CN114350327A - Composite material, preparation method and application - Google Patents
Composite material, preparation method and application Download PDFInfo
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- CN114350327A CN114350327A CN202111579717.2A CN202111579717A CN114350327A CN 114350327 A CN114350327 A CN 114350327A CN 202111579717 A CN202111579717 A CN 202111579717A CN 114350327 A CN114350327 A CN 114350327A
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- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000000919 ceramic Substances 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 66
- 229910052742 iron Inorganic materials 0.000 claims abstract description 57
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- 239000002105 nanoparticle Substances 0.000 claims abstract description 39
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 235000013305 food Nutrition 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 13
- 239000000446 fuel Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 9
- 229940031182 nanoparticles iron oxide Drugs 0.000 claims description 9
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 235000010981 methylcellulose Nutrition 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010433 feldspar Substances 0.000 claims description 6
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000391 magnesium silicate Substances 0.000 claims description 6
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 6
- 235000019792 magnesium silicate Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000011135 tin Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- 230000009467 reduction Effects 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 230000002269 spontaneous effect Effects 0.000 abstract 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 12
- 239000011148 porous material Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 238000009461 vacuum packaging Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
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Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a composite material, a preparation method and application thereof. The composite material comprises a ceramic matrix and porous iron nanoparticles; the porous iron nano particles are dispersed in the ceramic matrix; the thickness of the composite material is 10-150 mu m; the ceramic substrate is porous ceramic with the porosity of 10-40%; the content of the porous iron nano particles is 41-93%, and the content of the ceramic matrix is 7-59%; the preparation method comprises the following steps: mixing and dispersing the ferric oxide nano particles and the ceramic material in a liquid medium to obtain slurry; preparing the slurry into a thin strip material and drying; sintering; reduction; the composite material is used in self-heating bags for aerial reverse bait and food heating. The technical problem solved is how to provide an anhydrous spontaneous heating composite material, so that the preparation method does not need to use a high-concentration, hot and strong-corrosivity NaOH solution, does not need to provide a support body for the ignition material, avoids the safety risk of using the corrosive material, saves the cost, has high thermal efficiency, basically solves the environmental protection problem of the spontaneous combustion material, and is more suitable for practicality.
Description
Technical Field
The invention belongs to the technical field of self-heating materials, and particularly relates to a composite material, a preparation method and application thereof.
Background
The anhydrous self-heating composite material is a basic key material widely used in the fields of food, emergency rescue and passive interference infrared. In the field of food heating and self-heating, the material can be combined with oxygen in the air to generate oxidation-reduction reaction without water, thereby providing heat, having the advantages of safety, sanitation and convenience, and being a new generation of heating energy source selection for self-heating chafing dishes and self-heating meals. In the field of emergency rescue, the heat generated by the self-heating material can facilitate search and rescue personnel to capture infrared signals, so that the position of a person to be searched and rescued can be accurately positioned in a natural background. In the field of electronic countermeasure decoys, a bait signalling material is sprayed from an aircraft, which material spontaneously ignites when exposed to air, enabling the material to spread out in the form of a cloud, thereby mimicking the fuel exhaust or hot engine components of an aircraft.
In the prior art, the method for preparing the anhydrous self-heating and self-ignition material is limited, and the following two methods are mainly adopted:
one is a more traditional chemical leaching method, which mainly aims at forming a metal matrix with high specific surface area and reactivity to oxygen, and generally requires that iron powder, aluminum powder and the like are mixed and then added into slurry containing a proper solvent and a bonding agent; then coating the mixture on a very thin steel foil by a dip coating or spray coating method; heating the resulting material to evaporate the solvent and binder to produce a layer of metal powder on the steel foil; then, in a reducing atmosphere such as hydrogen and argon, the coated substrate is further heated to form an iron/aluminum alloy; finally, the aluminum in the alloy is leached with a high concentration of hot sodium hydroxide solution to form highly heat sensitive porous iron. The method utilizes chemical leaching to prepare the porous self-ignition iron, and a high-concentration, hot and strong-corrosivity NaOH solution is required to be used in the preparation process; the disposal of such corrosive materials increases the safety risk for the user, causes damage to human tissue, and in addition, the solution is not environmentally friendly.
