CN102531554A - Hexaaluminate-embedded alumina composite coating and preparation method thereof - Google Patents
Hexaaluminate-embedded alumina composite coating and preparation method thereof Download PDFInfo
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- CN102531554A CN102531554A CN2012100025279A CN201210002527A CN102531554A CN 102531554 A CN102531554 A CN 102531554A CN 2012100025279 A CN2012100025279 A CN 2012100025279A CN 201210002527 A CN201210002527 A CN 201210002527A CN 102531554 A CN102531554 A CN 102531554A
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Abstract
The invention discloses a hexaaluminate-embedded alumina composite coating and a preparation method thereof. The thickness of the composite coating ranges from 1 micrometer to 8 micrometers, the content of hexaaluminate in the coating ranges from 5 percent to 60 percent, and the content of alumina ranges from 40 percent to 95 percent. The preparation process comprises the steps as follows: structural material of metal sheets or cordierites is processed; aluminum sol is prepared, and then the structural material is coated in the aluminum sol so as to prepare an alumina layer; a metal salt solution is prepared; the structural material coated with the alumina layer is put in the metal salt solution to prepare hexaaluminate through in-situ growth; and then the hexaaluminate-embedded alumina composite coating is obtained on a basal body of the structural material after drying and roasting. The hexaaluminate-embedded alumina composite coating has the advantages as follows: the alumina composite coating which is modified through hexaaluminate can be used in a high-temperature environment, the heat stability and the adhesion performance of the alumina coating are improved, and the thought of the modification of the alumina coating material can be broadened.
Description
Technical field
The present invention relates to a kind of aluminum oxide compound coating that embeds hexa-aluminate and preparation method thereof, belong to the preparing technical field of aluminum oxide compound coating.
Background technology
Aluminum oxide can be widely used as heat insulating coat, high-temperaure coating, wear-resistant coating, insulating coating and structure catalyst coating, need carry out suitable modification to different purposes.When as support of the catalyst, aluminum oxide high temperature with have thermostability under the water vapor condition to have a strong impact on catalyzer work-ing life.At catalytic field; Structured material claims that again structure carrier also is usually used in handling the hydrocarbon fuel and the purifying vehicle exhaust of high temperature, high-speed, and this has high thermostability and mechanical stability (being the adhesivity between aluminum oxide and the structured material) with regard to the aluminum oxide coating layer that requires to apply on it.
Introducing single or the polycomponent additive at present is to improve one of important means of aluminum oxide thermostability.Ozawa etc. with immersion process for preparing different metal ion (rare earth ion: La
3+, Ce
3+, Sm
3+, Gd
3+, Dy
3+, Yb
3+, Y
3+And alkaline earth metal ion: Ba
2+, Sr
2+, Ca
2+Deng) adulterated alumina supporter.Alumina supporter after this modification still can keep high specific surface area after through 1200 ℃ of calcinings, and the result shows that the introducing of rare earth and alkaline earth metal ion all has good improvement to the thermostability of aluminum oxide, wherein with La
3+Best results.On this basis, continue to adopt pickling process with rare earth ion La
3+With transition metal ion Cu
2+Introduce in the aluminum oxide simultaneously, and investigated of the influence of this catalyzer respectively nitrogen protoxide and hydrocarbon polymer elimination reactivity worth.The result shows, Cu
2+: La
3+: Al
3+Mol ratio is that the composition of 10:5:200 is to NO and C
3H
6Elimination all have good catalytic activity and high-temperature stability, but be difficult to avoid complicated solid state reaction takes place between each component of catalyzer, cause gathering or catalyzer heat inactivation between the catalyst activity component.Kang etc. use pickling process and mechanical mixing to prepare BaO/Al respectively
2O
3Catalyzer has all suppressed γ-Al under the high temperature to a certain extent
2O
3To α-Al
2O
3Transformation, help stability raising.At present; Utilize additive to come the research of modified aluminas still generally to adopt solid reaction process and pickling process; This makes and disperses inhomogeneously between additive itself and additive and the aluminum oxide, a little less than the interaction between additive and the aluminum oxide, under follow-up high-temperature calcination and abominable working conditions, is prone to cause dopant ion to run off; Even it is the big crystal grain of migration gathering formation, thereby limited to the degree of alumina stable property improvement.Therefore; Be necessary to use the multi-component compound additive metal oxide of high-temperature stable to improve the thermostability of doping component; And through the effect between a kind of novel method enhancing additive and aluminum oxide and the structure carrier, thereby the thermostability and the mechanical stability of raising aluminum oxide coating layer.
