth Any one or any two or more combination, the content of R in Elements C e, Pr, Nd meet the range of x；M is in Mn, Cr Any one or any two or more combination, M content meet y range；The range that the range of x is 0~0.3, a is 0~ The range that the range that the range that 0.4, b range is 0~1.2, c is 1.2~1.6, α is 0~0.2, z is 0.04~0.12；

The obtained highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase, by matrix phase 1:13 phase and single Special miscellaneous phase Fe₂Ti composition；The content of matrix 1:13 phase is with volume percentage, 85% or more；Single special miscellaneous phase contains Amount is with volume percentage, below 15%；The content adduction of above two chemical component should be 100%.

A kind of application method of highly anticorrosive rare earth magnetic refrigerating material as described above in refrigeration machine, it is characterised in that: In When working in the recirculated water of magnetic refrigerator, the working face and water (flow) direction of highly anticorrosive rare earth magnetic refrigerating material are at 70 degree to 110 Spend angle.The corrosion rate that can be effectively reduced material further increases the highly anticorrosive rare earth magnetic refrigeration with special miscellaneous phase The anti-corrosion effect of material.

The chemical molecular formula of highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase of the invention is (La_1-xR_x) (Fe_13-a-b-cM_aCo_bSi_c)C_α+ zX (X:Fe₂Nb、Fe₂Ti、La₅Si₃+ Ni), wherein chemical formula (La_1-xR_x)(Fe_{13-a-b- c}M_aCo_bSi_c)C_αThe 1:13 phase in magnetic refrigerating material of the invention with magnetothermal effect is mainly provided, chemical formula zX is mainly mentioned The high corrosion proof special miscellaneous phase of material, specifically has: Fe₂Nb phase, Fe₂Ti phase, the La-rich phase containing Ni element.Corrosion experiment table Micro- galvanic corrosion bright, that the corrosion mechanism of the rare earth magnetic refrigerating material containing miscellaneous phase generates between miscellaneous phase and matrix phase, miscellaneous phase The corrosion rate of material is controlled with the difference of the electrochemical properties of matrix 1:13 phase；When not containing other miscellaneous phases in material, The corrosion of material depends on matrix 1:13 phase itself；Highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase of the invention is logical It crosses and adds special miscellaneous phase, significantly reduce the galvanic corrosion rate between matrix phase and miscellaneous phase, and be significantly lower than the corruption of 1:13 phase itself Rate is lost, the corrosion resistance of material entirety is substantially increased.

Further, the elements such as Nb, Ti, Ni in the present invention are after non-equilibrium proportion according to not entering in 1:13 phase, and It is directly formed special miscellaneous phase, therefore the crystal structure of matrix 1:13 phase is had little effect, will not be hindered heat treated The formation of 1:13 phase in journey, it is big that this maintains the highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase of the invention Magnetic entropy becomes, and has good magnetic heating performance；Additionally due to the presence of special miscellaneous phase, material also has very strong corrosion resistance, therefore It is optimal magnetic refrigerating material.

For X=La in the present invention₅Si₃The highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase of+Ni, chemistry Molecular formula is (La_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_α+zLa₅Si₃+ zNi, Ni element are added as corrosion proof element is improved After into material, it is more likely to enter in special miscellaneous phase La-rich phase compared with matrix 1:13 phase；Former La-rich phase is due to it Perishable element La far below the corrosion potential of 1:13 phase and containing high concentration, easily preferentially corrodes in water, and The local corrosion that the La-rich phase position of material surface occurs can destroy the electrochemical stability of alloy entirety, so that material adds Fast corrosion failure；However electrochemistry experiment shows after joined Ni element, the corrosion potential of La-rich phase increases, and slightly above The current potential of 1:13 phase, this leads to La-rich phase transition for the cathode in galvanic corrosion and is protected, and 1:13 phase and La- Galvanic Current density between rich phase substantially reduces, and galvanic corrosion rate reduces, and furthermore Ni is as raising alloy corrosion resistance Doped chemical enables to the highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase of the invention to be easy to happen passivation anti- It answers, this causes the corrosion resistance of material to further enhance.

Experiment of the invention show Ni content z in 0.04~0.12 range, with the element containing Ni La-rich phase this (the La of the single special miscellaneous phase of kind_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_α+zLa₅Si₃+ zNi magnetic refrigerating material has anticorrosive well Performance, when Ni content is more than 0.12, the resistance to corrosion that material has still had, but due to special miscellaneous phase volume fraction mistake More and excessive Ni can be progressed into 1:13 phase, (La_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_α+zLa₅Si₃+ zNi material Magnetic entropy change will be greatly reduced, and cannot get heat absorption and exothermal effect required for magnetic Refrigeration Technique.And after Ni content is less than 0.04, The resistance to corrosion of material reduces, and is corroded quickly in water.

For X=Fe in the present invention₂Nb、Fe₂The highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase of Ti is changed Credit minor is (La_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_α+zFe₂Nb、(La_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_α+zFe₂Ti； Nb and Ti element is added in material by non-equilibrium proportion, is not entered matrix 1:13 phase, but is formed special miscellaneous phase Fe₂Nb And Fe₂Ti, and both miscellaneous phases are more tiny compared with α-Fe and La-rich phase, corrosion area can be prevented further to expand Greatly；Electrochemistry experiment shows special miscellaneous phase Fe₂Nb and Fe₂The corrosion potential of Ti is higher than matrix 1:13 phase, therefore miscellaneous phase is as cathode It is protected, the matrix 1:13 phase around miscellaneous phase is preferentially corroded；Nb and Ti element has the energy of good anti-local corrosion Power, and the oxidation film for being capable of forming densification prevents from further corroding, therefore the perishable 1:13 phase around miscellaneous phase is due to Nb Presence with Ti element improves resistance to corrosion, and galvanic corrosion is suppressed, therefore special miscellaneous phase Fe₂Nb and Fe₂Ti is improved The corrosion resistance of highly anticorrosive rare earth magnetic refrigerating material of the invention.

Further, after Nb element being added, Nb can absorb C element, so that the sub- C content of gap element in matrix 1:13 phase It reduces；Although C element can shorten annealing time, promote the formation of 1:13 phase, since C element enters as interstitial atom The lattice of 1:13 phase destroys the first order phase change property of material so that lattice constant increases, and becoming the magnetic entropy of material reduces；It is special Miscellaneous phase Fe₂The presence of Nb can change C element in the distribution of main phase and special miscellaneous phase, and significantly improve the magnetic heating performance of material； But when the additive amount of Nb element is greater than 0.12, C element content is too low in 1:13 phase, it cannot be guaranteed that C element is to 1:13 phase shape At facilitation, the volume fraction of main phase 1:13 phase is difficult to reach 85%, and it is hot that this makes material no longer have preferable magnetic Energy；

Further, the content z that experiment shows Nb and Ti has Fe in 0.04~0.12 range₂Nb or Fe₂Ti is this (the La of single special miscellaneous phase_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_α+zFe₂Nb or (La_1-xR_x)(Fe_13-a-b-cM_aCo_bSi_c)C_α+ zFe₂Ti material has good corrosion resistance energy；When the content of Nb or Ti is more than 0.12, although material has good anti-corruption Erosion ability, however since a large amount of miscellaneous phases are precipitated, the volume fraction of matrix 1:13 phase is very few, and the magnetic heating performance of material reduces；And work as When Nb or Ti content is below 0.04, the corrosion resistance of material is significantly reduced.

Highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase of the invention, can by by La, Fe, Co, Si, R, M, the raw material such as C, Nb, Ti, Ni are prepared by above-mentioned chemical molecular formula, and after being smelted into ingot casting, ingot casting is vacuumized in the lehr Applying argon gas is annealed afterwards.Annealing temperature be 1000 DEG C~1300 DEG C temperature, annealing pressure be greater than 1.5 atmospheric pressure direct draught move back It directly uses within fire 50~400 hours.

Highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase of the invention, can by by La, Fe, Co, Si, R, M, the raw material such as C, Nb, Ti, Ni are prepared by above-mentioned chemical molecular formula, are smelted directly into ingot casting, and prepare by melt-quenching method Out with a thickness of the band of 0.4~0.9mm；Band is greater than 1.5 atmospheric pressure in 1000 DEG C~1300 DEG C temperature, annealing pressure Direct draught, which is annealed 2~24 hours, obtains having special miscellaneous phase and the high corrosion-resistant magnetic of matrix 1:13 phase refrigeration band, can be direct For in magnetic Refrigeration Technique.Or band is greater than to the positive pressure of 1.5 atmospheric pressure in 1000 DEG C~1300 DEG C temperature, annealing pressure Lower annealing 2~24 hours, then be cooled at 500 DEG C~800 DEG C vacuum annealing 2 hours, it is then cooled to room temperature, is heated to 250 DEG C~500 DEG C hydrogenate 2 hours, obtain Curie temperature near room temperature, resistance to by the height of special miscellaneous phase and matrix 1:13 phase composition Corrosion magnetic refrigeration band, can be applied in room-temperature magnetic refrigerator.

Highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase of the invention, above-mentioned preparation process can also be obtained Band 20-40 μm of powder is made, powder is bonded with binder and is used.

Highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase of the invention, can also be by (La_1-xR_x)(Fe_{13-a-b- c}M_aCo_bSi_c)C_αIt prepared respectively with special phase by above-mentioned chemical molecular formula, be smelted into ingot casting respectively.By (La_1-xR_x)(Fe_{13-a-b- c}M_aCo_bSi_c)C_αIngot casting is greater than the direct draught annealing 50~400 of 1.5 atmospheric pressure in 1000 DEG C~1300 DEG C temperature, annealing pressure Hour obtains the master alloy of 1:13 phase, then master alloy and special phase ingot casting are respectively prepared to 10-20 μm of powder, then closes mother Uniformly mixing is used directly in magnetic Refrigeration Technique after bonding in proportion for bronze end and special phase powder.Or by 1:13 phase Master alloy powder is then cooled to room temperature vacuum annealing 2 hours at 500 DEG C~800 DEG C, is heated to 250 DEG C~500 DEG C Hydrogenation 2 hours, obtain Curie temperature near room temperature, by the master alloy powder of matrix 1:13 phase composition, then by master alloy powder Uniformly mixing can be applied in room-temperature magnetic refrigerator last and special phase powder after bonding in proportion.

Highly anticorrosive rare earth magnetic refrigerating material with special miscellaneous phase of the invention is obtained by non-equilibrium proportion with base The alloy of body 1:13 phase and single special miscellaneous phase, and utilize the galvanic corrosion speed of the electrochemical properties of special miscellaneous phase control material Rate improves material integrally corrosion proof effect to reach.Cost is relatively low for alloying element used in the present invention, green non-poisonous, melting Method is simple, saves cost.

In conclusion the present invention has the advantages that

1, highly anticorrosive rare earth magnetic refrigerating material of the invention is the magnetic refrigerating material with special miscellaneous phase, using special miscellaneous The galvanic corrosion rate of the electrochemical properties control material of phase, greatly improves the corrosion resistance of material in water.

2, highly anticorrosive rare earth magnetic refrigerating material of the invention is by addition special elements and non-equilibrium proportion, eliminates pair Other unfavorable miscellaneous phases of the corrosion resistance and magnetic heating performance of material, with the single special miscellaneous phase of excellent corrosion resistance: Fe₂Nb phase, Fe₂Ti phase or La-rich phase containing Ni element replace.

3, in highly anticorrosive rare earth magnetic refrigerating material of the invention, the element of addition is mainly used to form special miscellaneous phase, and It will not enter in matrix 1:13 phase, therefore magnetic heating performance is not substantially change, be a kind of huge magnetic entropy change magnetic with practical value Refrigeration working medium.

4, highly anticorrosive rare earth magnetic refrigerating material of the invention can use under the flowing water environment of magnetic refrigerator, when high resistance to The working face of corrosion rare earth magnetic refrigerating material and water (flow) direction at 70 degree to 110 degree of angles when, material can be further increased Anti-corrosion effects.

Detailed description of the invention

Fig. 1 is 1# highly anticorrosive rare earth magnetic refrigerating material in embodiment 1 and control sample in 1050 degree, 1.6 atmosphere X ray diffracting spectrum after pressure annealing 7 days at room temperature.Wherein, abscissa is the angle of diffraction, and ordinate is diffracted intensity；

Fig. 2 is 1# highly anticorrosive rare earth magnetic refrigerating material and control sample LaFe in embodiment 1_11.5Si_1.5C_0.15、 LaFe_11.5Si_1.5C_0.15+0.05La₅Si₃Average corrosion rate after impregnating 12 hours in water；

Fig. 3 is 1# highly anticorrosive rare earth magnetic refrigerating material and control sample LaFe in embodiment 1_11.5Si_1.5C_0.15、 LaFe_11.5Si_1.5C_0.15+0.05La₅Si₃Microcosmic erosion profile after impregnating 2 hours in water；

Fig. 4 is that the 2# highly anticorrosive rare earth magnetic of the present invention band that freezes of embodiment 2 anneals 4 under 1100 degree, 2 atmospheric pressure X ray diffracting spectrum after hour at room temperature, wherein abscissa is the angle of diffraction, and ordinate is diffracted intensity；

Fig. 5 is 2# highly anticorrosive rare earth magnetic refrigeration band and control sample LaFe in embodiment 2_11.6Si_1.4C_0.17Band Average corrosion rate after impregnating 6,12,24 hours in water；

Fig. 6 is that 2# highly anticorrosive rare earth magnetic refrigeration band adds changes of magnetic field range to be magnetic under 0-1.5T outside in embodiment 2 Entropy Changes variation with temperature curve；

Fig. 7 is 3# highly anticorrosive rare earth magnetic refrigerating material and control sample La in embodiment 3_0.95Ce_0.05Fe_11.37Mn_{0.0 3}Co_0.1Si_1.5Polarization curve in water；

Fig. 8 is 4# highly anticorrosive rare earth magnetic refrigeration band and control sample in embodiment 4 La_0.8Ce_0.2Fe_11.3Mn_0.2Si_1.5Band works the microcosmic erosion profile after same time in magnetic refrigerator, and wherein fluid is situated between The flow velocity of matter pure water is 0.1m/s, and the working face of band is parallel and perpendicular to water (flow) direction respectively and is tested.

Specific embodiment