CN103121099B - Amorphous boron contained sliding nozzle refractory brick made by combing unfired metal with aluminum, carbon and zirconium materials and production method thereof - Google Patents
Amorphous boron contained sliding nozzle refractory brick made by combing unfired metal with aluminum, carbon and zirconium materials and production method thereof Download PDFInfo
- Publication number
- CN103121099B CN103121099B CN201210229417.6A CN201210229417A CN103121099B CN 103121099 B CN103121099 B CN 103121099B CN 201210229417 A CN201210229417 A CN 201210229417A CN 103121099 B CN103121099 B CN 103121099B
- Authority
- CN
- China
- Prior art keywords
- granularity
- corundum
- amorphous boron
- sliding nozzle
- zirconium
- 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.)
- Active
Links
Landscapes
- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to an amorphous boron contained sliding nozzle refractory brick made by combing unfired metal with aluminum, carbon and zirconium materials and a production method of the amorphous boron contained sliding nozzle refractory brick made by combing the unfired metal with the aluminum, carbon and zirconium materials. Raw materials of the sliding nozzle brick comprise 0.2% to 5% of amorphous boron, 55% to 78% of corundum, 5% to 15% of silicon carbide, 10% to 20% of zirconium mullite, 2% to 5% of graphite, 3% to 7% of aluminum-silicon alloy, 1% to 3% of lithium base bentonite and phenolic resin, and the amount of phenolic resin is 4% to 6% of the total amount of the raw materials. When the sliding nozzle brick is produced, powder and granule are respectively mixed, phenolic resin is added, pug is obtained by evenly mixing, and the sliding nozzle brick is obtained through molding and drying. The sliding nozzle brick possesses excellent inoxidizability and high strength and is good in performance of molten steel erosion resistance, anti-scouring capability, antioxidation, thermal shock resistance and the like. Compared with an unfired aluminum-carbon sliding nozzle brick, a product is excellent in heat shock resistance and anti-erosion performance, is capable of being used in a large-scale steel ladle and is long in service life. The production method of the amorphous boron contained sliding nozzle refractory brick made by combing the unfired metal with the aluminum, carbon and zirconium materials is simplified in process, short in production cycle, free from polluting the environment and good in comprehensive benefits.
Description
Technical field
The present invention relates to a kind of steel-making slide gate nozzle refractory material, particularly relate to a kind of containing amorphous boron do not burn corrupt split aluminium carbon zirconium mass slide gate nozzle refractory material and production method thereof.
Background technology
Along with the development of process for making, the service condition of slide gate nozzle refractory material requires day by day harsh.In order to improve the service life of slide gate nozzle refractory material, when refractory material contacts with melted material, prevent it and melted material such as liquid molten steel and slag from reacting.The damage of sliding sprue tile for smelting, one is the chemical action due to liquid metal and slag, moreover is impact due to the Rapid Thermal of motlten metal the crackle that causes and peel off and the physical action such as wearing and tearing of liquid metal.Therefore, in order to energy stable operation, must adopt and there is heat shock resistance and the good nozzle brick of erosion-resisting characteristics.Current sliding sprue tile for smelting mainly contains the refractory material adding the carbon such as aluminium zirconium carbon, the aluminium carbon combination that silicon metal powder burns till and the unfired Al-C material adding polymethyl silicane or organic siliconresin.The burnt aluminum carbon combined with carbon and aluminium carbon zirconium slide plate can meet the instructions for use of steel mill substantially, but due to elevated temperature strength not high, there is short, sliding area plucking and press from both sides the problems such as cold steel in service life.In addition, for burnt aluminum carbon slipper, aluminium carbon zirconium slide plate that carbon combines, the shortcoming that existence is burnt till costly, the production cycle is long, and after burning till, need oil immersion pitch, pollute the environment in production process.Substantially can meet the instructions for use of medium and small ladle and tundish for the aluminum-carbon sliding do not burnt, but due to thermal shock resistance not ideal enough, large ladle furnace uses and has radial crack to produce, there is short problem in service life.
