CN104163632A - Aluminium nitride-based multi-element nano-composite ceramic die material and preparation method thereof - Google Patents
Aluminium nitride-based multi-element nano-composite ceramic die material and preparation method thereof Download PDFInfo
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- CN104163632A CN104163632A CN201410381907.7A CN201410381907A CN104163632A CN 104163632 A CN104163632 A CN 104163632A CN 201410381907 A CN201410381907 A CN 201410381907A CN 104163632 A CN104163632 A CN 104163632A
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Abstract
The invention discloses an aluminium nitride-based multi-element nano-composite ceramic die material and a preparation method thereof. The material comprises the following raw materials in parts by weight: 60-80 parts of aluminium nitride, 10-20 parts of aluminium carbide, 15-25 parts of silicon boride, 2-6 parts of scandium oxide, 4-8 parts of neodymium oxide, 2-4 parts of chromium, 1-3 parts of tungsten and 1-3 parts of nickel, wherein nanoscale powder of all the materials is adopted; the grain size of aluminium nitride is 10-100 nanometers; the grain sizes of aluminium carbide and silicon boride are 1-10 nanometers; the grain sizes of the other raw materials are 1-100 nanometers. The preparation method is characterized by using aluminium nitride as the matrix, adding aluminium carbide and silicon boride as reinforcing phases, scandium oxide and neodymium oxide as stabilizing agents and chromium, tungsten and nickel as sintering aids and carrying out hot pressed sintering on the materials, thus preparing the material. A die has strong ageing and defect resistance, good comprehensive mechanical properties and excellent antifriction and wear resistance properties.
Description
Technical field
The present invention relates to a kind of ceramic die material, specifically a kind of aluminum-nitride-based polynary nanometer composite ceramic die material and preparation method thereof.
Background technology
Sintex has high hardness and wear resistance, when high speed cutting and dry cutting, shows excellent cutting ability, is the cutter material that a class has development prospect.But the ceramic cutting tool material of application is confined to a micron composite ceramics mostly at present, the mechanical property of material especially intensity, toughness still awaits further raising.According to Hall-petch relation: grain-size is less, and the intensity of stupalith is higher.Therefore, the research and development of nano modification, nano-micrometre composite ceramic tool material will be one of main direction of cutter material development from now on.
Current nano composite ceramic cutter material after deliberation mainly comprises Si
3n
4/ TiNn, Si
3n
4/ TiCn, Si
3n
4-Ai
2o
3n-TiC-Y
2o
3, Al
2o
3/ TiC/SiCn, Al
2o
3/ TiCn, Al
2o
3/ Al
2o
3n/SiCn, Al
2o
3/ Ti (C
07n
0.3) n/SiCn, Al
2o
3/ SiC/SiCn, Al
2o
3/ TiC/TiNn, etc., all have than the better mechanical property of micron composite ceramic tool material and cutting ability.But up to the present, not yet find to take the report of the nano composite ceramic cutter material that aluminium nitride ceramics is matrix.
On the other hand, thermostability and the wear resistance of stupalith are splendid, are the ideal materials of manufacturing shaping dies, have very much development prospect, but its toughness are very poor, therefore also aspect mould industry, are not used widely.From domestic and international present situation, the research of ceramic die is still in the research and development stage, be applied to mould industry stupalith kind seldom, applicable mould applications is very narrow, the report of this respect is also few.At present, the applied research of stupalith in all kinds of moulds is confined to a micron composite ceramic material mostly, as ZrO
2toughness reinforcing Al
2o
3base composite ceramic ZTA wortle, TZP/TiC/Al
2o
3, Al
2o
3/ TiC composite ceramics wortle, (Ce-TZP)-Al
2o
3hot-extrusion mold, 3Y-TZP-Al
2o
3pottery drawing die, PSZ pottery hot extruding die, Al
2o
3/ Cr
3c
2/ (W, Ti) C etc.Although nano composite ceramic is less in the research of moulding stock application aspect, as compound UP ceramic die, Al
2o
3/ Ti (C, N) etc., but also obtained good effect.
