CN102240803B - Surface treatment method for improving hydration resistance of aluminum powder - Google Patents
Surface treatment method for improving hydration resistance of aluminum powder Download PDFInfo
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- CN102240803B CN102240803B CN 201110198043 CN201110198043A CN102240803B CN 102240803 B CN102240803 B CN 102240803B CN 201110198043 CN201110198043 CN 201110198043 CN 201110198043 A CN201110198043 A CN 201110198043A CN 102240803 B CN102240803 B CN 102240803B
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- aluminium powder
- aluminum nitrate
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- treatment method
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Abstract
The invention relates to a surface treatment method for improving the hydration resistance of aluminum powder. The method is characterized in that industrial aluminum powder is taken as a raw material and a sol-gel process is used for wrapping a nanometer film on the surface of the aluminum powder so as to obviously improve the hydration resistance of the aluminum powder. After the aluminum powder is hydrated for 6 hours at 60-90 DEG C, no aluminum hydration product appears. The surface treatment method is simple, the preparation conditions are easily controlled and the hydration problem of aluminum powder is solved. The aluminum powder, which is wrapped according to the method, can be taken as an antioxidant for a pouring material containing carbon and a pouring material containing non-oxide (such as silicon carbide, silicon nitride, and the like), or can be added into a castable refractory for forming a non-oxide combined alumina-base pouring material in situ.
Description
Technical field
The invention belongs to technical field of inorganic nonmetallic materials, be specifically related to a kind of surface treatment method that improves the aluminium powder hydration resistance.
Background technology
Aluminium powder can be divided into industrial aluminium powder, coating aluminium powder, the aluminium powder of getting angry, inflammable aluminium powder etc. by purposes, is widely used in industries such as metallurgy, chemical industry, decoration, anticorrosion, building, agricultural chemicals, pyrotechnics, chemical catalyst, explosive.Industrial aluminium powder in Application in Refractory mainly is used as the anti-oxidant of carbon containing refractory or the anti-knock agent of castable refractory, and nitrogenize prepares Sialon combined aluminum oxide/silicon carbide articles etc. as raw material.When aluminium powder joins in the castable refractory because the easy aquation releasing hydrogen gas of Al limits its application in pours.At present, SiO is mainly adopted in the existing more research of domestic surface treatment to aluminium powder
2Sol-gel technique parcel aluminium powder.But the aluminium powder after this technical finesse adds in the carbon containing pours as anti-oxidant, can be because SiO
2Introducing, the anti-scour property of material is had adverse effect, and cost of material is higher.
Article name " colloidal sol
Gel method prepares SiO
2The coating type water aluminium powder " document (the China YouSe Acta Metallurgica Sinica, 2010,20 (6): 1241 ~ 1246) a kind of processing method of aluminium powder is provided: with ethyl orthosilicate (TEOS) is presoma, adopts Prepared by Sol Gel Method SiO
2The coating type water aluminium powder, suitable process conditions are: the mass ratio of TEOS, water, ethylenediamine and flake aluminum is 1.4 36 0.75 1, and reaction temperature is 40 ℃, and the reaction time is 6 h.It is characterized in that using SiO
2The colloidal sol parcel.
Paper is " Flake Aluminum Powder Coated SiO
2And Fe
2O
3Research " document a kind of processing method of aluminium powder is provided (Central South University's master thesis, in May, 2007); With the flake aluminum is raw material, ethyl orthosilicate and ammoniacal liquor respectively with after the isopropanol, are slowly dripped simultaneously, and the control reaction temperature reacts 6 hours between 35 ℃～40 ℃, and the TEOS addition is 20%, and water and silicon are than (n (H
2O)/and n (TEOS)) be 30, add the ammoniacal liquor that accounts for cumulative volume 0.016～0.024 and make catalyst, the aluminium powder that makes under this condition corrodes 50h in the hydrochloric acid solution of 0.5mol/L, and no hydrogen is separated out.Its used aluminium powder is the solvent-borne type aluminium powder, and its particle is flakey, and its radius-thickness ratio (ratio of diameter and thickness) is between 40～200, and employing SiO
2The colloidal sol parcel.