Do not see at present the bibliographical information that the composite oxides hexa-aluminate of introducing high-temperature stable improves the aluminum oxide thermostability as yet.Therefore, this patent proposes a kind of preparation method of aluminum oxide compound coating of the embedding hexa-aluminate that on structured material, applies first.Hexa-aluminate is the six side's laminate structures that have than large aspect ratio, and the anisotropy of crystal growth makes it at high temperature can keep high specific surface area and thermostability.Its skeleton symbol AAl
12O
19In A position ion can constitute by basic metal, earth alkali metal or rare earth ion, Al can the part by transition metal ion (like Cr
3+, Mn
3+, Fe
3+, Co
2+, Ni
2+, Cu
2+Deng) isomorphous substitution, thereby make it have the high-temperature catalytic activity.
Summary of the invention
The object of the present invention is to provide a kind of aluminum oxide compound coating that embeds hexa-aluminate and preparation method thereof; The compound coating that this method makes can strengthen solid support material and aluminum oxide and and active ingredient between interaction, improve the thermostability and the mechanical stability of aluminum oxide coating layer.Its preparation method process is simple.
The present invention realizes through following technical proposals; A kind of aluminum oxide compound coating that embeds hexa-aluminate is characterized in that: the thickness of this compound coating is 1 ~ 8 μ m, and the content of hexa-aluminate is 5% ~ 60% in this compound coating; The content of aluminum oxide is 40% ~ 95%, and its chemical general formula is: A
1-xB
xC
Y-zD
zAl
12-yO
19-Al
2O
3, 0≤x≤1,0≤z≤y≤3 wherein, A and B represent La respectively
3+, Ce
3+, Sr
2+, Ba
2+, Ca
2+In a kind of; C and D represent Cr respectively
3+, Fe
3+, Mn
3+, Cu
2+, Mg
2+, Mn
2+, Ni
2+And Co
2+In a kind of.
The preparation method of the aluminum oxide compound coating of above-mentioned embedding hexa-aluminate is characterized in that comprising following process:
1) structured material pre-treatment
With structured material is thickness at the alloy sheet of the iron-based of the different shape of 0.01 ~ 1mm, Ni-based, cobalt-based, titanium base, thallium base, niobium base or tungsten base; Earlier with sand papering to remove surperficial foul and increase roughness; Then be placed on acetone solvent and deionized water for ultrasonic respectively and clean 10 ~ 120min, put into 100 gL after cleaning
-1H
2SO
4With 100 gL
-1NaCl is in the 1:1 liquid mixture prepared according to volume ratio, at 25 ℃ ~ 90 ℃ following pickling 1 ~ 10min, cleans with deionized water again, places 50 ~ 150 ℃ the dry 0.5 ~ 6h of baking oven, subsequently with 1 ~ 20 ℃ of min of temperature rise rate
-1Be warming up to 900 ~ 1300 ℃ of calcining 2 ~ 10h down, cool to room temperature with the furnace and take out subsequent use;
Be honeycomb cordierite perhaps with structured material; Placing massfraction is that 20% nitric acid or massfraction are 50% oxalic acid; Use the deionized water ultrasonic cleaning behind processing 0.5 ~ 2h down at 25 ~ 90 ℃, put into 60 ~ 150 ℃ of baking oven dried overnight subsequently, place the moisture eliminator cooling subsequent use;
2) alumina sol preparation
