CN117680622A - Chromite type shell and preparation method thereof - Google Patents
Chromite type shell and preparation method thereof Download PDFInfo
- Publication number
- CN117680622A CN117680622A CN202410005601.5A CN202410005601A CN117680622A CN 117680622 A CN117680622 A CN 117680622A CN 202410005601 A CN202410005601 A CN 202410005601A CN 117680622 A CN117680622 A CN 117680622A
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- Prior art keywords
- layer
- chromite
- slurry
- preparing
- sand
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010410 layer Substances 0.000 claims abstract description 178
- 239000002002 slurry Substances 0.000 claims abstract description 113
- 239000004576 sand Substances 0.000 claims abstract description 74
- 230000007704 transition Effects 0.000 claims abstract description 65
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 57
- 239000002344 surface layer Substances 0.000 claims abstract description 48
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052863 mullite Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 10
- 229910052845 zircon Inorganic materials 0.000 claims description 7
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005266 casting Methods 0.000 abstract description 16
- 238000007670 refining Methods 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000005058 metal casting Methods 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000004513 sizing Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 65
- 239000000463 material Substances 0.000 description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005495 investment casting Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C13/00—Moulding machines for making moulds or cores of particular shapes
- B22C13/08—Moulding machines for making moulds or cores of particular shapes for shell moulds or shell cores
- B22C13/085—Moulding machines for making moulds or cores of particular shapes for shell moulds or shell cores by investing a lost pattern
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
- B22C9/04—Use of lost patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Mold Materials And Core Materials (AREA)
Abstract
The invention belongs to the technical field of metal casting, and particularly discloses a chromite shell and a preparation method thereof. The preparation method of the chromite mould shell comprises the steps of firstly preparing a wax mould; preparing a surface layer on a wax mould by using surface layer sizing agent; preparing a transition layer on the wax mould with the surface layer by using the transition layer slurry; then preparing a reinforcing layer on the wax mould with the transition layer by using reinforcing layer slurry to obtain the wax mould with the reinforcing layer; finally dewaxing and roasting to obtain the chromite shell, wherein a layer of chromite sand exists between every two adjacent layers of reinforcing layer slurry and the outer layer of the outermost reinforcing layer slurry. The number of layers of the reinforcing layer slurry and the chromite sand in the reinforcing layer disclosed by the invention is less than 3, the obtained chromite shell has high heat conductivity, the cooling speed of a casting is improved, directional solidification is promoted, thereby refining grains, obtaining the casting without loose defects, improving the strength of the casting, and meanwhile, three layers of chromite sand are easy to unshelling and cannot cause unshelling difficulty.
Description
Technical Field
The invention relates to the technical field of metal casting, in particular to a chromite shell and a preparation method thereof.
Background
Investment casting, also known as lost wax casting, is a long-history preparation method. Investment casting is first to make a wax pattern of the part to be cast from wax, and then to coat the wax pattern with a slurry to prepare a shell mold. After the shell mold is dried, the internal wax mold is melted by heating, and the melted wax mold is taken out and then the shell mold is baked. And (3) a pouring gate is reserved in the common shell-making mould, molten metal is poured into the pouring gate, and the required part is obtained after cooling and demoulding.
The size of the metal grains in the casting has a great influence on the performance of the casting. Generally, the finer the crystal grains, the higher the strength and hardness, and the better the plasticity and toughness. This is because the finer the crystal grains are, the more the plastic deformation is dispersed, and the more the plastic deformation is made to be uniform, the smaller the internal stress concentration is; and the finer the crystal grain, the more the grain boundary surface, the more the grain boundary is tortuous; the more chance that grains are staggered from grain to grain, the less favorable the crack propagation and development, the more firmly they are to each other, and the better the strength and toughness. Therefore, how to refine the crystal grains of the casting is the focus of research in the field.
The existing investment casting technology generally adopts mullite or fused quartz to make shells, and then a refiner is added into surface layer slurry to refine casting grains, but the shell making technology has higher cost and is not beneficial to mass production and application.
Therefore, how to provide a chromite mold shell and a preparation method thereof, which play a role in refining casting grains and ensure low-cost preparation of the mold shell, is a difficult problem to be solved in the field.
Disclosure of Invention
In view of the above, the invention provides a chromite shell and a preparation method thereof, which aims to solve the problem that the traditional shell does not have the effect of refining casting grains or is added with a refiner, so that the preparation cost is high.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the chromite mold shell comprises the following steps:
1) Preparing a wax pattern;
2) Preparing a surface layer on the wax mould by using surface layer slurry to obtain the wax mould with the surface layer;
3) Preparing a transition layer on the wax mould with the surface layer by using the transition layer slurry to obtain the wax mould with the transition layer;
4) Preparing a reinforcing layer on the wax mould with the transition layer by using the reinforcing layer slurry to obtain the wax mould with the reinforcing layer; wherein the reinforcing layer contains 2-3 layers of reinforcing layer slurry, a layer of chromite sand exists between every two adjacent layers of reinforcing layer slurry, and a layer of chromite sand exists on the outer layer of the outermost reinforcing layer slurry;
5) Dewaxing;
6) Roasting to obtain chromite mould shell.
