CN109967736A - A kind of Fe2O3@Ni composite granule and preparation method thereof with core-shell structure - Google Patents
A kind of Fe2O3@Ni composite granule and preparation method thereof with core-shell structure Download PDFInfo
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- CN109967736A CN109967736A CN201910217170.8A CN201910217170A CN109967736A CN 109967736 A CN109967736 A CN 109967736A CN 201910217170 A CN201910217170 A CN 201910217170A CN 109967736 A CN109967736 A CN 109967736A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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Abstract
The present invention relates to a kind of Fe with core-shell structure2O3@Ni composite granule and preparation method thereof.Its technical solution is: by Fe2O3Powder alternately washs in sodium hydroxide solution and in dilute sulfuric acid, dry, the Fe after being dried2O3Powder.Enveloping agent solution and nickel salt solution are stirred under water bath condition, obtain plating solution I；It adjusts pH value to 9~13, stabilizer is added, obtains plating solution II.The Fe after drying first is added in backward plating solution II2O3Reducing agent is added in powder and average rate, obtains covering liquid.Coated composite powder liquid is washed with deionized, it is dry, 1~3h is kept the temperature under the conditions of protective atmosphere and 400~700 DEG C.The Fe with core-shell structure is made2O3@Ni composite granule.The present invention has the characteristics that simple process and at low cost, and the Fe with core-shell structure is made with this method2O3The uniform excellent catalytic effect of the ingredient of@Ni composite granule.
Description
Technical field
The invention belongs to Fe2O3@Ni composite granule technical field.More particularly to a kind of Fe with core-shell structure2O3@Ni
Composite granule and preparation method thereof.
Background technique
Carbon containing refractory is due to its excellent anti-slag action performance and thermal shock is stability is widely used in metallurgy
Industry.Carbon containing refractory mainly includes magnesia carbon refractory, aluminum-carbon refractory material and SiC based refractories etc..Its
In, magnesia-carbon refractory material and aluminum-carbon refractory material are most widely used in steel industry, as converter, RH refining furnace and continuous casting are used
Equipment etc..Carburetting behavior and graphite resource but with the development of the smelting of clean steel and low energy consumption, environmental protection, in smelting process
It is non-renewable make carbon containing refractory to low-carbon develop.However, the reduction of carbon content will lead to thermal shock resistance and resist
The high-temperature behaviors such as aggressivity are remarkably decreased, this is because the product after the pyrolysis of its bonding agent phenolic resin is unformed charcoal, in height
It is oxidizable and be easy to happen brittle fracture (A.P.Luz, C.G.Renda, A.A.Lucas.Graphitization of under temperature
Phenolic resins for carbon-based refractories.Ceramics International, 2017,43
(13): 8171-8182 problem brought by carbon containing refractory low-carbon), is exposed.
To solve the above-mentioned problems, main at present by introducing transition element as catalyst, make phenolic resin in heat
The hydrocarbon gas generated in solution preocess is adsorbed, and forms the graphite of low-dimensional carbon material (such as carbon nanotube) Lai Tigao phenolic resin
Change degree.Meanwhile being introduced into catalyst and can improve the conversion of glass-like carbon in resin, improve the Residual carbon of resin.A kind of " refractory material
With phenol-formaldehyde resin modified and preparation method thereof " (CN101245128A) be made by collosol and gel, by or iron or cobalt or nickel
Presoma is introduced into phenolic resin, is made carbon nano-tube in situ in resin and is improved the Residual carbon of resin.Rastegar etc.
(H.Rastegar, M.Bavand-vandchali, A.Nemati.Catalytic graphitization behavior of
Phenolic resins by addition of in situ formed nano-Fe particles.Physica E:
Low-dimensional Systems and Nanostructures, 2018,101:50-61) use Fe (NO3)3As presoma
Nanometer Fe particle is formed in situ in phenolic resin, to improve degree of graphitization.The above results show to add in phenolic resin
Though adding magnesium-yttrium-transition metal salt that can play the purpose for improving phenolic resin degree of graphitization, effect is undesirable, introduces catalyst
Partial size and pattern it is uncontrollable, catalyst activity it is lower, if introducing excess catalyst (>=3wt%) can with substrate reaction give birth to
At eutectic phase, the high-temperature behavior of refractory material is reduced.Meanwhile the C decomposed in phenolic resin pyrolytic processxHyComplicated components are single
Catalyst be difficult to be catalyzed a variety of hydrocarbon gas.
