CN110878410A - 3D glass hard alloy die and manufacturing method thereof - Google Patents

3D glass hard alloy die and manufacturing method thereof Download PDF

Info

Publication number
CN110878410A
CN110878410A CN201811038058.XA CN201811038058A CN110878410A CN 110878410 A CN110878410 A CN 110878410A CN 201811038058 A CN201811038058 A CN 201811038058A CN 110878410 A CN110878410 A CN 110878410A
Authority
CN
China
Prior art keywords
glass
hard alloy
die
alloy
mold
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
Application number
CN201811038058.XA
Other languages
Chinese (zh)
Inventor
张月皎
罗恺
何海波
张迪钧
李军旗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Jingshi Yun Chuang Technology Co Ltd
Shenzhen Jingjiang Yunchuang Technology Co Ltd
Original Assignee
Shenzhen Jingshi Yun Chuang Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shenzhen Jingshi Yun Chuang Technology Co Ltd filed Critical Shenzhen Jingshi Yun Chuang Technology Co Ltd
Priority to CN201811038058.XA priority Critical patent/CN110878410A/en
Publication of CN110878410A publication Critical patent/CN110878410A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26Deposition of carbon only
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00Re-forming shaped glass
    • C03B23/02Re-forming glass sheets
    • C03B23/023Re-forming glass sheets by bending
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02Pretreatment of the material to be coated
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32Carbides

Abstract

The invention provides a manufacturing method of a 3D glass hard alloy die, which comprises the following steps: providing a hard alloy die blank; placing the hard alloy die blank into a reaction chamber and exhausting air in the reaction chamber; heating the reaction chamber, and reducing the oxide on the inner surface of the die cavity of the hard alloy die blank; introducing carbon-containing gas; and introducing halide gas of a substance to be deposited, and enabling the halide gas and carbon-containing gas to react and deposit on the inner surface of the blank die cavity of the hard alloy die so as to form a deposition layer and obtain the 3D glass hard alloy die. The invention further provides a 3D glass hard alloy die.