Is that 7 ~ 23:1 mix with pseudo-boehmite by mass ratio with deionized water, and behind the stirring 1h, dropping concentration is 1molL
-1With the deionized water volume ratio be that the salpeter solution continued of 0.1 ~ 0.5:1 stirs 3 ~ 7h, obtain alumina sol;
Or be 60 ~ 120:1 mix after with aluminum isopropylate by mass ratio with deionized water, Heating temperature to 50 ~ 100 ℃ use concentration to be 1molL
-1It is 3.5 ~ 4.5 that rare nitric acid is regulated pH, stirs, and closed system continues to stir 7 ~ 13h under the condensing reflux condition then, and aged at room temperature 12 ~ 36h obtains alumina sol;
Or be that 0.3 ~ 3:1 mix with aluminum nitrate by mass ratio with deionized water, under stirring at room, drip 0.5 ~ 1.5molL
-1Ammoniacal liquor, regulate pH and be 7.8 ~ 9.2 and obtain throw out, to the throw out washing and filtering to remove NO wherein
3 -Ion is dispersed in filter cake in the deionized water again, and in the time of 50 ~ 80 ℃, drips 0.5 ~ 1.5molL
-1Nitric acid be adjusted to pH to 3 ~ 4, at 85 ℃ of seal aging 10 ~ 24h, obtain alumina sol;
3) structured material coating alumina
With being immersed in step 2 through pretreated structural metallic materials or cordierite structure material in the step 1)) in a kind of alumina sol of preparation 2 ~ 10min take out; Blow the superfluous alumina sol of remained on surface off; Be placed in 100 ~ 150 ℃ of baking ovens dry 1 ~ 6h then, and in retort furnace with 1 ~ 20 ℃ of min
-1Temperature rise rate be raised to 500 ~ 700 ℃ of roasting 0.5 ~ 3h; Be cooled to room temperature with furnace temperature; Again with structured material be dipped in the alumina sol successively according to take out, dry up, process dry, roasting repeats 2 ~ 5 times, reaches 0.5 ~ 3% of structured material own wt until the charge capacity of aluminum oxide on structured material;
4) reaction solution preparation
General formula according to hexa-aluminate is A
1-xB
xC
Y-zD
zAl
12-yO
19, 0≤x≤1,0≤z≤y≤3 wherein, A and B represent La respectively
3+, Ce
3+, Sr
2+, Ba
2+, Ca
2+In a kind of; C and D represent Cr respectively
3+, Fe
3+, Mn
3+, Cu
2+, Mg
2+, Mn
2+, Ni
2+And Co
2+In a kind of; According to the mol ratio of [C+D] and [A+B] is that the ratio of 0 ~ 3:1 takes by weighing corresponding metal salt; Take by weighing an ammonium nitrate that mole number is 6 times of total metals ion mole numbers; Metal-salt and an ammonium nitrate are dissolved in the deionized water, and being made into total concentration of metal ions is 0.01 ~ 1.2molL
-1Mixing salt solution, under agitation in this solution, drip mass concentration and be 0.1 ~ 9.0% alkali lye and reach 5 ~ 10 until the pH value, said alkali lye is a kind of in ammoniacal liquor, volatile salt, bicarbonate of ammonia, sodium hydroxide or the Pottasium Hydroxide;
5) hexa-aluminate growth in situ
The structured material that scribbles aluminum oxide coating layer that step 3) is made is positioned in the made reaction soln of step 4); React 2 ~ 72h down at 25 ~ 150 ℃; Take out structured material; Using deionized water or pH is after 7 an ammonium nitrate washing lotion is cleaned, dry 24h in 50 ~ 150 ℃ baking oven, then in retort furnace with 1 ~ 10 ℃ of min
-1Temperature rise rate is warming up to 900 ~ 1300 ℃ of calcining 2 ~ 10h, on the structured material of metal or trichroite, obtains embedding the aluminum oxide compound coating of hexa-aluminate.
