CN102061417A - Nano silicon nitride and boron nitride reinforced titanium carbonitride based cermet - Google Patents

Nano silicon nitride and boron nitride reinforced titanium carbonitride based cermet Download PDF

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CN102061417A
CN102061417A CN2009101127850A CN200910112785A CN102061417A CN 102061417 A CN102061417 A CN 102061417A CN 2009101127850 A CN2009101127850 A CN 2009101127850A CN 200910112785 A CN200910112785 A CN 200910112785A CN 102061417 A CN102061417 A CN 102061417A
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nano
silicon nitride
boron nitride
titanium carbonitride
nitride
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张厚安
古思勇
葛晓宏
许龙山
章文献
谢能平
易继勇
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Xiamen University of Technology
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Xiamen University of Technology
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Abstract

The invention discloses a nano silicon nitride and boron nitride reinforced titanium carbonitride based cermet. A reinforced phase is added into a base material having a main phase of titanium carbonitride Ti(C, N) and a binder phase of nickel and cobalt metals, is at least one of nano silicon nitride and nano boron nitride, and is 0.5 to 2.5 volume percent of the base material. The preparation method comprises the following process flows: preparing raw material powder containing the nano silicon nitride and/or nano boron nitride; mixing; adding a forming agent; performing wet grinding; sieving; drying and granulating; performing compression molding; sintering in nitrogen; and obtaining the cermet. The cermet has the advantages of high hardness, high strength and high toughness, and can be widely applied to middle and low carbon steel and low alloy steel high-speed cutting tool materials; and the preparation process is easy to control and is suitable for large-scale industrial production.

Description

A kind of nano-silicon nitride and boron nitride enhanced base titanium carbonitride material
Technical field
The present invention relates to cermet material and technology of preparing, especially a kind of nano-silicon nitride and boron nitride enhanced titanium carbonitride (Ti (C, N)) base metal-ceramic material and preparation thereof.
Background technology
(Ti (C, N)) based ceramic metal grows up on titanium carbide (TiC) based ceramic metal basis titanium carbonitride, (C N) is main hard phase, and nickel, molybdenum are the cutter material of bonding phase with Ti.Antistick high when its high rigidity, high red hardness, high antioxidant and solidity to corrosion and cutting is worn and torn and anti-diffusive wear ability, is particularly suitable for the semi-finishing and the precision work of steel and cast iron.At present, abroad the consumption of this cutter material has accounted for 10%～30% of indexable tool material usage total amount.And domestic, cutting tool is still many with WC base cemented carbide or pottery.Traditional WC base cemented carbide is when high speed cutting carbon steel and cast iron, and wear resistance is low, and the life-span is short; And pottery is as Al 2O 3(aluminium sesquioxide), CBN (cubic boron nitride), man-made diamond etc., big because of fragility, cost is expensive, shortcoming such as easy tipping has limited it in industrial being extensive use of during machining.Present existing TiC base metal-ceramic material, though hardness is higher, bending strength is low, red hardness and oxidation-resistance and high-temperature creep resistance are poor, can't satisfy the requirement of high speed cutting.And common Ti (C, N) there are shortcomings such as hole multigap, soft, low bending strength and low toughness in base metal-ceramic material, has had a strong impact on the work-ing life of material.
Patent documentation CN1974205A has proposed surface-coated cutting insert and manufacture method thereof, be coated on the base titanium carbonitride matrix and make blade by using tens of a kind of carbide, nitride, oxide compound, boride and complex chemical compounds thereof, but the performance of body material does not improve to hundreds of microns Ti, Zr, Hf, Cr, Al, Si.The method have the surface-coated cutting tool member of hard coating layer and form this hard coating layer on the cutting tool surface is proposed among the CN1638900A, coating material wherein forms the compound of titanium by physical vapor deposition, coating layer is thinner, is unfavorable for improving the integral material bending strength.CN1477222A has proposed that (to improve the work-ing life of cermet material, parameters such as the intensity of cermet material, hardness are not quite clear for C, N) base ceramet tool bit with nano TiN modified TiC or Ti.CN101255512A has proposed the titanium carbide nitride based metal ceramic cutter material of boracic, boron wherein is to prepare after in pure boron, TiB2, boron nitride, the boron oxide one or more add with raw material form, improved cutting speed and work-ing life though relate to, parameters such as the intensity of cermet material, hardness are not quite clear.CN101092304A has proposed the crystal whisker toughened base titanium carbonitride blade of SiC, and the bending strength of its stupalith is lower than 1700MPa, hardness HAC≤94.2.Because of diameter of whiskers is micron number magnitude and its length range broad (10～40 μ m), thus be unfavorable for mixing, limited to improving bending strength and wear resisting property effect.CN101189090A has proposed cermet insert and cutting tool, improves ceramic-metallic wear resisting property with carbide.CN101265543A has proposed titanium carbonitride base metal ceramic machinery sealing material, and by carbide and Y, the Er that plays crystal grain inhibitor, additive effect, the preparation cermet material is to improve its bending strength and hardness.
Summary of the invention
At above-mentioned situation, the object of the present invention is to provide a kind of add nano-silicon nitride and boron nitride wild phase with Ti (C, N) for principal phase, serve as cermet material and preparation method thereof of bonding phase with metallic nickel, cobalt, it has high rigidity, high strength and high tenacity and preparation technology is easy to control and is fit to industrial production in enormous quantities.
To achieve these goals, solution of the present invention is as follows:
A kind of nano-silicon nitride and boron nitride enhanced base titanium carbonitride material, with titanium carbonitride Ti (C, N) be to add wild phase in principal phase and metallic nickel, the base material of cobalt for the bonding phase, add and strengthen at least a in nano-silicon nitride and the nm-class boron nitride, this wild phase volume content is a base material 0.5～2.5%
Titanium carbonitride [Ti (C, N)] principal phase raw material is Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-xIn at least a carbonitride, wherein the x numerical range is x=0.3～0.7.
Each component and content (weight percentage) are:
WC 10～20wt％ TaC 5～15wt％ Mo 2C 5～15wt％ Co 5～15wt％
Ni 5～10wt％ ZrC 0.1～2wt％ Cr 3C 2 0.1～2wt％ VC 0.1～2wt％
Si 3N 41.8～8.9wt% or BN 1.1～5.7wt% or (Si 3N 4) x+ (BN) 1-x1.1～6.8wt%
Ti (Cx, N 1-x) or (TiC) x+ (TiN) 1-xBe surplus.
Each component and content (weight percentage) are:
WC 10～20wt％ TaC 5～15wt％ Co 5～15wt％ Mo 4～15wt％
C 0.3～1.2wt％ Ni 5～10wt％ ZrC?0.1～2wt％ Cr 3C 2?0.1～2wt％
VC 0.1～2wt% Si 3N 41.8～8.9wt% or BN 1.1～5.7wt% or
(Si 3N 4) x+(BN) 1-x 1.1～6.8wt％。
Preparation technology's flow process of this nano-silicon nitride and boron nitride enhanced base titanium carbonitride material is:
Contain the raw material powder → mixing → adding forming agent → wet-milling of nano-silicon nitride and/or nm-class boron nitride → sieve → drying-granulating → compression molding → nitrogen atmosphere sintering → cermet material.
Each component and content (weight percentage) are in the raw material powder:
WC 10～20wt％ TaC 5～15wt％ Mo 2C 5～15wt％ Co 5～15wt％
Ni 5～10wt％ ZrC 0.1～2wt％ Cr 3C 2?0.1～2wt％ VC 0.1～2wt％
Si 3N 41.8～8.9wt% or BN 1.1～5.7wt% or (Si 3N 4) x+ (BN) 1-x1.1～6.8wt%
Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-xBe surplus.
Each component and content (weight percentage) are in the raw material powder:
WC 10～20wt％ TaC 5～15wt％ Co 5～15wt％ Mo 4～15wt％ C 0.3～1.2wt％
Ni 5～10wt％ ZrC 0.1～2wt％ Cr 3C 2 0.1～2wt％ VC 0.1～2wt％
Si 3N 41.8～8.9wt% or BN 1.1～5.7wt% or (Si 3N 4) x+ (BN) 1-x1.1～6.8wt%.
Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-xBe surplus.
Described nitrogen atmosphere agglomerating condition is: nitrogen pressure is 300～8000Pa, is rapidly heated temperature rise rate 〉=10 ℃/min between 1000 ℃～1430 ℃.
The present invention adopts and optimizes technology and prepare a kind of nano-silicon nitride and boron nitride enhanced dense carbon titanium nitride base metal-ceramic material.By in titanium carbonitride [Ti (C, N)] base-material, adding nano-silicon nitride and boron nitride, can obviously improve hardness, bending strength and the toughness of material, technology is simple and be convenient to mass production.The present invention is widely used in various cutter materials.
Description of drawings
Fig. 1 is a cermet material preparation technology schema of the present invention;
Fig. 2 is a cermet material sintering process graphic representation of the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Referring to accompanying drawing 1, adopt the powder metallurgical sintering process preparation, Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-xIn at least a carbonitride be principal phase, with Ni and Co serves as that bonding is with titanium carbonitride Ti (C, N) be in principal phase and metallic nickel, the base material of cobalt, add nano-silicon nitride and boron nitride or these 2 kinds of wild phases of compound interpolation (each volume content is 0.5～2.5%) for the bonding phase.
Preparation technology's flow process of this nano-silicon nitride and boron nitride enhanced base titanium carbonitride material is:
Other raw material powder+nano-silicon nitride and/or nm-class boron nitride → mixing → adding forming agent → wet-milling → sieve → drying-granulating → compression molding → nitrogen atmosphere sintering → cermet material.
Nitrogen atmosphere agglomerating condition is: nitrogen pressure is 300～8000Pa, is rapidly heated temperature rise rate 〉=10 ℃/min between 1000 ℃～1430 ℃.
In the following embodiments, with Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-xFor each component in the principal phase and content range (weight percentage) are respectively equipped with different combinations:
Combination 1:
WC 10～20wt％ TaC 5～15wt％
Mo 2C 5～15wt% or (Mo 4～15wt%+C 0.3～1.2wt%)
Co 5～15wt％ Ni 5～10wt％ ZrC 0.1～2wt％
Cr 3C 2 0～2wt％ VC 0.1～2wt％
Nano-silicon nitride Si 3N 41.8～8.9wt%
Surplus is Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-x, x=0.3～0.7 wherein
Combination 2:
WC 10～20wt％ TaC 5～15wt％
Mo 2C 5～15wt% or (Mo 4～15wt%+C 0.3～1.2wt%)
Co 5～15wt％ Ni 5～10wt％ ZrC 0.1～2wt％
Cr 3C 2 0～2wt％ VC 0.1～2wt％
Nm-class boron nitride BN 1.1～5.7wt%
Surplus is Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-x, x=0.3～0.7 wherein
Combination 3:
WC 10～20wt％ TaC 5～15wt％
Mo 2C 5～15wt% or (Mo 4～15wt%+C 0.3～1.2wt%)
Co 5～15wt％ Ni 5～10wt％ ZrC 0.1～2wt％
Cr 3C 2 0～2wt％ VC 0.1～2wt％
Nano-silicon nitride and nm-class boron nitride (Si 3N 4) x+ (BN) 1-x1.1～6.8wt%
Surplus is Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-x, x=0.3～0.7 wherein.
With reference to Fig. 1 as seen, by above-mentioned each feed composition batching through mixing, wet-milling, sieve, drying-granulating, mold pressing, sintering process (referring to accompanying drawing 2), prepare Ti (C, N) base metal-ceramic material.
Embodiment 1:
Preparation technology is referring to Fig. 1 and Fig. 2.
(1) contains Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-xAdmixtion in each component and weight percent
Content is:
WC 15wt％ TaC 10wt％ Mo 2C 8wt％ Co 10wt％
Ni 5wt％ ZrC 1.0wt％ VC 0.5wt％ (nm)Si 3N 4 8wt％
Surplus is Ti (C 0.5N 0.5).All the other powder sizes are≤2 μ m.
(2) mix: in mixer with raw material powder thorough mixing 24 hours.
(3) wet-milling: above-mentioned mixed powder is packed in the stainless steel jar mill, press 350ml/l and add hexane, select Φ 5 sintered carbide balls for use, ratio of grinding media to material is 5: 1, rotating speed 200rpm, ball milling 72 hours.
(4) add forming agent: take by weighing paraffin by 5wt%, be dissolved in the hexane, add ball grinder, continue ball milling 2h.
(5) sieve: the slip behind the ball milling is crossed 60 mesh sieves, precipitate 2 hours.
(6) drying-granulating: will precipitate material and put into loft drier, in 90 ℃ of insulations 2 hours, drying-granulating.
(7) compression molding: with dried powder, put into mould, the 280MPa forming under the pressure.
(8) sintering: press Fig. 2 technology sintering, nitrogen pressure is 4000Pa.
The hardness HRA92.5 of gained cermet material, bending strength 1950MPa, fracture toughness property 15.0MPam 1/2
Embodiment 2:
Preparation technology is referring to Fig. 1 and Fig. 2.
(1) contains Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-xAdmixtion in each component and weight percentage be:
WC 17wt％ TaC 7wt％ Mo 8wt％ C 0.6wt％
Co 8wt％ Ni 7wt％ ZrC 0.5wt％ Cr 3C 2 0.5wt％
VC 0.5wt% (nm) BN 3.0wt% surplus is (TiC) 0.6+ (TiN) 0.4All the other powder sizes are≤2 μ m.
(2) mix: with embodiment 1.
(3) wet-milling: with embodiment 1.
(4) add forming agent: with embodiment 1.
(5) sieve: with embodiment 1.
(6) drying-granulating: with embodiment 1.
(7) compression molding: with embodiment 1.
(8) sintering: press accompanying drawing 2 technology sintering, nitrogen pressure is 2000Pa.
The hardness HRA93.4 of gained cermet material, bending strength 1810MPa, fracture toughness property 14.2MPam 1/2
Embodiment 3:
Preparation technology is referring to Fig. 1 and Fig. 3.
(1) contains Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-xAdmixtion in each component and weight percentage be:
WC 16wt％ TaC 9wt％ Mo 2C 12wt％ Co
10wt％
Ni 5wt％ ZrC 1.0wt％ VC 0.5wt％
(nm)(Si 3N 4) 0.3+(BN) 0.7 2.0wt％
Surplus is Ti (C 0.7N 0.3).All the other powder sizes are≤2 μ m.
(2) mix: with embodiment 1.
(3) wet-milling: above-mentioned mixed powder is packed in the stainless steel jar mill, press 400ml/l and add ethanol, select Φ 5 sintered carbide balls for use, ratio of grinding media to material is 10: 1, rotating speed 200rpm, ball milling 48 hours.
(4) add forming agent: take by weighing rubber by 1.5wt%, be dissolved in the gasoline, add ball grinder, continue ball milling 2h.
(5) sieve: with embodiment 1.
(6) drying-granulating: with embodiment 1
(7) compression molding: with embodiment 1.
(8) sintering: press accompanying drawing 2 technology sintering, nitrogen pressure is 3000Pa.
The hardness HRA93.0 of gained cermet material, bending strength 1900MPa, fracture toughness property 14.6MPam 1/2
To sum up book, the present invention be by adding nano-silicon nitride and boron nitride and these two kinds of wild phases of compound interpolation, Ti (C, N) based ceramic metal have high rigidity (HRA 〉=92.0), high-flexural strength (〉=1800MPa) and high tenacity (〉=14.2MPam 1/2).The present invention adopts at titanium carbonitride [Ti (C, N)] add nano-silicon nitride and boron nitride in the base-material, can obviously improve hardness, bending strength and the toughness of material, technology is simple and be convenient to mass production, can be widely used in the cutter Materials for High Speed Cutting of middle low carbon steel and low alloy steel.
Being preferred embodiment of the present invention only below, is not the qualification to protection scope of the present invention, and all various modifications, combination, part combination and replacements of making according to the mentality of designing of this case all fall into the protection domain of this case.

Claims (6)

1. nano-silicon nitride and boron nitride enhanced base titanium carbonitride material, it is characterized in that: with titanium carbonitride Ti (C, N) be to add wild phase in principal phase and metallic nickel, the base material of cobalt for the bonding phase, this wild phase is at least a in nano-silicon nitride and the nm-class boron nitride, and this wild phase volume content is a base material 0.5～2.5%.
2. a kind of nano-silicon nitride as claimed in claim 1 and boron nitride enhanced base titanium carbonitride material is characterized in that: (C, N) the principal phase raw material is Ti (C to titanium carbonitride Ti x, N 1-x) or (TiC) x+ (TiN) 1-xIn at least a carbonitride, wherein the x numerical range is x=0.3～0.7.
3. a kind of nano-silicon nitride as claimed in claim 1 and boron nitride enhanced base titanium carbonitride material is characterized in that preparation technology's flow process is:
Contain the raw material powder → mixing → adding forming agent → wet-milling of nano-silicon nitride and/or nm-class boron nitride → sieve → drying-granulating → compression molding → nitrogen atmosphere sintering → cermet material.
4. a kind of nano-silicon nitride as claimed in claim 3 and boron nitride enhanced base titanium carbonitride material is characterized in that: each component and weight percentage are in the described raw material powder that contains nano-silicon nitride and/or nm-class boron nitride:
WC?10～20wt％，TaC?5～15wt％，Mo 2C?5～15wt％，Co?5～15wt％，
Ni?5～10wt％，ZrC?0.1～2wt％，Cr 3C 2?0.1～2wt％，VC?0.1～2wt％，
Si 3N 41.8～8.9wt% or BN 1.1～5.7wt% or (Si 3N 4) x+ (BN) 1-x1.1～6.8wt%,
Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-xBe surplus.
5. a kind of nano-silicon nitride as claimed in claim 3 and boron nitride enhanced base titanium carbonitride material is characterized in that: each component and weight percentage are in the described raw material powder that contains nano-silicon nitride and/or nm-class boron nitride:
WC?10～20wt％，TaC?5～15wt％，Co?5～15wt％，Mo?4～15wt％，C?0.3～1.2wt％，Ni?5～10wt％，ZrC?0.1～2wt％，Cr 3C 2?0.1～2wt％，VC?0.1～2wt％，
Si 3N 41.8～8.9wt% or BN 1.1～5.7wt% or (Si 3N 4) x+ (BN) 1-x1.1～6.8wt%,
Ti (C x, N 1-x) or (TiC) x+ (TiN) 1-xBe surplus.
6. a kind of nano-silicon nitride as claimed in claim 3 and boron nitride enhanced base titanium carbonitride material, it is characterized in that: described nitrogen atmosphere agglomerating condition is: nitrogen pressure is 300～8000Pa, between 1000 ℃～1430 ℃, be rapidly heated temperature rise rate 〉=10 ℃/min.
CN2009101127850A 2009-11-13 2009-11-13 Nano silicon nitride and boron nitride reinforced titanium carbonitride based cermet Pending CN102061417A (en)

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CN102534335A (en) * 2012-01-17 2012-07-04 四川大学 Rare earth alloy powder-modified Ti(C,N)-based metal ceramic and preparation method thereof
CN102828096A (en) * 2012-09-17 2012-12-19 天津瑞克曼德科技发展有限公司 Metal ceramic cutting tool material and preparation method thereof
CN102864357A (en) * 2012-09-24 2013-01-09 厦门理工学院 Titanium-carbonitride-based metal ceramic material reinforced by nano boron carbide and boron nitride, and preparation process thereof
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CN107675057A (en) * 2017-10-09 2018-02-09 南昌工程学院 Cermet material of high temperature resistant Castor Oil a kind of of bearing and preparation method thereof
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CN102534335A (en) * 2012-01-17 2012-07-04 四川大学 Rare earth alloy powder-modified Ti(C,N)-based metal ceramic and preparation method thereof
CN102828096A (en) * 2012-09-17 2012-12-19 天津瑞克曼德科技发展有限公司 Metal ceramic cutting tool material and preparation method thereof
CN102864357A (en) * 2012-09-24 2013-01-09 厦门理工学院 Titanium-carbonitride-based metal ceramic material reinforced by nano boron carbide and boron nitride, and preparation process thereof
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Application publication date: 20110518