Summary of the invention
The present invention is directed to overcome prior art defect, it is therefore an objective to provide a kind of simple process and at low cost have nucleocapsid knot
The Fe of structure2O3@Ni composite granule, with the Fe of core-shell structure made from this method2O3@Ni composite granule ingredient is uniform to urge
It is good to change effect.
For with realizing above-mentioned mesh, the technical solution adopted by the present invention is that:
Step 1, by Fe2O3Powder, which is placed in sodium hydroxide solution, washs 3~5min, then be placed in dilute sulfuric acid washing 3~
Then 5min is washed with deionized to neutrality, dry, the Fe after being dried2O3Powder.
Step 2, under 75~85 DEG C of water bath conditions, complexing agent and nickel salt are dissolved in deionized water respectively, obtain concentration be 5
The enveloping agent solution and concentration of~18g/L is the nickel salt solution of 4~21g/L.
Step 3 presses complexing agent: the mass ratio of nickel salt is (0.9~1.6): 1, by the enveloping agent solution and the nickel salt
Solution mixing, stirs 3~5min, obtains plating solution I；It is 9~13 that ammonium hydroxide to pH value is added dropwise into the plating solution I again, is then added
The stabilizer of the plating solution I0.09~0.17wt%, continues 1~5min of stirring, obtains plating solution II.
Step 4 presses the plating solution II: the Fe after the drying2O3The mass ratio of powder is 1: 0.08~0.15, Xiang Suoshu
Fe after the drying is added in plating solution II2O3Powder；Press reducing agent again: the mass ratio of nickel salt is 0.3~0.7: 1, is by concentration
The reducing agent solution of 1.6~10g/L is added drop-wise in plating solution II, is continued 20~45min of stirring, is obtained covering liquid.
The process of material is added in step 3~step 4 or mixed process carries out under agitation.
The covering liquid is washed with deionized to neutrality step 5, dry under the conditions of 110 DEG C, then at protective atmosphere
1~3h is kept the temperature under the conditions of with 400~700 DEG C, obtains the Fe with core-shell structure2O3@Ni composite granule.
The complexing agent is one of trisodium citrate, ethylenediamine tetra-acetic acid and sodium potassium tartrate tetrahydrate.
The nickel salt is one of nickel sulfate, nickel nitrate and nickel chloride.
The stabilizer is one of 2,2 '-bipyridyls, thiocarbamide and potassium sulfate.
The reducing agent is one of sodium borohydride, sodium hypophosphite and hydrazine solution.
The Fe2O3The purity of powder is technical pure or more；The Fe2O3The partial size of powder is 0.5~8 μm.
The purity of the complexing agent is technical pure or more.
The purity of the nickel salt is technical pure or more.
The purity of the stabilizer is technical pure or more.
The purity of the reducing agent is technical pure or more.
The protective atmosphere is nitrogen, argon gas and CO2One of atmosphere.
Due to the adoption of the above technical scheme, the present invention has following good effect compared with prior art:
The present invention is using chemically coated nickel method in Fe2O3Electroless plating on powders W metal is made with core-shell structure
Fe2O3@Ni composite granule.Fe in the present invention2O3Powder need to only carry out simple carrying out washing treatment as matrix, without doing complexity
Sensitization priming reaction.Simple process, it is easy to operate.The raw material sources that the present invention uses are extensive, and the preparation process period is short, cost
It is low.