Preferably, the particle size of the chromite sand is 30-60 meshes.
Preferably, the chromite sand is coated by dipping slurry and spraying sand.
Preferably, the preparation method of the reinforcing layer comprises the steps of immersing the wax mould with the transition layer into the reinforcing layer slurry, wherein the time for immersing the wax mould into the reinforcing layer slurry is independently 0.8-1.5 min.
Preferably, the surface layer contains 1-layer slurry, and a layer of refractory sand material exists between the surface layer slurry and the transition layer slurry; when the surface layer is prepared, the wax-bearing mold is required to be immersed into the surface layer slurry for 1.8-2.5 min.
Preferably, the transition layer contains 3-4 layers of transition layer slurry, one layer of refractory sand material exists between every two adjacent layers of transition layer slurry, and one layer of refractory sand material exists between the transition layer slurry and the reinforcing layer slurry.
Preferably, when preparing the transition layer, the wax mould with the surface layer slurry needs to be immersed in the transition layer slurry, and the time for immersing in the transition layer slurry is independently 0.8-1.5 min.
Preferably, the refractory sand material comprises mullite sand and/or zircon sand.
Preferably, the roasting temperature in the step 6) is 1000-1200 ℃, and the roasting time is 1-1.5 h.
The invention also aims to provide the chromite shell prepared by the preparation method of the chromite shell.
Compared with the prior art, the invention has the following beneficial effects:
1. the heat conductivity of the chromite sand used in the invention is far greater than that of the silica sand, so that the cooling speed of the casting can be improved, and directional solidification is promoted, thereby refining grains and obtaining the casting without loose defects;
2. the density of the chromite sand is higher than that of the traditional silica sand, so that the material is required to be uniformly coated on the module by adopting a slurry dipping and sand spraying mode, and the chromite sand can be mixed with various binders for use during slurry dipping and sand spraying, and the selection of the binders is not limited;
3. the number of the shell making layers of the chromite sand is not more than 3, the casting is easy to shell, and if the number of the shell making layers of the chromite sand is too high, the casting is difficult to shell.
Detailed Description
The invention provides a preparation method of chromite type shells, which comprises the following steps:
1) Preparing a wax pattern;
2) Preparing a surface layer on the wax mould by using surface layer slurry to obtain the wax mould with the surface layer;
3) Preparing a transition layer on the wax mould with the surface layer by using the transition layer slurry to obtain the wax mould with the transition layer;
4) Preparing a reinforcing layer on the wax mould with the transition layer by using the reinforcing layer slurry to obtain the wax mould with the reinforcing layer; wherein the reinforcing layer contains 2-3 layers of reinforcing layer slurry, preferably 3 layers; a layer of chromite sand exists between every two adjacent layers of reinforcing layer slurry, and a layer of chromite sand exists on the outer layer of the outermost reinforcing layer slurry;
5) Dewaxing;
6) Roasting to obtain chromite mould shell.
In the present invention, the chromite sand has a particle size of 30 to 60 mesh, preferably 40 to 50 mesh, and more preferably 45 mesh.
In the invention, the chromite sand is coated in a slurry dipping and sand spraying mode, and the concrete steps of the slurry dipping and sand spraying are that the module is fully wetted and soaked in a slurry barrel, the module is placed in a roller type sand spraying machine after slurry is leached until the slurry is not dripped, and chromite sand is uniformly sprayed on the surface of the module.
In the method for preparing the reinforcing layer, the wax mould with the transition layer is immersed in the reinforcing layer slurry, and the time of immersing in the reinforcing layer slurry is independently 0.8-1.5 min, preferably 0.9-1.2 min, and more preferably 1min.
In the invention, the transition layer contains 3-4 layers of transition layer slurry, preferably 3 layers.
In the invention, the surface layer contains 1-layer slurry, and a layer of refractory sand is arranged between the surface layer slurry and the transition layer slurry; when preparing the surface layer, the wax-bearing mold is immersed into the surface layer slurry for 1.8-2.5 min, preferably 1.9-2.2 min, and more preferably 2min.
In the invention, the surface layer slurry is preferably a mixture of zirconium powder and silica sol, and the mass ratio of the zirconium powder to the silica sol is 1:2.5 to 3.5, preferably 1:2.8 to 3.2, and more preferably 1:3; the particle size of the zirconium powder is 180 to 220 mesh, preferably 190 to 210 mesh, and more preferably 200 mesh.
