CN106582116B - A kind of preparation method and device of medicine intermediate filtering material - Google Patents
A kind of preparation method and device of medicine intermediate filtering material Download PDFInfo
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- CN106582116B CN106582116B CN201710021627.9A CN201710021627A CN106582116B CN 106582116 B CN106582116 B CN 106582116B CN 201710021627 A CN201710021627 A CN 201710021627A CN 106582116 B CN106582116 B CN 106582116B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2068—Other inorganic materials, e.g. ceramics
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5144—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the metals of the iron group
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
A kind of preparation method and device of medicine intermediate filtering material, are related to technical field of medicine preparation, method are as follows: a, the solution that ferric nitrate, nickel sulfate, EDTANa2, hydrazine hydrate are prepared into mass fraction 10-25% adjust PH=4-6；B, silica solution, boric acid, dimethylamine are mixed to and be diluted to mass fraction 30-60%, ultrasonic vibration 2-5h, adjusts PH=3-7；C, by the product of a, b preparation, 1-8:1 is placed in the plasma torch that plasma gun sprays by volume；D, plasma torch is sprayed on the supporting body surfaces such as cellular alumina ceramics or stainless steel plate and carries out reaction in-situ, is prepared into medicine intermediate filtering material.Its preparation facilities are as follows: feeding casing is equipped on front side of plasma gun spout, the outer tube of feeding casing is connected with the first peristaltic pump delivery hose, inner tube is connected with the second peristaltic pump delivery hose.Have many advantages, such as simple process, high production efficiency, pore size filter range-controllable.
Description
Technical field
The present invention relates to technical field of medicine preparation, elaborating is a kind of simple process, high production efficiency, pore size filter model
It encloses controllably, nano-bacteria and impurity, synthesis high-purity medicine, the medicine of the excellent performances such as heatproof, pressure resistance, bending strength can be removed
The preparation method and device of intermediate filtering material.
Background technique
It is known that medicine intermediate is the indispensable semi-finished stock of pharmaceutical synthesis industry, purity is directly affected
The medical quality and clinical effectiveness of synthesis.Therefore need during pharmaceutical synthesis to carry out intermediate stringent filtering removal bacterium with
And other impurities.Being applied to medicine intermediate filtering material at present is mainly 316L powder of stainless steel sintered porous filter material.Its
Preparation process needs the processes such as high temperature sintering, electrobrightening, cleaning, and preparation process is complicated, and electrolytic polishing liquid generally has poison
Property, it needs sufficiently to clean.In addition, the pore size filter of the filtering material of preparation is generally in 0.05-10um range, it is smaller for diameter
Bacterium and impurity (10-50nm) be difficult to effectively remove, the medicine for synthesizing high-purity is restricted.
Summary of the invention:
Present invention aim to address above-mentioned the deficiencies in the prior art, a kind of simple process, high production efficiency, filtering are provided
Pore diameter range is controllable, can remove nano-bacteria and impurity, synthesis high-purity medicine, the excellent performances such as heatproof, pressure resistance, bending strength
Medicine intermediate filtering material preparation method and device.
The present invention solves technical solution used by the deficiencies in the prior art:
A kind of preparation method of medicine intermediate filtering material, it is characterised in that include the following steps:
A, by ferric nitrate, nickel sulfate, EDTANa2, hydrazine hydrate, 6-7:1-2.5:10-12:7-8 is uniformly mixed in molar ratio
It closes, and is prepared into the solution of mass fraction 10-25% with deionized water dissolving, and be adjusted to pH=4-6 with nitric acid, be prepared into metal
Complex salts solution for later use；
B, by silica solution, boric acid, dimethylamine, 2-4:1-2:1-3 is mixed in molar ratio, is diluted to quality with deionized water
Score 30-60%, and ultrasonic vibration (frequency 20-40KHz) 2-5h at 70-90 DEG C, while pH is adjusted to ammonium acetate or acetic acid
It is stand-by to be prepared into silicon boron colloidal sol precursor by=3-7；
C, by the metal complex salting liquid of step a, b preparation and silicon boron colloidal sol precursor, 1-8:1(is preferred by volume
2.8-3.5:1) in the plasma torch (plasma arc) that merging plasma gun sprays；
D, metal complex salting liquid and silicon boron colloidal sol precursor are sprayed on oxygen by the plasma torch that plasma gun sprays
Change the supporting body surfaces such as aluminum honeycomb ceramics or stainless steel plate and carry out reaction in-situ, is prepared into medicine intermediate filtering material.
In present invention c step, metal complex salting liquid and silicon boron colloidal sol precursor prepared by step a, b is by volume
2.8-3.5:1 is placed in the plasma torch (plasma arc) that plasma gun sprays.
Heretofore described plasma gun power parameter are as follows: voltage: 65-80V, electric current: 600-750A select argon gas
Gas source occurs for plasma arc, hydrogen is protective gas；Argon gas, hydrogen flowing quantity are respectively as follows: 45-50L/min and 10-25L/min.
What heretofore described metal complex salting liquid and silicon boron colloidal sol precursor merging plasma gun sprayed etc.
When ionic flame (plasma arc) is interior, metal complex salting liquid is coated on silicon boron colloidal sol precursor surrounding, can after reaction
Continuous iron-nickel alloy network is formed, silicon boron oxygen nitrogen/iron nickel porous metalloceramic (that is: the medicine intermediate filtering being prepared into is improved
Material) intensity and toughness
A kind of preparation facilities of medicine intermediate filtering material is equipped with plasma gun, it is characterised in that plasma gun
Spout front side top be equipped with feeding casing, feeding casing be double-jacket tube, the outer tube of feeding casing and the first peristaltic pump conveying it is soft
The discharge port of pipe is connected, and the inner tube of feeding casing is connected with the discharge port of the second peristaltic pump delivery hose.
Heretofore described plasma gun power parameter are as follows: voltage: 65-80V, electric current: 600-750A select argon gas
Gas source occurs for plasma arc, hydrogen is protective gas；Argon gas, hydrogen flowing quantity are respectively as follows: 45-50L/min and 10-25L/min.
Heretofore described plasma spray gun body is equipped with bracket, and feeding casing is fixedly mounted on bracket.
Heretofore described feeding casing is concentric double-jacket tube, and the discharge port of feeding casing is located at plasma gun spray
Above plasma torch out.The material of feeding casing discharge port outflow is fallen into the plasma torch of plasma gun ejection,
Metal complex salting liquid in material is restored by plasma high-temperature, formation iron-nickel alloy melt, while outer layer sleeve
Silicon boron colloidal sol precursor cracks to form silicon boron oxygen nitrogen ceramic droplet by plasma high-temperature.The wherein iron nickel that high temperature reduction obtains
Alloy-coated is sprayed on the supporting body surfaces such as cellular alumina ceramics or stainless steel plate in silicon boron oxygen nitrogen top ceramic layer,
Accelerate by plasma torch, high-speed impact is laminated to form porous structure.Due to gold in the material of feeding casing discharge port outflow
Belong to complex salts solution to be coated on the outside of silicon boron colloidal sol precursor, keeps metal reduction, melting more thorough, advantageously form continuous iron
Nickel alloy network improves the intensity and toughness of metalloceramic filter body.
The supporter fixed frame for fixed support body is equipped in front of the spout of heretofore described plasma gun.
Preparation facilities of the invention is when in use, first by the metal complex salting liquid of step a, b preparation and silicon boron colloidal sol
It drives body and is respectively implanted in the magazine of the first peristaltic pump and the second peristaltic pump that (feed end of peristaltic pump delivery hose is located at storage
In material container), it opens plasma gun, its spout is made to generate plasma torch, by cellular alumina ceramics or stainless steel plate
Equal supporters are placed in 15-20cm on front side of plasma torch, set the rate of discharge of the first peristaltic pump and the second peristaltic pump as 0.6-
1.5L/min and 0.2-0.5L/min；The silicon boron oxygen nitrogen/iron nickel coating for spraying required thickness on supporter as needed, is made
Silicon boron oxygen nitrogen/iron nickel (silicon boron oxygen nitrogen/Fe of nano-pore structure0.75Ni0.25) porous metalloceramic (that is: medicine intermediate filter material
Material).
Method and process of the invention is simple, high production efficiency, according to the thickness of product, can control the model of pore size filter
It encloses, nano-bacteria and impurity, synthesis high-purity medicine, the excellent performances such as heatproof, pressure resistance, bending strength of product can be removed.This
The apparatus structure of invention is simple, easy to use, high production efficiency.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the preparation facilities of traditional Chinese medicine intermediate filtering material of the present invention.
Fig. 2 is silicon boron oxygen nitrogen/iron nickel (silicon boron oxygen nitrogen/Fe prepared by the present invention0.75Ni0.25) porous metalloceramic scanning electricity
Mirror shape appearance figure.From the figure, it can be seen that uniformly being accumulated by silicon boron oxygen nitrogen/iron nickel particle and being formed pore structure, pore-size distribution is relatively narrow, hole
Diameter < 500 nm.
Specific embodiment
A kind of preparation method of medicine intermediate filtering material, it is characterised in that include the following steps:
A, by ferric nitrate, nickel sulfate, EDTANa2(disodium ethylene diamine tetraacetate), hydrazine hydrate 6-7:1-2.5 in molar ratio:
10-12:7-8 is uniformly mixed, and the solution of mass fraction 10-25% is prepared into deionized water dissolving, and be adjusted to nitric acid
PH=4-6 is prepared into metal complex salt solution for later use；
B, by silica solution, boric acid, dimethylamine, 2-4:1-2:1-3 is mixed in molar ratio, is diluted to quality with deionized water
Score 30-60%, and (frequency 20-40KHz) ultrasonic vibration 2-5h at 70-90 DEG C, while pH is adjusted to ammonium acetate or acetic acid
It is stand-by to be prepared into silicon boron colloidal sol precursor by=3-7；
C, by the metal complex salting liquid of step a, b preparation and silicon boron colloidal sol precursor, 1-8:1(is preferred by volume
2.8-3.5:1) in the plasma torch (plasma arc) that merging plasma gun sprays；The metal complex salting liquid and silicon stated
When the plasma torch (plasma arc) that boron colloidal sol precursor merging plasma gun sprays is interior, metal complex salting liquid cladding
In silicon boron colloidal sol precursor surrounding.
D, metal complex salting liquid and silicon boron colloidal sol precursor are sprayed on oxygen by the plasma torch that plasma gun sprays
Change the supporting body surfaces such as aluminum honeycomb ceramics or stainless steel plate and carry out in-situ reducing reaction, is prepared into medicine intermediate filter material
Material.
Heretofore described plasma gun power parameter are as follows: voltage: 65-80V, electric current: 600-750A select argon gas
Gas source occurs for plasma arc, hydrogen is protective gas；Argon gas, hydrogen flowing quantity are respectively as follows: 45-50L/min and 10-25L/min.
A kind of preparation facilities of medicine intermediate filtering material is equipped with plasma gun 1, plasma gun power parameter
Are as follows: voltage: 65-80V, electric current: 600-750A, selecting argon gas is that gas source occurs for plasma arc, and hydrogen is protective gas；Argon gas,
Hydrogen flowing quantity is respectively as follows: 45-50L/min and 10-25L/min.The spout front side top of plasma gun 1 is equipped with feeding casing,
As can be seen from Figure 1 plasma spray gun body is equipped with bracket, and feeding casing is fixedly mounted on bracket；Feeding casing is concentric
Double-jacket tube, the discharge port of feeding casing be located at plasma gun ejection plasma torch above.The outer tube 7 of feeding casing with
The discharge port of the delivery hose 5 of first peristaltic pump 4 is connected, and the delivery hose of the inner tube 6 of feeding casing and the second peristaltic pump 8 goes out
Material mouth is connected.
The material of feeding casing discharge port outflow is fallen into the plasma torch of plasma gun ejection, the metal in material
Metal salt solution in salting liquid is reduced into iron-nickel alloy and melts.The silicon boron colloidal sol precursor process etc. of outer layer sleeve simultaneously
Gas ions Pintsch process forms silicon boron oxygen nitrogen ceramic droplet, and is sprayed on the supports such as cellular alumina ceramics or stainless steel plate
Body surface face forms silicon boron oxygen nitrogen/iron nickel filter layer.Due to metal complex salting liquid in the material of feeding casing discharge port outflow
It is coated on the outside of silicon boron colloidal sol precursor, keeps metal reduction, melting more thorough, advantageously form continuous iron-nickel alloy network, mention
The intensity and toughness of high metal ceramic filtering body.
The present invention is further improved, and the supporter for fixed support body is equipped in front of the spout of the plasma gun
Fixed frame.The supporters such as cellular alumina ceramics or stainless steel plate can be fixed in front of spout, be carried out the spraying of material
Reaction.
Embodiment 1
A. by ferric nitrate, nickel sulfate, EDTANa2(disodium ethylene diamine tetraacetate), hydrazine hydrate 6:1:10 in molar ratio:
7 uniformly mixing, and it is prepared into deionized water dissolving the solution of mass fraction 10-25%, and use nitre acid for adjusting pH=4, preparation is golden
Belong to salt complex solution for later use.
B. by silica solution, boric acid, dimethylamine, 2:1:1 is mixed in molar ratio, is diluted to mass fraction with deionized water
30%, and the ultrasonic vibration 2h at 70 DEG C, while with ammonium acetate and vinegar acid for adjusting pH=3, it is stand-by to be prepared into silicon boron colloidal sol precursor.
C, the metal salt solution of step a, b preparation, silicon boron colloidal sol are respectively implanted medicine intermediate filter material of the invention
In the magazine 4 of first peristaltic pump of the preparation facilities of material and in the magazine 9 of the second peristaltic pump, peristaltic pump delivery hose
Feed end be connected to the bottom of magazine；The rate of discharge for adjusting the first peristaltic pump and the second peristaltic pump is respectively
0.6L/min and 0.2L；Adjust plasma gun power parameter (voltage: 65V；Electric current: 600A), selection argon gas is plasma arc
Gas source occurs, hydrogen is protective gas.Argon gas, hydrogen flowing quantity are respectively as follows: 45L/min and 10L/min.
D, the supporters such as cellular alumina ceramics or stainless steel plate will be placed in the plasma torch of ion spray gun ejection
Front side, metal complex salting liquid and silicon boron colloidal sol precursor are sprayed on the supports such as cellular alumina ceramics or stainless steel plate
Body surface face carries out reaction in-situ, is prepared into silicon boron oxygen nitrogen/iron nickel porous metalloceramic (that is: medicine intermediate filtering material).
The medicine intermediate filtering material prepared in the present embodiment with a thickness of 400-500 um, measure its pore size filter
It is distributed as 5-10nm.
Embodiment 2
A. by ferric nitrate, nickel sulfate, EDTANa2, 7:1.5:10:7 is uniformly mixed hydrazine hydrate in molar ratio, and spend
Ionized water, which dissolves, is prepared into the solution of mass fraction 10%, and with nitre acid for adjusting pH=4-6, prepares metal complex salting liquid and wait for
With.
B. by silica solution, boric acid, dimethylamine, 3:1.5:2 is mixed in molar ratio, is diluted to mass fraction with deionized water
40%, and the ultrasonic vibration 3h at 80 DEG C, while with ammonium acetate and vinegar acid for adjusting pH=5, it is stand-by to be prepared into silicon boron colloidal sol precursor.
C, the metal salt solution of step a, b preparation, silicon boron colloidal sol are respectively implanted medicine intermediate filter material of the invention
In the magazine 4 of first peristaltic pump of the preparation facilities of material and in the magazine 9 of the second peristaltic pump, peristaltic pump delivery hose
Feed end be located at the bottom of magazine；The rate of discharge for adjusting the first peristaltic pump and the second peristaltic pump is respectively 1L/min
And 0.3L；Adjust plasma gun power parameter (voltage: 75V；Electric current: 650A), selecting argon gas is that gas occurs for plasma arc
Source, hydrogen are protective gas.Argon gas, hydrogen flowing quantity are respectively as follows: 50L/min and 25L/min.
D, the supporters such as cellular alumina ceramics or stainless steel plate will be placed in the plasma torch of ion spray gun ejection
Front side, metal complex salting liquid and silicon boron colloidal sol precursor are sprayed on the supports such as cellular alumina ceramics or stainless steel plate
Body surface face carries out reaction in-situ, is prepared into silicon boron oxygen nitrogen/iron nickel porous metalloceramic (that is: medicine intermediate filtering material).
The medicine intermediate filtering material prepared in the present embodiment with a thickness of 300-400um, measure its pore size filter
It is distributed as 10-100nm.
Embodiment 3
A. by ferric nitrate, nickel sulfate, EDTANa2, hydrazine hydrate 7:2.5:12:8 in molar ratio) uniformly mixing, and spend
Ionized water, which dissolves, is prepared into the solution of mass fraction 25%, and uses nitre acid for adjusting pH=6, preparation metal complex salt solution for later use.
B. by silica solution, boric acid, dimethylamine, 4:2:3 is mixed in molar ratio, is diluted to mass fraction with deionized water
60%, and the ultrasonic vibration 5h at 90 DEG C, while with ammonium acetate and vinegar acid for adjusting pH=7, it is stand-by to be prepared into silicon boron colloidal sol precursor.
C, the metal salt solution of step a, b preparation, silicon boron colloidal sol are respectively implanted medicine intermediate filter material of the invention
In the magazine 4 of first peristaltic pump of the preparation facilities of material and in the magazine 9 of the second peristaltic pump, peristaltic pump delivery hose
Feed end be located at the bottom of magazine；The rate of discharge for adjusting the first peristaltic pump and the second peristaltic pump is respectively 1.5L/
Min and 0.5L；Adjust plasma gun power parameter (voltage: 80V；Electric current: 750A), selecting argon gas is that gas occurs for plasma arc
Source, hydrogen are protective gas.Argon gas, hydrogen flowing quantity are respectively as follows: 50L/min and 25L/min.
D, the supporters such as cellular alumina ceramics or stainless steel plate will be placed in the plasma torch of ion spray gun ejection
Front side, metal complex salting liquid and silicon boron colloidal sol precursor are sprayed on the supports such as cellular alumina ceramics or stainless steel plate
Body surface face carries out reaction in-situ, is prepared into silicon boron oxygen nitrogen/iron nickel porous metalloceramic (that is: medicine intermediate filtering material).
The medicine intermediate filtering material prepared in the present embodiment with a thickness of 100-300um, measure its pore size filter
It is distributed as 100-250nm.
The pore size filter and its thickness of medicine intermediate filtering material prepared by the present invention are in inverse ratio, can be prepared as needed
The filtering material of different pore size filters within the scope of 10 nm-1um out；It can be provided for medicine intermediate synthesis industry different
Filtering accuracy selection.
Method and process of the invention is simple, high production efficiency, according to the thickness of product, can control the model of pore size filter
It encloses, nano-bacteria and impurity, synthesis high-purity medicine, the excellent performances such as heatproof, pressure resistance, bending strength of product can be removed.This
The apparatus structure of invention is simple, easy to use, high production efficiency.
Claims (4)
1. a kind of preparation method of medicine intermediate filtering material, it is characterised in that include the following steps:
A, by ferric nitrate, nickel sulfate, EDTANa2, hydrazine hydrate, 6-7:1-2.5:10-12:7-8 is uniformly mixed in molar ratio, and
It is prepared into the solution of mass fraction 10-25% with deionized water dissolving, and is adjusted to pH=4-6 with nitric acid, is prepared into metal complex
Object salting liquid is stand-by；
B, by silica solution, boric acid, dimethylamine, 2-4:1-2:1-3 is mixed in molar ratio, is diluted to mass fraction with deionized water
30-60%, and the ultrasonic vibration 2-5h at 70-90 DEG C, while it being adjusted to pH=3-7 with ammonium acetate or acetic acid, it is molten to be prepared into silicon boron
Glue precursor is stand-by；
C, by the metal complex salting liquid of step a, b preparation and silicon boron colloidal sol precursor, 1-8:1 is placed in plasma by volume
In the plasma torch that spray gun sprays；
D, metal complex salting liquid and silicon boron colloidal sol precursor are sprayed on aluminium oxide by the plasma torch that plasma gun sprays
The supporting body surfaces such as ceramic honey comb or stainless steel plate carry out reaction in-situ, are prepared into medicine intermediate filtering material.
2. the preparation method of medicine intermediate filtering material according to claim 1, it is characterised in that in c step, will walk
2.8-3.5:1 is placed in plasma gun spray to the metal complex salting liquid and silicon boron colloidal sol precursor of rapid a, b preparation by volume
In plasma torch out.
3. the preparation method of medicine intermediate filtering material according to claim 1 or 2, it is characterised in that it is described it is equal from
Sub- spray gun power parameter are as follows: voltage: 65-80V, electric current: 600-750A, selecting argon gas is that gas source occurs for plasma arc, and hydrogen is
Protective gas；Argon gas, hydrogen flowing quantity are respectively as follows: 45-50L/min and 10-25L/min.
4. the preparation method of medicine intermediate filtering material according to claim 3, it is characterised in that the metal network
When in the plasma torch that adduct salt solution and silicon boron colloidal sol precursor merging plasma gun spray, metal complex salting liquid
It is coated on silicon boron colloidal sol precursor surrounding.
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| CN201710021627.9A CN106582116B (en) | 2017-01-12 | 2017-01-12 | A kind of preparation method and device of medicine intermediate filtering material |
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2017
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| CN1644564A (en) * | 2004-12-22 | 2005-07-27 | 哈尔滨工业大学 | SiALONC ceramic with hydrogen silicone oil and Al powder and production thereof |
| CN101104518A (en) * | 2007-08-24 | 2008-01-16 | 哈尔滨工业大学 | Process for preparing nano SiBON ceramic powder |
| CN201670734U (en) * | 2009-03-03 | 2010-12-15 | 简临君 | Spraying device for preparing nano-porous tin oxide film |
| CN104195499A (en) * | 2014-09-11 | 2014-12-10 | 扬州大学 | Method for preparing coating with micro-nano composite structure through liquid plasma spraying |
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| Title |
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