The Fe with core-shell structure prepared with this method2O3@Ni composite granule realizes nano-scale Ni and is dispersed in
Fe2O3Particle surface improves the reuniting effect of nano-sized particles, improves the dispersibility of major catalyst Ni, makes it preferably
Catalytic effect is played, while there is good chemical stability.Add the Fe with core-shell structure2O3@Ni composite granule is used as and urges
Phenolic resin, which is added, in agent makes degree of graphitization after its heat treatment be increased to 61.2%, has good catalytic effect.
The Fe with core-shell structure is made in the present invention2O3@Ni composite granule partial size be 1~10 μm, clad Ni with a thickness of
0.2~1.0 μm.
Therefore, the present invention has the characteristics that simple process and the Fe with core-shell structure at low cost, prepared2O3@Ni is multiple
Close the uniform excellent catalytic effect of ingredient of powder.
Detailed description of the invention
Fig. 1 is a kind of Fe with core-shell structure prepared by the present invention2O3@Ni composite granule.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and detailed description, not to the scope of the present invention
Restriction.
It is first that the raw materials used Unify legislation of present embodiment is as follows to avoid repeating, it is repeated no more in example:
The Fe2O3The purity of powder is technical pure or more；The Fe2O3The partial size of powder is 0.5~8 μm.
The purity of the complexing agent is technical pure or more.
The purity of the nickel salt is technical pure or more.
The purity of the stabilizer is technical pure or more.
The purity of the reducing agent is technical pure or more.
Embodiment 1
A kind of Fe with core-shell structure2O3@Ni composite granule and preparation method thereof, the step of preparation method described in this example
Suddenly it is:
Step 1, by Fe2O3Powder, which is placed in sodium hydroxide solution, washs 3~5min, then be placed in dilute sulfuric acid washing 3~
Then 5min is washed with deionized to neutrality, dry, the Fe after being dried2O3Powder.
Step 2, under 75~85 DEG C of water bath conditions, complexing agent and nickel salt are dissolved in deionized water respectively, obtain concentration be 5
The enveloping agent solution and concentration of~12g/L is the nickel salt solution of 4~11g/L.
Step 3 presses complexing agent: the mass ratio of nickel salt is (0.9~1.2): 1, by the enveloping agent solution and the nickel salt
Solution mixing, stirs 3~5min, obtains plating solution I；It is 9~11 that ammonium hydroxide to pH value is added dropwise into the plating solution I again, is then added
The stabilizer of the plating solution I0.11~0.15wt%, continues 1~5min of stirring, obtains plating solution II.
Step 4 presses the plating solution II: the Fe after the drying2O3The mass ratio of powder is 1: 0.08~0.11, Xiang Suoshu
Fe after the drying is added in plating solution II2O3Powder；Press reducing agent again: the mass ratio of nickel salt is 0.3~0.5: 1, is by concentration
The reducing agent solution of 1.6~6g/L is added drop-wise in plating solution II, is continued 20~35min of stirring, is obtained covering liquid.
The process of material is added in step 3~step 4 or mixed process carries out under agitation.
The covering liquid is washed with deionized to neutrality step 5, dry under the conditions of 110 DEG C, then at protective atmosphere
1~3h is kept the temperature under the conditions of with 400~600 DEG C, obtains the Fe with core-shell structure2O3@Ni composite granule.
The complexing agent is trisodium citrate.
The nickel salt is nickel sulfate.
The stabilizer is 2,2 '-bipyridyls.
The reducing agent is sodium borohydride.
The protective atmosphere is nitrogen atmosphere.
Embodiment 2
A kind of Fe with core-shell structure2O3@Ni composite granule and preparation method thereof.Remaining is with embodiment 1: in addition to following:
The complexing agent is ethylenediamine tetra-acetic acid.
The nickel salt is nickel nitrate.
The stabilizer is thiocarbamide.
The reducing agent is sodium hypophosphite.
The protective atmosphere is argon atmosphere.
Embodiment 3
A kind of Fe with core-shell structure2O3@Ni composite granule and preparation method thereof.Remaining is with embodiment 1: in addition to following:
The complexing agent is sodium potassium tartrate tetrahydrate.
The nickel salt is nickel chloride.