In the invention, the transition layer contains 3-4 layers of transition layer slurry, preferably 3 layers; a layer of refractory sand material exists between every two adjacent layers of transition layer slurry, and a layer of refractory sand material exists between the transition layer slurry and the reinforcing layer slurry.
In the invention, when preparing the transition layer, the wax mould with the surface layer slurry needs to be immersed in the transition layer slurry, and the time of immersing in the transition layer slurry independently ranges from 0.8 to 1.5min, preferably from 0.9 to 1.2min, and more preferably 1min.
In the invention, the transition layer slurry and the reinforcing layer slurry are independently and preferably a mixture of mullite powder and silica sol, wherein the mass ratio of the mullite powder to the silica sol is 1:2.5 to 3.5, preferably 1:2.8 to 3.2, and more preferably 1:3; the mullite powder has a particle size of 180 to 220 mesh, preferably 190 to 210 mesh, and more preferably 200 mesh.
In the present invention, the refractory sand material includes mullite sand and/or zircon sand.
In the invention, the roasting temperature in the step 6) is 1000-1200 ℃, and the roasting time is 1-1.5 h.
The invention also provides the chromite shell prepared by the preparation method of the chromite shell.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing a wax pattern;
immersing a wax mould in surface layer slurry for 2min (the surface layer slurry is a mixture of zirconium powder and silica sol with the mass ratio of 1:3), taking out, scattering a layer of zircon sand refractory sand material, drying to obtain the wax mould with a surface layer, immersing the wax mould with the surface layer in transition layer slurry for 1min (the transition layer slurry is a mixture of mullite powder and silica sol with the mass ratio of 1:3), taking out, scattering a layer of mullite sand refractory sand material, drying, repeating the steps, immersing in the transition layer slurry for 3 times, and completing the preparation of the transition layer; immersing a wax mould with a transition layer in reinforcing layer slurry for 1min (the reinforcing layer slurry is a mixture of mullite powder with 200 meshes and silica sol according to the mass ratio of 1:3), taking out, coating a layer of chromite sand with 45 meshes in a slurry dipping and sand spraying mode, drying, repeating the steps, immersing in the reinforcing layer slurry for 2 times, and finishing the preparation of the reinforcing layer;
high-temperature steam dewaxing is carried out in a steam dewaxing kettle, and then roasting is carried out for 1.2 hours at 1100 ℃ to obtain chromite type shells.
Example 2
Preparing a wax pattern;
immersing a wax mould in surface layer slurry for 2min (the surface layer slurry is a mixture of zirconium powder and silica sol with the mass ratio of 1:3), taking out, scattering a layer of zircon sand refractory sand material, drying to obtain the wax mould with a surface layer, immersing the wax mould with the surface layer in transition layer slurry for 1min (the transition layer slurry is a mixture of mullite powder and silica sol with the mass ratio of 1:3), taking out, scattering a layer of mullite sand refractory sand material, drying, repeating the steps, immersing in the transition layer slurry for 3 times, and completing the preparation of the transition layer; immersing a wax mould with a transition layer in reinforcing layer slurry for 1min (the reinforcing layer slurry is a mixture of mullite powder with 200 meshes and silica sol according to the mass ratio of 1:3), taking out, coating a layer of 30-mesh chromite sand in a slurry dipping and sand spraying mode, drying, repeating the steps, immersing in the reinforcing layer slurry for 1 time, and completing the preparation of the reinforcing layer;
high-temperature steam dewaxing is carried out in a steam dewaxing kettle, and then roasting is carried out for 1.5 hours at 1000 ℃ to obtain chromite type shells.
Example 3
Preparing a wax pattern;
immersing a wax mould in surface layer slurry for 2min (the surface layer slurry is a mixture of zirconium powder and silica sol with the mass ratio of 1:3), taking out, scattering a layer of zircon sand refractory sand material, drying to obtain the wax mould with a surface layer, immersing the wax mould with the surface layer in transition layer slurry for 1min (the transition layer slurry is a mixture of mullite powder and silica sol with the mass ratio of 1:3), taking out, scattering a layer of mullite sand refractory sand material, drying, repeating the steps, immersing in the transition layer slurry for 2 times, and completing the preparation of the transition layer; immersing a wax mould with a transition layer in reinforcing layer slurry for 1min (the reinforcing layer slurry is a mixture of mullite powder with 200 meshes and silica sol according to the mass ratio of 1:3), taking out, coating a layer of chromite sand with 60 meshes in a slurry dipping and sand spraying mode, drying, repeating the steps, immersing in the reinforcing layer slurry for 2 times, and finishing the preparation of the reinforcing layer;
high-temperature steam dewaxing is carried out in a steam dewaxing kettle, and then roasting is carried out for 1h at 1200 ℃ to obtain chromite type shells.
