CN112552776A - Hard alloy sintering anti-sticking coating and preparation method and application thereof - Google Patents
Hard alloy sintering anti-sticking coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN112552776A CN112552776A CN202011301501.5A CN202011301501A CN112552776A CN 112552776 A CN112552776 A CN 112552776A CN 202011301501 A CN202011301501 A CN 202011301501A CN 112552776 A CN112552776 A CN 112552776A
- Authority
- CN
- China
- Prior art keywords
- parts
- sticking coating
- coating
- agent
- sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000956 alloy Substances 0.000 description 91
- 229910045601 alloy Inorganic materials 0.000 description 90
- 238000000576 coating method Methods 0.000 description 70
- 239000011248 coating agent Substances 0.000 description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 60
- 229910002804 graphite Inorganic materials 0.000 description 54
- 239000010439 graphite Substances 0.000 description 54
- 238000005245 sintering Methods 0.000 description 47
- 239000007787 solid Substances 0.000 description 43
- 239000007788 liquid Substances 0.000 description 41
- 239000000843 powder Substances 0.000 description 37
- 239000000047 product Substances 0.000 description 37
- 239000000853 adhesive Substances 0.000 description 35
- 230000001070 adhesive effect Effects 0.000 description 35
- 238000002955 isolation Methods 0.000 description 30
- 238000000498 ball milling Methods 0.000 description 24
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 22
- 239000011247 coating layer Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 229920001223 polyethylene glycol Polymers 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 229910000420 cerium oxide Inorganic materials 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 229920000136 polysorbate Polymers 0.000 description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 description 7
- 239000002518 antifoaming agent Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 6
- 229920000053 polysorbate 80 Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- -1 Polydimethylsiloxane Polymers 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 229910000531 Co alloy Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- RFRMMZAKBNXNHE-UHFFFAOYSA-N 6-[4,6-dihydroxy-5-(2-hydroxyethoxy)-2-(hydroxymethyl)oxan-3-yl]oxy-2-(hydroxymethyl)-5-(2-hydroxypropoxy)oxane-3,4-diol Chemical compound CC(O)COC1C(O)C(O)C(CO)OC1OC1C(O)C(OCCO)C(O)OC1CO RFRMMZAKBNXNHE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09D161/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a hard alloy sintering anti-sticking coating and a preparation method and application thereof, wherein the anti-sticking coating is formed by mixing solid isolation powder and a liquid adhesive, and the solid isolation powder comprises the following components in parts by weight: 22-40 parts of zirconium oxide, 5-8 parts of cerium oxide, 3-6 parts of magnesium oxide, 13-26 parts of flake graphite and 14-27 parts of fine carbon black; the liquid adhesive comprises the following components in parts by weight: 80-120 parts of water-soluble modified phenolic resin, 1.0-3.0 parts of thickening agent, 3-6 parts of dispersing agent, 4-8 parts of active agent, 1-5 parts of curing agent, 0.5-1.0 part of defoaming agent and 80-120 parts of diluent; the mass ratio of the solid isolation powder to the liquid adhesive is 1: (2.0-3.0). The coating has high bonding strength and hardness after being coated, and is not easy to fall off and fall off during alloy product placement and transportation and charging; the paint still keeps higher hardness and bonding strength after sintering, and alloy carburization does not occur.
Description
Technical Field
The invention relates to the technical field of metal ceramic and hard alloy manufacturing, in particular to a hard alloy sintering anti-sticking coating and a preparation method and application thereof.
Background
Sintering is one of the important processes in the production of cemented carbide, and the anti-sticking coating on the graphite boat or graphite plate is an important factor influencing the quality of cemented carbide products. At present, the following hard alloy sintering anti-sticking coatings are mainly used in China.
1: plasma sprayed zirconia and rare earth stabilizer coating
When the numerical control blade, the superfine crystal grain hard alloy extrusion bar and the multi-component alloy material are sintered, a stable atmosphere environment needs to be kept in a vacuum-pressure furnace during sintering, the interference of a coating layer on the quality of a hard alloy product is reduced, and metal oxides such as aluminum oxide diffuse on the surface of the alloy, and a plasma spraying method is generally adopted to prepare the sintering anti-sticking coating.