The Chinese invention patent (patent No.: ZL 200810034125.0) that the Chinese patent name is called " process that surface modification aluminium powder body and water reaction produce hydrogen " has proposed a kind of aluminium powder surface-treated method, uses Al
2O
3, TiO
2Or ZrO
2Oxide or their hydroxide mix with a certain amount of aluminium powder, subsequently it are cold-pressed into block; This block is heated under vacuum, and in 600～650 ℃ of temperature ranges, calcined 1～2 hour, be cooled to room temperature then; Promptly obtain the mixed powder of the aluminium of surface modification activation after block after the calcining pulverized, sieves.Its technology needs under vacuum, to calcine, and the aluminium powder that makes is the mixed powder of oxide and aluminium powder.
The Chinese patent name is called the Chinese invention patent (patent No.: ZL200710098870.7) a kind of processing method of aluminium powder is provided of " a kind of nanometer Al contained Ni and preparation method thereof "; With nickel salt and ball aluminum powder is raw material; Use boron hydride to add hydrazine hydrate and be reducing agent; Pour nickel salt aqueous solution in the ball aluminum powder container that fills the reducing agent aqueous solution soaking into, stir fast, when nickel salt aqueous solution becomes colorless, just generated nanometer Al contained Ni; Warp filters, and in the argon atmospher that flows, makes the nanometer Al contained Ni of favorable dispersibility after the oven dry.It is characterized by and adopt the nickel salt aqueous solution parcel, product is nanometer nickel parcel aluminium powder.
The Chinese invention patent (patent No.: ZL 200910040162.7) that the Chinese patent name is called " organic-inorganic hybrid nanometer film coating aluminum powder pigment and preparation method thereof and use " provides a kind of processing method of aluminium powder; Utilize the organic inorganic hybridization technology; With the aluminium powder pigment is nuclear; Polymerizable carbon-carbon double bond class reactive monomer at first carries out radical polymerization with carbon-carbon double bond class organosiloxane; Polymer that obtains and ethyl orthosilicate be through the mode and the aluminium powder pigment surface bond of hydrolysis, and then coat one deck organic-inorganic hybrid nanometer film on the aluminium powder surface.It is characterized by raw materials used for the pigment aluminium powder, use SiO
2Colloidal sol parcel aluminium powder.
Document (Chinese the 6th the academic annual meeting of particuology meeting and the both sides of the Straits granule technology seminar of article " multilayer on aluminium powder surface coats and performance study " by name; In December, 2008: 150-153) a kind of aluminium powder surface treatment method is provided, has adopted sol-gel process coated Si O successively on flake aluminum
2, optimum condition is: silester: absolute ethyl alcohol: water: ammonia=1:10:4:l (mol ratio), and reaction temperature is 20 ℃, and the reaction time is 5h, and the colloidal sol digestion time is 7 days.It is raw materials used to be flake aluminum, use SiO
2The colloidal sol parcel.
The document (Advances in Applied Ceramics, 2005,104 (2) 2:79-82) of article name " Improving hydration resistance of Al powder for carbon containing castables using inorganic – organic hybrid coatings " provides a kind of aluminium powder surface treatment method; The ethanolic solution of ethyl orthosilicate is joined in the solution of polyvinyl alcohol; With the powerful 30min that stirs of magnetic stirrer, the pH value that adds hydrochloric acid conditioning solution is about 3, processes transparent colloidal sol; Aluminium powder added stir 10min in the colloidal sol; With centrifuge aluminium powder is separated from colloidal sol then, dry 4h under 110 ℃ forms gel on its surface; Obtain the aluminium powder that plural gel coats, it is SiO
2The colloidal sol parcel.
Still do not retrieve at present document and open patent of invention about alumina sol parcel aluminium powder aspect.
Summary of the invention
The objective of the invention is in order to provide a kind of is raw material with industrial aluminium powder, adopts alumina sol-gel technique parcel aluminium powder, improves its anti-hydration capability and technology is simple, cost is low a kind of surface treatment method that improves the aluminium powder hydration resistance.