The other is an alternative method of preparing self-heating materials without using chemical hazardous materials such as NaOH, and the preparation process is a method of performing water-based treatment on a substrate structure capable of providing support for the ignition material, such as ceramics, metals, nano materials, and the like, and then reducing iron oxide with hydrogen to form the ignition nano iron.
The prior art can not solve the problems of environmental pollution and removal of the non-ignitable support, so that the material efficiency is low, the cost is high and the loss is large.
Disclosure of Invention
The invention mainly aims to provide a composite material, a preparation method and application thereof, and aims to solve the technical problem of how to provide an anhydrous self-heating composite material, so that the anhydrous self-heating composite material is prepared without using a high-concentration, hot and highly corrosive NaOH solution or providing a support body for a firing material, the safety risk of using a corrosive material is avoided, the cost is saved, the heat efficiency is high, the environmental protection problem of the self-heating material is basically solved, and the anhydrous self-heating composite material is more suitable for practical use.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The composite material provided by the invention comprises a ceramic matrix and porous iron nano particles; the porous iron nanoparticles are dispersed within the ceramic matrix; the composite material is a sheet with the thickness of 10-150 mu m; wherein the ceramic substrate is porous ceramic, and the porosity of the ceramic substrate is 10-40%; the content of the porous iron nano particles is 41-93% by mass percentage, and the content of the ceramic matrix is 7-59%.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the composite material of the foregoing, wherein the material of the ceramic matrix is selected from at least one of suzhou earth, montmorillonite, bentonite, aluminum silicate, sodium silicate, magnesium silicate, zeolite, feldspar and cement.
Preferably, the aforementioned composite further comprises a fuel; the fuel is selected from at least one of aluminum, silicon, tin and magnesium.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The preparation method of the composite material provided by the invention comprises the following steps:
1) mixing iron oxide nano particles and a ceramic material, and dispersing the mixture in a liquid medium to obtain slurry; wherein the mass ratio of the iron oxide nanoparticles to the ceramic material is 50-90%: 10-50%;
2) preparing the slurry into a thin strip material with the thickness of 10-150 mu m, and drying;
3) sintering, wherein the sintering atmosphere is air or inert atmosphere, the sintering temperature is 980-1200 ℃, and the sintering time is 5 min-6 h;
4) reducing under the condition of hydrogen at the temperature of 350-600 ℃ for 3h to obtain a composite material; the composite material comprises a ceramic matrix and porous iron nanoparticles; the porous iron nanoparticles are dispersed within the ceramic matrix; the ceramic substrate is porous ceramic, and the porosity of the ceramic substrate is 10-40%.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the aforementioned method of preparation, wherein said liquid medium is selected from water or alcohol.
Preferably, the preparation method further comprises a binder; the binder is at least one selected from methylcellulose, hydroxypropyl methylcellulose and ethylcellulose.
Preferably, the method of manufacturing is further characterized in that the ceramic matrix is made of at least one material selected from the group consisting of suzhou clay, montmorillonite, bentonite, aluminum silicate, sodium silicate, magnesium silicate, zeolite, feldspar and cement.
Preferably, the preparation method, wherein the preparation method of the ribbon material in step 2) is coating molding or tape casting.
Preferably, the preparation method comprises the following steps: the drying temperature is 50-75 ℃, the relative humidity is 15-55%, and the drying time is 10 h.
Preferably, the method further comprises a step of cooling the composite material under an atmosphere of flowing hydrogen or inert gas after the reduction.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the invention, the aerial reverse bait comprises the composite material.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the invention, the self-heating bag for heating food comprises the composite material.
By means of the technical scheme, the composite material and the preparation method and the application thereof provided by the invention at least have the following advantages:
1. the invention provides a composite material and a preparation method thereof, which are characterized in that iron oxide nano particles and ceramic powder are uniformly mixed, and then slurry is hung or cast to a required thickness. During reduction, reducing the iron oxide dispersed in the ceramic film to convert the iron oxide into porous iron nano particles; the self-heating degree of the iron can be controlled according to the weight ratio of the iron to the ceramic material, and can also be adjusted by adding other combustible metal powder fuels (such as magnesium, aluminum powder and the like) into the slurry; the use of high-concentration and strong-corrosiveness sodium hydroxide solution is avoided; the reactant is hydrogen which is harmless to the environment, and the discharged by-product is water; the environment is protected, and no environmental problem exists;
2. according to the composite material and the preparation method, a bottom layer structure for supporting the ignition material is not needed, and the material prepared by the method is an active composite structure capable of self-heating, so that the energy density of the material is improved, and the thermal efficiency of the material is high; and on the other hand also cost savings.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given of the specific embodiments, structures, characteristics and effects of a composite material and a preparation method and applications thereof according to the present invention in combination with the preferred embodiments.
The invention provides a composite material, which comprises a ceramic matrix and porous iron nano particles; the porous iron nanoparticles are dispersed within the ceramic matrix; the composite material is a sheet with the thickness of 10-150 mu m; wherein the ceramic substrate is porous ceramic, and the porosity of the ceramic substrate is 10-40%; the content of the porous iron nano particles is 41-93% by mass percentage, and the content of the ceramic matrix is 7-59%.
According to the technical scheme, the porous iron nanoparticles of the heating material are dispersed in the ceramic matrix, and the heating material is not prepared on a common support body, so that a bottom layer structure for supporting the heating material is not needed, and the cost is saved; on the other hand, the energy density of the material can be improved, and the thermal efficiency of the material is high.
In the technical scheme, the porous iron nanoparticles are embedded in the pores of the ceramic, and are different from the traditional nano iron particles; the nano iron particles in the traditional sense generally do not generate heat, particularly the nano iron particles existing in a dispersed state do not generate heat, and the nano iron particles can slowly generate heat only after being accumulated to a certain number and a certain density. The porous iron nanoparticles are actually formed by reducing the nano iron oxide particles under specific conditions, each porous iron nanoparticle is in a spongy structure comprising countless micropores, the specific pore size of the micropores can not be detected by means, and the appearance of the porous iron nanoparticles cannot be clearly observed under the existing high-magnification electron microscope; the porous iron nano particle has higher specific surface area which is measured to be more than 35m2/g。
The porous nano iron particles can not self-heat when existing independently, the ceramic matrix is used as a carrier, and self-heat can be generated after the porous nano iron particles are uniformly dispersed in the ceramic matrix, and the possible mechanism is inferred to be that the ceramic matrix has certain heat insulation and heat storage performances and can store the energy of the porous nano iron particles; furthermore, the ceramic matrix of the invention must be a porous ceramic matrix, the porosity of which is controlled within the range of 10-40%, and the pore structure enables oxygen to be introduced into the ceramic to induce the heating of the porous nano iron particles, and also provides enough strength for the composite material, so that the composite material can be normally molded even when the composite material is prepared into a sheet with the thickness of only 10-150 μm. In the technical scheme of the invention, the limitation of the thickness of the composite material to be 10-150 μm is caused by the limitation of the preparation process of the composite material, and only when the composite material is made into a thin sheet, the iron oxide nanoparticles in the raw material can be completely reduced into the porous iron nanoparticles from outside to inside during hydrogen reduction, so that the composite material is obtained. In practical application, when a composite material with a relatively thick thickness is required, a plurality of composite materials can be superposed for use.
The content of the porous iron nano particles can be changed in a large range, the content of the porous iron nano particles is 41-93%, the content of the ceramic matrix is 7-59%, and the self-heating degree of iron can be controlled by adjusting the proportion of the porous iron nano particles to the ceramic matrix material.
The ceramic substrate is selected to be porous ceramic, and the main reason is that air is introduced through pores, so that the oxygen permeability of the composite material is improved, and the nano porous iron can self-heat and self-ignite. When the porosity is lower than 10%, the oxygen permeability is insufficient due to narrow air channels, which may affect the heat generation performance of the composite material; and when the porosity is higher than 40%, the strength of the composite material is affected, and the composite material is pulverized.
The porosity of the porous ceramic is controlled without specially controlling the pore diameter, and the pore diameter is naturally determined by the type and the proportion of raw materials through a processing technology and is generally micron-sized.
Preferably, the material of the ceramic matrix is selected from at least one of suzhou earth, montmorillonite, bentonite, aluminum silicate, sodium silicate, magnesium silicate, zeolite, feldspar and cement.
Preferably, the composite material can also comprise fuel; the fuel is selected from at least one of aluminum, silicon, tin and magnesium. The fuel is not necessary, but the performance of the composite material is further optimized by adding the fuel, so the fuel is the fuel which can be selectively added with various metal powders, and the main purpose of the fuel is to adjust the output energy of the self-heating and self-ignition material, because the combustion temperature of the metal powders such as magnesium powder, aluminum powder and the like is higher. The fuel additive consists essentially of at least one of aluminum, silicon, tin, and magnesium; tin is particularly preferred.
The invention also provides a preparation method of the composite material, wherein the composite material comprises a ceramic matrix and porous iron nano particles; the porous iron nanoparticles are dispersed within the ceramic matrix; the ceramic substrate is porous ceramic, and the porosity of the ceramic substrate is 10-40%. The preparation method of the composite material comprises the following steps: 1) mixing iron oxide nano particles and a ceramic material, and dispersing the mixture in a liquid medium to obtain slurry; the slurry is a free-flowing slurry; wherein the mass ratio of the iron oxide nanoparticles to the ceramic material is 50-90%: 10-50%; 2) preparing the slurry into a thin strip material with the thickness of 10-150 mu m, and drying; drying the slurry after preparing the slurry into a thin strip material aiming at removing a liquid medium and a dispersing agent in the slurry; 3) sintering, wherein the sintering atmosphere is air or inert atmosphere, the sintering temperature is 980-1200 ℃, and the sintering time is 5 min-6 h; 4) reducing the mixture under the condition of hydrogen at the reducing temperature of 350-600 ℃ for 3h to obtain the composite material. The purpose of the reduction of the thin strip material after sintering is to produce nano-sized heat generating iron particles within the ceramic matrix.
In the above technical scheme, the mass ratio of the iron oxide nanoparticles to the ceramic material is controlled, and the ratio of the porous iron nanoparticles to the ceramic material in the composite material is adjusted, so that the self-heating degree of iron can be controlled by adjusting the ratio of the porous iron nanoparticles to the ceramic material.
In the technical scheme, the thickness of the thin strip material is controlled to be 10-150 mu m; on one hand, the method is to facilitate that the nano iron oxide particles in the raw material can be completely reduced into the porous iron nano particles from outside to inside; on the other hand, the thickness of the thin strip material is closely related to the heating time of the self-heating material, the heating time of the self-heating material can be controlled by adjusting the thickness of the thin film, and composite materials with different specifications and models can be manufactured. And drying the thin strip material. It may be cut to the desired shape and length or rolled up for storage.
The thin strip material mainly comprises a ceramic material and a nano iron oxide material, so that reduction treatment is required to be carried out on the thin strip material. Sintering is required before the thin strip material is reduced, and the main purpose of sintering is to remove the binder in the slurry through sintering; if the adhesive is not removed in advance, the adhesive may overflow in the form of water and/or gas when the thin strip material is processed at a high temperature, so that too many pores are generated in the thin strip material to affect the strength of the thin strip material; the invention can reduce the porosity of the thin strip material by the sintering process before the reduction, which is beneficial to ensuring the porosity and the strength of the composite material.
In the technical scheme, the sintering is different from conventional calcination, and the crystal form of the sintered material is changed and is in a stable state. The sintering process comprises the following steps: the sintering atmosphere is air or inert atmosphere, the sintering temperature is 980-1200 ℃, and the sintering time is 5 min-6 h. The sintering temperature is in a large relationship with the material selection of the ceramic substrate, and generally sintering is required to be carried out within a temperature range of 10-15 ℃ above the melting point of the ceramic material, so that the raw material is melted and sintered to form the ceramic substrate. The process temperature and sintering time of the sintering can be controlled according to methods known in the art.
In the above technical scheme, the reduction process under hydrogen conditions is as follows: the reducing atmosphere is hydrogen, the reducing temperature is 350-600 ℃, and the reducing time is 3 h. Under the reduction reaction conditions, reducing the nano iron oxide in the composite material into porous nano iron particles; water produced by reaction with hydrogen gas is produced as a byproduct. The reactants of the reduction reaction are hydrogen and nano iron oxide, and the product of the reaction is water, so the process has better environmental protection property.
Preferably, the liquid medium is water or an organic solvent, for example, alcohol; the liquid medium is preferably water, in view of product performance, product cost, environmental protection and the like.
Preferably, the slurry also comprises a binder; the binder is at least one selected from methylcellulose, hydroxypropyl methylcellulose and ethylcellulose. The binder can be selectively added into the mixture of the slurry, and the main purpose is to ensure that dispersed materials can be stably distributed in the slurry after being uniformly dispersed, so that aggregation and sedimentation of ceramic materials and iron oxide nano materials are avoided, and the construction performance of the slurry is not influenced; the adhesive is selected to be a high viscosity adhesive that is soluble in the selected solvent.
Preferably, the material of the ceramic matrix is selected from at least one of suzhou earth, montmorillonite, bentonite, aluminum silicate, sodium silicate, magnesium silicate, zeolite, feldspar and cement. On one hand, the ceramic material aims to form a carrier of the porous iron nano particles, so that the carrier has certain strength, and can provide enough oxygen channels for the porous nano iron to ensure that the porous nano iron can self-heat and self-ignite; on the other hand, it may store energy of the porous iron nanoparticles, thereby enabling the porous iron nanoparticles to self-heat.
Preferably, the preparation method of the ribbon material in the step 2) is coating forming or casting forming. And preparing the slurry into a film by coating forming or tape casting forming. The slurry can be formed into a wet film strip by hand coater, doctor blade, or can be processed using a well-established equipped ceramic casting machine. Regardless of the means used to form the film, the slurry should be laid down in a thin, flat, uniform ribbon.
The thin strip material needs to be dried after being formed into a film, and can be naturally dried under the environmental condition or subjected to temperature-controlled humidity-controlled drying under the specific drying condition. By carrying out temperature and humidity control drying on the composite material under specific drying conditions, cracks or surface stress of the composite material can be avoided. Preferably, the drying process is as follows: the drying temperature is 50-75 ℃, the relative humidity is 15-55%, and the drying time is 10 h.
Preferably, the method for producing the composite material further includes a step of cooling the composite material under an atmosphere of flowing hydrogen gas or inert gas after the reduction.
By the above preparation method, a self-heating composite material can be obtained. The self-heating composite material can self-heat in air, so that it cannot be directly stored in air. Generally, after said cooling, a step of packaging said composite material may also be included; and during packaging, controlling the vacuum condition in the package or filling inert gas for protection. The composite material can maintain the performance thereof by vacuum condition or inert gas protection. Alternatively, the self-heating composite material may be stored by immersing it in a liquid such as water, alcohol, kerosene, etc.
The invention also provides an aerial reverse bait; the aerial reverse bait comprises the composite material of the invention; the invention also provides a self-heating bag for heating food; the self-heating bag for heating food comprises the composite material provided by the invention. The aerial reaction bait and the self-heating bag for food heating can be used in a manner similar to conventional heating materials, and will not be described herein.
The technical scheme of the present invention is further illustrated by the following specific examples, wherein the raw materials and reagents used in the following examples are commercially available, and the heat generating performance of the prepared composite material is evaluated by monitoring the exposure time-heat generating temperature data in real time.
Example 1
1) Weighing 27 g of nano iron oxide particles, 3 g of aluminum silicate, 1.5 g of methyl cellulose and 67.5 ml of water;
2) dispersing methylcellulose powder in water to completely hydrate the methylcellulose within 16 hours;
3) adding nano iron oxide and aluminum silicate into a mixing container containing a methyl cellulose solution for dispersing and mixing to obtain free-flowing slurry;
4) coating the slurry onto a teflon or other suitable non-stick sheet or film with a coater blade to obtain a thin strip of material having a thickness of 50 μm;
5) drying the thin strip material for 10 hours under the environmental conditions of 50 ℃ and 45% of relative humidity; then cutting the thin strip material into a desired shape;
6) sintering the thin strip of the composite material in air at 1155 ℃ for 90 minutes;
7) reducing the sintered thin strip material under a reducing condition; the hydrogen flow rate during reduction is 4 liters per minute, the reduction temperature is 550 ℃, and the reduction time is 3 hours;
8) and finally, performing performance test on the composite material, and filling inert gas or vacuum packaging.
In the composite material prepared by the embodiment of the invention, the specific surface area of the porous iron nano-particles is 47m2(ii)/g; the porosity of the porous ceramic is 38.6%; 80 sheets of the composite material were stacked to a total thickness of about 4mm, placed at ambient temperature, and the temperature of the composite material itself was monitored as a function of its exposure time to air under ambient conditions, with the results shown in Table 1 below:
TABLE 1
| Time(s) | Temperature (. degree.C.) | Time(s) | Temperature (. degree.C.) |
| 0 | 24 | 320 | 458 |
| 20 | 43 | 340 | 465 |
| 40 | 85 | 360 | 471 |
| 60 | 112 | 380 | 475 |
| 80 | 150 | 400 | 468 |
| 100 | 184 | 420 | 462 |
| 120 | 210 | 440 | 468 |
| 140 | 248 | 460 | 462 |
| 160 | 290 | 480 | 465 |
| 180 | 322 | 500 | 459 |
| 200 | 351 | 520 | 458 |
| 220 | 394 | 540 | 454 |
| 240 | 422 | 560 | 447 |
| 260 | 434 | 580 | 441 |
| 280 | 441 | 600 | 436 |
| 300 | 454 |
Example 2
1) Taking 73% of nano iron oxide particles and 27% of Suzhou soil by mass percent, mixing and dispersing the nano iron oxide particles and the Suzhou soil in water to obtain free-flowing slurry;
2) coating was carried out in the same manner as in example 1 to obtain a thin strip having a thickness of 50 μm;
3) drying and cutting according to the same procedure as example 1;
4) sintering the thin strip of the composite material in air at the sintering temperature of 1000 ℃ for 30 minutes;
5) it was reduced according to the procedure of example 1;
6) and finally, performing performance test on the composite material, and filling inert gas or vacuum packaging.
In the composite material prepared by the embodiment of the invention, the specific surface area of the porous iron nano-particles is 39m2(ii)/g; the porosity of the porous ceramic is 29.7%; 80 sheets of the composite material were stacked to a total thickness of about 4mm, placed at ambient temperature, and the temperature of the composite material itself was monitored as a function of its exposure time to air under ambient conditions, with the results shown in Table 2 below:
TABLE 2
| Time(s) | Temperature (. degree.C.) | Time(s) | Temperature (. degree.C.) |
| 0 | 23 | 320 | 437 |
| 20 | 35 | 340 | 423 |
| 40 | 63 | 360 | 431 |
| 60 | 89 | 380 | 428 |
| 80 | 126 | 400 | 416 |
| 100 | 174 | 420 | 420 |
| 120 | 188 | 440 | 412 |
| 140 | 211 | 460 | 408 |
| 160 | 278 | 480 | 411 |
| 180 | 299 | 500 | 401 |
| 200 | 312 | 520 | 394 |
| 220 | 365 | 540 | 397 |
| 240 | 396 | 560 | 392 |
| 260 | 412 | 580 | 383 |
| 280 | 423 | 600 | 388 |
| 300 | 434 |
The features of the invention claimed and/or described in the specification may be combined, and are not limited to the combinations set forth in the claims by the recitations therein. The technical solutions obtained by combining the technical features in the claims and/or the specification also belong to the scope of the present invention.
Claims (12)
1. A composite material, comprising a ceramic matrix and porous iron nanoparticles; the porous iron nanoparticles are dispersed within the ceramic matrix; the composite material is a sheet with the thickness of 10-150 mu m; wherein the ceramic substrate is porous ceramic, and the porosity of the ceramic substrate is 10-40%; the content of the porous iron nano particles is 41-93% by mass percentage, and the content of the ceramic matrix is 7-59%.
2. The composite material of claim 1, wherein the material of the ceramic matrix is selected from at least one of suzhou earth, montmorillonite, bentonite, aluminum silicate, sodium silicate, magnesium silicate, zeolite, feldspar, and cement.
3. The composite material of claim 1, further comprising a fuel; the fuel is selected from at least one of aluminum, silicon, tin and magnesium.
4. A preparation method of a composite material is characterized by comprising the following steps:
1) mixing iron oxide nano particles and a ceramic material, and dispersing the mixture in a liquid medium to obtain slurry; wherein the mass ratio of the iron oxide nanoparticles to the ceramic material is 50-90%: 10-50%;
2) preparing the slurry into a thin strip material with the thickness of 10-150 mu m, and drying;
3) sintering, wherein the sintering atmosphere is air or inert atmosphere, the sintering temperature is 980-1200 ℃, and the sintering time is 5 min-6 h;
4) reducing under the condition of hydrogen at the temperature of 350-600 ℃ for 3h to obtain a composite material; the composite material comprises a ceramic matrix and porous iron nanoparticles; the porous iron nanoparticles are dispersed within the ceramic matrix; the ceramic substrate is porous ceramic, and the porosity of the ceramic substrate is 10-40%.
5. The method of claim 4, wherein the liquid medium is selected from water and alcohol.
6. The method according to claim 4, wherein the slurry further comprises a binder; the binder is at least one selected from methylcellulose, hydroxypropyl methylcellulose and ethylcellulose.
7. The method of claim 4, wherein the ceramic matrix is made of at least one material selected from the group consisting of Suzhou earth, montmorillonite, bentonite, aluminum silicate, sodium silicate, magnesium silicate, zeolite, feldspar, and cement.
8. The method according to claim 4, wherein the ribbon material of step 2) is formed by coating or casting.
9. The method according to claim 4, wherein the drying process comprises the following steps: the drying temperature is 50-75 ℃, the relative humidity is 15-55%, and the drying time is 10 h.
10. The method of claim 4, further comprising, after the reducing, the step of cooling the composite material under an atmosphere of flowing hydrogen or inert gas.
11. An airborne counteraction bait, characterized in that it comprises a composite material according to any of claims 1 to 5.
12. Self-heating bag for heating food, characterized in that it comprises a composite material according to any one of claims 1 to 5.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008060698A2 (en) * | 2006-05-25 | 2008-05-22 | High Performance Coatings Inc | Heat resistant composite materials containing nanoparticles |
| KR20120108652A (en) * | 2011-03-25 | 2012-10-05 | 주식회사 다물엔씨티 | Surface-activated porous ceramics with different formed iron oxides and method for preparing thereof |
| US9828304B1 (en) * | 2015-04-21 | 2017-11-28 | The United States Of America As Represented By The Secretary Of The Army | Composites of porous pyrophoric iron and ceramic and methods for preparation thereof |
| CN108892533A (en) * | 2018-08-10 | 2018-11-27 | 张家港市沐和新材料技术开发有限公司 | A kind of formula of Diatomite-based Porous Ceramics slurry |
| CN112321270A (en) * | 2020-10-26 | 2021-02-05 | 佛山市东鹏陶瓷有限公司 | Photocatalytic anion ceramic tile containing modified porous material and preparation process thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008060698A2 (en) * | 2006-05-25 | 2008-05-22 | High Performance Coatings Inc | Heat resistant composite materials containing nanoparticles |
| KR20120108652A (en) * | 2011-03-25 | 2012-10-05 | 주식회사 다물엔씨티 | Surface-activated porous ceramics with different formed iron oxides and method for preparing thereof |
| US9828304B1 (en) * | 2015-04-21 | 2017-11-28 | The United States Of America As Represented By The Secretary Of The Army | Composites of porous pyrophoric iron and ceramic and methods for preparation thereof |
| CN108892533A (en) * | 2018-08-10 | 2018-11-27 | 张家港市沐和新材料技术开发有限公司 | A kind of formula of Diatomite-based Porous Ceramics slurry |
| CN112321270A (en) * | 2020-10-26 | 2021-02-05 | 佛山市东鹏陶瓷有限公司 | Photocatalytic anion ceramic tile containing modified porous material and preparation process thereof |
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