Summary of the invention
The technical problem to be solved in the present invention is: overcome defect of the prior art, propose a kind ofly not burn corrupt split aluminium carbon zirconium mass sliding sprue tile for smelting and production method thereof containing amorphous boron, this product has the advantages such as the erosion of intensity high, anti-molten steel, antiscour, anti-oxidant and anti-thermal shock are good.
Technical scheme of the present invention:
A kind of containing amorphous boron do not burn corrupt split aluminium carbon zirconium mass sliding sprue tile for smelting, this brick is made up of the raw material of following weight percentage, the lithium bentonite of the carborundum of the amorphous boron of 0.2-5%, the corundum of 55-78%, 5-15%, the zirconium mullite of 10-20%, the graphite of 2-5%, the alusil alloy of 3-7% and 1-3%, above raw material gross weight is 100%, the phenolic resin binder of additional above-mentioned raw materials total amount 4-6%.
Described corundum comprises schmigel and corundum in granules, the weight ratio of schmigel and corundum in granules is 1:1.2-2.5, granularity≤400 order of schmigel, corundum in granules comprises the particle three kinds of 1mm < granularity≤3mm, 0.5mm < granularity≤1mm and granularity≤0.5mm, and the weight ratio of three kinds of corundum in granules is 2-4:1-2.5:1.
Described graphite is granularity≤200 object crystalline graphite powders; Described alusil alloy is the aluminium of mass ratio 1:1 and the alloyed powder of elemental silicon, granularity≤500 order; Described amorphous boron is granularity≤1000 object amorphous boron powders, and lithium bentonite is granularity≤325 object lithium bentonite powder; Wherein granularity≤the 1mm of zirconium mullite, the granularity≤0.5mm of carborundum.
The described production method of not burning corrupt split aluminium carbon zirconium mass sliding sprue tile for smelting containing amorphous boron, comprises the following steps,
(1) weigh each raw material by proportioning, powder raw material is wherein added in muller and mixes, obtain mixed powder;
(2) add in edge runner-wet mill by particulate material wherein, then add phenolic resins, phenolic resins adds at twice, first add the phenolic resins of 2/3 weight, mix, then add described mixed powder and remaining phenolic resins, mix further and obtain pug; By compressing through friction press for the pug mixed, then drying, cuff, grind, be coated with, namely obtain described aluminium carbon zirconium mass sliding sprue tile for smelting.
Wherein dry requirement is as follows: be warming up to 80 DEG C by room temperature through 12-14h, be warming up to 150 DEG C through 10-12h by 80 DEG C, be warming up to 230 ± 10 DEG C through 8-10h by 150 DEG C, then at 230 ± 10 DEG C of insulation 6-12h, through naturally cooling to room temperature.
positive beneficial effect of the present invention:
1, the present invention adopts corundum, carborundum, zirconium mullite, graphite, alusil alloy, lithium bentonite to be primary raw material, add anti-oxidant good amorphous boron, phenolic resin binder is adopted to be prepared into aluminium carbon zirconium mass sliding sprue tile for smelting, this product has excellent antioxygenic property and higher-strength in the temperature range of 400-1600 DEG C, the better performances such as anti-molten steel erosion, antiscour, anti-oxidant and anti-thermal shock.Specific performance is in table 1.
2, the raw material alusil alloy powder of the present invention's employing, be a kind of antioxidant preferably, it not only can improve the non-oxidizability of carbon containing refractory, can also improve high temperature break resistant intensity and the scour resistance of material, and its hydration resistance is better than common metal aluminium powder; Wherein lithium bentonite can carry out modification to phenolic resins, improves the compressive resistance of product; Introduce the thermal shock resistance that graphite can improve material, overcome the easy fracture of general material, the shortcoming of poor toughness, graphite and molten steel are difficult to infiltrate in addition, can improve anti-erosion and the antioxygenic property of material.
