CN103667843B - A kind of preparation method of deep hole machining ultra-fine cemented carbide cutter material - Google Patents
A kind of preparation method of deep hole machining ultra-fine cemented carbide cutter material Download PDFInfo
- Publication number
- CN103667843B CN103667843B CN201310715220.8A CN201310715220A CN103667843B CN 103667843 B CN103667843 B CN 103667843B CN 201310715220 A CN201310715220 A CN 201310715220A CN 103667843 B CN103667843 B CN 103667843B
- Authority
- CN
- China
- Prior art keywords
- ball
- powder
- solid solution
- milling
- vacuum
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a kind of preparation method of deep hole machining ultra-fine cemented carbide cutter material, it is characterized in that adopting VC-Co saturated solid solution to be Binder Phase, and make Surface coating Tween 80 molecular film by ultrasonic disperse and pH value adjustment; (WC, VC) binary composite powder is adopted to realize VC to WC crystal boundary face inhibition of metastasis; Controlling the weight * particle mean size of weight * particle mean size=(WC, VC) powder of (W, Ta) C powder for improving red hardness, making the two granule number coupling.Being difficult to that the preparation method of ultra-fine cemented carbide material of the present invention can avoid the mode of adding after inhibitor in traditional handicraft to cause is dispersed, inhibitor self is reunited and liquid-phase sintering time dissolve in Binder Phase and cause the problem that inhibitory action can not give full play to, the composite request of deep hole processing cutter material high-strength tenacity and high rigidity can be met.
Description
Technical field
The present invention relates to a kind of preparation method of Hardmetal materials, especially for the preparation method of the ultra-fine cemented carbide cutter material of deep hole machining, belong to Hardmetal materials field.
Background technology
Carbide alloy is using infusibility transition metal carbides such as WC as base, using iron group metal elements such as Co as binding agent, adopts the multiphase solid material that powder metallurgy process is prepared into.Carbide alloy has the excellent performance such as high rigidity, wear resistant corrosion resistant, high elastic modulus, low thermal coefficient of expansion, and therefore carbide alloy is widely used in cutting tool, is described as " tooth of industry ".There are the intrinsic contradictions of intensity and hardness as fragile material in carbide alloy, generally more high strength is lower for its hardness, and intensity more high rigidity is lower.In the W-Co kind carbide alloy that composition is identical, WC grain is thinner, and the hardness of carbide alloy is higher, and wearability is better; WC grain is thicker, and bending strength is higher, and impact flexibility is better, and hardness and wear resistance declines.And in many occasions of machining, as required during deep hole machining, cutter has the Good All-around Property of high strength and high hardness, can meet the demands through fine.
At present, ultra-fine cemented carbide has become an important development direction of carbide alloy, but how to suppress growing up of WC grain in sintering process to be the difficult problem that needs solve.Patent of invention 200510032406.9 discloses a kind of preparation method of ultrahigh hardness ultra-fine cemented carbide.Batching selects the ultra-fine WC powder of Fsss0.2 ~ 0.4 μm to be hard phase, adopt the Mo of trace≤3.0wt% or the Ni of≤1.0wt% and or Co powder as binding agent, the Fisher particle size of Ni and Co powder is 0.85 ~ 1.4 μm, inhibitor (VC+Cr
3c
2) content control in the scope of (0.45 ~ 0.9) wt %, wherein Cr
3c
2: VC=1.8 ~ 1.1.Select the ultra-fine WC powder of 0.4 μm as hard phase when patent of invention 201110347141.7 is prepared burden, percentage by weight be the Co powder of 8% as Binder Phase, the Fisher particle size of cobalt powder is 1.42 μm, and the addition of inhibitor is VC:0.2%, NbC:0.4%.
Visible, VC, Cr
3c
2become effective WC grain Deng transition metal carbide to grow up inhibitor.But there are some adverse effects in the mode of adding after extensively adopting inhibitor when current ultra-fine cemented carbide manufactures.On the one hand, due to VC, Cr
3c
2little Deng the grow up addition of inhibitor of WC grain, volume fraction is little, and usually about about 1%, be difficult to evenly spread to around WC grain and suppress it to grow; The inhibitor self that these trace contrary add is easy to reunite and forms defect.On the other hand, the inhibitor that in sintering process, trace adds preferentially dissolves in liquid phase binding metal, although stop WC Ostwald slaking in the liquid phase to a certain extent, but it reduces at WC grain interfacial segregation, be difficult to the effect by hindering the interfacial migration of WC to realize suppressing WC particle agglomeration.
Summary of the invention
That adds after adopting during current manufacture deep hole machining ultra-fine cemented carbide cutter material that the mode of inhibitor exists is difficult to the problem that dispersed, easy reunion and optimum solvation causes inhibitory action not give full play to after liquid phase.The present invention is directed to current technology Problems existing, take VC as inhibitor, adds TaC and improves red hardness.Adopt (WC, VC) binary composite powder, VC-Co saturated solid solution powder and (W, Ta) C binary solid solution powder is raw material, control its composition, blending powder mode and manufacturing process, invent a kind of ultra-fine cemented carbide material preparation method, the composite request of deep hole processing cutter material high-strength tenacity and high rigidity can have been met.
The preparation method of deep hole machining ultra-fine cemented carbide cutter material of the present invention, is characterized in that comprising following steps successively:
(1) surface treatment of VC-Co saturated solid solution: take the VC-Co saturated solid solution powder that granularity is 1.0 ~ 1.5 μm by 6 ~ 11wt%, in solid-solution powder, VC content is its saturation solubility 10wt% in Co; Solid-solution powder is put into the absolute ethyl alcohol being added with Tween 80 and carry out the process of 30 ~ 60min ultrasonic disperse, adopt NH
3.H
2o and HCOOH adjust ph, to 7.5 ~ 8.5, makes VC-Co saturated solid solution powder coated one deck Tween 80 molecular film;
(2) matching treatment of (W, Ta) C binary solid solution powder: take (WC, TaC) binary solid solution powder by 20 ~ 50wt%, powder size is 2.0 ~ 3.0 μm, and TaC content is 15 ~ 45wt%; 12 ~ 72h planetary ball mill is carried out to (W, Ta) C, makes the weight * particle mean size of weight * particle mean size=(WC, VC) powder of (W, Ta) C powder; The volume fraction of the two is mated;
(3) the pre-ball milling of (WC, VC) binary composite powder: (WC, VC) binary composite powder is surplus, powder size is 0.2 ~ 0.45 μm, and VC content is 0.5wt%, joins (W after precise, Ta) ball milling 12 ~ 72h in C binary solid solution, makes the two Homogeneous phase mixing;
(4) green compact preparation: VC-Co saturated solid solution, (W, Ta) C binary solid solution are mixed with the slip of (WC, VC) binary composite powder, and adds after ball mill carries out ball milling, filtration, drying and be pressed into green compact;
(5) vacuum-sintering: vacuum-sintering is carried out in a vacuum furnace, at 300 DEG C ~ 600 DEG C, be first incubated 2 ~ 4h to remove forming agent, vacuum is 10 ~ 15Pa; At 1350 ~ 1450 DEG C temperature retention time be 1 ~ 3h to complete vacuum-sintering, vacuum is 1 ~ 5 Pa;
(6) low pressure sintering: low pressure sintering carries out in low-pressure sintering furnace, sintering temperature is 1450 DEG C ~ 1550 DEG C, temperature retention time 2 ~ 5h, and argon pressure is 5 ~ 10MPa.
The preparation method of deep hole machining ultra-fine cemented carbide cutter material of the present invention, is further characterized in that:
(1), during the surface treatment of VC-Co saturated solid solution, first VC-Co saturated solid solution material powder and absolute ethyl alcohol are made into the suspension that mass percent is 5 ~ 30%, add the Tween 80 of 1 ~ 5vol%;
(2) (W, during the matching treatment of Ta) C binary solid solution powder, ball-milling medium is absolute ethyl alcohol, its dosage is 100 ~ 500ml/kg, ball milling speed is 200 ~ 400r/min, milling time is 12h ~ 60h, and mill ball is the WC-6wt%Co sintered carbide ball of Φ 6, and ball material weight ratio is 5:1 ~ 10:1;
(3) (WC, VC) during the pre-ball milling of binary composite powder, ball-milling medium is absolute ethyl alcohol, its dosage is 100 ~ 500ml/kg, ball milling speed is 60 ~ 100r/min, milling time is 12h ~ 60h, and mill ball is the WC-8wt%Co sintered carbide ball of Φ 6 ~ 8mm, and ball material weight ratio is 3:1 ~ 5:1;
(4) when prepared by compound, ball-milling medium is absolute ethyl alcohol, and its dosage is 100 ~ 500ml/kg, ball milling speed is 60 ~ 100r/min, milling time is 12h ~ 60h, and mill ball is the WC-8wt%Co sintered carbide ball of Φ 6 ~ 8mm, and ball material weight ratio is 3:1 ~ 5:1; The addition of wax moulding agent is 2 ~ 8wt%, and the joining day is that wet-milling terminates front 2 ~ 6h; After ball milling, cermet slip filters through 400 orders, and vacuum drying treatment temperature is 85 DEG C ~ 120 DEG C, and vacuum is 1 ~ 5 Pa; Green compact are pressed under 300 ~ 500MPa.
The invention has the advantages that: (1) ultra-fine cemented carbide Binder Phase adopts VC-Co saturated solid solution powder, and VC can be made dispersed at Co Binder Phase; And its content is saturated, its Coarse Grain effect can not be reduced because of the dissolving of VC in Co in sintering process.(2) ultra-fine cemented carbide hard phase adopts (WC, VC) binary composite powder, and VC is uniformly distributed near WC particle, can make its in sintering process near WC crystal boundary segregation, realize original position inhibiting grain growth; Simultaneously with WC compound after its scale amplifying, be no longer add after trace, that can avoid in mechanical milling process is uneven.(3) TaC for improving red hardness adopts (W, Ta) mode of C binary solid solution is added, it can be made dispersed, control (W simultaneously, Ta) C binary solid solution and (WC, VC) grain size proportion of binary composite powder, makes the granule number of the two suitable, the microcell Homogeneous phase mixing of both realizations.
Detailed description of the invention
The granularity of example 1:VC-Co saturated solid solution is 1.5 μm, VC content 10wt%; (W, Ta) C binary solid solution granularity is 2.6 μm, TaC content 35wt%; (WC, VC) binary composite powder granularity is 0.4 μm, VC content 0.5wt%; The content of three kinds of raw materials is respectively 6wt%, 25wt%, 69wt%.First VC-Co saturated solid solution powder and absolute ethyl alcohol are made into mass percent be 20% suspension carry out ultrasonic process, the addition of Tween 80 is 1vol%, and the ultrasonic disperse time is 30min.Then by (W, Ta) C binary solid solution planetary ball mill 72h, the weight * particle mean size of weight * particle mean size=(WC, VC) powder of (W, Ta) C powder is made.Ball-milling medium is absolute ethyl alcohol, and its dosage is 200ml/kg, and ball milling speed is 380r/min, and mill ball is the WC-6wt%Co sintered carbide ball of Φ 6mm, and ball material weight ratio is 10:1.Again by (WC, VC) binary composite powder joins the complete (W of matching treatment, Ta) pre-ball milling is carried out in C slip, ball-milling medium is absolute ethyl alcohol, its dosage is 300ml/kg, and ball milling speed is 80r/min, and milling time is 24h, mill ball is the WC-8wt%Co sintered carbide ball of Φ 6mm, and ball material weight ratio is 3:1.Finally by VC-Co saturated solid solution, (W, Ta) C binary solid solution and (WC, VC) the slip mixing of binary composite powder, add ball mill together and carry out ball milling, ball-milling medium is absolute ethyl alcohol, and its dosage is 300ml/kg, ball milling speed is 60r/min, milling time is 24h, and mill ball is the WC-8wt%Co sintered carbide ball of Φ 8mm, and ball material weight ratio is 4:1; The addition of wax moulding agent is 3wt%, and the joining day is that wet-milling terminates front 6h; After ball milling, carbide alloy mixture slip filters through 400 orders, and vacuum drying treatment temperature is 90 DEG C, and vacuum is 5 Pa; Green compact are pressed under 300MPa.Green compact carry out at 500 DEG C in a vacuum furnace, and insulation 2h, vacuum is remove forming agent under 10Pa.Be 1430 DEG C in sintering temperature, temperature retention time is complete sintering under 1h, vacuum 5Pa.By the carbide alloy that sinters in low-pressure sintering furnace, low pressure sintering carries out at 1500 DEG C, temperature retention time 2h, and argon pressure is 5MPa.The WC grain degree of prepared ultra-fine cemented carbide is 0.4 ~ 0.5 μm, hardness 93.1HRA, bending strength 3500MPa.
The granularity of example 2:VC-Co saturated solid solution is 1.4 μm, VC content 10wt%; (W, Ta) C binary solid solution granularity is 2.1 μm, TaC content 21wt%; (WC, VC) binary composite powder granularity is 0.45 μm, VC content 0.5wt%; The content of three kinds of raw materials is respectively 10wt%, 45wt%, 45wt%.First VC-Co saturated solid solution powder and absolute ethyl alcohol are made into mass percent be 20% suspension carry out ultrasonic process, the addition of Tween 80 is 2vol%, and the ultrasonic disperse time is 40min.Then by (W, Ta) C binary solid solution planetary ball mill 42h, the weight * particle mean size of weight * particle mean size=(WC, VC) powder of (W, Ta) C powder is made.Ball-milling medium is absolute ethyl alcohol, and its dosage is 250ml/kg, and ball milling speed is 340r/min, and mill ball is the WC-6wt%Co sintered carbide ball of Φ 6mm, and ball material weight ratio is 8:1.Again by (WC, VC) binary composite powder joins the complete (W of matching treatment, Ta) pre-ball milling is carried out in C slip, ball-milling medium is absolute ethyl alcohol, its dosage is 300ml/kg, and ball milling speed is 90r/min, and milling time is 36h, mill ball is the WC-8wt%Co sintered carbide ball of Φ 6mm, and ball material weight ratio is 4:1.Finally by VC-Co saturated solid solution, (W, Ta) C binary solid solution and (WC, VC) the slip mixing of binary composite powder, add ball mill together and carry out ball milling, ball-milling medium is absolute ethyl alcohol, and its dosage is 350ml/kg, ball milling speed is 70r/min, milling time is 36h, and mill ball is the WC-8wt%Co sintered carbide ball of Φ 8mm, and ball material weight ratio is 3:1; The addition of wax moulding agent is 2wt%, and the joining day is that wet-milling terminates front 4h; After ball milling, carbide alloy mixture slip filters through 400 orders, and vacuum drying treatment temperature is 95 DEG C, and vacuum is 1 Pa; Green compact are pressed under 350MPa.Green compact carry out at 550 DEG C in a vacuum furnace, and insulation 2.5h, vacuum is remove forming agent under 15Pa.Be 1400 DEG C in sintering temperature, temperature retention time is complete sintering under 2h, vacuum 5Pa.By the carbide alloy that sinters in low-pressure sintering furnace, low pressure sintering carries out at 1510 DEG C, temperature retention time 2h, and argon pressure is 6MPa.The WC grain degree of prepared coarse grain hard alloy is 0.45 ~ 0.5 μm, hardness 92.5HRA, bending strength 3800MPa.
Claims (2)
1. a deep hole machining preparation method for ultra-fine cemented carbide cutter material, is characterized in that comprising following steps successively:
(1) surface treatment of VC-Co saturated solid solution: take the VC-Co saturated solid solution powder that granularity is 1.0 ~ 1.5 μm by 6 ~ 11wt%, in solid-solution powder, VC content is its saturation solubility 10wt% in Co; Solid-solution powder is put into the absolute ethyl alcohol being added with Tween 80 and carry out the process of 30 ~ 60min ultrasonic disperse, adopt NH
3.H
2o and HCOOH adjust ph, to 7.5 ~ 8.5, makes VC-Co saturated solid solution powder coated one deck Tween 80 molecular film;
(2) matching treatment of (W, Ta) C binary solid solution powder: take (W, Ta) C binary solid solution powder by 20 ~ 50wt%, powder size is 2.0 ~ 3.0 μm, and TaC content is 15 ~ 45wt%; 12 ~ 72h planetary ball mill is carried out to (W, Ta) C, makes the weight * particle mean size of weight * particle mean size=(WC, VC) powder of (W, Ta) C powder; The volume fraction of the two is mated;
(3) the pre-ball milling of (WC, VC) binary composite powder: (WC, VC) binary composite powder is surplus, powder size is 0.2 ~ 0.45 μm, and VC content is 0.5wt%, joins (W after precise, Ta) ball milling 12 ~ 72h in C binary solid solution, makes the two Homogeneous phase mixing;
(4) green compact preparation: VC-Co saturated solid solution, (W, Ta) C binary solid solution are mixed with the slip of (WC, VC) binary composite powder, and adds after ball mill carries out ball milling, filtration, drying and be pressed into green compact;
(5) vacuum-sintering: vacuum-sintering is carried out in a vacuum furnace, at 300 DEG C ~ 600 DEG C, be first incubated 2 ~ 4h to remove forming agent, vacuum is 10 ~ 15Pa; At 1350 ~ 1450 DEG C temperature retention time be 1 ~ 3h to complete vacuum-sintering, vacuum is 1 ~ 5 Pa;
(6) low pressure sintering: low pressure sintering carries out in low-pressure sintering furnace, sintering temperature is 1450 DEG C ~ 1550 DEG C, temperature retention time 2 ~ 5h, and argon pressure is 5 ~ 10MPa.
2. the preparation method of deep hole machining ultra-fine cemented carbide cutter material according to claim 1, is further characterized in that:
(1), during the surface treatment of VC-Co saturated solid solution, first VC-Co saturated solid solution material powder and absolute ethyl alcohol are made into the suspension that mass percent is 5 ~ 30%, add the Tween 80 of 1 ~ 5vol%;
(2) (W, during the matching treatment of Ta) C binary solid solution powder, ball-milling medium is absolute ethyl alcohol, its dosage is 100 ~ 500ml/kg, ball milling speed is 200 ~ 400r/min, milling time is 12h ~ 60h, and mill ball is the WC-6wt%Co sintered carbide ball of Φ 6mm, and ball material weight ratio is 5:1 ~ 10:1;
(3) (WC, VC) during the pre-ball milling of binary composite powder, ball-milling medium is absolute ethyl alcohol, its dosage is 100 ~ 500ml/kg, ball milling speed is 60 ~ 100r/min, milling time is 12h ~ 60h, and mill ball is the WC-8wt%Co sintered carbide ball of Φ 6 ~ 8mm, and ball material weight ratio is 3:1 ~ 5:1;
(4) when prepared by compound, ball-milling medium is absolute ethyl alcohol, and its dosage is 100 ~ 500ml/kg, ball milling speed is 60 ~ 100r/min, milling time is 12h ~ 60h, and mill ball is the WC-8wt%Co sintered carbide ball of Φ 6 ~ 8mm, and ball material weight ratio is 3:1 ~ 5:1; The addition of wax moulding agent is 2 ~ 8wt%, and the joining day is that wet-milling terminates front 2 ~ 6h; After ball milling, cermet slip filters through 400 orders, and vacuum drying treatment temperature is 85 DEG C ~ 120 DEG C, and vacuum is 1 ~ 5 Pa; Green compact are pressed under 300 ~ 500MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310715220.8A CN103667843B (en) | 2013-12-23 | 2013-12-23 | A kind of preparation method of deep hole machining ultra-fine cemented carbide cutter material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310715220.8A CN103667843B (en) | 2013-12-23 | 2013-12-23 | A kind of preparation method of deep hole machining ultra-fine cemented carbide cutter material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103667843A CN103667843A (en) | 2014-03-26 |
| CN103667843B true CN103667843B (en) | 2015-08-05 |
Family
ID=50306611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310715220.8A Expired - Fee Related CN103667843B (en) | 2013-12-23 | 2013-12-23 | A kind of preparation method of deep hole machining ultra-fine cemented carbide cutter material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103667843B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106346002A (en) * | 2016-11-16 | 2017-01-25 | 湖南文理学院 | Cemented carbide sintering process |
| CN107952969B (en) * | 2017-11-29 | 2019-09-17 | 首都航天机械公司 | A kind of hard alloy valve base lathe tool and its application |
| CN111961941B (en) * | 2020-09-02 | 2021-02-12 | 四川大学 | Preparation method of superfine hard alloy cutter material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7384443B2 (en) * | 2003-12-12 | 2008-06-10 | Tdy Industries, Inc. | Hybrid cemented carbide composites |
| CN101565183B (en) * | 2009-05-31 | 2010-12-29 | 四川大学 | Surface finishing high-energy ball milling method for dispersing nanometer TiC powder |
| CN102304657B (en) * | 2011-09-26 | 2012-10-24 | 四川大学 | Molybdenum-free Ti (C, N)-based cermet wear resistant and corrosion resistant material and preparation method thereof |
| CN102383020A (en) * | 2011-11-16 | 2012-03-21 | 重庆市科学技术研究院 | Ultrathin hard alloy with high hardness and preparation method thereof |
| CN102732766B (en) * | 2012-07-06 | 2014-08-06 | 四川大学 | Coarse grain hard alloy material and preparation method thereof |
-
2013
- 2013-12-23 CN CN201310715220.8A patent/CN103667843B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103667843A (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109112378B (en) | Preparation method of novel binder phase hard alloy material | |
| CN111378888B (en) | Nano particle interface reinforced Ti (C, N) -based metal ceramic material with high nitrogen content and preparation method thereof | |
| CN101985717B (en) | Method for preparing high-tenacity super-coarse-grained tungsten and cobalt hard alloy | |
| CN102409215B (en) | Superfine hard alloy for cutter with large cutting amount | |
| CN105950935A (en) | Hard alloy mold material for fastener formed through cold upsetting and preparation method of hard alloy mold material | |
| CN109295373A (en) | A kind of application of high-entropy alloy and preparation method thereof | |
| CN102363854A (en) | Superfine YG type hard alloy containing light-heavy rare earth and preparation method thereof | |
| CN104831098A (en) | Preparation method of WC-Co hard alloy with in-situ addition of rare earth oxide crystal grain refiner | |
| CN104630590B (en) | A kind of composite hard alloy material and preparation method thereof | |
| CN103741001A (en) | High-hardness and high-strength PY30T hard alloy and preparation method of high-hardness and high-strength PY30T hard alloy product | |
| CN110964965A (en) | High-entropy alloy binding phase tungsten carbide hard alloy for water jet cutter and preparation method thereof | |
| CN105945292B (en) | A kind of diamond compact and preparation method thereof | |
| CN106636836A (en) | Preparation method of ultra-coarse hard alloy | |
| CN103667843B (en) | A kind of preparation method of deep hole machining ultra-fine cemented carbide cutter material | |
| CN107099720A (en) | A kind of aluminium alloy sintered carbide tool material for processing and preparation method thereof | |
| CN102732766B (en) | Coarse grain hard alloy material and preparation method thereof | |
| CN103667757A (en) | Preparation method of hard alloy bar for PCB (Printed Circuit Board) micro drill | |
| CN107245628A (en) | Make Hardmetal materials of Binder Phase and preparation method thereof using Ni Cu continuous solid solutions | |
| CN103276268A (en) | High-performance hard alloy and manufacturing method thereof | |
| CN113201677A (en) | Production process for producing ultrafine grain hard alloy by using sub-fine tungsten carbide | |
| CN106566972B (en) | The preparation method of plate-like shape WC grains hard alloy with gradient-structure | |
| KR100868074B1 (en) | WC-Ni HARD METAL AND METHOD FOR PRODUCING THE SAME | |
| CN111961941B (en) | Preparation method of superfine hard alloy cutter material | |
| CN104131206A (en) | Titanium carbonitride-based hard alloy high-speed wire guide wheel material and preparation method thereof | |
| CN104451217A (en) | Preparation method of ultrafine cemented carbide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150805 Termination date: 20191223 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |