CN101543894B - Method for preparing metal and alloy material with sol-gel self-combustion method - Google Patents
Method for preparing metal and alloy material with sol-gel self-combustion method Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000000956 alloy Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000007769 metal material Substances 0.000 title claims abstract description 18
- 238000009841 combustion method Methods 0.000 title abstract 2
- 239000002184 metal Substances 0.000 claims abstract description 33
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000002485 combustion reaction Methods 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000009767 auto-combustion synthesis reaction Methods 0.000 claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
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- 239000000203 mixture Substances 0.000 claims description 6
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- 238000007323 disproportionation reaction Methods 0.000 claims description 5
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- 150000001413 amino acids Chemical class 0.000 claims description 4
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- 230000008020 evaporation Effects 0.000 claims description 4
- 150000002429 hydrazines Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
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- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- -1 inorganic acid salt Chemical class 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 2
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229960001051 dimercaprol Drugs 0.000 claims description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 24
- 239000000446 fuel Substances 0.000 abstract description 7
- 230000036632 reaction speed Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 2
- 229910002065 alloy metal Inorganic materials 0.000 abstract 1
- 239000000499 gel Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000002689 soil Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002555 FeNi Inorganic materials 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing metal and alloy material with a sol-gel self-combustion method, which comprising the following steps: metal salt and complexing agent combust in solvent to form sol, and the pH value of the sol is adjusted to be in a range of 1-10 by regulating agent in the soil forming process; the solvent is removed through heating and evaporating to form gel, and fuel and oxidizer are kept in the gel; the gel taken as a precursor for self-combustion is put in a reactor and ignited under the protection of flowing non-oxidative gas or in vacuum to generate gaseous products, and resultant resulted from combustion is taken away by the flowing non-oxidative gas so that the metal and alloy material or composite material of metal, alloy and nonmetal are prepared.The invention has the advantages of simplicity, low cost, rapid reaction speed, low temperature and safe preparation process.
Description
Technical field
The present invention relates to a kind of method for preparing metal or alloy, specifically a kind of method of utilizing the collosol and gel auto-combustion method to prepare metal or alloy.
Background technology
Methods such as electrochemical reduction, hydrogen (other gas) reduction, carbon reduction are mainly adopted in the preparation of metal current.Smelting process is mainly adopted in the preparation of alloy.Metal/non-metal composite material, the technology that also needs metal to prepare during preparation.And the collosol and gel auto-combustion method is mainly used to synthesis oxide.
In the method for preparing metal that people use, need high temperature and expensive equipment, perhaps need accurate electrochemical apparatus.Need conditions such as vacuum, high temperature during the smelting method for preparing alloy, and can only prepare the stable metal alloy.The cycle of preparation metal or alloy is long, expense is big.The preparation of composite also needs the technology of metal preparation.And the collosol and gel auto-combustion method was used for synthesis oxide in the past, was not used for preparing metal or its alloy.
Summary of the invention
In order to overcome the problem that prior art exists, the purpose of this invention is to provide the method that a kind of collosol and gel auto-combustion method prepares metal or alloy, low, the safe preparation process of temperature that this method for preparing metal or alloy is simple, with low cost, reaction speed fast, need provide.
The objective of the invention is to be achieved through the following technical solutions:
A kind of collosol and gel auto-combustion method prepares the method for metal or alloy material, it is characterized in that it may further comprise the steps:
1) utilizes slaine and complexing agent fuel in solvent, to form colloidal sol, and in the process that forms colloidal sol, utilize conditioning agent to regulate pH value, make pH value in the 1-10 scope;
2) remove solvent by heating or evaporation, form gel, and in gel, preserve fuel and oxidant;
3) presoma of gel as spontaneous combustion reaction is placed in the reactor, under the non-oxidizing gas protection of flowing or light in the vacuum;
4) gaseous product of burning generation is taken away by the non-oxidizing gas that flows, and is perhaps taken away by vavuum pump; Product after the burning obtains the metal or alloy material, perhaps metal or alloy and nonmetallic composite.
The present invention is in step 1), and described slaine is an inorganic acid salt, the mixture of one or several of acylate or alkoxide (in nitrate, acetate, perchlorate, oxalates, citrate, alkoxide, the carboxylic acid hydrazonium salt).Described complexing agent is 1,10-Phen, EDTA, dimercaprol dimercaptopropanol, mercaptoethylmaine, TGA, thiocarbamide, ammonium fluoride, oxine, cyanide, acetylacetone,2,4-pentanedione, citric acid, tartaric acid, oxalic acid, sulfosalicylic acid, triethanolamine, EGTA, ethylenediamine tetrapropionic acid, triethylenetetramine, carboxylic acid, amino acid, polyvinyl alcohol, hydrazine and hydrazine derivative, ethylenediamine, the mixture of one or several in the urea.Described solvent is a water, alcohol, ether, amine, nitrile, ketone, dioxane, the mixture of one or more in the oxolane; The pH value conditioning agent is an ammoniacal liquor, urea, ammonium salt (as carbonic acid ammonia, ammonium nitrate, oxalic acid ammonia, Ammoniom-Acetate).
In step 3), the presoma of spontaneous combustion reaction is the compound with disproportionation performance, as: carboxylate or carboxylate metal hydrazonium salt or its solid solution.Non-oxidizing gas is helium, neon, argon gas, nitrogen, hydrogen, CO gas, carbon dioxide or methane gas.Also the presoma of gel as the spontaneous combustion reaction can be placed in the reactor, under vacuum environment, light.
The present invention also can be used to prepare composite, generates the composite of metal or alloy and nonmetallic materials.Compared with prior art, the collosol and gel auto-combustion method of the present invention advantage for preparing metal or alloy, composite shows following several aspect:
(1) temperature that need provide is very low, only needs 100 to spend to 500 degree, and typical temperature is 240 degree.Such temperature just can provide with alcolhol burner or lighter.
(2) reaction speed is fast.Because use the spontaneous combustion technology, reaction speed is very fast, and can once synthetic in a large number metal or alloy.
(3) equipment cheapness.Method of the present invention is used the spontaneous combustion technology, needs the minute quantity heat credit except lighting, and course of reaction does not need the outside that heat is provided, and does not need expensive high temperature furnace.And the temperature that afterproduct is finished in burning reduces rapidly, does not need resistant to elevated temperatures equipment.
(4) raw material cheapness.Salt (inorganic salts, organic salt, alkoxide etc.), complexing agent (carboxylic acid, polyvinyl alcohol etc.), the oxidant (ammoniacal liquor, ammonium nitrate, urea etc.) of raw material that needs for metal ion is provided.Material is simple, and is cheap.
(5) safe preparation process.Owing to do not need high temperature, electric power etc. can not wanted vacuum yet, and the material preparation process is safe and reliable.
(6) can prepare the metastable phase material.Because this method can make the synthetic back of material temperature in the extremely short time be reduced to ambient temperature, so can synthesize the metastable phase material.
(7) the material atom level of Sheng Chenging is even, and product is a bubble powder, loose, nano-powder that surface-active is big.
(8) combustion process is kept by self heat release, does not need the external world that energy is provided.
The metal or alloy that the present invention makes and the composite of nonmetallic materials are at nano metal or alloy, magnetic material (Hard Magnetic, soft magnetism, absorbing material), aspects such as catalyst, conductive material (silver slurry, antistatic film), coating preparation, novel metastable phase material are with a wide range of applications.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the metallic cobalt of collosol and gel auto-combustion method preparation.
Fig. 2 is the X ray diffracting spectrum of the cobalt-nickel alloy of collosol and gel auto-combustion method preparation.
Fig. 3 is the X ray diffracting spectrum of the metallic nickel/alumina composite material of collosol and gel auto-combustion method preparation.
The specific embodiment
A kind of collosol and gel auto-combustion method prepares the method for metal or alloy material, and it may further comprise the steps:
1) utilizes oxidant slaine and complexing agent fuel in solvent, to form colloidal sol, and in the process that forms colloidal sol, utilize conditioning agent to regulate pH value, make pH value in the 1-10 scope;
2) remove solvent by heating or evaporation, form gel, and in gel, preserve fuel and oxidant;
3) presoma of gel as the spontaneous combustion reaction is placed in the reactor, (perhaps in the vacuum) lights under the non-oxidizing gas protection of flowing;
4) gaseous product of burning generation is taken away (perhaps being pumped away) by the non-oxidizing gas that flows; In the combustion products, obtain the metal or alloy material, perhaps metal or alloy and nonmetallic composite.
Specific as follows:
Slaine: metal nitrate, acylate, alkoxide, perchlorate etc.
Complexing agent fuel: carboxylic acid, amino acid, hydrazine and hydrazine derivative, ethylenediamine, disproportionation compounds such as urea are presoma: carboxylate, carboxylate metal hydrazonium salt or its solid solution for example: nitrate → citric acid → ammoniacal liquor → drying → xerogel → light.
Utilize metal salt (as nitrate, acetate, perchlorate, oxalates, citrate, alkoxide, carboxylic acid hydrazonium salt etc.) and complexing agent (as carboxylic acid, amino acid, polyvinyl alcohol, hydrazine and hydrazine derivative, ethylenediamine, urea) formation colloidal sol in appropriate solvent (as water, ethanol etc.), in the process that forms colloidal sol, utilize conditioning agent (as ammoniacal liquor, ammonium nitrate etc.) to regulate pH value.By (heating etc.) evaporation process, remove solvent, form gel.Presoma as the spontaneous combustion reaction.Carrying out for guaranteeing that gel can be kept spontaneous combustion must guarantee to have an amount of fuel and oxidant in the gel.Compound (as: carboxylate, carboxylate metal hydrazonium salt or its solid solution etc.) with disproportionation performance also can be used for as the presoma of spontaneous combustion reaction.
Then presoma is placed in the suitable reactor, in non-oxidizing gas (as helium, neon, argon gas, nitrogen, hydrogen, CO gas, carbon dioxide, the alkanes gas) protection of flowing down, lights by suitable mode; Perhaps under vacuum environment, light, utilize vavuum pump to keep vacuum state simultaneously.The gaseous product that burning generates will be taken away rapidly by the non-oxidizing gas that flows.The metal or alloy that burning generates or the composite of metal or alloy and nonmetallic materials by suitable passivation, prevent that the metal or alloy that produces again be oxidized, and have just obtained the prepared material of the present invention.
Embodiment 1
The preparation metal Co
Utilize cobalt nitrate, citric acid, ammoniacal liquor is done raw material, utilizes water to make solvent, the preparation collosol and gel, regulating PH is 6, obtains colloidal sol.Transpiring moisture under 90 degree obtains gel.Gel is put in the quartz ampoule,, under 300 degree, lights by nitrogen protection.Obtain the cobalt metal.Fig. 1 is the X ray diffracting spectrum of the metallic cobalt of collosol and gel auto-combustion method preparation.Slaine is changed into nickel nitrate, copper nitrate, silver nitrate, bismuth nitrate obtains monometallic nickel respectively, copper, silver and bismuth.
Embodiment 2
The preparation cobalt-nickel alloy
Utilize cobalt nitrate, and nickel nitrate (atomic ratio Co: Ni=1: 1), citric acid, ammoniacal liquor is done raw material, utilizes water to make solvent, the preparation collosol and gel, regulating PH is 6, obtains colloidal sol.Transpiring moisture under 90 degree obtains gel.Gel is put in the quartz ampoule,, under 300 degree, lights by nitrogen protection.Obtain the metallic cobalt nickel alloy.Fig. 2 is the X ray diffracting spectrum of the cobalt-nickel alloy of collosol and gel auto-combustion method preparation.Change cobalt nitrate, the component ratio of nickel nitrate, we have obtained alloy Co
xNi
1-x(x=10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%90%).Utilize ferric nitrate, nickel nitrate is as slaine, and we have obtained alloy FeNi with identical method
3
Embodiment 3
Preparation metallic nickel/alumina composite material
Utilize nickel nitrate, alumina powder jointed, citric acid, ammoniacal liquor is done raw material, utilizes water to make solvent, the preparation collosol and gel, regulating PH is 6, obtains colloidal sol.Transpiring moisture under 90 degree obtains gel.Gel is put in the quartz ampoule,, under 300 degree, lights by nitrogen protection.Obtain metallic nickel/alumina composite material.Fig. 3 is the X ray diffracting spectrum of the metallic nickel/alumina composite material of collosol and gel auto-combustion method preparation.
Embodiment 4
Preparation metal Ni
Utilize nickel nitrate as slaine respectively; Ammoniacal liquor utilizes water to make solvent as the pH value conditioning agent; Utilize citric acid respectively, glycine, EDTA are made complexing agent and are prepared collosol and gel.Transpiring moisture under 90 degree obtains gel.Gel is put in the quartz ampoule,, under 300 degree, lights by nitrogen protection.Corresponding three kinds of complexing agents obtain metallic nickel respectively.
Claims (9)
1. a collosol and gel auto-combustion method prepares the method for metal or alloy material, it is characterized in that it may further comprise the steps:
1) utilize slaine, complexing agent and oxidant form colloidal sol in solvent, and utilize the ammoniacal liquor conditioning agent to regulate pH value in the process that forms colloidal sol, make pH value in 1 to 10 scope;
2) remove solvent by heating or evaporation, form gel, and in gel, preserve complexing agent and oxidant;
3) presoma of gel as the spontaneous combustion reaction is placed in the reactor, under non-oxidizing gas that flows or vacuum protection, lights;
4) gaseous product of burning generation is taken away by the non-oxidizing gas that flows; Product after the burning obtains the metal or alloy material, perhaps one of metal or alloy and nonmetallic composite.
2. collosol and gel auto-combustion method according to claim 1 prepares the method for metal or alloy material, it is characterized in that: in the step 1), add oxide in slaine, nitride or boride prepare one of metal or alloy and nonmetallic composite.
3. collosol and gel auto-combustion method according to claim 1 prepares the method for metal or alloy material, it is characterized in that: in the step 1), described slaine is an inorganic acid salt, the mixture of one or several of acylate or alkoxide.
4. collosol and gel auto-combustion method according to claim 1 prepares the method for metal or alloy material, it is characterized in that: in the step 1), described complexing agent is 1, the 10-Phen, EDTA, dimercaprol dimercaptopropanol, mercaptoethylmaine, TGA, thiocarbamide, ammonium fluoride, oxine, cyanide, acetylacetone,2,4-pentanedione, citric acid, tartaric acid, oxalic acid, sulfosalicylic acid, triethanolamine, EGTA, ethylenediamine tetrapropionic acid, triethylenetetramine, carboxylic acid, amino acid, polyvinyl alcohol, hydrazine and hydrazine derivative, ethylenediamine, the mixture of one or several in the urea.
5. collosol and gel auto-combustion method according to claim 1 prepares the method for metal or alloy material, it is characterized in that: in the step 1), described solvent is a water, alcohol, ether, amine, nitrile, ketone, dioxane, the mixture of one or more in the oxolane.
6. collosol and gel auto-combustion method according to claim 5 prepares the method for metal or alloy material, it is characterized in that: in the step 1), can utilize urea or ammonium salt to replace the ammoniacal liquor conditioning agent to regulate pH value.
7. collosol and gel auto-combustion method according to claim 1 prepares the method for metal and alloy material, it is characterized in that: in the step 3), the presoma of spontaneous combustion reaction is the compound with disproportionation performance.
8. collosol and gel auto-combustion method according to claim 7 prepares the method for metal or alloy material, it is characterized in that: described compound with disproportionation performance is carboxylate or carboxylate metal hydrazonium salt or its solid solution.
9. collosol and gel auto-combustion method according to claim 1 prepares the method for metal or alloy material, it is characterized in that: in the step 3), non-oxidizing gas is helium, neon, argon gas, nitrogen, hydrogen, CO gas, carbon dioxide or alkanes gas.
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| CN105312588A (en) * | 2014-07-15 | 2016-02-10 | 南京理工大学 | Preparation method of nickel nanoparticles |
| CN104815983B (en) * | 2015-04-20 | 2016-11-02 | 齐鲁工业大学 | A kind of carbon cladding nickel oxide/metallic nickel and simple method for synthesizing thereof |
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| CN108723379B (en) * | 2018-07-23 | 2021-03-23 | 安徽工业大学 | Preparation method of multi-principal-element alloy nano powder |
| CN109231974B (en) * | 2018-10-19 | 2021-02-26 | 扬州大学 | Method for synthesizing epsilon-type iron oxide nano permanent magnet by sol-gel self-combustion |
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