The object of the invention can be realized through following technique measures:
The surface treatment method of aluminium powder of the present invention comprises the steps:
A. with the aluminum nitrate (Al (NO of 10-50g
3)
3) add in the deionized water of 100ml, process aluminum nitrate solution through stirring;
B. in the prepared aluminum nitrate solution of a step, add citric acid or polyvinyl alcohol as surface modifier, its addition is the 1-10% of aluminum nitrate percentage by weight; Stir 5-20min at 60 ℃ of following constant temperature;
The pH value of c. regulating b step gained solution is to 5-6;
D. the industrial aluminium powder 3g-10g with granularity < 0.074mm, purity weight ratio are: Al>98.5% joins in the c step gained solution, ageing processing under 25-60 ℃ of condition behind the stirring 5-20min, and the ageing processing time is 24-96h;
E. with centrifuge aluminium powder is separated from colloidal sol, dry 2-10h under 110 ℃ obtains aluminium oxide Al
2O
3The aluminium powder of colloidal sol parcel.
Aluminum nitrate described in the present invention is for analyzing pure or technical pure; Can be to take from aluminum nitrate Al (NO
3)
3And/or the ANN aluminium nitrate nonahydrate Al (NO of the band crystallization water
3)
39H
2O.
The pH value that adopts hydrochloric acid or ammoniacal liquor to regulate b step gained solution in the present invention is a faintly acid, and pH is 5-6.
Centrifuge speed described in the present invention is 1000-2000 rev/min.
Beneficial effect of the present invention is following:
1, preparation technology is simple, need not complicated process equipment and technical process.
2, the aluminium powder that the alumina sol for preparing with the present invention wraps up has hydration resistance preferably, and the hydrated product of no aluminium behind 60-90 ℃ of aquation 6-8h (gibbsite and boehmite) occurs.
With the aluminium powder of the present invention preparation can be applicable to carbon containing or (with) contain non-oxidized substance (SiC, Si
3N
4, Sialon etc.) the anti-oxidant of pours, and prepare Sialon combined aluminum oxide material as the reactant moulding by casting.
The specific embodiment
The present invention is further described below with reference to embodiment:
Embodiment 1:
The aluminum nitrate of 10g is added the deionized water of 100mL, stir and process aluminum nitrate solution; In aluminum nitrate solution, add 0.4g surface modifier citric acid, stir 5-20min at 60 ℃ of following constant temperature; Using the pH value of hydrochloric acid, ammoniacal liquor regulator solution is 5; (< 0.074mm, the purity weight ratio is: Al>98.5%) joins in the above-mentioned solution with the 3g aluminium powder, stirs after 10 minutes at 40 ℃ of ageing 24h; (1000 change/min) separate aluminium powder from colloidal sol, dry 2h under 110 ℃ obtains the aluminium powder that alumina gel wraps up with centrifuge.
Product constant temperature in 80 ℃ of water is soaked 6h, takes out aluminium powder, through 80 ℃ of 4h dryings after, uses XRD analysis wrap up back its thing of aluminium powder mutually as Al, do not have the hydrated product of aluminium.
Embodiment 2:
The aluminum nitrate of 20g is joined in the deionized water of 100mL, stir and process aluminum nitrate solution; In aluminum nitrate solution, add 0.8g surface modifier citric acid, stir 5-20min at 60 ℃ of following constant temperature; Using the pH value of hydrochloric acid, ammoniacal liquor regulator solution is 5.5; (< 0.074mm, the purity weight ratio is: Al>98.5%) joins in the above-mentioned solution with the 5g aluminium powder, stirs behind the 15min at 40 ℃ of ageing 48h; (1500 change/min) separate aluminium powder from colloidal sol, dry 4h under 110 ℃ obtains the aluminium powder that alumina gel wraps up with centrifuge.
Product constant temperature in 80 ℃ of water is soaked 6h, takes out aluminium powder, through 80 ℃ of 4h dryings after, uses XRD analysis wrap up back its thing of aluminium powder mutually as Al, do not have the hydrated product of aluminium.
Embodiment 3:
The aluminum nitrate of 50g is joined in the deionized water of 100mL, stir and process aluminum nitrate solution; In aluminum nitrate solution, add 3g surface modifier citric acid, stir 5-20min at 60 ℃ of following constant temperature; Using the pH value of hydrochloric acid, ammoniacal liquor regulator solution is 6; (< 0.074mm, the purity weight ratio is: Al>98.5%) joins in the above-mentioned solution with the 7g aluminium powder, stirs behind the 10min at 50 ℃ of following ageing 24h; (2000 change/min) separate aluminium powder from colloidal sol, at 110 ℃ following dry 6h, obtain the aluminium powder of alumina gel parcel with centrifuge.
Product is soaked 6h in 80 ℃ of water of constant temperature, takes out aluminium powder through 80 ℃ of 4h dryings after, uses XRD analysis wrap up back its thing of aluminium powder mutually as Al, do not have the hydrated product of aluminium.
Embodiment 4:
The 30g aluminum nitrate is joined in the deionized water of 100mL, stir and process aluminum nitrate solution; In aluminum nitrate solution, add 3g surface modifier polyvinyl alcohol, stir 5-20min at 60 ℃ of following constant temperature; Using the pH value of hydrochloric acid, ammoniacal liquor regulator solution is 6; (< 0.074mm, the purity weight ratio is: Al>98.5%) joins in the above-mentioned solution with the 9g aluminium powder, stirs behind the 10min at 25 ℃ of ageing 72h; (1200 change/min) separate aluminium powder from colloidal sol, dry 5h under 110 ℃ obtains the aluminium powder that alumina gel wraps up with centrifuge.
Product is soaked 6h in 80 ℃ of water of constant temperature, take out aluminium powder through 80 ℃ of 4h dryings after, with XRD analysis parcel back aluminium powder, its thing is Al mutually, do not have the hydrated product of aluminium.
Embodiment 5:
The 20g aluminum nitrate is joined in the deionized water of 100mL, stir and process aluminum nitrate solution; In aluminum nitrate solution, add 0.6g surface modifier polyvinyl alcohol, stir 5-20min at 60 ℃ of following constant temperature; Using the pH value of hydrochloric acid, ammoniacal liquor regulator solution is 5.5; (< 0.074mm, the purity weight ratio is: Al>98.5%) joins in the above-mentioned solution with the 4g aluminium powder, stirs behind the 10min at 40 ℃ of ageing 96h; (1800 change/min) separate aluminium powder from colloidal sol, dry 5h under 110 ℃ obtains the aluminium powder that alumina gel wraps up with centrifuge.
Product is soaked 6h in 80 ℃ of water of constant temperature, take out aluminium powder through 80 ℃ of 4h dryings after, with XRD analysis parcel back aluminium powder, its thing is Al mutually, do not have the hydrated product of aluminium.
Embodiment 6:
The 30g aluminum nitrate is joined in the deionized water of 100mL, stir and process aluminum nitrate solution; In aluminum nitrate solution, add 1g surface modifier polyvinyl alcohol, stir 5-20min at 60 ℃ of following constant temperature; Using the pH value of hydrochloric acid, ammoniacal liquor regulator solution is 5; (< 0.074mm, the purity weight ratio is: Al>98.5%) joins in the above-mentioned solution with the 10g aluminium powder, stirs behind the 10min at 60 ℃ of ageing 24h; (1400 change/min) separate aluminium powder from colloidal sol, dry 4h under 110 ℃ obtains the aluminium powder that alumina gel wraps up with centrifuge.
Product is soaked 6h in 80 ℃ of water of constant temperature, take out aluminium powder through 80 ℃ of 4h dryings after, with XRD analysis parcel back aluminium powder, its thing is Al mutually, do not have the hydrated product of aluminium.
Claims (5)
1. surface treatment method that improves the aluminium powder hydration resistance, it is characterized in that: said method comprises the steps:
A. the aluminum nitrate with 10-50g adds in the deionized water of 100mL, processes aluminum nitrate solution through stirring;
B. in the prepared aluminum nitrate solution of a step, add citric acid or polyvinyl alcohol as surface modifier, its addition is the 1-10% of aluminum nitrate percentage by weight; Stir 5-20min at 60 ℃ of following constant temperature;
The pH value of c. regulating b step gained solution is to 5-6;
D. the industrial aluminium powder 3g-10g with granularity < 0.074mm, purity weight ratio are: Al>98.5% joins in the c step gained solution, ageing processing under 25-60 ℃ of condition behind the stirring 5-20min, and the ageing processing time is 24-96h;
E. with centrifuge aluminium powder is separated from colloidal sol, dry 2-10h under 110 ℃ obtains the aluminium powder that alumina gel wraps up.
2. surface treatment method according to claim 1 is characterized in that: said aluminum nitrate is for analyzing pure or technical pure.
3. surface treatment method according to claim 2 is characterized in that: said aluminum nitrate is taken from aluminum nitrate Al (NO
3)
3And/or the ANN aluminium nitrate nonahydrate Al (NO of the band crystallization water
3)
39H
2O.
4. surface treatment method according to claim 1 is characterized in that: the pH value that adopts hydrochloric acid or ammoniacal liquor to regulate b step gained solution is a faintly acid, and the pH value is 5-6.
5. surface treatment method according to claim 1 is characterized in that: said centrifuge speed is 1000-2000 rev/min.
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| CN104151931B (en) * | 2013-05-13 | 2016-06-15 | 中原工学院 | The sol gel type ink-jet printer processing method of nanometer aluminium powder ink |
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| CN111704466B (en) * | 2020-07-07 | 2021-09-21 | 中钢集团洛阳耐火材料研究院有限公司 | Silicon carbide-magnesium aluminate spinel-aluminum composite refractory material |
| CN111957951B (en) * | 2020-08-18 | 2022-09-20 | 中科南京绿色制造产业创新研究院 | Preparation method and application of modified aluminum powder for refractory castable |
| CN115028455B (en) * | 2022-07-11 | 2023-06-02 | 中钢集团洛阳耐火材料研究院有限公司 | Baking-free silicon carbide-magnesia alumina spinel refractory material, preparation method and product thereof |
| CN115321946A (en) * | 2022-07-22 | 2022-11-11 | 安徽瑞泰新材料科技有限公司 | Long-life low-cost refractory castable and preparation method thereof |
| CN115650742B (en) * | 2022-10-30 | 2023-09-19 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method of metal-containing Al in-situ composite carbon-containing refractory material |
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| WO1990000528A1 (en) * | 1988-07-15 | 1990-01-25 | Toshiba Tungaloy Co., Ltd. | Mold material for molding optical parts and process for its production |
| CN1607179A (en) * | 2003-10-15 | 2005-04-20 | 孙家跃 | Preparation technology of size controllable incompact superfine alumina powder material |
| CN101619177A (en) * | 2009-07-31 | 2010-01-06 | 孝感学院 | Preparation method of nano-titanium dioxide coated nano-aluminium oxide |
| CN101817545A (en) * | 2010-03-03 | 2010-09-01 | 上海交通大学 | Mesoporous alumina powder based on saccharides and preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1143178A (en) * | 1997-07-28 | 1999-02-16 | Toppan Printing Co Ltd | Powder-food packaging body |
-
2011
- 2011-07-15 CN CN 201110198043 patent/CN102240803B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990000528A1 (en) * | 1988-07-15 | 1990-01-25 | Toshiba Tungaloy Co., Ltd. | Mold material for molding optical parts and process for its production |
| CN1607179A (en) * | 2003-10-15 | 2005-04-20 | 孙家跃 | Preparation technology of size controllable incompact superfine alumina powder material |
| CN101619177A (en) * | 2009-07-31 | 2010-01-06 | 孝感学院 | Preparation method of nano-titanium dioxide coated nano-aluminium oxide |
| CN101817545A (en) * | 2010-03-03 | 2010-09-01 | 上海交通大学 | Mesoporous alumina powder based on saccharides and preparation method |
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