Example 4
Preparing a wax pattern;
immersing a wax mould in surface layer slurry for 2min (the surface layer slurry is a mixture of zirconium powder and silica sol with the mass ratio of 1:3), taking out, scattering a layer of zircon sand refractory sand material, drying to obtain the wax mould with a surface layer, immersing the wax mould with the surface layer in transition layer slurry for 1min (the transition layer slurry is a mixture of mullite powder and silica sol with the mass ratio of 1:3), taking out, scattering a layer of mullite sand refractory sand material, drying, repeating the steps, immersing in the transition layer slurry for 2 times, and completing the preparation of the transition layer; immersing a wax mould with a transition layer in reinforcing layer slurry for 1min (the reinforcing layer slurry is a mixture of mullite powder with 200 meshes and silica sol according to the mass ratio of 1:3), taking out, coating a layer of 50-mesh chromite sand in a slurry dipping and sand spraying mode, drying, repeating the steps, immersing in the reinforcing layer slurry for 1 time, and completing the preparation of the reinforcing layer;
high-temperature steam dewaxing is carried out in a steam dewaxing kettle, and then roasting is carried out for 1.4 hours at 1100 ℃ to obtain chromite type shells.
Comparative example 1
This comparative example differs from example 1 only in that mullite sand was used instead of chromite sand.
Experimental example 1
The chromite mold shells obtained in examples 1 to 4 and the mold shell preparation castings obtained in comparative example 1 were each examined by a vickers hardness tester according to ASTM E92. The test results are shown in Table 1.
Table 1 results of hardness test of the chromite form shells of examples 1 to 4 and the form shell castings obtained in comparative example 1
The hardness of the back plate of the chromite type shell casting prepared by the method is obviously improved through the table 1, and the hardness of the plum blossom head is slightly improved. In addition, the comparison shows that the crystal grains of the shell back plate prepared by the invention are obviously increased and the crystal grains are thinned.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the chromite mold shell is characterized by comprising the following steps of:
1) Preparing a wax pattern;
2) Preparing a surface layer on the wax mould by using surface layer slurry to obtain the wax mould with the surface layer;
3) Preparing a transition layer on the wax mould with the surface layer by using the transition layer slurry to obtain the wax mould with the transition layer;
4) Preparing a reinforcing layer on the wax mould with the transition layer by using the reinforcing layer slurry to obtain the wax mould with the reinforcing layer; wherein the reinforcing layer contains 2-3 layers of reinforcing layer slurry, a layer of chromite sand exists between every two adjacent layers of reinforcing layer slurry, and a layer of chromite sand exists on the outer layer of the outermost reinforcing layer slurry;
5) Dewaxing;
6) Roasting to obtain chromite mould shell.
2. The method for preparing chromite mould shell according to claim 1, wherein the particle size of the chromite sand is 30-60 mesh.
3. The method for preparing chromite mould shell according to claim 2, wherein the chromite sand is coated by dipping slurry and spraying sand.
4. A method for preparing a chromite shell according to any of claims 1 to 3, wherein the method for preparing the reinforcing layer comprises immersing a wax mould with a transition layer in the slurry of the reinforcing layer, wherein the time for immersing each time in the slurry of the reinforcing layer is independently 0.8 to 1.5min.
5. The method for preparing chromite mould shell according to claim 4, wherein the surface layer comprises 1-layer slurry, and a layer of refractory sand is arranged between the surface layer slurry and the transition layer slurry; when the surface layer is prepared, the wax-bearing mold is required to be immersed into the surface layer slurry for 1.8-2.5 min.
6. The method for preparing a chromite mould shell according to claim 5, wherein the transition layer comprises 3-4 layers of transition layer slurry, a layer of refractory sand is arranged between every two adjacent layers of transition layer slurry, and a layer of refractory sand is arranged between the transition layer slurry and the reinforcing layer slurry.
7. The method for preparing a chromite shell according to claim 5 or 6, wherein when preparing the transition layer, the wax mould with the surface layer slurry is immersed in the transition layer slurry, and the time for immersing in the transition layer slurry is independently 0.8-1.5 min.
8. The method of producing chromite form according to claim 7, wherein said refractory sand comprises mullite sand and/or zircon sand.
9. The method for preparing chromite form shells according to claim 8, wherein the roasting temperature in the step 6) is 1000-1200 ℃ and the roasting time is 1-1.5 h.
10. The chromite form shell produced by the production method according to any one of claims 1 to 9.
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CN202410005601.5A CN117680622A (en) | 2024-01-03 | 2024-01-03 | Chromite type shell and preparation method thereof |
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CN202410005601.5A CN117680622A (en) | 2024-01-03 | 2024-01-03 | Chromite type shell and preparation method thereof |
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