The coating prepared by the method has the advantages that: the spraying layer does not contain PEG, Tween, cellulose and other organic matters, and the interference of carbon, aluminum and sulfur atmosphere on the hard alloy is eliminated in the sintering process of the carbon black and the flake graphite. The performance of the sintered product is not only stable, but also the performance is kept at a high level. The melting point of the zirconium oxide is 2800 ℃, the high-temperature performance is very stable, and the zirconium oxide component is not detected on the surface of the sintered hard alloy in the energy spectrum analysis of the surface of the sintered hard alloy.
The disadvantages are that: the processing cost is high, 4000-6000 yuan is needed per square meter, and a common hard alloy manufacturer cannot bear the high cost of thermal spraying. In addition, when high-cobalt hard alloy and alloy products with large single weight are sintered, the contact surfaces of the hard alloy and the graphite plate are bonded together due to the precipitation of liquid-phase cobalt, so that the zirconia coating is damaged, and the service life of the zirconia coating is seriously shortened. The coating plate manufactured by adopting thermal spraying of zirconia needs to be taken down one piece of alloy product after being sintered out of a furnace, which is time-consuming and labor-consuming, and the method is not suitable for sintering common hard alloy products.
2: the adhesive adopts PEG, Tween and deionized water, and the solid isolating layer adopts the coating of alumina, fine carbon black and coarse carbon black
Most of domestic hard alloy manufacturers always adopt the anti-sticking coating, but because the viscosity of the adhesives PEG and Tween in the anti-sticking coating is low, a large amount of PEG and Tween have to be added in order to improve the viscosity strength of the anti-sticking coating, so that the pollution atmosphere in a furnace is improved, and the quality of the alloy is influenced.
Before sintering, the anti-sticking coating is easy to fall off in alloy product placement and transportation or furnace charging; after sintering, the anti-sticking coating is loose, the coating and the alloy are easily mixed together, and troubles are caused to the cleaning and finishing of alloy products. When the high cobalt alloy is sintered, the coating layer needs to be brushed for 2 times, or anti-sticking paper is added; excessive organic matters volatilize in the sintering process, so that the atmosphere in the furnace is polluted, and the stability of alloy products and the quality of the alloy are influenced. When sintering larger alloy products or high cobalt alloy, the graphite plate is easy to contact, and the products are carburized. The paint has low liquid viscosity, poor capability of suspending solid isolating layer, uneven distribution of solid powder in the paint, uneven painting of the paint layer, short storage time and easy drying into blocks.
3: the adhesive is water soluble cellulose, PEG, Tween and deionized water, and the solid isolating layer is made of paint containing alumina, fine carbon black and coarse carbon black
The viscosity of the anti-sticking coating is higher than that of PEG, so that the problem that the coating falls off when an alloy product is placed and transported before the coating is sintered is solved due to the increase of the viscosity; after sintering, the problem of mixing the coating with the alloy article is also reduced. However, it has disadvantages in that: (1) cellulose, PEG and Tween are all organic matters, the organic matters in the coating layer are completely volatilized after high-temperature sintering, and the hardness and the strength of the coating layer are lost and are still not ideal; (2) the large alloy product and the high cobalt alloy product are easy to contact with the graphite plate, and the alloy is carburized; (3) performing energy spectrum analysis on the surface of the sintered hard alloy, wherein the alloy contains 20-30% of aluminum element, and the source of the aluminum element is caused by aluminum oxide added in the solid isolating layer; this is absolutely intolerable for sintering high-quality numerically controlled blades, bars.
Disclosure of Invention
The invention mainly aims to provide a hard alloy sintering anti-sticking coating and a preparation method and application thereof, the anti-sticking coating has enough bonding strength and hardness after being coated, and a coating layer is not easy to fall off and fall off in the processes of placing hard alloy products on graphite boats and plates and transporting and charging; the sintered coating layer can still keep higher hardness and bonding strength, and the condition of alloy carburization can not occur.
In order to achieve the above object, according to one aspect of the present invention, there is provided a cemented carbide sintered release coating material, which is formed by mixing a solid barrier powder and a liquid binder, the solid barrier powder comprising, in parts by weight: 22-40 parts of zirconium oxide, 5-8 parts of cerium oxide, 3-6 parts of magnesium oxide, 13-26 parts of flake graphite and 14-27 parts of fine carbon black; the liquid adhesive comprises the following components in parts by weight: 80-120 parts of water-soluble modified phenolic resin, 1.0-3.0 parts of thickening agent, 3-6 parts of dispersing agent, 4-8 parts of active agent, 1-5 parts of curing agent, 0.5-1.0 part of defoaming agent and 80-120 parts of diluent; the mass ratio of the solid isolation powder to the liquid adhesive is 1: (2.0-3.0); the water-soluble modified phenolic resin is modified by introducing maleic anhydride; the diluent is deionized water or a mixture of ethanol and deionized water.
According to the invention, the water-soluble modified phenolic resin is added into the formula of the anti-sticking coating, the water-soluble modified phenolic resin has high viscosity, high temperature resistance and good stability, the heat resistance and the bonding strength of the anti-sticking coating can be improved, the anti-sticking coating also has very high hardness and strength after being heated at high temperature, and the high carbon residue rate is realized at high temperature, so that a three-dimensional carbon network structure is formed, the integrity and the size stability of the resin are maintained, and the high-temperature performance, the stability, the hardness and the strength of the anti-sticking coating can be improved. The characteristic of the high carbon residue of the water-soluble modified phenolic resin is that the bonding shear strength of the water-soluble modified phenolic resin with a graphite boat and a graphite plate is still 8-15 MPa even at 1500-2500 ℃.
The invention adopts the water-soluble modified phenolic resin as the main adhesive, reduces the dosage of PEG, Tween and the like, reduces the polluted atmosphere, and simultaneously ensures that the sintered coating still has high hardness and strength; the water-soluble modified phenolic resin can be compatible with various organic matters and inorganic matters, can be slowly decomposed at high temperature to generate hydrogen and hydrocarbon, has no adverse effect on hard alloy products, and can also prevent the hard alloy from decarbonizing.
At high temperatures (e.g., above 1500 ℃), the water-soluble modified phenolic resin is brittle and, in addition, expands significantly in volume, causing cracks that can damage the sintered release coating. The invention adds cerium oxide and magnesium oxide with lower melting points, wherein the cerium oxide and the magnesium oxide are in a molten state at high temperature, thereby increasing the bonding strength of the phenolic resin with the graphite boat and the graphite plate and greatly reducing the cracks of the water-soluble modified phenolic resin.
Due to the characteristic that the water-soluble modified phenolic resin is compatible with various inorganic matters and organic matters, the phenolic resin quickly penetrates into the loose graphite boat and board at a lower temperature. At high temperature, the low melting point molten oxide can also permeate into the interior of graphite boat and plate to increase adhesive strength, and can react with residual carbon of water-soluble modified phenolic resin to be fused into one body, and the low melting point oxide can be adsorbed on the external surface of the residual carbon to produce fine composite. Through the synergistic effect of the water-soluble modified phenolic resin, cerium oxide and magnesium oxide, the expansion of the phenolic resin is retarded, the cracks of the resin are reduced, and the bonding strength of the coating is increased.
According to the invention, the high-temperature-resistant zirconium oxide is adopted to play a role in isolating the graphite boat from the hard alloy, and the crystalline flake graphite and the fine carbon black are adopted to play a role in regulating alloy decarburization; the cerium oxide and the magnesium oxide with lower melting points are added, the zirconium oxide with high melting point is matched with the cerium oxide and the magnesium oxide with low melting point for use, the cerium oxide and the magnesium oxide with low melting point are in a molten state at the sintering temperature while the zirconium oxide with high melting point ensures the sintering stability of the alloy, the solid-phase bonding effect is realized, and the bonding strength of the anti-sticking coating with the graphite boat and the graphite plate is increased. By adding the thickening agent, the dispersing agent, the active agent, the curing agent, the defoaming agent and the like, the anti-sticking coating has good leveling property and lubricity and thickness controllability of a coating layer.