From existing research, can find out, performance, the price advantage of nano combined especially nano-micron compound pottery could not be not fully exerted in mould applications.With regard to current general status, the kind of ceramic die material, performance and range of application all await further expanding and improving.
Summary of the invention
The object of the present invention is to provide a kind of aluminum-nitride-based polynary nanometer composite ceramic die material and preparation method thereof, this mould resistance to deterioration and defect are strong to ability, have good comprehensive mechanical property and good properties of antifriction and wear resistance.
For achieving the above object, the invention provides following technical scheme:
An aluminum-nitride-based polynary nanometer composite ceramic die material, according to the raw material of weight part is: aluminium nitride 60-80 part, aluminium carbide 10-20 part, silicon boride 15-25 part, Scium trioxide 2-6 part, Neodymium trioxide 4-8 part, chromium 2-4 part, tungsten 1-3 part, nickel 1-3 part; Above-mentioned all raw materials all adopt nanoscale powder, and wherein the footpath grain size of aluminium nitride is 10-100 nanometer, and the footpath grain size of aluminium carbide and silicon boride is 1-10 nanometer, and other footpath grain size is 1-100 nanometer.
As the further scheme of the present invention: described aluminum-nitride-based polynary nanometer composite ceramic die material and preparation method thereof, according to the raw material of weight part is: aluminium nitride 65-75 part, aluminium carbide 14-16 part, silicon boride 18-22 part, Scium trioxide 3-5 part, Neodymium trioxide 5-7 part, chromium 2.5-3.5 part, tungsten 1.5-2.5 part, nickel 1-3 part.
The preparation method of described aluminum-nitride-based polynary nanometer composite ceramic die material, take aluminium nitride as matrix, adds aluminium carbide and silicon boride as wild phase, take Scium trioxide and Neodymium trioxide as stablizer, usings chromium, tungsten and nickel as sintering aid, through hot pressed sintering, forms; Concrete preparation process is as follows:
Step 1: take above-mentioned all raw materials according to weight part;
Step 2: aluminium nitride, aluminium carbide and silicon boride are added in the mixing solutions of dehydrated alcohol and polyoxyethylene glycol, then fully stir, ultrasonic dispersion 20-30 minute, obtains the first suspension simultaneously;
Step 3: Scium trioxide, Neodymium trioxide, chromium, tungsten and nickel are added in the mixing solutions of dehydrated alcohol and polyoxyethylene glycol, then fully stir, ultrasonic dispersion 20-30 minute, obtains the second suspension simultaneously;
Step 4: the first suspension and second is suspended and mixed, then fully stir, ultrasonic dispersion 10-20 minute, obtains total mixture suspension simultaneously;
Step 5: total mixture suspension is poured in ball grinder, be take rare gas element as protective atmosphere, take dehydrated alcohol as medium, the iron ball that diameter is 1-2mm is mill ball, under the microwave environment of 2450MHz, ball milling 12-24 hour, filters and obtains lapping liquid; The gross weight of all raw materials and the weight ratio of mill ball are 1: 10-20;
Step 6: by lapping liquid vacuum-drying at 110-120 ℃ of temperature, sieve in inert gas flow after complete drying, obtain mixed powder, seal standby;
Step 7: adopt pressure sintering sintering, in hot pressing furnace by the mixed powder pressing mold sinter molding of step 6 gained and get final product.
As the further scheme of the present invention: the volume ratio of dehydrated alcohol and polyoxyethylene glycol described in step 2 and step 3 is 1: 0.5-2.
As the further scheme of the present invention: rare gas element described in step 5 and step 6 is nitrogen or rare gas.
As the further scheme of the present invention: in step 7, pressure sintering sintering process parameter is: heating-up time 20-30min, holding temperature 1400-1600 ℃, hot pressing pressure 30-40MPa, soaking time 40-60min, is then cooled to room temperature.
