CN102531554B - 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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- CN102531554B CN102531554B CN 201210002527 CN201210002527A CN102531554B CN 102531554 B CN102531554 B CN 102531554B CN 201210002527 CN201210002527 CN 201210002527 CN 201210002527 A CN201210002527 A CN 201210002527A CN 102531554 B CN102531554 B CN 102531554B
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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 alumina composite coating that embeds hexa-aluminate and preparation method thereof, belong to the preparing technical field of alumina composite 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 to carry out suitable modification for different purposes.When as support of the catalyst, aluminum oxide is at high temperature and have thermostability under the water vapor condition to have a strong impact on catalyzer work-ing life.At catalytic field, structured material claims again structure carrier also to be usually used in processing 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.
At present introducing single or the polycomponent additive is one of important means of improving thermal stability of alumina.Ozawa etc. have prepared different metal ion (rare earth ion: La with pickling process
3+, Ce
3+, Sm
3+, Gd
3+, Dy
3+, Yb
3+, Y
3+And alkaline-earth metal ions: Ba
2+, Sr
2+, Ca
2+Deng) alumina supporter that mixes.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 ions 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 respectively the impact of this catalyzer on 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 occurs between the catalyst components, cause gathering or catalyzer heat inactivation between the catalyst activity component.The Kang philosophy uses pickling process and mechanical mixing to prepare BaO/Al
2O
3Catalyzer has all suppressed γ-Al under the high temperature to a certain extent
2O
3To α-Al
2O
3Transformation, be conducive to stability raising.At present, utilize additive to come the research of modified aluminas still generally to adopt solid reaction process and pickling process, this is so that disperse inhomogeneous 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, easily cause dopant ion to run off, even the large crystal grain of migration gathering formation, thereby limited to the degree of alumina stable property improvement.Therefore, be necessary to improve with the multi-component compound additive metal oxide of high-temperature stable the thermostability of doping component, and by the effect between a kind of novel method enhancing additive and aluminum oxide and the structure carrier, thereby thermostability and the mechanical stability of raising aluminum oxide coating layer.
Have not yet to see the bibliographical information that the composite oxides hexa-aluminate of introducing high-temperature stable improves thermal stability of alumina.Therefore, this patent proposes a kind of preparation method of alumina composite coating of the embedding hexa-aluminate that applies at structured material first.Hexa-aluminate is the six side's laminate structures that have than large aspect ratio, and the anisotropy of crystal growth is so that it at high temperature can keep high specific surface area and thermostability.Its skeleton symbol AAl
12O
19In A position ion can be consisted of by basic metal, alkaline-earth metal or rare earth ion, Al can the part by transition metal ion (such as 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 alumina composite coating that embeds hexa-aluminate and preparation method thereof, the compound coating that the method makes can strengthen solid support material and aluminum oxide and and active ingredient between interaction, improve thermostability and the mechanical stability of aluminum oxide coating layer.Its preparation method process is simple.
The present invention is realized by following technical proposals, a kind of alumina composite 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 respectively La
3+, Ce
3+, Sr
2+, Ba
2+, Ca
2+In a kind of; C and D represent respectively Cr
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 alumina composite coating of above-mentioned embedding hexa-aluminate is characterized in that comprising following process:
1) structured material pre-treatment
Be 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 with structured material, first with sand papering to remove surperficial foul and to increase roughness, then be placed on respectively acetone solvent and deionized water for ultrasonic and clean 10 ~ 120min, put into 100 gL after cleaning
-1H
2SO
4With 100 gL
-1NaCl is in the mixed solution of 1:1 preparation according to volume ratio, at 25 ℃ ~ 90 ℃ lower 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 lower calcining 2 ~ 10h, cool to room temperature with the furnace and take out for subsequent use;
Be honeycomb cordierite with structured material perhaps, placing massfraction is that 20% nitric acid or massfraction are 50% oxalic acid, behind 25 ~ 90 ℃ of lower processing 0.5 ~ 2h, use the deionized water ultrasonic cleaning, put into subsequently 60 ~ 150 ℃ of baking oven dried overnight, place the moisture eliminator cooling for subsequent use;
2) alumina sol preparation
Be that 7 ~ 23:1 mixes in mass ratio with deionized water and pseudo-boehmite, stir 1h after, dropping concentration is 1molL
-1Be to continue to stir 3 ~ 7h behind the salpeter solution of 0.1 ~ 0.5:1 with the deionized water volume ratio, obtain alumina sol;
Or be after 60 ~ 120:1 mixes in mass ratio with deionized water and aluminum isopropylate, Heating temperature to 50 ~ 100 ℃ are 1molL with concentration
-1Rare nitre acid for adjusting pH is 3.5 ~ 4.5, stirs, and then closed system continues to stir 7 ~ 13h under the condensing reflux condition, and aged at room temperature 12 ~ 36h obtains alumina sol;
Or be that 0.3 ~ 3:1 mixes in mass ratio with deionized water and aluminum nitrate, under stirring at room, drip 0.5 ~ 1.5molL
-1Ammoniacal liquor, regulate pH and be 7.8 ~ 9.2 and be precipitated thing, to the throw out washing and filtering to remove NO wherein
3 -Ion is dispersed in filter cake in the deionized water again, and drips 0.5 ~ 1.5molL in the time of 50 ~ 80 ℃
-1Nitric acid be adjusted to pH to 3 ~ 4, at 85 ℃ of seal aging 10 ~ 24h, obtain alumina sol;
3) structured material coating alumina
Will be in the step 1) be immersed in step 2 through pretreated structural metallic materials or cordierite structure material) in a kind of alumina sol of preparation 2 ~ 10min take out, blow the superfluous alumina sol of remained on surface off, then be placed in 100 ~ 150 ℃ of baking ovens dry 1 ~ 6h, 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 structured material is dipped in the alumina sol successively according to take out, dry up, process dry, roasting repeats 2 ~ 5 times, until the charge capacity of aluminum oxide on structured material reaches 0.5 ~ 3% of structured material own wt;
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 respectively La
3+, Ce
3+, Sr
2+, Ba
2+, Ca
2+In a kind of; C and D represent respectively Cr
3+, Fe
3+, Mn
3+, Cu
2+, Mg
2+, Mn
2+, Ni
2+And Co
2+In a kind of; Be that the ratio of 0 ~ 3:1 takes by weighing corresponding metal-salt according to the mol ratio of [C+D] and [A+B], take by weighing the ammonium nitrate that mole number is 6 times of total metal ion mole numbers, metal-salt and 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 drip mass concentration in this solution and be 0.1 ~ 9.0% alkali lye until the pH value reaches 5 ~ 10, described alkali lye is a kind of in ammoniacal liquor, volatile salt, bicarbonate of ammonia, sodium hydroxide or the potassium 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), at 25 ~ 150 ℃ of lower reaction 2 ~ 72h, take out structured material, be after 7 ammonium nitrate washing lotion is cleaned with deionized water or pH, 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, obtains embedding the alumina composite coating of hexa-aluminate at the structured material of metal or trichroite.
Advantage of the present invention has: the employing of this compound coating does not add the aluminium source also by the Al in the method activation aluminum oxide that uses 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 metal 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.The mechanical shock resistance test shows coating 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 the prepared compound coating of embodiment 1 and embodiment 3.
Among the figure: curve a is the XRD figure spectrum that embodiment 1 makes compound coating; Curve b is the XRD figure spectrum that embodiment 3 makes compound coating.Δ represents 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-mechanical shock aptitude tests comparison diagram as a result of the prepared coating of embodiment 1, embodiment 3 and Comparative Examples.
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, heavy 7.782g altogether vertically polishes respectively after 4 times with 100 orders and 600 order sand paper, carries out ultrasonic cleaning 30min with acetone, water successively, at 60 ℃ in 100 gL
-1H
2SO
4With 100 gL
-1Process 5min in the mixing solutions of NaCl, clean with deionized water afterwards, and in 60 ℃ of baking ovens dry 1h, cooling is placed in the moisture eliminator for subsequent use.
Take by weighing the 18g pseudo-boehmite and add in the 270g deionized water, behind the stirring 1h, drip the 1molL of 55mL
-1Salpeter solution after continue to 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 with after the preliminary oven dry of blower in 120 ℃ of baking ovens dry 1h, afterwards in retort furnace with 5 ℃ of min
-1Be warmed up in 500 ℃ and calcine 1h, repeat once this coating procedure after cooling is taken out again, having a net increase of weight after applying twice is 0.088g.