3, the aluminium carbon zirconium mass sliding sprue tile for smelting that the inventive method is burnt till with tradition is compared, and the present invention does not need to burn till and oil immersion pitch, and technique simplifies, and with short production cycle, free from environmental pollution, comprehensive benefit is better; Product is compared with the aluminium carbon sliding sprue tile for smelting do not burnt, and the anti-thermal shock of this product and erosion-resisting characteristics excellence, can use, and service life is longer on large ladle furnace.
4, product of the present invention in use effectively can alleviate the problem of oxidation of phenolic resins at 500-700 DEG C.This be due to amorphous boron in air atmosphere 300 DEG C namely start oxidation, 700 DEG C can burn, its oxidation product and combustion product are the diboron trioxide of low melting point (450 DEG C), the diboron trioxide of a large amount of low melting point is filled with the pore of sliding sprue tile for smelting, block oxygen transmission passage, thus play anti-oxidation effect.Phenolic resin starts oxidation more than 500 DEG C, and namely amorphous boron has started anti-oxidation effect at 500 DEG C, and the two combination ensure that the stable performance of slide plate at each temperature section, and this is that other boride cannot replace.
5, product of the present invention and tundish can use on the large and medium-sized ladle of steel and iron industry, and the life-span is longer, and market potential is comparatively large, is suitable for applying.
Detailed description of the invention
Following examples only in order to further illustrate the present invention, do not represent any limitation of the invention.Wen Zhongru is not particularly illustrated, and percentage composition is wherein weight percentage.
Embodiment 1: a kind of containing amorphous boron do not burn corrupt split aluminium carbon zirconium mass sliding sprue tile for smelting and production method thereof
1, raw material composition: represent with percentage by weight, comprise the corundum of 56.2%, 0.3% amorphous boron, 15% carborundum, 20% zirconium mullite, the graphite of 3%, the alusil alloy of 3.5% and 2% lithium bentonite, the phenolic resin binder of additional above-mentioned raw materials total amount 5%.
Wherein corundum comprises schmigel and corundum in granules, and schmigel granularity≤400 order, accounts for 24.2%; Corundum in granules comprises that 1mm < granularity≤3mm accounts for 16%, 0.5mm < granularity≤1mm accounts for 10%, the particle of granularity≤0.5mm accounts for 6%.
Amorphous boron is granularity≤1000 order amorphous boron powders; Granularity≤the 0.5mm of carborundum, the granularity≤1mm of zirconium mullite, graphite is granularity≤200 object crystalline graphite powders; Alusil alloy is the aluminium of mass ratio 1:1 and the alloyed powder of elemental silicon, granularity≤500 order; Lithium bentonite is granularity≤325 object lithium bentonite powder.
2, production method:
Weigh each raw material by proportioning, powder is wherein mixed as schmigel, alusil alloy powder, scale graphite powder, amorphous boron powder and lithium bentonite powder add in muller, obtains mixed powder; By particulate material wherein as corundum in granules, zirconium mullite, carborundum add in edge runner-wet mill, then phenolic resins is added, phenolic resins adds at twice, first add 2/3 of phenolic resins total amount, mix, add described mixed powder and remaining phenolic resins again, mix further and obtain pug.
By compressing through friction press for the above-mentioned pug mixed, then drying, cuff, grind, be coated with, namely do not burnt the aluminium carbon zirconium mass sliding sprue tile for smelting of corrupt split.
Temperature curve wherein during drying requires: be warming up to 80 DEG C by room temperature through 12-14h, be warming up to 150 DEG C through 10-12h by 80 DEG C, be warming up to 230 ± 10 DEG C through 8-10h by 150 DEG C, then at 230 ± 10 DEG C of insulation more than 6h, naturally cools to room temperature.
Embodiment 2: substantially identical with embodiment 1, difference is:
Raw material forms: represent with percentage by weight, comprise the corundum of 69%, 1.5% amorphous boron, 10% carborundum, 10% zirconium mullite, the graphite of 2%, the alusil alloy of 4.5% and 3% lithium bentonite, the phenolic resin binder of additional above-mentioned raw materials total amount 5.5%.
Wherein corundum comprises schmigel and corundum in granules, and schmigel granularity≤400 order, accounts for 22%; Corundum in granules comprises that 1mm < granularity≤3mm accounts for 25%, 0.5mm < granularity≤1mm accounts for 15%, the particle of granularity≤0.5mm accounts for 7%.
Other ingredient requirements and production method are with embodiment 1.
Embodiment 3: substantially identical with embodiment 1, difference is:
Raw material form: represent with percentage by weight, comprise the corundum of 66%, 3% amorphous boron, 5% carborundum, 15% zirconium mullite, the graphite of 4%, the alusil alloy of 6% and 1% lithium bentonite, the phenolic resin binder of additional above-mentioned raw materials total amount 6%.
Wherein corundum comprises schmigel and corundum in granules, schmigel granularity≤400 order, account for 19%, corundum in granules comprises that 1mm < granularity≤3mm accounts for 24%, 0.5mm < granularity≤1mm accounts for 13%, the particle of granularity≤0.5mm accounts for 10%.
Other ingredient requirements and production method are with embodiment 1.
Embodiment 4: substantially identical with embodiment 1, difference is:
Raw material forms: represent with percentage by weight, comprise the corundum of 75%, 0.5% amorphous boron, 6.5% carborundum, 12% zirconium mullite, the graphite of 2%, the alusil alloy of 3% and 1% lithium bentonite, the phenolic resin binder of additional above-mentioned raw materials total amount 5%.
Wherein corundum comprises schmigel and corundum in granules, schmigel granularity≤400 order, account for 25%, corundum in granules comprises that 1mm < granularity≤3mm accounts for 30%, 0.5mm < granularity≤1mm accounts for 10%, the particle of granularity≤0.5mm accounts for 10%.
Other ingredient requirements and production method are with embodiment 1.
Embodiment 5: substantially identical with embodiment 1, difference is:
Raw material form: represent with percentage by weight, comprise the corundum of 60%, 2% amorphous boron, 12% carborundum, 17% zirconium mullite, the graphite of 3%, the alusil alloy of 4% and 2% lithium bentonite, the phenolic resin binder of additional above-mentioned raw materials total amount 5%.
Wherein corundum comprises schmigel and corundum in granules, schmigel granularity≤400 order, account for 25%, corundum in granules comprises that 1mm < granularity≤3mm accounts for 18%, 0.5mm < granularity≤1mm accounts for 12%, the particle of granularity≤0.5mm accounts for 5%.
The performance indications of not burning corrupt split aluminium carbon zirconium mass sliding sprue tile for smelting that table 1 embodiment obtains
| Product performance index | Number range |
| Bulk density (g/cm 3） | 3.12-3.16 |
| Apparent porosity (%) | 3-4 |
| Cold crushing strength (MPa) | 210-240 |
| High temperature break resistant intensity (1400 DEG C × 0.5h), MPa | 23-29 |
| Non-oxidizability | Excellent |
| Scour resistance | Excellent |
| Thermal shock resistance | Excellent |
Claims (7)
1. one kind containing amorphous boron do not burn corrupt split aluminium carbon zirconium mass sliding sprue tile for smelting, it is characterized in that: this brick is made up of the raw material of following weight percentage, the lithium bentonite of the carborundum of the amorphous boron of 0.2-5%, the corundum of 55-78%, 5-15%, the zirconium mullite of 10-20%, the graphite of 2-5%, the alusil alloy of 3-7% and 1-3%, above raw material gross weight is 100%, the phenolic resin binder of additional above-mentioned raw materials total amount 4-6%;
Described graphite is granularity≤200 object crystalline graphite powders; Described alusil alloy is the aluminium of mass ratio 1:1 and the alloyed powder of elemental silicon, granularity≤500 order; Described amorphous boron is granularity≤1000 object amorphous boron powders, and lithium bentonite is granularity≤325 object lithium bentonite powder.