Advantage of the present invention has: this compound coating adopts and does not add the aluminium source and activate the Al in the aluminum oxide through the method for using alkali lye accent change pH values
3+, the Al that is activated out
3+Obtain compound coating at activated positions growth in situ hexa-aluminate with other metals ion in the reaction solution after interacting.The more single aluminum oxide coating layer of this compound coating has abundanter hole, good thermostability and mechanical stability.Mechanical shock resistance test shows coating is under the 40KHz/100W of 5 ~ 100min ultrasonic impact, and this compound coating shows the low rate of weight loss of more single aluminum oxide coating layer.
Description of drawings:
Fig. 1 is the XRD figure spectrum of embodiment 1 and embodiment 3 prepared composite coatings.
Among the figure: curve a makes the XRD figure spectrum of compound coating for embodiment 1; Curve b makes the XRD figure spectrum of compound coating for embodiment 3.Δ is represented lanthanum manganese hexa-aluminate among the figure, and О represents α-Al
2O
3
Fig. 2 is the SEM shape appearance figure on the compound coating surface of embodiment 1 system.
Fig. 3 is the SEM shape appearance figure on the compound coating surface of embodiment 3 systems.
Fig. 4 is the anti-physical shock aptitude tests comparison diagram as a result of embodiment 1, embodiment 3 and Comparative Examples coatings prepared.
Among the figure: curve a is that the rate of weight loss of the prepared single aluminum oxide coating layer of Comparative Examples is with the ultrasonic impact time changing curve; Curve b is that the rate of weight loss of embodiment 1 prepared compound coating is with the ultrasonic impact time changing curve; Curve c is that the rate of weight loss of embodiment 3 prepared compound coatings is with the ultrasonic impact time changing curve.
Fig. 5 is the SEM shape appearance figure in the compound coating cross section of embodiment 1 system.
Embodiment
Embodiment 1
With the FeCrAl alloy slice of 30mm * 10mm of 50 * 0.3mm, gross weight 7.782g respectively vertically after the polishing 4 times, carries out ultrasonic cleaning 30min with acetone, water with 100 orders and 600 order sand paper successively, at 60 ℃ in 100 gL
-1H
2SO
4With 100 gL
-1Handle 5min in the mixing solutions of NaCl, the back is cleaned with deionized water, and in 60 ℃ of baking ovens dry 1h, cooling is placed in the moisture eliminator subsequent use.
Take by weighing the 18g pseudo-boehmite and add in the 270g deionized water, behind the stirring 1h, the 1molL of Dropwise 5 5mL
-1The salpeter solution continued stir 5h and make alumina sol.
Then pretreated tinsel is suspended in the alumina sol behind the 3min and slowly proposes, blow the superfluous alumina sol of remained on surface off, and tentatively dry back dry 1h in 120 ℃ of baking ovens with blower, the back in retort furnace with 5 ℃ of min
-1Be warmed up in 500 ℃ and calcine 1h, repeat once this coating procedure again after cooling is taken out, having a net increase of weight after applying twice is 0.088g.
Take by weighing Lanthanum trinitrate 3.248g, manganous acetate 1.838g and an ammonium nitrate 7.204g are dissolved in the 150ml deionized water.Stir down at magnetic that to drip massfraction in the solution be that the weak ammonia of 1 % is 6 afterwards also to stablize 5min up to pH.Get 50 above-mentioned Al of being coated with
2O
3The alloy slice of coating connects with line and hangs in the solution that mixes up the pH value, bottle is moved in 60 ℃ of baking ovens take out behind the constant temperature 72h then.Other takes by weighing an ammonium nitrate 7.204g and is dissolved in the 150ml deionized water, and the dropping massfraction is that the weak ammonia of 1 % is 7 up to pH under magnetic stirs.Wash the tinsel that takes out in the baking oven successively respectively 10 times with this solution and deionized water.Sample is placed 60 ℃ of baking oven loft dried 24h, then in the high temperature retort furnace with 2 ℃ of min
-1Be warming up to 1100 ℃ of calcining 5h, obtain embedding the aluminum oxide compound coating of lanthanum manganese hexa-aluminate.