Take by weighing lanthanum nitrate 3.248g, manganous acetate 1.838g and ammonium nitrate 7.204g are dissolved in the 150ml deionized water.Under stirring, magnetic in solution, drips the weak ammonia that massfraction is 1 % until pH is the 6 rear 5min that also stablize.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, then bottle is moved in 60 ℃ of baking ovens and takes out behind the constant temperature 72h.Other takes by weighing ammonium nitrate 7.204g and is dissolved in the 150ml deionized water, and dripping massfraction under magnetic stirs is that the weak ammonia of 1 % is until pH is 7.Wash successively the tinsel that takes out in the baking oven each 10 times with this solution and deionized water.Sample is placed 60 ℃ of baking oven loft dried 24h, then in high temperature Muffle furnace with 2 ℃ of min
-1Be warming up to 1100 ℃ of calcining 5h, obtain embedding the alumina composite coating of lanthanum manganese hexa-aluminate.
The above-mentioned sample that makes is carried out the mechanical shock resistance test.Testing method is: a 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 at regular intervals sample, the dry rear weight loss of measuring catalyzer.
Test result is as follows: the rate of weight loss of this coating increases gradually along with the increase of ultrasonic vibration time, and after time of vibration surpassed 40min, rate of weight loss substantially 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.Then closed system continues to stir 10h under the condensing reflux condition.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 ammonium nitrate 7.204g are dissolved in the 150ml deionized water.Under stirring, magnetic in solution, drips the ammoniacal liquor that massfraction is 1 % until pH is the 8 rear 5min that also stablize.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, then bottle is moved in 60 ℃ of baking ovens and takes out behind the constant temperature 96h.Other takes by weighing ammonium nitrate 7.204g and is dissolved in the 150ml deionized water, drips the ammonia soln of 1 % until pH=7 under magnetic stirs.Wash successively the tinsel that takes out in the baking oven each 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 alumina composite 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 nitrate 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 simultaneously salts solution and sal volatile, and the monitoring pH 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 alumina composite 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 as follows: the rate of weight loss of this coating increases gradually along with the increase of ultrasonic vibration time, and after time of vibration surpassed 10min, rate of weight loss substantially no longer changed, and is stabilized in 0.27%.
Embodiment 4
The compound coating preparation process is as follows: 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 slowly while stirring lmolL
-1Ammoniacal liquor be 9.2 to be precipitated to pH, need not ageing and directly remove wherein NO with the deionized water filtration washing
3 -Ion will precipitate and again use water-dispersion, 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 nitrate 1.299g, nitrocalcite 0.177g, manganous acetate 0.643g, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 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 simultaneously salts solution and sal volatile, and the monitoring pH 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 high temperature Muffle furnace with 10 ℃ of min
-1Be warming up to 1300 ℃ of calcining 2h, obtain embedding the alumina composite coating of lanthanum manganese hexa-aluminate.
Embodiment 5
The compound coating preparation process is as follows: 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 nitrate 1.624g, manganous acetate 0.919g and ammonium nitrate 3.602g are dissolved in the 150ml deionized water.Under stirring, magnetic in solution, drips 1% sodium hydroxide solution until pH is the 8 rear 5min that also stablize.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, then bottle is moved in 60 ℃ of baking ovens and takes out behind the constant temperature 2h.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 high temperature Muffle furnace with 5 ℃ of min
-1Be warming up to 1000 ℃ of calcining 8h, obtain embedding the alumina composite coating of lanthanum manganese hexa-aluminate.
Comparative Examples
Single Al
2O
3Coating is prepared as follows: 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 as follows: single Al
2O
3The rate of weight loss of coating increases gradually along with the increase of ultrasonic vibration time, and after time of vibration surpassed 10min, rate of weight loss substantially no longer changed, and is stabilized in 0.76%.
Claims (1)
1. preparation method who embeds the alumina composite coating of hexa-aluminate, the thickness of described 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 respectively La
3+, Ce
3+, Sr
2+, Ba
2+, Ca
2+In a kind of; C and D represent respectively Cr
3+, Fe
3+, Mn
3+, Cu
2+, Mg
2+, Mn
2+, Ni
2+And Co
2+In a kind of, it is characterized in that comprising following process:
1) structured material pre-treatment
Be 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 with structured material, first with sand papering to remove surperficial foul and to increase roughness, then be placed on respectively acetone solvent and deionized water for ultrasonic and clean 10 ~ 120min, put into 100 gL after cleaning
-1H
2SO
4With 100 gL
-1NaCl is in the mixed solution of 1:1 preparation according to volume ratio, at 25 ℃ ~ 90 ℃ lower 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 lower calcining 2 ~ 10h, cool to room temperature with the furnace and take out for subsequent use;
Be honeycomb cordierite with structured material perhaps, placing massfraction is that 20% nitric acid or massfraction are 50% oxalic acid, behind 25 ~ 90 ℃ of lower processing 0.5 ~ 2h, use the deionized water ultrasonic cleaning, put into subsequently 60 ~ 150 ℃ of baking oven dried overnight, place the moisture eliminator cooling for subsequent use;
2) alumina sol preparation
Be that 7 ~ 23:1 mixes in mass ratio with deionized water and pseudo-boehmite, stir 1h after, dropping concentration is 1molL
-1Be to continue to stir 3 ~ 7h behind the salpeter solution of 0.1 ~ 0.5:1 with the deionized water volume ratio, obtain alumina sol;
Or be after 60 ~ 120:1 mixes in mass ratio with deionized water and aluminum isopropylate, Heating temperature to 50 ~ 100 ℃ are 1molL with concentration
-1Rare nitre acid for adjusting pH is 3.5 ~ 4.5, stirs, and then closed system continues to stir 7 ~ 13h under the condensing reflux condition, and aged at room temperature 12 ~ 36h obtains alumina sol;
Or be that 0.3 ~ 3:1 mixes in mass ratio with deionized water and aluminum nitrate, under stirring at room, drip 0.5 ~ 1.5molL
-1Ammoniacal liquor, regulate pH and be 7.8 ~ 9.2 and be precipitated thing, to the throw out washing and filtering to remove NO wherein
3 -Ion is dispersed in filter cake in the deionized water again, and drips 0.5 ~ 1.5molL in the time of 50 ~ 80 ℃
-1Nitric acid be adjusted to pH to 3 ~ 4, at 85 ℃ of seal aging 10 ~ 24h, obtain alumina sol;
3) structured material coating alumina
Will be in the step 1) be immersed in step 2 through pretreated structural metallic materials or cordierite structure material) in a kind of alumina sol of preparation 2 ~ 10min take out, blow the superfluous alumina sol of remained on surface off, then be placed in 100 ~ 150 ℃ of baking ovens dry 1 ~ 6h, 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 structured material is dipped in the alumina sol successively according to take out, dry up, process dry, roasting repeats 2 ~ 5 times, until the charge capacity of aluminum oxide on structured material reaches 0.5 ~ 3% of structured material own wt;
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 respectively La
3+, Ce
3+, Sr
2+, Ba
2+, Ca
2+In any; C and D represent respectively Cr
3+, Fe
3+, Mn
3+, Cu
2+, Mg
2+, Mn
2+, Ni
2+And Co
2+In any; Be that the ratio of 0 ~ 3:1 takes by weighing corresponding metal-salt according to the mol ratio of [C+D] and [A+B], take by weighing the ammonium nitrate that mole number is 6 times of total metal ion mole numbers, metal-salt and 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 drip mass concentration in this solution and be 0.1 ~ 9.0% alkali lye until the pH value reaches 5 ~ 10, described alkali lye is any in ammoniacal liquor, volatile salt, bicarbonate of ammonia, sodium hydroxide or the potassium 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), at 25 ~ 150 ℃ of lower reaction 2 ~ 72h, take out structured material, be after 7 ammonium nitrate washing lotion is cleaned with deionized water or pH, 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, obtains embedding the alumina composite coating of hexa-aluminate at the structured material of metal or trichroite.
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| CN103614713B (en) * | 2013-12-05 | 2015-07-22 | 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 |
| 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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| CN101628806A (en) * | 2009-08-05 | 2010-01-20 | 郑州九环科贸有限公司 | Nanometer composite ceramic lining material and preparation method thereof |
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