The stabilizer is potassium sulfate.
The reducing agent is hydrazine solution.
The protective atmosphere is CO2Atmosphere.
Embodiment 4
A kind of Fe with core-shell structure2O3@Ni composite granule and preparation method thereof, the step of preparation method described in this example
Suddenly it is:
Step 1, by Fe2O3Powder, which is placed in sodium hydroxide solution, washs 3~5min, then be placed in dilute sulfuric acid washing 3~
Then 5min is washed with deionized to neutrality, dry, the Fe after being dried2O3Powder.
Step 2, under 75~85 DEG C of water bath conditions, complexing agent and nickel salt are dissolved in deionized water respectively, obtain concentration be 8
The enveloping agent solution and concentration of~15g/L is the nickel salt solution of 14~21g/L.
Step 3 presses complexing agent: the mass ratio of nickel salt is (1.1~1.4): 1, by the enveloping agent solution and the nickel salt
Solution mixing, stirs 3~5min, obtains plating solution I；It is 10~12 that ammonium hydroxide to pH value is added dropwise into the plating solution I again, is then added
The stabilizer of the plating solution I0.13~0.17wt%, continues 1~5min of stirring, obtains plating solution II.
Step 4 presses the plating solution II: the Fe after the drying2O3The mass ratio of powder is 1: 0.1~0.13, to the plating
Fe after the drying is added in liquid II2O3Powder；Press reducing agent again: the mass ratio of nickel salt is 0.4~0.6: 1, is 6 by concentration
The reducing agent solution of~10g/L is added drop-wise in plating solution II, is continued 25~40min of stirring, is obtained covering liquid.
The process of material is added in step 3~step 4 or mixed process carries out under agitation.
The covering liquid is washed with deionized to neutrality step 5, dry under the conditions of 110 DEG C, then at protective atmosphere
1~3h is kept the temperature under the conditions of with 450~650 DEG C, obtains the Fe with core-shell structure2O3@Ni composite granule.
The complexing agent is trisodium citrate.
The nickel salt is nickel sulfate.
The stabilizer is 2,2 '-bipyridyls.
The reducing agent is sodium borohydride.
The protective atmosphere is nitrogen atmosphere.
Embodiment 5
A kind of Fe with core-shell structure2O3@Ni composite granule and preparation method thereof.Remaining is with embodiment 4 in addition to following:
The complexing agent is ethylenediamine tetra-acetic acid.
The nickel salt is nickel nitrate.
The stabilizer is thiocarbamide.
The reducing agent is sodium hypophosphite.
The protective atmosphere is argon atmosphere.
Embodiment 6
A kind of Fe with core-shell structure2O3@Ni composite granule and preparation method thereof.Remaining is with embodiment 4 in addition to following:
The complexing agent is sodium potassium tartrate tetrahydrate.
The nickel salt is nickel chloride.
The stabilizer is potassium sulfate.
The reducing agent is hydrazine solution.
The protective atmosphere is CO2Atmosphere.
Embodiment 7
A kind of Fe with core-shell structure2O3@Ni composite granule and preparation method thereof, the step of preparation method described in this example
Suddenly it is:
Step 1, by Fe2O3Powder, which is placed in sodium hydroxide solution, washs 3~5min, then be placed in dilute sulfuric acid washing 3~
Then 5min is washed with deionized to neutrality, dry, the Fe after being dried2O3Powder.
Step 2, under 75~85 DEG C of water bath conditions, complexing agent and nickel salt are dissolved in deionized water respectively, obtaining concentration is
The enveloping agent solution and concentration of 11~18g/L is the nickel salt solution of 9~16g/L.
Step 3 presses complexing agent: the mass ratio of nickel salt is (1.3~1.6): 1, by the enveloping agent solution and the nickel salt
Solution mixing, stirs 3~5min, obtains plating solution I；It is 11~13 that ammonium hydroxide to pH value is added dropwise into the plating solution I again, is then added
The stabilizer of the plating solution I0.09~0.13wt%, continues 1~5min of stirring, obtains plating solution II.
Step 4 presses the plating solution II: the Fe after the drying2O3The mass ratio of powder is 1: 0.12~0.15, Xiang Suoshu
Fe after the drying is added in plating solution II2O3Powder；Press reducing agent again: the mass ratio of nickel salt is 0.5~0.7: 1, is by concentration
The reducing agent solution of 4~8g/L is added drop-wise in plating solution II, is continued 30~45min of stirring, is obtained covering liquid.
The process of material is added in step 3~step 4 or mixed process carries out under agitation.
The covering liquid is washed with deionized to neutrality step 5, dry under the conditions of 110 DEG C, then at protective atmosphere
1~3h is kept the temperature under the conditions of with 500~700 DEG C, obtains the Fe with core-shell structure2O3@Ni composite granule.
The complexing agent is trisodium citrate.
The nickel salt is nickel sulfate.
The stabilizer is 2,2 '-bipyridyls.
The reducing agent is sodium borohydride.
The protective atmosphere is nitrogen atmosphere.
Embodiment 8
A kind of Fe with core-shell structure2O3@Ni composite granule and preparation method thereof.Remaining is with embodiment 7 in addition to following:
The complexing agent is ethylenediamine tetra-acetic acid.
The nickel salt is nickel nitrate.
The stabilizer is thiocarbamide.
The reducing agent is sodium hypophosphite.
The protective atmosphere is argon atmosphere.
Embodiment 9
A kind of Fe with core-shell structure2O3@Ni composite granule and preparation method thereof.Remaining is with embodiment 7 in addition to following:
The complexing agent is sodium potassium tartrate tetrahydrate.
The nickel salt is nickel chloride.
The stabilizer is potassium sulfate.
The reducing agent is hydrazine solution.
The protective atmosphere is CO2Atmosphere.
Present embodiment has following good effect compared with prior art:
Present embodiment is using chemically coated nickel method in Fe2O3Electroless plating on powders W metal, being made has nucleocapsid knot
The Fe of structure2O3@Ni composite granule.Fe in present embodiment2O3Powder need to only carry out simple washup as matrix
Reason, without doing complicated sensitization priming reaction.Simple process, it is easy to operate.The raw material sources that present embodiment uses are wide
General, the preparation process period is short, at low cost.
The Fe with core-shell structure prepared with this method2O3@Ni composite granule realizes nano-scale Ni and is dispersed in
Fe2O3Particle surface improves the reuniting effect of nano-sized particles, improves the dispersibility of major catalyst Ni, makes it preferably
Catalytic effect is played, while there is good chemical stability.Add the Fe with core-shell structure2O3@Ni composite granule is used as and urges
Phenolic resin, which is added, in agent makes degree of graphitization after its heat treatment be increased to 61.2%, has good catalytic effect.
The present embodiment Fe obtained with core-shell structure2O3@Ni composite granule partial size is 1~10 μm, clad
Ni is with a thickness of 0.2~1.0 μm.The present embodiment Fe obtained with core-shell structure2O3@Ni composite granule such as Fig. 1 institute
Show, Fig. 1 is a kind of Fe with core-shell structure prepared by embodiment 12O3@Ni composite granule.As can be seen from Figure 1: the tool of preparation
There is the Fe of core-shell structure2O3The grain diameter of@Ni composite granule is 4~5 μm, and clad Ni is with a thickness of 0.3~0.5 μm.
Therefore, present embodiment has the characteristics that simple process and at low cost, and being made with this method has nucleocapsid knot
The Fe of structure2O3The uniform excellent catalytic effect of the ingredient of@Ni composite granule.
Claims (8)
1. a kind of Fe with core-shell structure2O3The preparation method of@Ni composite granule, it is characterised in that the step of the preparation method
Suddenly it is:
Step 1, by Fe2O3Powder, which is placed in sodium hydroxide solution, washs 3~5min, then is placed in 3~5min of washing in dilute sulfuric acid,
Then it is washed with deionized to neutrality, dry, the Fe after being dried2O3Powder；
Step 2, under 75~85 DEG C of water bath conditions, complexing agent and nickel salt are dissolved in deionized water respectively, obtain concentration be 5~
The enveloping agent solution and concentration of 18g/L is the nickel salt solution of 4~21g/L；
Step 3 presses complexing agent: the mass ratio of nickel salt is (0.9~1.6): 1, by the enveloping agent solution and the nickel salt solution
Mixing stirs 3~5min, obtains plating solution I；It is 9~13 that ammonium hydroxide to pH value is added dropwise into the plating solution I again, then described in addition
The stabilizer of plating solution I0.09~0.17wt% continues 1~5min of stirring, obtains plating solution II；
Step 4 presses the plating solution II: the Fe after the drying2O3The mass ratio of powder is 1: 0.08~0.15, Xiang Suoshu plating solution
Fe after the drying is added in II2O3Powder；Press reducing agent again: the mass ratio of nickel salt is 0.3~0.7: 1, is 1.6 by concentration
The reducing agent solution of~10g/L is added drop-wise in plating solution II, is continued 20~45min of stirring, is obtained covering liquid；
The process of material is added in step 3~step 4 or mixed process carries out under agitation；
The covering liquid is washed with deionized to neutrality step 5, dry under the conditions of 110 DEG C, then at protective atmosphere and
1~3h is kept the temperature under the conditions of 400~700 DEG C, obtains the Fe with core-shell structure2O3@Ni composite granule；
The complexing agent is one of trisodium citrate, ethylenediamine tetra-acetic acid and sodium potassium tartrate tetrahydrate；
The nickel salt is one of nickel sulfate, nickel nitrate and nickel chloride；
The stabilizer is one of 2,2 '-bipyridyls, thiocarbamide and potassium sulfate；
The reducing agent is one of sodium borohydride, sodium hypophosphite and hydrazine solution.
2. according to claim 1 with the Fe of core-shell structure2O3The preparation method of@Ni composite granule, it is characterised in that described
Fe2O3The purity of powder is technical pure or more；The Fe2O3The partial size of powder is 0.5~8 μm.
3. according to claim 1 with the Fe of core-shell structure2O3The preparation method of@Ni composite granule, it is characterised in that described
The purity of complexing agent is technical pure or more.
4. according to claim 1 with the Fe of core-shell structure2O3The preparation method of@Ni composite granule, it is characterised in that described
The purity of nickel salt is technical pure or more.
5. according to claim 1 with the Fe of core-shell structure2O3The preparation method of@Ni composite granule, it is characterised in that described
The purity of stabilizer is technical pure or more.
6. according to claim 1 with the Fe of core-shell structure2O3The preparation method of@Ni composite granule, it is characterised in that described
The purity of reducing agent is technical pure or more.
7. according to claim 1 with the Fe of core-shell structure2O3The preparation method of@Ni composite granule, it is characterised in that described
Protective atmosphere is nitrogen, argon gas and CO2One of atmosphere.
8. a kind of Fe with core-shell structure2O3@Ni composite granule, it is characterised in that the Fe with core-shell structure2O3@Ni is multiple
Close powder be any one of according to claim 1~7 described in the Fe with core-shell structure2O3The preparation method of@Ni composite granule
The prepared Fe with core-shell structure2O3@Ni composite granule.
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Cited By (3)
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| CN111424267A (en) * | 2020-04-24 | 2020-07-17 | 昆明理工大学 | Method for preparing nickel-coated bismuth sulfur chloride |
| CN114226744A (en) * | 2021-11-25 | 2022-03-25 | 中国科学院金属研究所 | Preparation method of permalloy powder microwave absorbent with controllable shape |
| CN115124350A (en) * | 2022-06-24 | 2022-09-30 | 林萍华 | Preparation process of ceramic composite material applied to high-temperature environment |
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| CN115124350A (en) * | 2022-06-24 | 2022-09-30 | 林萍华 | Preparation process of ceramic composite material applied to high-temperature environment |
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