According to the invention, the materials are combined according to a specific proportion, so that the surface of the coating layer of the anti-sticking coating before sintering is smooth and good in leveling property, and has enough bonding strength and hardness, and the coating layer is not easy to fall off and block in the processes of placing a hard alloy product on a graphite boat and transporting and charging; after the hard alloy is sintered, the coating layer can still keep higher hardness and bonding strength, and the condition of alloy carburization cannot occur. The sintering frequency of the anti-sticking coating is more than two times, while the prior sintered anti-sticking coating can be sintered only once and needs to be coated with the coating again.
Further, the thickening agent is one or more of hydroxypropyl methyl cellulose, hydroxyethyl cellulose and methyl cellulose. From the viewpoint of the viscosity of the adhesive, hydroxypropylmethylcellulose having a high viscosity is preferably used.
Further, the dispersant is one or more of polyethylene glycol, polyacrylic acid and hydroxylamine. The less expensive polyethylene glycols are preferred.
Further, the active agent is one or more of tween-80, hard alcohol polyoxyethylene ether, polyvalent carboxylic acid and water-soluble cellulose. Preferably, Tween-80 is used.
Further, the curing agent is one or more of urotropin and isocyanate. Urotropin is preferably used.
Further, the defoaming agent is one or more of a silicone defoaming agent and a polyether defoaming agent. Polydimethylsiloxane is preferably used.
According to another aspect of the invention, a preparation method of the cemented carbide sintered anti-sticking coating is provided, which comprises the following steps:
mixing zirconium oxide, cerium oxide, magnesium oxide, crystalline flake graphite and fine carbon black according to a ratio to obtain solid isolation powder, adding the solid isolation powder into a ball milling barrel, and putting grinding balls into the ball milling barrel;
adding water-soluble modified phenolic resin, a thickening agent, a dispersing agent, an active agent, a curing agent and a defoaming agent into a container according to a ratio, then adding a diluent according to a ratio, stirring until solid substances are completely dissolved to obtain a liquid adhesive, pouring the liquid adhesive into a ball milling barrel, ball milling the liquid adhesive and solid isolator powder for 12-24 hours, taking the liquid adhesive out of the barrel, and sieving to obtain the anti-sticking coating.
According to another aspect of the invention, the application of the anti-sticking coating or the anti-sticking coating obtained by the preparation method in a graphite plate or graphite boat for sintering hard alloy is further provided, the surface of the graphite plate or graphite boat for sintering hard alloy is cleaned, the anti-sticking coating is uniformly coated or sprayed on the graphite plate or graphite boat, and the coating is dried and cured.
Compared with the prior art, the invention has the beneficial effects that:
the anti-sticking coating comprises solid isolation powder, namely solid matters which play an isolation role between the hard alloy and the graphite boat and plate. The solid isolation powder can prevent the high-temperature chemical reaction of the hard alloy and the graphite boat and the graphite plate, and ensure the normal alloy structure of the sintered and combined gold product.
The water-soluble modified phenolic resin in the liquid adhesive is a high-temperature adhesive, so that the high-temperature performance, stability, hardness and strength of the anti-sticking coating are improved; meanwhile, cerium oxide and magnesium oxide with lower melting points are added, so that the activity of the anti-sticking coating is improved, the hardness and the bonding strength of the surface of the coating layer are increased, and the stability of the hard alloy sintering anti-sticking coating is improved.
The anti-sticking coating disclosed by the invention has good surface lubrication and leveling property of a coating layer before sintering; has sufficient adhesive strength and hardness. The coating layer can not fall off and fall off in the processes of placing hard alloy products on the graphite boat and the graphite plate, transporting and charging. After the hard alloy is sintered, the coating layer can still keep higher hardness and bonding strength, and carburization can be avoided. The preparation method of the anti-sticking coating is simple to operate and low in cost.
Drawings
FIG. 1 is a photograph of a graphite sheet coated with a release coating of the present invention.
Fig. 2 is a photograph of a graphite sheet coated with an anti-sticking coating dried in a drying oven.
Fig. 3 is a photograph of an alloy article placed on a graphite plate.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the hard alloy sintering anti-sticking coating is formed by mixing solid isolation powder and a liquid adhesive. Wherein, the solid isolation powder consists of the following materials:
the liquid adhesive consists of the following materials:
the preparation method of the hard alloy sintering anti-sticking coating comprises the following steps:
mixing the materials in the solid isolation powder in proportion to obtain solid isolation powder, and putting the solid isolation powder into a ball milling barrel; putting hard alloy grinding balls into a ball milling barrel, wherein the mass ratio of the balls to the materials is 3: 1;
firstly, adding water-soluble modified phenolic resin liquid, hydroxypropyl methylcellulose powder, tween-80 liquid, sheet PEG, granular urotropine and polydimethylsiloxane liquid into a container in proportion; and then adding diluent ethanol and deionized water in proportion, uniformly stirring, standing for several hours, dissolving all solid substances to obtain a liquid adhesive, pouring the liquid adhesive into a ball milling barrel, ball milling the liquid adhesive and the solid isolation powder together for 12-24 hours, taking the mixture out of the barrel after the ball milling is finished, and sieving the mixture through a 100-mesh sieve to obtain the anti-sticking coating.
The surface of a graphite plate for sintering hard alloy is cleaned, the anti-sticking coating of the embodiment is uniformly coated on the graphite plate (see figure 1), and the coated graphite plate is dried in an electric oven at 150 ℃ (see figure 2) for 120 min. Then placing YG8 and YG10 alloy products on a graphite plate (see figure 3), removing forming agents in a vacuum low-pressure furnace, and obtaining the alloy products through partial pressure sintering, pressure sintering and sintering (the junction temperature is 1450 ℃) and temperature reduction (the total time is about 24 hours). And after the product is taken out of the furnace, the color of the alloy product is normal, and the anti-sticking coating layer on the graphite plate does not fall off. Through detection, the cobalt magnetic value, the coercive force value, the density value and the hardness value of the alloy product are normal. Through metallographic analysis, the alloy product has two normal structures, and the alloy performance meets the standard.
Example 2:
the hard alloy sintering anti-sticking coating provided by the embodiment of the invention comprises solid isolation powder and a liquid adhesive, wherein the solid isolation powder consists of the following materials:
the liquid adhesive consists of the following materials:
the preparation method of the hard alloy sintering anti-sticking coating comprises the following steps:
mixing the materials in the solid isolation powder in proportion to obtain solid isolation powder, and putting the solid isolation powder into a ball milling barrel; putting hard alloy grinding balls into a ball milling barrel, wherein the mass ratio of the balls to the materials is 3: 1;
firstly, adding water-soluble modified phenolic resin liquid, hydroxypropyl methylcellulose powder, tween-80 liquid, sheet PEG, granular urotropine and polydimethylsiloxane liquid into a container in proportion; and then adding diluent ethanol and deionized water in proportion, uniformly stirring, standing for several hours, dissolving all solid substances to obtain a liquid adhesive, pouring the liquid adhesive into a ball milling barrel, ball milling the liquid adhesive and the solid isolation powder together for 12-24 hours, taking the mixture out of the barrel after the ball milling is finished, and sieving the mixture through a 100-mesh sieve to obtain the anti-sticking coating.
Cleaning the surface of a graphite boat for sintering hard alloy, uniformly coating the anti-sticking coating on the graphite boat, and drying the coated graphite boat in an electric oven at 150 ℃ for 120 min; then placing YG9C and YG12 alloy products on a graphite boat, removing forming agents in a vacuum low-pressure furnace, and performing partial pressure sintering, pressure sintering (sintering temperature 1450 ℃) and temperature reduction (the total time is about 24 hours) to obtain the alloy products. After the product is taken out of the furnace, the color of the alloy product is normal, and the anti-sticking coating layer on the graphite boat does not fall off. Through detection, the cobalt magnetic value, the coercive force value, the density value and the hardness value of the alloy are normal. Through metallographic analysis, the alloy has two normal structures, and the alloy performance meets the standard.
Example 3:
the hard alloy sintering anti-sticking coating provided by the embodiment of the invention comprises solid isolation powder and a liquid adhesive, wherein the solid isolation powder consists of the following materials:
the liquid adhesive consists of the following materials:
the preparation method of the hard alloy sintering anti-sticking coating comprises the following steps:
mixing the materials in the solid isolation powder in proportion to obtain solid isolation powder, and putting the solid isolation powder into a ball milling barrel; putting hard alloy grinding balls into a ball milling barrel, wherein the mass ratio of the balls to the materials is 3: 1;
firstly, adding water-soluble modified phenolic resin liquid, hydroxypropyl methylcellulose powder, Tween 80 liquid, sheet PEG, granular urotropine and polydimethylsiloxane liquid into a container in proportion; and then adding diluent ethanol and deionized water in proportion, uniformly stirring, standing for several hours, dissolving all solid substances to obtain a liquid adhesive, pouring the liquid adhesive into a ball milling barrel, ball milling the liquid adhesive and the solid isolation powder together for 12-24 hours, taking the mixture out of the barrel after the ball milling is finished, and sieving the mixture through a 100-mesh sieve to obtain the anti-sticking coating.
The surface of a graphite boat for sintering the hard alloy is cleaned, the anti-sticking coating of the embodiment is uniformly coated on the graphite boat, and then the graphite boat coated with the anti-sticking coating is obtained after drying and curing for 36 hours at room temperature. YG12C and YG16C alloy products were placed on a graphite boat, the forming agent was removed in a vacuum low pressure furnace, and the alloy products were obtained by partial pressure sintering, pressure sintering (sintering temperature 1450 ℃ C.) and temperature reduction (total 24 hours above). After the product is taken out of the furnace, the color of the alloy product is normal, and the anti-sticking coating layer on the graphite boat does not fall off. Through detection, the cobalt magnetic value, the coercive force value, the density value and the hardness value of the alloy are normal. Through metallographic analysis, the alloy has two normal structures, and the alloy performance meets the standard.
Example 4:
the hard alloy sintering anti-sticking coating provided by the embodiment of the invention comprises solid isolation powder and a liquid adhesive, wherein the solid isolation powder consists of the following materials:
the liquid adhesive consists of the following materials:
the preparation method of the hard alloy sintering anti-sticking coating comprises the following steps:
mixing the materials in the solid isolation powder in proportion to obtain solid isolation powder, and putting the solid isolation powder into a ball milling barrel; putting hard alloy grinding balls into a ball milling barrel, wherein the mass ratio of the balls to the materials is 3: 1;
firstly, adding water-soluble modified phenolic resin liquid, hydroxypropyl methylcellulose powder, tween-80 liquid, sheet PEG, granular urotropine and polydimethylsiloxane liquid into a container in proportion; and then adding diluent ethanol and deionized water in proportion, uniformly stirring, standing for several hours, dissolving all solid substances to obtain a liquid adhesive, pouring the liquid adhesive into a ball milling barrel, ball milling the liquid adhesive and the solid isolation powder together for 12-24 hours, taking the mixture out of the barrel after the ball milling is finished, and sieving the mixture through a 100-mesh sieve to obtain the anti-sticking coating.
The surface of a graphite boat for sintering the hard alloy is cleaned, the anti-sticking coating of the embodiment is uniformly coated on the graphite boat, and then the graphite boat coated with the anti-sticking coating is obtained after drying and curing for 36 hours at room temperature. Placing YG12C and YG16C alloy products on a graphite boat, removing forming agent in a vacuum low-pressure furnace, and performing partial pressure sintering, pressure sintering at 1450 ℃, heat preservation for 60min and temperature reduction (the total time is about 24 h) to obtain the alloy products. After the product is taken out of the furnace, the color of the alloy product is normal, and the anti-sticking coating layer on the graphite boat does not fall off. Through detection, the cobalt magnetic value, the coercive force value, the density value and the hardness value of the alloy are normal. Through metallographic analysis, the alloy has two normal structures, and the alloy performance meets the standard.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The hard alloy sintering anti-sticking coating is characterized by being formed by mixing solid isolation powder and a liquid adhesive, wherein the solid isolation powder comprises the following components in parts by weight: 22-40 parts of zirconium oxide, 5-8 parts of cerium oxide, 3-6 parts of magnesium oxide, 13-26 parts of flake graphite and 14-27 parts of fine carbon black; the liquid adhesive comprises the following components in parts by weight: 80-120 parts of water-soluble modified phenolic resin, 1.0-3.0 parts of thickening agent, 3-6 parts of dispersing agent, 4-8 parts of active agent, 1-5 parts of curing agent, 0.5-1.0 part of defoaming agent and 80-120 parts of diluent; the mass ratio of the solid isolation powder to the liquid adhesive is 1: (2.0-3.0); the water-soluble modified phenolic resin is modified by introducing maleic anhydride; the diluent is deionized water or a mixture of ethanol and deionized water.
2. The cemented carbide sintered release coating according to claim 1, wherein the thickener is one or more of hydroxypropyl methylcellulose, hydroxyethyl cellulose, methyl cellulose.
3. The cemented carbide sintered anti-sticking coating of claim 1, wherein the dispersant is one or more of polyethylene glycol, polyacrylic acid, hydroxylamine.
4. The cemented carbide sintering anti-sticking coating as claimed in claim 1, wherein the active agent is one or more of tween-80, hard alcohol polyoxyethylene ether, polyvalent carboxylic acid, and water-soluble cellulose.
5. The cemented carbide sintered release coating according to claim 1, wherein the curing agent is one or more of urotropine and isocyanate.
6. The cemented carbide sintering anti-sticking coating according to claim 1, wherein the defoaming agent is one or more of a silicone defoaming agent and a polyether defoaming agent.
7. The method for preparing the cemented carbide sintered anti-sticking coating as claimed in any one of claims 1 to 6, comprising the steps of:
mixing zirconium oxide, cerium oxide, magnesium oxide, crystalline flake graphite and fine carbon black according to a ratio to obtain solid isolation powder, adding the solid isolation powder into a ball milling barrel, and putting grinding balls into the ball milling barrel;
adding water-soluble modified phenolic resin, a thickening agent, a dispersing agent, an active agent, a curing agent and a defoaming agent into a container according to a ratio, then adding a diluent according to a ratio, stirring until solid substances are completely dissolved to obtain a liquid adhesive, pouring the liquid adhesive into a ball milling barrel, ball milling the liquid adhesive and solid isolation powder for 12-24 h, taking out of the barrel, and sieving to obtain the anti-sticking coating.
8. The application of the anti-sticking coating as defined in any one of claims 1 to 6 or the anti-sticking coating obtained by the preparation method as defined in claim 7 in a graphite plate or graphite boat for sintering hard alloy, which is characterized in that the surface of the graphite plate or graphite boat for sintering hard alloy is cleaned, the anti-sticking coating is uniformly coated or sprayed on the graphite plate or graphite boat, and the coating is dried and cured.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011301501.5A CN112552776A (en) | 2020-11-19 | 2020-11-19 | Hard alloy sintering anti-sticking coating and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011301501.5A CN112552776A (en) | 2020-11-19 | 2020-11-19 | Hard alloy sintering anti-sticking coating and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112552776A true CN112552776A (en) | 2021-03-26 |
Family
ID=75043947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011301501.5A Pending CN112552776A (en) | 2020-11-19 | 2020-11-19 | Hard alloy sintering anti-sticking coating and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112552776A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114940837A (en) * | 2022-06-17 | 2022-08-26 | 武汉钢铁有限公司 | Coating composite material and preparation method thereof, coating, crystallizer copper plate and surface treatment method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277019A (en) * | 2011-07-20 | 2011-12-14 | 中南大学 | High-temperature anti-adhesive coating for producing hard alloy and preparation method thereof |
| EP2623635A1 (en) * | 2010-09-29 | 2013-08-07 | JFE Steel Corporation | Production method for galvanized steel sheet and galvanized steel sheet |
| CN103788808A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | High temperature resistant anticorrosive coating, and making method of coat based on it |
-
2020
- 2020-11-19 CN CN202011301501.5A patent/CN112552776A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2623635A1 (en) * | 2010-09-29 | 2013-08-07 | JFE Steel Corporation | Production method for galvanized steel sheet and galvanized steel sheet |
| CN102277019A (en) * | 2011-07-20 | 2011-12-14 | 中南大学 | High-temperature anti-adhesive coating for producing hard alloy and preparation method thereof |
| CN103788808A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | High temperature resistant anticorrosive coating, and making method of coat based on it |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114940837A (en) * | 2022-06-17 | 2022-08-26 | 武汉钢铁有限公司 | Coating composite material and preparation method thereof, coating, crystallizer copper plate and surface treatment method thereof |
| CN114940837B (en) * | 2022-06-17 | 2023-03-24 | 武汉钢铁有限公司 | Coating composite material and preparation method thereof, coating, crystallizer copper plate and surface treatment method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101503297A (en) | Tape casting preparation for gradient material in rotating magnetic field | |
| CN109467457B (en) | Composition, high-emissivity antioxidant coating prepared from composition and used for porous carbon fiber heat-insulating material surface and preparation method of high-emissivity antioxidant coating | |
| CN115849885B (en) | High-purity high-strength alumina ceramic substrate and preparation method thereof | |
| CN101224488A (en) | A kind of graphite coating for titanium and titanium alloy casting | |
| CN108642431B (en) | Cermet coating/powder resistant to corrosion by molten zinc, method for making the same, and sinking roll | |
| CN108299001B (en) | Silicon-based ceramic core forming method | |
| CN116332630B (en) | Preparation method of alumina ceramic for semiconductor equipment | |
| CN113912395A (en) | Anti-static ceramic and preparation method thereof | |
| CN112552776A (en) | Hard alloy sintering anti-sticking coating and preparation method and application thereof | |
| CN108530956B (en) | Hard alloy sintering anti-sticking coating bonded by organic and inorganic composite adhesives and preparation and use methods thereof | |
| CN101532775B (en) | Crucible with ZrO2 etching resistant coating and method for producing ZrO2 etching resistant coating using slip casting moulding technique | |
| CN110483080B (en) | Silicon carbide powder and preparation method thereof | |
| CN113073302B (en) | ZMO target material and preparation method thereof | |
| US5273699A (en) | Moisture-resistant aluminum nitride powder and methods of making and using | |
| CN111004025A (en) | Component of slag adhering resisting coating for ladle lining and preparation method thereof | |
| CN112457738A (en) | Hard alloy sintering anti-sticking coating adopting alcohol-soluble boron modified phenolic resin and preparation method and application thereof | |
| CN115365452B (en) | A low-cost, fast-drying water-based casting coating and its preparation method | |
| CN116655383A (en) | Porous boron carbide ceramic material for neutron shielding material and preparation method thereof | |
| CN113174615B (en) | Metal ceramic material for aluminum electrolysis inert anode and preparation method thereof | |
| CN116462516A (en) | A kind of silicon nitride ceramic and preparation method thereof | |
| CN108585832A (en) | The preparation method of tin indium oxide target material | |
| CN106673661A (en) | Thick-plate silicon carbide ceramic material and preparation method and application thereof | |
| CN109722069B (en) | Environment-friendly high-adhesion hard alloy anti-sticking coating and preparation method and application thereof | |
| CN114411085A (en) | Preparation method of dense thick thermal barrier coating | |
| CN109251020B (en) | High-density, non-complex phase and high-purity quartz ceramic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210326 |