The above-mentioned sample that makes is carried out the mechanical shock resistance test.Testing method is: small amount of sample is placed in the beaker that sherwood oil is housed of sealing, 5 ~ 100min then vibrates in the ultrasonic washing instrument of 40KHz/100W.Take out sample at regular intervals, the weight loss of catalyzer is measured in dry back.
Test result is following: the rate of weight loss of this coating increases along with the increase of ultrasonic vibration time gradually, and after time of vibration surpassed 40min, rate of weight loss basically no longer changed, and is stabilized in 0.62%.
Embodiment 2
To the preprocessing process of FeCrAl alloy slice with embodiment 1.
Take by weighing the 540g ionized water and be heated to 85 ℃, under the whipped state, the 6g aluminum isopropylate is added in the above deionized water, drip again rare nitric acid to pH be 3.8.Under 85 ℃ constant temperature, fully stir and make the aluminum isopropylate volatilization.Closed system continues to stir 10h under the condensing reflux condition then.Aged at room temperature 24h makes alumina sol.
The coating procedure of aluminum oxide coating layer is with embodiment 1.
Take by weighing strontium nitrate 1.587g, magnesium nitrate 0.577g, manganous acetate 1.287g and an ammonium nitrate 7.204g are dissolved in the 150ml deionized water.Stir down at magnetic that to drip massfraction in the solution be that the ammoniacal liquor of 1 % is 8 afterwards also to stablize 5min up to pH.Get 50 above-mentioned coating Al
2O
3The alloy slice of coating connects with line and hangs in the solution that mixes up the pH value, bottle is moved in 60 ℃ of baking ovens take out behind the constant temperature 96h then.Other takes by weighing an ammonium nitrate 7.204g and is dissolved in the 150ml deionized water, and the ammonia soln that under magnetic stirs, drips 1 % is up to pH=7.Wash the tinsel that takes out in the baking oven successively respectively 10 times with this solution and deionized water.Sample is placed 60 ℃ of baking oven loft dried 24h, then in retort furnace with 1 ℃ of min
-1Be warming up to 900 ℃ of calcining 10h, obtain embedding the aluminum oxide compound coating of strontium manganese hexa-aluminate.
Embodiment 3
To the pre-treatment of FeCrAl alloy slice and aluminum oxide coating layer preparation and coating procedure with embodiment 1.
Take by weighing Lanthanum trinitrate 1.624g, manganous acetate 0.919g is dissolved in that compound concentration is 0.5 molL in the 150mL deionized water
-1Metal salt solution.Taking by weighing volatile salt 15.712g is dissolved in the 100mL deionized water and prepares 1molL
-1Solution.Take reaction unit, in the 500ml four-hole bottle, add the 150mL deionized water, under agitation drip salts solution and sal volatile simultaneously, and monitoring pH value of solution value makes it be stable at pH about 8 to drip to salt, solution in the four-hole bottle is poured in the ready beaker.Get 50 of good tinsels of pre-treatment and connect with line and be suspended in the beaker, take out after putting into 60 ℃ of baking oven constant temperature 4h, with deionized water wash 10 times.Sample is placed 60 ℃ of baking oven loft dried 24h, then in retort furnace with 2 ℃ of min
-1Be warming up to 1100 ℃ of calcining 5h, obtain embedding the aluminum oxide compound coating of lanthanum manganese hexa-aluminate.
Above coating sample is carried out the mechanical shock resistance test, and test condition is with embodiment 1.
Test result is following: the rate of weight loss of this coating increases along with the increase of ultrasonic vibration time gradually, and after time of vibration surpassed 10min, rate of weight loss basically no longer changed, and is stabilized in 0.27%.