Compared with prior art, the invention has the beneficial effects as follows: polynary nanometer composite ceramic die of the present invention, by adding nano silicon carbide aluminium and nanometer silicon boride is realized the nano combined of different-grain diameter as wild phase in nano silicon nitride aluminum substrate, add adding of nano silicon carbide aluminium and nanometer silicon boride, can form typical intracrystalline/intergranular hybrid architecture with nano aluminum nitride, cause thus along crystalline substance/transcrystalline mixed-mode crack pattern, the multiple toughened and reinforced mechanism synergies such as these highly malleablized mechanism and aluminium nitride transformation toughening, jointly improve mechanical property and the use properties of material, and research shows: Scium trioxide and Neodymium trioxide are as the compound interpolation of stablizer, not only make material there is quite high resistance to deterioration and defect resistivity, and crystal grain phase transformation critical size is larger, lower to material fineness requirement, thus make material there is good over-all properties.Finally, utilize the little abrading-ball of metallic, what after metal is subject to microwave exposure, occur is dissipated in whole reaction system micro-wave reflection and refraction, has played the effect of microwave heating, can accelerated reaction carry out.Compare with existing ceramic die material, this polynary nanometer composite ceramic die material has better comprehensive mechanical property and good properties of antifriction and wear resistance, can be used for making potter's moulds such as overflow mould, drawing die and cutting tool.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
An aluminum-nitride-based polynary nanometer composite ceramic die material, according to the raw material of weight part is: 60 parts of aluminium nitride, carbon. change 10 parts, aluminium, 15 parts of silicon borides, 2 parts of Scium trioxides, 4 parts of Neodymium trioxide, 2 parts of chromium, 1 part, tungsten, 1 part, nickel; Above-mentioned all raw materials all adopt nanoscale powder, and wherein the footpath grain size of aluminium nitride is 10-100 nanometer, and the footpath grain size of aluminium carbide and silicon boride is 1-10 nanometer, and other footpath grain size is 1-100 nanometer; Its preparation method is to take aluminium nitride as matrix, adds aluminium carbide and silicon boride as wild phase, take Scium trioxide and Neodymium trioxide as stablizer, usings chromium, tungsten and nickel as sintering aid, through hot pressed sintering, forms; Concrete preparation process is as follows:
Step 1: take above-mentioned all raw materials according to weight part;
Step 2: aluminium nitride, aluminium carbide and silicon boride are added in the mixing solutions of dehydrated alcohol and polyoxyethylene glycol, then fully stir, ultrasonic dispersion simultaneously 20 minutes, obtains the first suspension; The volume ratio of described dehydrated alcohol and polyoxyethylene glycol is 1: 0.5;
Step 3: Scium trioxide, Neodymium trioxide, chromium, tungsten and nickel are added in the mixing solutions of dehydrated alcohol and polyoxyethylene glycol, then fully stir, ultrasonic dispersion simultaneously 20 minutes, obtains the second suspension; The volume ratio of described dehydrated alcohol and polyoxyethylene glycol is 1: 0.5;
Step 4: the first suspension and second is suspended and mixed, then fully stir, ultrasonic dispersion simultaneously 10 minutes, obtains total mixture suspension;
Step 5: total mixture suspension is poured in ball grinder, be take nitrogen as protective atmosphere, take dehydrated alcohol as medium, the iron ball that diameter is 1mm is mill ball, under the microwave environment of 2450MHz, ball milling 12 hours, filters and obtains lapping liquid; The gross weight of all raw materials and the weight ratio of mill ball are 1: 10;
Step 6: by lapping liquid vacuum-drying at 110 ℃ of temperature, sieve in stream of nitrogen gas after complete drying, obtain mixed powder, seal standby;
Step 7: adopt pressure sintering sintering, in hot pressing furnace by the mixed powder pressing mold sinter molding of step 6 gained and get final product; The processing parameter of pressure sintering sintering: heating-up time 20min, 1400 ℃ of holding temperatures, hot pressing pressure 30MPa, soaking time 40min, is then cooled to room temperature.
Embodiment 2
An aluminum-nitride-based polynary nanometer composite ceramic die material, according to the raw material of weight part is: 2 parts, 70 parts of aluminium nitride, 15 parts of aluminium carbides, 20 parts of silicon borides, 4 parts of Scium trioxides, 6 parts of Neodymium trioxide, 3 parts of chromium, 2 parts, tungsten and nickel; Above-mentioned all raw materials all adopt nanoscale powder, and wherein the footpath grain size of aluminium nitride is 10-100 nanometer, and the footpath grain size of aluminium carbide and silicon boride is 1-10 nanometer, and other footpath grain size is 1-100 nanometer; Its preparation method is to take aluminium nitride as matrix, adds aluminium carbide and silicon boride as wild phase, take Scium trioxide and Neodymium trioxide as stablizer, usings chromium, tungsten and nickel as sintering aid, through hot pressed sintering, forms; Concrete preparation process is as follows:
Step 1: take above-mentioned all raw materials according to weight part;
Step 2: aluminium nitride, aluminium carbide and silicon boride are added in the mixing solutions of dehydrated alcohol and polyoxyethylene glycol, then fully stir, ultrasonic dispersion simultaneously 25 minutes, obtains the first suspension; The volume ratio of described dehydrated alcohol and polyoxyethylene glycol is 1: 1;
Step 3: Scium trioxide, Neodymium trioxide, chromium, tungsten and nickel are added in the mixing solutions of dehydrated alcohol and polyoxyethylene glycol, then fully stir, ultrasonic dispersion simultaneously 25 minutes, obtains the second suspension; The volume ratio of described dehydrated alcohol and polyoxyethylene glycol is 1: 1;
Step 4: the first suspension and second is suspended and mixed, then fully stir, ultrasonic dispersion simultaneously 15 minutes, obtains total mixture suspension;
Step 5: total mixture suspension is poured in ball grinder, be take nitrogen as protective atmosphere, take dehydrated alcohol as medium, the iron ball that diameter is 1.5mm is mill ball, under the microwave environment of 2450MHz, ball milling 18 hours, filters and obtains lapping liquid; The gross weight of all raw materials and the weight ratio of mill ball are 1: 15;
Step 6: by lapping liquid vacuum-drying at 115 ℃ of temperature, sieve in stream of nitrogen gas after complete drying, obtain mixed powder, seal standby;
Step 7: adopt pressure sintering sintering, in hot pressing furnace by the mixed powder pressing mold sinter molding of step 6 gained and get final product; The processing parameter of pressure sintering sintering: heating-up time 25min, 1500 ℃ of holding temperatures, hot pressing pressure 35MPa, soaking time 50min, is then cooled to room temperature.
Embodiment 3
An aluminum-nitride-based polynary nanometer composite ceramic die material, according to the raw material of weight part is: 3 parts, 80 parts of aluminium nitride, 20 parts of aluminium carbides, 25 parts of silicon borides, 6 parts of Scium trioxides, 8 parts of Neodymium trioxide, 4 parts of chromium, 3 parts, tungsten and nickel; Above-mentioned all raw materials all adopt nanoscale powder, and wherein the footpath grain size of aluminium nitride is 10-100 nanometer, and the footpath grain size of aluminium carbide and silicon boride is 1-10 nanometer, and other footpath grain size is 1-100 nanometer; Its preparation method is to take aluminium nitride as matrix, adds aluminium carbide and silicon boride as wild phase, take Scium trioxide and Neodymium trioxide as stablizer, usings chromium, tungsten and nickel as sintering aid, through hot pressed sintering, forms; Concrete preparation process is as follows:
Step 1: take above-mentioned all raw materials according to weight part;
Step 2: aluminium nitride, aluminium carbide and silicon boride are added in the mixing solutions of dehydrated alcohol and polyoxyethylene glycol, then fully stir, ultrasonic dispersion simultaneously 30 minutes, obtains the first suspension; The volume ratio of described dehydrated alcohol and polyoxyethylene glycol is 1: 2;
Step 3: Scium trioxide, Neodymium trioxide, chromium, tungsten and nickel are added in the mixing solutions of dehydrated alcohol and polyoxyethylene glycol, then fully stir, ultrasonic dispersion simultaneously 30 minutes, obtains the second suspension; The volume ratio of described dehydrated alcohol and polyoxyethylene glycol is 1: 2;
Step 4: the first suspension and second is suspended and mixed, then fully stir, ultrasonic dispersion simultaneously 20 minutes, obtains total mixture suspension;
Step 5: total mixture suspension is poured in ball grinder, be take argon gas as protective atmosphere, take dehydrated alcohol as medium, the iron ball that diameter is 2mm is mill ball, under the microwave environment of 2450MHz, ball milling 24 hours, filters and obtains lapping liquid; The gross weight of all raw materials and the weight ratio of mill ball are 1: 20;
Step 6: by lapping liquid vacuum-drying at 120 ℃ of temperature, sieve in argon stream after complete drying, obtain mixed powder, seal standby;
Step 7: adopt pressure sintering sintering, in hot pressing furnace by the mixed powder pressing mold sinter molding of step 6 gained and get final product; The processing parameter of pressure sintering sintering: heating-up time 30min, 1600 ℃ of holding temperatures, hot pressing pressure 40MPa, soaking time 60min, is then cooled to room temperature.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and in the situation that not deviating from spirit of the present invention or essential characteristic, can realize the present invention with other specific form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, is therefore intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in scope.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should make specification sheets as a whole, and the technical scheme in each embodiment also can, through appropriately combined, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (6)
1. an aluminum-nitride-based polynary nanometer composite ceramic die material, it is characterized in that, according to the raw material of weight part, be: aluminium nitride 60-80 part, aluminium carbide 10-20 part, silicon boride 15-25 part, Scium trioxide 2-6 part, Neodymium trioxide 4-8 part, chromium 2-4 part, tungsten 1-3 part, nickel 1-3 part; Above-mentioned all raw materials all adopt nanoscale powder, and wherein the footpath grain size of aluminium nitride is 10-100 nanometer, and the footpath grain size of aluminium carbide and silicon boride is 1-10 nanometer, and other footpath grain size is 1-100 nanometer.
2. aluminum-nitride-based polynary nanometer composite ceramic die material according to claim 1, it is characterized in that, described aluminum-nitride-based polynary nanometer composite ceramic die material and preparation method thereof, according to the raw material of weight part is: aluminium nitride 65-75 part, aluminium carbide 14-16 part, silicon boride 18-22 part, Scium trioxide 3-5 part, Neodymium trioxide 5-7 part, chromium 2.5-3.5 part, tungsten 1.5-2.5 part, nickel 1.5-2.5 part.
3. the preparation method of an aluminum-nitride-based polynary nanometer composite ceramic die material as claimed in claim 1 or 2, it is characterized in that, take aluminium nitride as matrix, add aluminium carbide and silicon boride as wild phase, take Scium trioxide and Neodymium trioxide as stablizer, using chromium, tungsten and nickel as sintering aid, through hot pressed sintering, form; Concrete preparation process is as follows:
Step 1: take above-mentioned all raw materials according to weight part;
Step 2: aluminium nitride, aluminium carbide and silicon boride are added in the mixing solutions of dehydrated alcohol and polyoxyethylene glycol, then fully stir, ultrasonic dispersion 20-30 minute, obtains the first suspension simultaneously;
Step 3: Scium trioxide, Neodymium trioxide, chromium, tungsten, nickel are added in the mixing solutions of dehydrated alcohol and polyoxyethylene glycol, then fully stir, ultrasonic dispersion 20-30 minute, obtains the second suspension simultaneously;
Step 4: the first suspension and second is suspended and mixed, then fully stir, ultrasonic dispersion 10-20 minute, obtains total mixture suspension simultaneously;
Step 5: total mixture suspension is poured in ball grinder, be take rare gas element as protective atmosphere, take dehydrated alcohol as medium, the iron ball that diameter is 1-2mm is mill ball, under the microwave environment of 2450MHz, ball milling 12-24 hour, filters and obtains lapping liquid; The gross weight of all raw materials and the weight ratio of mill ball are 1: 10-20;
Step 6: by lapping liquid vacuum-drying at 110-120 ℃ of temperature, sieve in inert gas flow after complete drying, obtain mixed powder, seal standby;
Step 7: adopt pressure sintering sintering, in hot pressing furnace by the mixed powder pressing mold sinter molding of step 6 gained and get final product.
4. the preparation method of aluminum-nitride-based polynary nanometer composite ceramic die material according to claim 3, is characterized in that, the volume ratio of dehydrated alcohol and polyoxyethylene glycol described in step 2 and step 3 is 1: 0.5-2.
5. the preparation method of aluminum-nitride-based polynary nanometer composite ceramic die material according to claim 1, is characterized in that, rare gas element described in step 5 and step 6 is nitrogen or rare gas.
6. the preparation method of aluminum-nitride-based polynary nanometer composite ceramic die material according to claim 1, it is characterized in that, in step 7, pressure sintering sintering process parameter is: heating-up time 20-30min, holding temperature 1400-1600 ℃, hot pressing pressure 30-40MPa, soaking time 40-60min, is then cooled to room temperature.
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| CN201410381907.7A CN104163632B (en) | 2014-08-04 | A kind of aluminum-nitride-based polynary nanometer composite ceramic die material and preparation method thereof |
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| CN201410381907.7A CN104163632B (en) | 2014-08-04 | A kind of aluminum-nitride-based polynary nanometer composite ceramic die material and preparation method thereof |
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| CN104163632B CN104163632B (en) | 2017-01-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106747448A (en) * | 2016-12-09 | 2017-05-31 | 姚旭 | A kind of tungsten carbide-base polynary nanometer composite ceramic die material and preparation method thereof |
| CN108973136A (en) * | 2018-07-31 | 2018-12-11 | 浙江天翀车灯集团有限公司 | A kind of car light hot plate welding hot-die gauge finder and hot plate welding heating mould |
| CN114054682A (en) * | 2021-11-26 | 2022-02-18 | 江苏智疆航空科技发展有限公司 | Preparation process of ceramic core for aircraft engine |
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| CN103204682A (en) * | 2012-01-16 | 2013-07-17 | 佛山市陶瓷研究所有限公司 | High thermal conductive aluminum nitride ceramic heat dissipation substrate and preparation method thereof |
| CN103553691A (en) * | 2013-11-01 | 2014-02-05 | 广东工业大学 | Particle dispersion toughening aluminum nitride ceramic substrate and preparation method thereof |
| CN103626496A (en) * | 2013-12-05 | 2014-03-12 | 燕山大学 | Non-stoichiometric ratio TiC, AlN and TiN composite material |
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| US5336454A (en) * | 1993-03-26 | 1994-08-09 | Advanced Ceramics Corporation | Ceramic composite and method |
| CN103204682A (en) * | 2012-01-16 | 2013-07-17 | 佛山市陶瓷研究所有限公司 | High thermal conductive aluminum nitride ceramic heat dissipation substrate and preparation method thereof |
| CN103553691A (en) * | 2013-11-01 | 2014-02-05 | 广东工业大学 | Particle dispersion toughening aluminum nitride ceramic substrate and preparation method thereof |
| CN103626496A (en) * | 2013-12-05 | 2014-03-12 | 燕山大学 | Non-stoichiometric ratio TiC, AlN and TiN composite material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106747448A (en) * | 2016-12-09 | 2017-05-31 | 姚旭 | A kind of tungsten carbide-base polynary nanometer composite ceramic die material and preparation method thereof |
| CN108973136A (en) * | 2018-07-31 | 2018-12-11 | 浙江天翀车灯集团有限公司 | A kind of car light hot plate welding hot-die gauge finder and hot plate welding heating mould |
| CN114054682A (en) * | 2021-11-26 | 2022-02-18 | 江苏智疆航空科技发展有限公司 | Preparation process of ceramic core for aircraft engine |
| CN114054682B (en) * | 2021-11-26 | 2022-12-09 | 江苏智疆航空科技发展有限公司 | Preparation process of ceramic core for aircraft engine |
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Effective date of registration: 20170724 Address after: 124013 Xinglongtai Panjin petroleum hi tech Industrial Park Liaoning Liaoning trans Petroleum Equipment Co., Ltd. Patentee after: Liaoning Kuak Petroleum Equipment Co., Ltd. Address before: 315400 Zhejiang province Yuyao City Yangming streets Kang Shan Cun of more than 47-1 Patentee before: YUYAO QIAODI ELECTRIC FACTORY |