2. aluminium carbon zirconium mass sliding sprue tile for smelting according to claim 1, it is characterized in that: described corundum is made up of schmigel and corundum in granules, the weight ratio of schmigel and corundum in granules is 1:1.2-2.5, granularity≤400 order of schmigel, corundum in granules is made up of the particle three kinds of 1mm < granularity≤3mm, 0.5mm < granularity≤1mm and granularity≤0.5mm, and the weight ratio of three kinds of corundum in granules is 2-4:1-2.5:1.
3. aluminium carbon zirconium mass sliding sprue tile for smelting according to claim 1, is characterized in that: the wherein granularity≤1mm of zirconium mullite, the granularity≤0.5mm of carborundum.
4. contain the production method of not burning corrupt split aluminium carbon zirconium mass sliding sprue tile for smelting of amorphous boron described in claim 1, its feature
Be: the method comprises the following steps,
(1) weigh each raw material by proportioning, powder raw material is wherein added in muller and mixes, obtain mixed powder;
(2) add in edge runner-wet mill by particulate material wherein, then add phenolic resins, phenolic resins adds at twice, first add the phenolic resins of 2/3 weight, mix, then add described mixed powder and remaining phenolic resins, mix further and obtain pug; By compressing through friction press for the pug mixed, then drying, cuff, grind, be coated with, namely obtain described aluminium carbon zirconium mass sliding sprue tile for smelting.
5. production method according to claim 4, it is characterized in that: wherein dry requirement is as follows: be warming up to 80 DEG C by room temperature through 12-14h, 150 DEG C are warming up to by 80 DEG C through 10-12h, 230 ± 10 DEG C are warming up to by 150 DEG C through 8-10h, then at 230 ± 10 DEG C of insulation 6-12h, through naturally cooling to room temperature.
6. production method according to claim 4, it is characterized in that: described corundum is made up of schmigel and corundum in granules, the weight ratio of schmigel and corundum in granules is 1:1.2-2.5, granularity≤400 order of schmigel, particle is made up of the particle three kinds of 1mm < granularity≤3mm, 0.5mm < granularity≤1mm and granularity≤0.5mm, and the weight ratio of three kinds of corundum in granules is 2-4:1-2.5:1.
7. production method according to claim 4, is characterized in that: the granularity≤1mm of described zirconium mullite, the granularity≤0.5mm of carborundum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210229417.6A CN103121099B (en) | 2012-07-04 | 2012-07-04 | Amorphous boron contained sliding nozzle refractory brick made by combing unfired metal with aluminum, carbon and zirconium materials and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210229417.6A CN103121099B (en) | 2012-07-04 | 2012-07-04 | Amorphous boron contained sliding nozzle refractory brick made by combing unfired metal with aluminum, carbon and zirconium materials and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103121099A CN103121099A (en) | 2013-05-29 |
| CN103121099B true CN103121099B (en) | 2015-05-27 |
Family
ID=48452346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210229417.6A Active CN103121099B (en) | 2012-07-04 | 2012-07-04 | Amorphous boron contained sliding nozzle refractory brick made by combing unfired metal with aluminum, carbon and zirconium materials and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103121099B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162604B (en) * | 2017-04-27 | 2021-03-05 | 无锡市南方耐材有限公司 | Medium-high temperature fired impregnation-free sliding plate brick and preparation method thereof |
| CN109180165B (en) * | 2018-08-26 | 2022-02-22 | 洛阳科创新材料股份有限公司 | Preparation method of sliding plate brick |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986002633A1 (en) * | 1984-10-23 | 1986-05-09 | Nippon Crucible Co., Ltd. | Refractory containing aluminum nitride oxide, refractory for sliding nozzle, and nozzle for continuously casting steel |
| JPH11254125A (en) * | 1998-03-10 | 1999-09-21 | Kawasaki Refract Co Ltd | Sliding nozzle plate |