Embodiment 4
It is following that compound coating prepares process: to the preprocessing process of FeCrAl alloy slice with embodiment 1.
Taking by weighing aluminum nitrate 7.503g is dissolved in deionized water and is made into 0.5molL
-1Solution, at room temperature drip lmolL while stirring slowly
-1Ammoniacal liquor be 9.2 to obtain deposition to pH, need not ageing directly with deionized water filtration washing removal NO wherein
3 -Ion will precipitate and use water-dispersion again, and when being lower than 80 ℃, drip rare nitric acid to pH be 3.8, make aluminium colloidal sol at 85 ℃ of seal aging 24h.
The coating procedure of aluminum oxide coating layer is with embodiment 1.
Take by weighing Lanthanum trinitrate 1.299g, nitrocalcite 0.177g, manganous acetate 0.643g, Xiao Suangu 0.327g are dissolved in that compound concentration is 0.5 molL in the 150ml deionized water
-1Solution.Taking by weighing volatile salt 15.712g is dissolved in the 100ml deionized water and prepares 1molL
-1Solution.Take reaction unit, in the 500ml four-hole bottle, add the 150ml deionized water, under agitation drip salts solution and sal volatile simultaneously, and monitoring pH value of solution value makes it be stable at pH about 8 to drip to salt, solution in the four-hole bottle is poured in the ready beaker.Get 50 of good tinsels of pre-treatment and connect with line and be suspended in the beaker, take out after putting into 60 ℃ of baking oven constant temperature 10h, with deionized water wash 10 times.Sample is placed 60 ℃ of baking oven loft dried 24h, then in the high temperature retort furnace with 10 ℃ of min
-1Be warming up to 1300 ℃ of calcining 2h, obtain embedding the aluminum oxide compound coating of lanthanum manganese hexa-aluminate.
Embodiment 5
It is following that compound coating prepares process: to the preprocessing process of FeCrAl alloy slice with embodiment 1.The preparation of aluminum oxide coating layer and coating procedure are with embodiment 2.
Take by weighing Lanthanum trinitrate 1.624g, manganous acetate 0.919g and an ammonium nitrate 3.602g are dissolved in the 150ml deionized water.Stir down at magnetic and to drip 1% sodium hydroxide solution until pH in the solution and 8 afterwards also stablize 5min.Get and apply single Al among 10 embodiment 1
2O
3The alloy slice of coating connects with line and hangs in the solution that mixes up the pH value, bottle is moved in 60 ℃ of baking ovens take out behind the constant temperature 2h then.With the tinsel that takes out in the deionized water wash baking oven 10 times.Sample is placed 60 ℃ of baking oven loft dried 24h, then in the high temperature retort furnace with 5 ℃ of min
-1Be warming up to 1000 ℃ of calcining 8h, obtain embedding the aluminum oxide compound coating of lanthanum manganese hexa-aluminate.
Comparative Examples
Single Al
2O
3Coating prepn is following: to the coating procedure of the pre-treatment of FeCrAl alloy slice and aluminum oxide coating layer with embodiment 1.
Above coating sample is carried out the mechanical shock resistance test, and test condition is with embodiment 1.
Test result is following: single Al
2O
3The rate of weight loss of coating increases along with the increase of ultrasonic vibration time gradually, and after time of vibration surpassed 10min, rate of weight loss basically no longer changed, and is stabilized in 0.76%.
Claims (2)
1. aluminum oxide compound coating that embeds hexa-aluminate, it is characterized in that: the thickness of this compound coating is 1 ~ 8 μ m, and the content of hexa-aluminate is 5% ~ 60% in this compound coating, and the content of aluminum oxide is 40% ~ 95%, and its chemical general formula is: A
1-xB
xC
Y-zD
zAl
12-yO
19-Al
2O
3, 0≤x≤1,0≤z≤y≤3 wherein, A and B represent La respectively
3+, Ce
3+, Sr
2+, Ba
2+, Ca
2+In a kind of; C and D represent Cr respectively
3+, Fe
3+, Mn
3+, Cu
2+, Mg
2+, Mn
2+, Ni
2+And Co
2+In a kind of.
2. method for preparing the aluminum oxide compound coating of the described embedding hexa-aluminate of claim 1 is characterized in that comprising following process:
1) structured material pre-treatment
With structured material is thickness at the alloy sheet of the iron-based of the different shape of 0.01 ~ 1mm, Ni-based, cobalt-based, titanium base, thallium base, niobium base or tungsten base; Earlier with sand papering to remove surperficial foul and increase roughness; Then be placed on acetone solvent and deionized water for ultrasonic respectively and clean 10 ~ 120min, put into 100 gL after cleaning
-1H
2SO
4With 100 gL
-1NaCl is in the 1:1 liquid mixture prepared according to volume ratio, at 25 ℃ ~ 90 ℃ following pickling 1 ~ 10min, cleans with deionized water again, places 50 ~ 150 ℃ the dry 0.5 ~ 6h of baking oven, subsequently with 1 ~ 20 ℃ of min of temperature rise rate
-1Be warming up to 900 ~ 1300 ℃ of calcining 2 ~ 10h down, cool to room temperature with the furnace and take out subsequent use;
Be honeycomb cordierite perhaps with structured material; Placing massfraction is that 20% nitric acid or massfraction are 50% oxalic acid; Use the deionized water ultrasonic cleaning behind processing 0.5 ~ 2h down at 25 ~ 90 ℃, put into 60 ~ 150 ℃ of baking oven dried overnight subsequently, place the moisture eliminator cooling subsequent use;
2) alumina sol preparation
Is that 7 ~ 23:1 mix with pseudo-boehmite by mass ratio with deionized water, and behind the stirring 1h, dropping concentration is 1molL
-1With the deionized water volume ratio be that the salpeter solution continued of 0.1 ~ 0.5:1 stirs 3 ~ 7h, obtain alumina sol;
Or be 60 ~ 120:1 mix after with aluminum isopropylate by mass ratio with deionized water, Heating temperature to 50 ~ 100 ℃ use concentration to be 1molL
-1It is 3.5 ~ 4.5 that rare nitric acid is regulated pH, stirs, and closed system continues to stir 7 ~ 13h under the condensing reflux condition then, and aged at room temperature 12 ~ 36h obtains alumina sol;
Or be that 0.3 ~ 3:1 mix with aluminum nitrate by mass ratio with deionized water, under stirring at room, drip 0.5 ~ 1.5molL
-1Ammoniacal liquor, regulate pH and be 7.8 ~ 9.2 and obtain throw out, to the throw out washing and filtering to remove NO wherein
3 -Ion is dispersed in filter cake in the deionized water again, and in the time of 50 ~ 80 ℃, drips 0.5 ~ 1.5molL
-1Nitric acid be adjusted to pH to 3 ~ 4, at 85 ℃ of seal aging 10 ~ 24h, obtain alumina sol;
3) structured material coating alumina
With being immersed in step 2 through pretreated structural metallic materials or cordierite structure material in the step 1)) in a kind of alumina sol of preparation 2 ~ 10min take out; Blow the superfluous alumina sol of remained on surface off; Be placed in 100 ~ 150 ℃ of baking ovens dry 1 ~ 6h then, and in retort furnace with 1 ~ 20 ℃ of min
-1Temperature rise rate be raised to 500 ~ 700 ℃ of roasting 0.5 ~ 3h; Be cooled to room temperature with furnace temperature; Again with structured material be dipped in the alumina sol successively according to take out, dry up, process dry, roasting repeats 2 ~ 5 times, reaches 0.5 ~ 3% of structured material own wt until the charge capacity of aluminum oxide on structured material;
4) reaction solution preparation
General formula according to hexa-aluminate is A
1-xB
xC
Y-zD
zAl
12-yO
19, 0≤x≤1,0≤z≤y≤3 wherein, A and B represent La respectively
3+, Ce
3+, Sr
2+, Ba
2+, Ca
2+In any; C and D represent Cr respectively
3+, Fe
3+, Mn
3+, Cu
2+, Mg
2+, Mn
2+, Ni
2+And Co
2+In any; According to the mol ratio of [C+D] and [A+B] is that the ratio of 0 ~ 3:1 takes by weighing corresponding metal salt; Take by weighing an ammonium nitrate that mole number is 6 times of total metals ion mole numbers; Metal-salt and an ammonium nitrate are dissolved in the deionized water, and being made into total concentration of metal ions is 0.01 ~ 1.2molL
-1Mixing salt solution, under agitation in this solution, drip mass concentration and be 0.1 ~ 9.0% alkali lye and reach 5 ~ 10 until the pH value, said alkali lye is any in ammoniacal liquor, volatile salt, bicarbonate of ammonia, sodium hydroxide or the Pottasium Hydroxide;
5) hexa-aluminate growth in situ
The structured material that scribbles aluminum oxide coating layer that step 3) is made is positioned in the made reaction soln of step 4); React 2 ~ 72h down at 25 ~ 150 ℃; Take out structured material; Using deionized water or pH is after 7 an ammonium nitrate washing lotion is cleaned, dry 24h in 50 ~ 150 ℃ baking oven, then in retort furnace with 1 ~ 10 ℃ of min
-1Temperature rise rate is warming up to 900 ~ 1300 ℃ of calcining 2 ~ 10h, on the structured material of metal or trichroite, obtains embedding the aluminum oxide compound coating of hexa-aluminate.
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| CN103614713A (en) * | 2013-12-05 | 2014-03-05 | 广西大学 | Method for preparing high-temperature composite coating on niobium-based surface by utilizing sol-gel method |
| CN107597199A (en) * | 2017-09-13 | 2018-01-19 | 武汉凯迪工程技术研究总院有限公司 | Recirculating fluidized bed hydrocarbon reforming catalyst and its preparation method and application |
| CN109650935A (en) * | 2019-02-15 | 2019-04-19 | 中国计量大学 | A kind of preparation method of the adjustable alumina porous ceramic film of hole shape |
| CN115093209A (en) * | 2022-07-05 | 2022-09-23 | 江苏锡沂高新材料产业技术研究院有限公司 | Preparation method of high-strength high-stability multilayer composite structure fused quartz material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815928A (en) * | 2012-08-27 | 2012-12-12 | 哈尔滨工业大学 | Rare earth ions-doped hexaaluminate high-emissivity material and preparation method thereof |
| CN102815928B (en) * | 2012-08-27 | 2013-09-25 | 哈尔滨工业大学 | Preparation method of rare earth ions-doped hexaaluminate high-emissivity material |
| CN103041822A (en) * | 2012-12-20 | 2013-04-17 | 天津大学 | Integral type metal catalyst for methane catalytic combustion and preparation method |
| CN103614713A (en) * | 2013-12-05 | 2014-03-05 | 广西大学 | Method for preparing high-temperature composite coating on niobium-based surface by utilizing sol-gel method |
| CN107597199A (en) * | 2017-09-13 | 2018-01-19 | 武汉凯迪工程技术研究总院有限公司 | Recirculating fluidized bed hydrocarbon reforming catalyst and its preparation method and application |
| CN109650935A (en) * | 2019-02-15 | 2019-04-19 | 中国计量大学 | A kind of preparation method of the adjustable alumina porous ceramic film of hole shape |
| CN109650935B (en) * | 2019-02-15 | 2022-03-22 | 中国计量大学 | Preparation method of porous alumina ceramic membrane with adjustable pore shape |
| CN115093209A (en) * | 2022-07-05 | 2022-09-23 | 江苏锡沂高新材料产业技术研究院有限公司 | Preparation method of high-strength high-stability multilayer composite structure fused quartz material |
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