Description

3D glass hard alloy die and manufacturing method thereof
Technical Field
The invention relates to a 3D glass mold, in particular to a 3D glass hard alloy mold and a manufacturing method thereof.
Background
Because of the unique properties of the 3D glass material, the 3D glass is widely applied to the field of electronic products such as mobile phones, flat plates and the like, at present, the graphite mold is mainly used for forming the 3D glass, and the graphite mold has a thermal expansion coefficient similar to that of the glass and does not react with the glass at high temperature. The graphite material is a porous material, and the porous structure of the graphite material can cause concave-convex points, pockmarks and the like on the surface of the glass during molding, thereby reducing the appearance quality and yield. Meanwhile, the graphite material is very easy to be oxidized and scratched, and the service life is short, so that the cost of the die is too high. The hard alloy has high density, no obvious pores on the surface of the material, oxidation resistance and excellent performance, and can be used as a substitute of a graphite mold in the field of 3D glass. However, cemented carbide materials are likely to react with glass at high temperatures, resulting in the formation of a sticky film.
Disclosure of Invention
In view of the above, there is a need for a method for manufacturing a 3D glass cemented carbide mold that can solve the above problems.
The 3D glass hard alloy die manufactured by the manufacturing method is also provided.
A manufacturing method of a 3D glass hard alloy mold comprises the following steps: providing a hard alloy die blank; placing the hard alloy die blank into a reaction chamber and exhausting air in the reaction chamber; heating the reaction chamber, and reducing the oxide on the inner surface of the die cavity of the hard alloy die blank; introducing carbon-containing gas; and introducing halide gas of a substance to be deposited, and enabling the halide gas and carbon-containing gas to react and deposit on the inner surface of the blank die cavity of the hard alloy die so as to form a deposition layer and obtain the 3D glass hard alloy die.
The utility model provides a 3D glass carbide mould, 3D glass carbide mould includes cope match-plate pattern and the lower bolster of mutually supporting, the die cavity that cope match-plate pattern and lower bolster formed jointly is used for adding man-hour shaping 3D glass, the cope match-plate pattern with the lower bolster adopts the alloy to make, the cope match-plate pattern with the lower bolster is formed with a sedimentary deposit on the die cavity internal surface at least, the sedimentary deposit mainly is carbon or carbide.
According to the 3D glass hard alloy mold, the carbon or carbide deposition layer is formed on the inner surface of the hard alloy mold cavity in a chemical vapor deposition mode, so that the hard alloy material can be used as a 3D glass forming mold, the defect that graphite is used as the forming mold is overcome, and the cost is low.
Drawings
Fig. 1 is a perspective view of a 3D glass cemented carbide mold in one embodiment of the invention.
FIG. 2 is a flow chart of the method for manufacturing the 3D glass cemented carbide mold of the present invention.
Description of the main elements
3D glass carbide die 100
Upper template 10
Lower template 20
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that when an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. When an element is referred to as being "disposed on" another element, it can be directly on the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, the present invention provides a 3D glass cemented carbide mold 100 for molding 3D glass. The 3D glass cemented carbide mold 100 includes an upper mold plate 10 and a lower mold plate 20 that are fitted to each other. The upper mold plate 10 and the lower mold plate 20 together form a mold cavity for molding 3D glass during processing.
The upper template 10 and the lower template 20 are made of alloy with the same material. Preferably, the upper and lower templates 10 and 20 are made of an alloy having a thermal expansion coefficient similar to that of 3D glass and no significant pores on the surface of the material.
Specifically, the upper mold plate 10 and the lower mold plate 20 may be made of one of WC-Co (or referred to as WC-Co), WC-TiC-Co (or referred to as WC-ti-Co), WC-TiC-tac (nbc) -Co, WC-based alloy, and WC-based alloy, which have thermal expansion coefficients centered at 4.5 to 7.4 × 10 "6/° c, according to the 3D glass to be formed.
For example, when the processing structure is complex and 3D glass with high impact pressure is needed, the tungsten-cobalt alloy is suitable for being used. The composite material mainly comprises tungsten carbide and cobalt, wherein other carbides (tantalum carbide, niobium carbide, vanadium carbide and the like) with the content of less than 2% are added as additives, and the content of the cobalt is 3-30%. And the high cobalt alloy with 20-30% cobalt content is suitable for 3D glass forming die materials with high impact pressure.
The tungsten titanium cobalt alloy contains 4-40% of titanium carbide and 4-15% of cobalt, and compared with the tungsten cobalt alloy, the tungsten titanium cobalt alloy has higher oxidation resistance and longer service life, but has weaker impact resistance, and is more suitable for being used as a 3D glass mold with a simpler structure.
The NbC-Co alloy comprises 5-15% of titanium carbide, 2-10% of tantalum carbide (niobium carbide), 5-15% of cobalt and the balance of tungsten carbide. Compared with tungsten-titanium-cobalt alloy, the alloy has better high-temperature oxidation resistance and better thermal shock resistance, and is suitable for high forming temperature (650-1000 ℃) and frequent cold and hot impact (the high-temperature to room temperature conversion within 15-50 min).
The tungsten carbide-based alloy and the titanium carbide-based alloy consist of tungsten carbide or titanium carbide and carbon steel or alloy steel. The annealing has higher cutting processing performance compared with other alloys. And the raw material price is low, the manufacturing process is simple, the processing cost is low, and the cost is lower.
The upper mold plate 10 and the lower mold plate 20 are subjected to a surface treatment process at least on the inner surface of the mold cavity to form a deposition layer. Preferably, the contact surfaces of the upper template 10 and the lower template 20 are both subjected to surface treatment to form a deposition layer. The deposition layer has high temperature resistance and thermal shock resistance, and does not react with glass at high temperature. In particular, the deposit is primarily carbon or carbide. The carbon or carbide as a deposition layer can bear the high temperature of 650-1000 ℃, can still keep good bonding force with the hard alloy under frequent high-low temperature conversion, and the deposition layer can not be adhered to the glass after the glass is formed.
Referring to fig. 2, the present invention further provides a method for manufacturing a 3D glass cemented carbide mold by Chemical Vapor Deposition (CVD), which comprises the following steps:
in step S1, a cemented carbide mold blank is provided. The hard alloy mold blank comprises an upper template 10 and a lower template 20 which are matched with each other, and a mold cavity formed by the upper template 10 and the lower template 20 is used for molding 3D glass during machining.
Step S2, the inner surface of the cavity of the cemented carbide mold blank is pretreated. Specifically, the contact surface between the upper mold plate 10 and the lower mold plate 20 and the inner surface of the mold cavity formed on the contact surface are polished, cleaned, and dried.
And step S3, placing the cleaned hard alloy die blank into a reaction chamber, and removing air in the reaction chamber. Specifically, the upper template 10 and the lower template 20 are placed in a reaction chamber of an induction furnace, and vacuum pumping is performed until the pressure is below 1 Pa.
And step S4, heating the reaction chamber, and reducing the oxide on the inner surface of the die cavity of the hard alloy die blank. Specifically, the upper template 10 and the lower template 20 are heated to a temperature above 1000 ℃, and dry hydrogen is introduced into the reaction chamber to reduce oxides on the contact surface of the upper template 10 and the lower template 20 and the inner surface of the mold cavity.
And step S5, introducing carbon-containing gas. Specifically, methane is introduced into the reaction chamber, and the air pressure in the reaction chamber is maintained at 1-2 kPa for 1-3 h.
And step S6, introducing halide gas of the substance to be deposited, and reacting the halide gas with the carbon-containing gas to deposit on the inner surface of the cavity of the mold, thereby forming a deposited layer.
Specifically, hydrogen is used as a carrier, and halide gas such as SiCl4, TiCl4 and the like of a substance to be deposited is introduced, so that the halide gas and the methane gas are subjected to reaction deposition on the contact surface of the upper template 10 and the lower template 20 and the inner surface of the mold cavity, and the reaction time is about 5-20 hours. The thickness of the deposited layer is increased along with the prolonging of the reaction time, the ratio of the hydrogen to the methane gas and the total pressure are kept, or the ratio of the hydrogen to the methane gas and the total pressure are linearly adjusted along with the time, so that the carbon or carbide deposited layer with fixed components or gradient change is formed.
And step S7, cooling. Specifically, after the deposition is finished, the temperature in the reaction chamber and the hydrogen atmosphere are maintained for a period of time, and then the mold is gradually cooled as the temperature in the reaction chamber decreases, thereby obtaining the 3D glass cemented carbide mold 100 containing the desired deposition layer.
According to the 3D glass hard alloy mold 100, the carbon or carbide deposition layer is formed on the inner surface of the hard alloy mold cavity in a chemical vapor deposition mode, so that the hard alloy material can be used as a 3D glass forming mold, the defect that graphite is used as the forming mold is overcome, and the cost is low.
In addition, other modifications within the spirit of the invention may occur to those skilled in the art, and such modifications are, of course, included within the scope of the invention as claimed.

Claims (10)

1. A manufacturing method of a 3D glass hard alloy mold comprises the following steps:
providing a hard alloy die blank;
placing the hard alloy die blank into a reaction chamber and exhausting air in the reaction chamber;
heating the reaction chamber, and reducing the oxide on the inner surface of the die cavity of the hard alloy die blank;
introducing carbon-containing gas; and
and introducing halide gas of a substance to be deposited, and reacting and depositing the halide gas and carbon-containing gas on the inner surface of the blank die cavity of the hard alloy die to form a deposition layer, thereby obtaining the 3D glass hard alloy die.
2. The method of making a 3D glass-cemented carbide mold of claim 1, wherein: the method also comprises the step of pretreating the inner surface of the die cavity of the hard alloy die blank before the step of placing the hard alloy die blank into the reaction chamber and exhausting air in the reaction chamber.
3. The method of making a 3D glass-cemented carbide mold of claim 1, wherein: the hard alloy die blank can be made of one of WC-Co alloy, WC-TiC-TaC-Co alloy, tungsten carbide base alloy and titanium carbide base alloy.
4. The method of making a 3D glass-cemented carbide mold of claim 1, wherein: the step of forming the deposition layer comprises the steps of taking hydrogen as a carrier, introducing halide gas of a substance to be deposited, enabling the halide gas and carbon-containing gas to react and deposit on the inner surface of the die cavity of the hard alloy die blank, and keeping the proportion and the total pressure of the hydrogen and the carbon-containing gas or linearly adjusting the proportion and the total pressure of the hydrogen and the carbon-containing gas with time, thereby forming the carbon or carbide deposition layer with fixed components or gradient change.
5. The method of making a 3D glass-cemented carbide mold of claim 1, wherein: after the step of forming the deposition layer, the method also comprises the step of cooling.
6. The utility model provides a 3D glass carbide mould which characterized in that: the 3D glass hard alloy die comprises an upper die plate and a lower die plate which are matched with each other, a die cavity formed by the upper die plate and the lower die plate is used for forming 3D glass during machining, the upper die plate and the lower die plate are made of alloy, a deposition layer is at least formed on the inner surface of the die cavity by the upper die plate and the lower die plate, and the deposition layer is mainly carbon or carbide.
7. The 3D glass-cemented carbide mold of claim 6, wherein: the upper template and the lower template are made of the same material.
8. The 3D glass-cemented carbide mold of claim 6, wherein: the deposited layers are formed on the contact surfaces of the upper template and the lower template.
9. The 3D glass-cemented carbide mold of claim 6, wherein: the composition of the deposited layer is fixed or varies in a gradient.
10. The 3D glass-cemented carbide mold of claim 6, wherein: the upper template and the lower template are made of one of WC-Co alloy, WC-TiC-TaC-Co alloy, tungsten carbide base alloy and titanium carbide base alloy.
CN201811038058.XA 2018-09-06 2018-09-06 3D glass hard alloy die and manufacturing method thereof Pending CN110878410A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811038058.XA CN110878410A (en) 2018-09-06 2018-09-06 3D glass hard alloy die and manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811038058.XA CN110878410A (en) 2018-09-06 2018-09-06 3D glass hard alloy die and manufacturing method thereof

Publications (1)

Publication Number Publication Date
CN110878410A true CN110878410A (en) 2020-03-13

Family

ID=69727198

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811038058.XA Pending CN110878410A (en) 2018-09-06 2018-09-06 3D glass hard alloy die and manufacturing method thereof

Country Status (1)

Country Link
CN (1) CN110878410A (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3124872A1 (en) * 1981-06-24 1983-01-13 Moskovskij institut inženerov železnodorožnogo transporta Process for applying wear-resistant coatings of titanium carbide or titanium carbonitride to products made of sintered hard alloys
JPS63140084A (en) * 1986-12-01 1988-06-11 Sumitomo Electric Ind Ltd Hard carbon coated parts
CN1342215A (en) * 1999-02-11 2002-03-27 哈迪德有限公司 Tungsten carbide coatings and method for producing the same
CN1670245A (en) * 2004-03-20 2005-09-21 鸿富锦精密工业(深圳)有限公司 Die with superhard filming
CN1721346A (en) * 2004-07-16 2006-01-18 鸿富锦精密工业(深圳)有限公司 The die of moulded glass and manufacture method thereof
CN101454479A (en) * 2006-05-31 2009-06-10 柯尼卡美能达精密光学株式会社 Method for film formation, mold, and method for manufacturing mold
CN105039928A (en) * 2015-06-17 2015-11-11 姜辛 Preparation method of diamond/silicon carbide three-dimensional composite structure and prepared product
CN105543803A (en) * 2015-12-16 2016-05-04 中国科学院深圳先进技术研究院 Diamond/boron carbide composite coating of hard alloy substrate and preparation method thereof
CN107848868A (en) * 2015-07-10 2018-03-27 恩特格里斯公司 For glass shaping die coating and include the mould of the coating

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3124872A1 (en) * 1981-06-24 1983-01-13 Moskovskij institut inženerov železnodorožnogo transporta Process for applying wear-resistant coatings of titanium carbide or titanium carbonitride to products made of sintered hard alloys
JPS63140084A (en) * 1986-12-01 1988-06-11 Sumitomo Electric Ind Ltd Hard carbon coated parts
CN1342215A (en) * 1999-02-11 2002-03-27 哈迪德有限公司 Tungsten carbide coatings and method for producing the same
CN1670245A (en) * 2004-03-20 2005-09-21 鸿富锦精密工业(深圳)有限公司 Die with superhard filming
CN1721346A (en) * 2004-07-16 2006-01-18 鸿富锦精密工业(深圳)有限公司 The die of moulded glass and manufacture method thereof
CN101454479A (en) * 2006-05-31 2009-06-10 柯尼卡美能达精密光学株式会社 Method for film formation, mold, and method for manufacturing mold
CN105039928A (en) * 2015-06-17 2015-11-11 姜辛 Preparation method of diamond/silicon carbide three-dimensional composite structure and prepared product
CN107848868A (en) * 2015-07-10 2018-03-27 恩特格里斯公司 For glass shaping die coating and include the mould of the coating
CN105543803A (en) * 2015-12-16 2016-05-04 中国科学院深圳先进技术研究院 Diamond/boron carbide composite coating of hard alloy substrate and preparation method thereof

Similar Documents

Publication Publication Date Title
KR20120014825A (en) Open-porous metal foam body and a method of fabricating the same
CN111217611B (en) Aluminum nitride and boron nitride composite ceramic material and preparation method thereof
CN107117802A (en) The manufacture method of glass-forming die and bend glass
US10435325B2 (en) Molds with coatings for high temperature use in shaping glass-based material
CN110079720B (en) Gradient hard alloy and preparation method and application thereof
CN113234950B (en) Preparation method of Ti (C, N) -based metal ceramic
CN109972100A (en) A kind of preparation method of tubulose chromium target
CN113930635B (en) Stainless steel reinforced aluminum silicon carbide composite material and preparation method thereof
CN106521202A (en) Preparing method for molybdenum-hafnium alloy panel
CN110878410A (en) 3D glass hard alloy die and manufacturing method thereof
CN111187959A (en) Metal-rich phase gradient structure titanium carbonitride base cermet and preparation method thereof
CN114835496B (en) Cr (chromium) 3 C 2 Preparation method of block material
CN104193422B (en) A kind of glass moulding silicon carbide ceramics die and preparation method thereof
CN109963672B (en) Heat treatment method and manufacturing method of metal formed product
TWI297331B (en) Heat transfer plate for molding glass
CN112125673B (en) Method for preparing right-angle stringer based on precursor impregnation cracking process
CN108975886B (en) Micro-texture self-lubricating wire drawing die based on 3D printing technology
TWI590939B (en) Imprinting mold and method for manufacturing the same
CN110125332A (en) Automobile die material smelting technology
CN115286222B (en) 3D glass hot-bending graphite die and preparation method thereof
CN116855902B (en) Low-aluminum-content titanium-based target material and preparation method thereof
CN100419119C (en) Superhard filming mold
CN109465456B (en) Improved artificial diamond sintered body preparation process
JP4052210B2 (en) Manufacturing method of ceramic structure
CN107434435B (en) Graphite enamel material and manufacturing method thereof

Legal Events

Date Code Title Description
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20200313

WD01 Invention patent application deemed withdrawn after publication