| JP2004082125A (en) * | 2002-06-28 | 2004-03-18 | Kawasaki Refract Co Ltd | Plate refractory for sliding nozzle |
| CN1229302C (en) * | 2002-09-26 | 2005-11-30 | 山东淄川特种耐火材料厂 | Al-C fireproof material for continuous casting and its production method |
| JP2006026728A (en) * | 2004-07-22 | 2006-02-02 | Jfe Refractories Corp | Sliding nozzle plate and its producing method |
| CN1765818A (en) * | 2005-08-29 | 2006-05-03 | 罗发 | Burn-free sliding gate brick |
| CN100425569C (en) * | 2006-10-19 | 2008-10-15 | 武汉科技大学 | Slide board refractory containing titanium carbo-nitride and its preparing method |
| CN101417889A (en) * | 2008-11-10 | 2009-04-29 | 卫辉熔金高温材料有限责任公司 | Boron-containing unfired Al-C-Zr sliding gate brick |
-
2012
- 2012-07-04 CN CN201210229417.6A patent/CN103121099B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103121099A (en) | 2013-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101244940B (en) | Metallic composite low carbon magnesium carbon brick for ladle slag wire and manufacture method thereof | |
| CN101220195B (en) | Phenolic resin containing nano-carbon powder, nano-carbon modified low carbon magnesium carbon brick and production method thereof | |
| CN101550016B (en) | Magnesia chrome carbon coating and preparation method thereof | |
| CN102249718B (en) | Aluminum magnesium carbon sliding plate brick for stopping slag at steel tapping hole of converter | |
| CN101851106B (en) | Antioxidation aluminium unburned carbon brick and preparation method thereof | |
| CN102329137B (en) | Carbon-free alumina-magnesia unburned brick and preparation method and application thereof | |
| CN102898157B (en) | Al4O4C/Al-Al2O3 composite carbon-free sliding plate and preparation method thereof | |
| CN108484138A (en) | A kind of sliding plate brick and preparation method thereof adding composite alumina micro mist and carbon source | |
| CN102765953B (en) | Magnesia carbon brick containing composite antioxidant and preparation thereof | |
| CN102584293B (en) | Method for preparing magnesium-zirconium-carbon slide gate nozzle | |
| CN103464738B (en) | Add corrupt split slide plate and the production method thereof of titanium | |
| CN103214257A (en) | Novel stemming at tap hole | |
| CN105801145A (en) | Unfired, impregnation-free and environment-friendly sliding plate brick bound through organic silicone modified phenolic resin, production method and application | |
| CN101723685A (en) | Magnesia-alumina spinel stemming | |
| CN103420683A (en) | Tundish low-carbon corundum spinel impact brick and preparation method thereof | |
| CN102898156A (en) | Ladle slag line magnesia carbon brick and preparation method thereof | |
| CN102838361A (en) | MgCa-SiC-C fireproof material and preparation method thereof | |
| CN100519005C (en) | Aluminium carbon zirconium sliding gate brick produced by unburning process | |
| CN103011867B (en) | Preparation method of unfired Al-Al2O3 carbon-free composite sliding plate | |
| CN103121099B (en) | Amorphous boron contained sliding nozzle refractory brick made by combing unfired metal with aluminum, carbon and zirconium materials and production method thereof | |
| CN107673767B (en) | Low-carbon aluminum sliding plate added with magnesium-calcium-aluminum sand and preparation method thereof | |
| CN104086194B (en) | Blast furnace iron outlet groove ramming mass and preparation method thereof | |
| CN102276266A (en) | Low-carbon magnesia carbon brick | |
| CN103304245B (en) | Unfired ferro silicon nitride-alumina composite carbon-free sliding plate and preparation method thereof | |
| CN103214256A (en) | Al23O27N5-combined corundum composite slide plate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 453100 No. 76 worker peasant Road, Xinxiang, Henan, Weihui Applicant after: WEIHUI RONGJIN HIGH TEMPERATURE MATERIAL CO., LTD. Address before: 453100 No. 76 worker peasant Road, Xinxiang, Henan, Weihui Applicant before: Weihui Rongjin Refractory Co., Ltd. |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: WEIHUI RONGJIN REFRACTORY CO., LTD. TO: HENAN RONGJIN HIGH TEMPERATURE MATERIAL CO., LTD. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |