CN108034881A - A kind of steel knot TiCN base cemented carbides and application - Google Patents

A kind of steel knot TiCN base cemented carbides and application Download PDF

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CN108034881A
CN108034881A CN201711443017.4A CN201711443017A CN108034881A CN 108034881 A CN108034881 A CN 108034881A CN 201711443017 A CN201711443017 A CN 201711443017A CN 108034881 A CN108034881 A CN 108034881A
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powder
ticn
steel
cemented carbides
base cemented
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陈明
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ZHUZHOU JINGGONG CEMENTED CARBIDE CO Ltd
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ZHUZHOU JINGGONG CEMENTED CARBIDE CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/006—Making ferrous alloys compositions used for making ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0292—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with more than 5% preformed carbides, nitrides or borides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a kind of steel knot TiCN base cemented carbides, the steel knot TiCN base cemented carbides are using TiCN as hard phase, using steel matrix as Binder Phase, using Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloys as additive, the percentage by weight of the TiCN is that the percentage by weight of 30 ~ 40%, steel matrix is 59.2 ~ 69.5%, and the percentage by weight of the Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloys is 0.5 ~ 0.8%.The invention also discloses the method for preparing the material, after first prepared by Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloys, dispensing, ball mill mixing, compression molding, sintering, heat treatment again, the TiCN Steel-bonded Cemented Carbides consistency of the present invention is high, excellent combination property, cost-effective.Preparation method cost of the invention is low, technique is simple, suitable for industrialized production.

Description

A kind of steel knot TiCN base cemented carbides and application
Technical field
The present invention relates to field of powder metallurgy, and in particular to a kind of steel knot TiCN base cemented carbides and preparation method thereof.
Background technology
Hard alloy has the advantages that hardness height, wearability, heat resistance are good, is widely used in industrial each neck Domain.The production of common tungsten-cobalt series hard alloy need to use the national strategy resources such as substantial amounts of tungsten, cobalt, such as the hard that the trade mark is YG8 Wolfram element, 8% cobalt element in alloy containing about 86%, the in recent years prices of raw materials continuous rise such as tungsten, cobalt.In addition, hard closes Bonding phase constituent-cobalt of gold, because its toxicity has been included in carcinogen list by international cancer research institution, triggers people to duty The healthy and safe great attention of industry.The research for finding a kind of advanced composite material (ACM) that can partially or completely substitute hard alloy is subject to The attention of more and more researchers.Steel bonded carbide be using steel as Binder Phase, using insoluble metal carbide, nitride as A kind of advanced composite material (ACM) of great potential of hard phase.Its mechanical property compared with steel, has between hard alloy and steel The hardness of higher, wearability, elasticity modulus and compression strength；Compared with hard alloy, there is good bending strength and impact Toughness, embodies excellent comprehensive performance., can meanwhile steel bonded carbide also has extensive operational characteristic, such as machinability Heat-treatability and malleability etc..
Steel knot TiCN base cemented carbides are the steel bonded carbide using TiCN as hard phase, using steel as Binder Phase, such material Expect the Binder Phase by the use of iron substituting cobalt as alloy, and Binder Phase accounting reaches 50 ~ 90%, significantly reduces cost of material, at the same time Reduce harm of the elements such as cobalt to the career safety ＆ health of operator.Contain higher nitrogen content in TiCN, in sintering process The tendentiousness that crystal grain is grown up is small, hard phase organization fine uniform structure, toughness, the plasticity_resistant deformation ability of steel knot TiCN base cemented carbides Higher than TiC base steel bonded carbide, intensity is high, density is low, friction coefficient is low, wearability, good corrosion resistance, has excellent height Warm red hardness and inoxidizability etc., are the ideal materials for making high speed cutting tool and hot forming tool.Prepare steel knot TiCN bases The method of cemented carbide material mainly has powder metallurgic method, casting, in-situ synthesis, infusion process and pressure sintering etc., but at present The alloy fails to realize large-scale industrial production at home.And powder metallurgic method is industrialized production prepares steel knot hard The common method of alloy, but at present using the method production TiC base steel bonded carbide when, due to TiCN hard phases and steel matrix Compatibility is bad, and wetability is poor, and surface is easily attached to thing pollution so that the interface cohesion shape of hard phase TiCN particles and matrix Condition is bad, and the enhancing effect of TiCN particles cannot be brought into play well.
Therefore, in the prior art, in the technique that steel knot TiCN base cemented carbides are prepared using powder metallurgic method, how to change Kind metallic matrix improves interface bond strength, how to improve the microstructure of matrix by being heat-treated to the wetability of enhancing phase Structure, improves Fracture of Material, is always the problem of scientific research personnel's research.
The content of the invention
It is an object of the invention to the deficiency for the prior art, there is provided a kind of steel knot TiCN base cemented carbides, it has The advantages of proportion is small, and consistency is high, high temperature red hardness and good in oxidation resistance.
Another object of the present invention is to provide a kind of production method of steel knot TiCN base cemented carbides, it, which has, is produced into This is low, technique is simple, advantages of nontoxic raw materials side effect, the preparation method for being adapted to industrialized production.
The present invention is achieved by the following technical solutions：
A kind of steel knot TiCN base cemented carbides, the steel knot TiCN base cemented carbides using TiCN as hard phase, using steel matrix as Binder Phase, using Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloys as additive, with the gross weight of steel knot TiCN base cemented carbides On the basis of amount, the percentage by weight of the TiCN is that the percentage by weight of 30 ~ 40%, steel matrix is 59.2 ~ 69.5%, institute The percentage by weight of the Fe stated-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloys is 0.5 ~ 0.8%, the raw material of the steel matrix Component includes W powder, Mo powder, V powder, Cr powder, Ni powder, Cu powder, carbon black powder, carbonyl iron dust, reduced iron powder.
As a further refinement of the present invention, the material composition of the steel matrix and each component account for alloy gross mass Mass percent is as follows：3.0 ~ 6.0%W powder, 2.5 ~ 4.2%Mo powder, 0.8 ~ 2.0%V powder, 1.6 ~ 4.0%Cr powder, 0.3 ~ 0.8%Ni Powder, 0.2 ~ 0.6%Cu powder, 0.6 ~ 1.2% carbon black powder, 12 ~ 18% carbonyl iron dusts, surplus are reduced iron powder.
The preparation method of above-mentioned steel knot TiCN base cemented carbides, using powder metallurgic method, comprises the following steps：
Step 1：Prepared by intermediate alloy, total with Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloys using Fe, Ce, La as raw material Quality meter, Ce, 8 ~ 20% La by weight percentage for 20 ~ 30%, surplus are that Fe carries out dispensing, are prepared using conventional smelting process Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloy melts are obtained, among the Fe-(20 ~ 30%) Ce-(8 ~ 20%) La Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloy powder is made using conventional water atomization in alloy melt；
Step 2：Dispensing, by Fe made from steel matrix raw material powder, step 1-(20 ~ 30%) Ce-(8 ~ 20%) La master alloyed powders End carries out dispensing by weight percentage with TiCN powder；
Step 3：Raw material obtained by step 2 dispensing is subjected to ball mill mixing；
Step 4：The mixture compression molding that the step 3 is obtained；
Step 5：The pressed compact that the step 4 obtains is sintered；
Step 6：The sintered body that the step 5 obtains is heat-treated, first by steel knot TiCN base cemented carbides 1100 ~ Quenching treatment is carried out at 1250 DEG C, hardening media is oil, and quenching protective atmosphere is argon gas, is carried out afterwards at 520 ~ 570 DEG C to burning Steel knot TiCN base cemented carbides after knot carry out double tempering, obtain steel knot TiCN base cemented carbides.
As a further refinement of the present invention, in the step 2, mole carbon-nitrogen ratio C/N in the TiCN is 1:1.
As a further refinement of the present invention, in the step 2, the TiCN is less than 5 μm of powder, institute for granularity The granularity of Fe-(20 ~ 30%) Ce-(8 ~ 20%) La master alloyed powders is stated less than 10 μm, reduced iron in the steel matrix raw material powder For the granularity of powder less than 75 μm, the granularity of the raw material powder in the steel matrix raw material powder in addition to reduced iron powder is less than 25 μm.
As a further refinement of the present invention, in the step 3, the ratio of grinding media to material of the ball mill mixing is 5:1~10:1, Rotating speed is 270 ~ 380rpm, and Ball-milling Time is 8 ~ 20h, and milling atmosphere is argon gas.
As a further refinement of the present invention, in the step 5, it is described to be sintered to vacuum-sintering, the vacuum-sintering Vacuum be less than 0.5Pa, sintering temperature is 1380 ~ 1460 DEG C, and soaking time is 45 ~ 70min, the steel after the vacuum-sintering Tie TiCN base cemented carbide furnace coolings.
As a further refinement of the present invention, in the step 4, the pressing pressure of the compression molding for 200 ~ 650Mpa, obtains steel knot TiCN base cemented carbide pressed compacts.
Above-mentioned steel knot TiCN base cemented carbides can be applicable to high speed cutting tool, hot forming tool and wear part neck Domain.
The beneficial effects of the present invention are：
Steel knot TiCN base cemented carbides provided by the invention, using TiCN as hard phase, steel matrix is Binder Phase, and is added with for it Iron-rare earth intermediate alloy as additive, wherein, W, Mo, V and the Cr contained in steel matrix is carbide former, above-mentioned Element can not only improve the sintering character of steel bonded carbide, moreover it is possible to form corresponding carbide and be centered around tiny TiCN particles Around, play the part of a kind of role of interphase, the problem of significantly improving TiCN hard phases wetability is poor in steel matrix, improve Interface bond strength between TiCN hard phases and steel matrix.In addition, because of the characteristic that TiCN has by oneself, make steel knot TiCN base hard Alloy with than common tungsten-cobalt series hard alloy with more excellent high temperature red hardness and inoxidizability.In the present invention, rare earth member Element is added in the form of Fe-(30 ~ 36%) Ce-(15 ~ 20%) La intermediate alloys, on the one hand, rare earth element can reduce W, Mo Deng the segregation phenomena of alloying element, refining eutectic carbide；On the other hand, in being 201210104964.1 with number of patent application Rare earth oxide La is added in state's patent2O3Compare, the Fe- rare earth intermediate alloys that the present invention is added are with Fe2Ce, CeFe3、 CeFe7Based on intermetallic compound and La simple substance, except can in addition to crystal grain thinning and dispersion-strengtherning, also have more preferable deoxidation, Desulfurization effect；At a sintering temperature, rare earth element reducing iron oxides, so as to reduce the carbon caused by carbon in alloy and oxygen react Loss.In addition, after iron powder surface film oxide is removed, the obstacle migrated between atom is reduced, and, changes to atoms permeating advantageously The wetability being apt between powder, improves the consistency of alloy, reduces hole.Therefore, the addition of rare earth intermediate alloy carries The high sintering character of material, improves microstructure, material comprehensive performance is improved.Steel knot TiCN bases provided by the invention The main performances such as hardness, fracture toughness and the wearability of cemented carbide material are suitable with tungsten-cobalt series hard alloy, or even compare part The W-Co kind Cemented Carbide Properties of the trade mark are more excellent, reach in Art sections such as cutting tool, moulds or substitute W-Co kind completely The purpose of hard alloy.
The method provided by the invention for preparing steel knot TiCN base cemented carbides, it uses powder metallurgic method to prepare, and sets There are the means such as subsequent heat treatment, effectively improve alloy heterogeneous microstructure, improve interface bond strength.Even more important It is that method of the invention need not use the elements such as tungsten, cobalt as primary raw material, but selects cheap iron as main Raw material, saved the national grand strategy resource such as tungsten, cobalt, at the same cost reduction more than half.In addition, substituted completely with iron Binder Phase of the cobalt as alloy, avoids actual bodily harm of the cobalt element to production operator, improves production environment, protect work The occupational safety and health of people.
Brief description of the drawings
Fig. 1 prepares process flow chart for steel knot TiCN base cemented carbides provided by the present invention.
Fig. 2 is that the SEM of steel knot TiCN base cemented carbides provided by the present invention schemes.
Embodiment
In order to which technical problem, technical solution and beneficial effect solved by the invention is more clearly understood, below in conjunction with Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining The present invention, is not intended to limit the present invention.
A kind of steel knot TiCN base cemented carbides, the steel knot TiCN base cemented carbides are using TiCN as hard phase, with base steel Body is Binder Phase, using Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloys as additive, with steel knot TiCN base cemented carbides On the basis of gross weight, the percentage by weight of the TiCN be the percentage by weight of 30 ~ 40%, steel matrix be 59.2 ~ 69.5%, the percentage by weight of the Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloys is 0.5 ~ 0.8%, the base steel The material composition of body includes W powder, Mo powder, V powder, Cr powder, Ni powder, Cu powder, carbon black powder, carbonyl iron dust, reduced iron powder.
The preparation method of above-mentioned steel knot TiCN base cemented carbides, using powder metallurgic method, comprises the following steps：
Step 1：Prepared by intermediate alloy, total with Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloys using Fe, Ce, La as raw material Quality meter, Ce, 8 ~ 20% La by weight percentage for 20 ~ 30%, surplus are that Fe carries out dispensing, are prepared using conventional smelting process Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloy melts are obtained, among the Fe-(20 ~ 30%) Ce-(8 ~ 20%) La Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloy powder is made using conventional water atomization in alloy melt；
Step 2：Dispensing, by Fe made from steel matrix raw material powder, step 1-(20 ~ 30%) Ce-(8 ~ 20%) La master alloyed powders End carries out dispensing by weight percentage with TiCN powder；
Step 3：Raw material obtained by step 2 dispensing is subjected to ball mill mixing；
Step 4：The mixture compression molding that the step 3 is obtained；
Step 5：The pressed compact that the step 4 obtains is sintered；
Step 6：The sintered body that the step 5 obtains is heat-treated, first by steel knot TiCN base cemented carbides 1100 ~ Quenching treatment is carried out at 1250 DEG C, hardening media is oil, and quenching protective atmosphere is argon gas, is carried out afterwards at 520 ~ 570 DEG C to burning Steel knot TiCN base cemented carbides after knot carry out double tempering, obtain steel knot TiCN base cemented carbides.
Those skilled in the art have found that it is to improve alloy structure that rare earth element is added in steel bonded carbide under study for action With the effective means of performance.For example, the Chinese patent literature of Application No. 201310091944.X disclose it is a kind of rare earth modified Steel bonded carbide and preparation method, for this material using TiC as hard phase, potassium steel is Binder Phase matrix, it with the addition of 0.2 ~ 0.5% rare earth element, wherein rare-earth elements La add in the form of an oxide.La2O3Addition, although crystal grain can be hindered to grow up, And play the role of dispersion-strengtherning to matrix, but La2O3Easily assemble on crystal boundary, so as to deteriorate the continuity of matrix, sintered Densifying materials process is hindered in journey, consistency is not high, and the desulfating and deoxidation effect unobvious of rare earth oxide.
And steel knot TiCN base cemented carbides provided by the invention, it is using TiCN as hard phase, using steel matrix as Binder Phase, its In, rare earth element is added in the form of intermediate alloy, i.e., added with iron-rare earth intermediate alloy as additive.Due in this hair In bright, W, Mo, V and Cr for containing in steel matrix are carbide formers, and above-mentioned element can not only improve steel bonded carbide Sintering character, moreover it is possible to form corresponding carbide and be centered around around tiny TiCN particles, play the part of a kind of role of interphase, The problem of significantly improving TiCN hard phases wetability is poor in steel matrix, improve between TiCN hard phases and steel matrix Interface bond strength.Combined with above-mentioned steel matrix characteristic, rare earth elements of the present invention with Fe-(30 ~ 36%) Ce-(15 ~ 20%) form of La intermediate alloys adds, on the one hand, rare earth element can reduce the segregation phenomena of the alloying elements such as W, Mo, refinement Eutectic carbide；On the other hand, with number of patent application be 201210104964.1 Chinese patent in add rare earth oxide La2O3Compare, the Fe- rare earth intermediate alloys that the present invention is added are with Fe2Ce, CeFe3、CeFe7It is mono- Deng intermetallic compound and La Based on matter, except that can also have more preferable deoxidation, desulfurization effect in addition to crystal grain thinning and dispersion-strengtherning；At a sintering temperature, rare earth Element reduction iron oxide, so as to reduce the carbon loss caused by carbon in alloy and oxygen react.In addition, used in steel matrix Iron powder is reduced iron powder and carboxyl iron powder, and iron powder surface film oxide is removed, and the obstacle migrated between atom is reduced, and atom is expanded Dissipate advantageously, improve the wetability between powder, improve the consistency of alloy, reduce hole.Therefore, among rare earth The addition of alloy improves the sintering character of material, improves microstructure, and material comprehensive performance is improved.In addition TiCN from Some good characteristics, have the steel knot TiCN base cemented carbides that the present invention is obtained more excellent than common tungsten-cobalt series hard alloy High temperature red hardness and inoxidizability.More above-mentioned patent does steel matrix ratio using potassium steel, has hardness higher, wearability is more The advantages of good.In short, in the present invention, by selecting TiCN as hard phase, using steel matrix as Binder Phase, and rare earth element with iron- The form addition of rare earth intermediate alloy, effectively improves the performance of steel knot TiCN based hard alloy materials, its hardness, fracture are tough The main performance such as property and wearability is suitable with tungsten-cobalt series hard alloy, even more excellent, reaches in fields such as cutting tool, moulds Partially or completely substitute the purpose of tungsten-cobalt series hard alloy.
The method provided by the invention for preparing steel knot TiCN base cemented carbides, it uses powder metallurgic method to prepare, specifically, After Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloy melts are prepared using conventional smelting process in the present invention, then by Fe- Fe-(20 ~ 30%) Ce-(8 ~ 20%) are made using conventional water atomization in (20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloy melts La intermediate alloy powder；Compared with traditional crush method flouring technology, the powder processed of Fe- rare earth intermediate alloys is prepared using water fog method Technique, can make powder purity higher, and component evenly, simplifies production technology, reduces production cost.The present invention passes through setting Sintered products continue heat treatment step, effectively improve alloy heterogeneous microstructure, improve interface bond strength, are heat-treated Tempering in step can eliminate quenching internal stress, improve structure stability.During double tempering, Transformation of Retained Austenite is into horse Family name's body, and the carbide former such as W, Cr, Mo, V in alloy separates out corresponding carbide, post-curing phenomenon occurs, closes The hardness of gold, obdurability are improved.
The specific embodiment of the invention is as follows：
Embodiment 1
A kind of steel knot TiCN base cemented carbides, the steel knot TiCN base cemented carbides are using TiCN as hard phase, using steel matrix as bonding Phase, it is described on the basis of the gross weight of steel knot TiCN base cemented carbides using Fe -28%Ce -10%La intermediate alloys as additive TiCN percentage by weight be 35%, the percentage by weight of the steel matrix be 64.3%, the Fe -28%Ce -10%La The percentage by weight of intermediate alloy is 0.7%, and the material composition of the steel matrix includes W powder, Mo powder, V powder, Cr powder, Ni powder, Cu Powder, carbon black powder, carbonyl iron dust, reduced iron powder.Each component of steel matrix accounts for the quality hundred of the gross mass of steel knot TiCN base cemented carbides Divide ratio as follows：4.2%W powder, 3.5%Mo powder, 1.4%V powder, 2.5%Cr powder, 0.5%Ni powder, 0.4%Cu powder, 0.6% carbon black powder, 14% carbonyl Base iron powder, 37.4% reduced iron powder.
The preparation method of above-mentioned steel knot TiCN base cemented carbides comprises the following steps：
Step 1：It is prepared by intermediate alloy, using Fe, Ce, La as raw material, in terms of Fe -28%Ce -10%La intermediate alloy gross masses, Fe -28%Ce -10%La master alloyed powders are that Fe carries out dispensing by weight percentage for 28% Ce, 10% La, surplus, in Fe -28%Ce -10%La intermediate alloy melts are prepared using conventional smelting process in frequency electric induction furnace, then by the Fe - Fe -28%Ce -10%La intermediate alloy powder is made using conventional water atomization in 28%Ce -10%La intermediate alloy melts.
Step 2：Dispensing, by intermediate alloy powder and TiCN powder etc. among Fe-28%Ce made from step 1-10%La its He carries out dispensing at raw materials by weight；I.e. by purity higher than 99.9%, Fisher particle size be less than 5 μm, mole carbon-nitrogen ratios for C/N= 1:1 TiCN powder, purity are less than 10 μm of Fe- rare earth intermediate alloys higher than 99.8%, granularity, and purity is small higher than 99.9%, granularity It is small higher than 99.9%, granularity in 25 μm of tungsten powder, molybdenum powder, chromium powder, vanadium powder, nickel powder, copper powder, carbon black, carbonyl iron dust, and purity In 75 μm of reduced iron powder, dispensing according to the following percentages by weight：35% TiCN powder, among 0.6% Fe -28%Ce -10%La Alloyed powder, 4.2%W powder, 3.5%Mo powder, 1.4%V powder, 2.5%Cr powder, 0.5%Ni powder, 0.4%Cu powder, 0.6% carbon black powder, 14% carbonyl Base iron powder, 37.4% reduced iron powder.
Step 3：Dispensing in step 2 is subjected to ball milling；Ball mill is high-energy planetary formula ball mill, the ball of ball mill mixing Material is than being 10:1, rotating speed 300rpm, Ball-milling Time 15h, milling atmosphere are argon gas；Ball-milling medium is alcohol, and abrasive body is Sintered carbide ball.
The mixing method of this high-energy ball milling in the present embodiment can concentrate raw material powder particle size distribution, and shape is more advised Then, for part composition in the process there occurs mechanical alloying reaction, interface bond strength raising, is conducive to follow-up sintering, Materials microstructure is improved with performance.
Step 4：The qualified mixture compression molding that will be obtained in step 3；The composite powder after batch mixing is done It is dry, and pelletized with granulator, it is compressing under the pressure of 520Mpa, obtain steel knot TiCN base cemented carbide pressed compacts.
Step 5：The pressed compact obtained in step 4 is sintered；In the present embodiment, vacuum-sintering is sintered to, vacuum is burnt The temperature of knot is that vacuum is less than 0.5Pa, soaking time 60min, and the steel knot TiCN bases after vacuum-sintering are hard at 1400 DEG C Matter alloy furnace cooling.
Step 6：The sintered body obtained in step 5 is heat-treated, first by steel knot TiCN base cemented carbides in horse Not carry out quenching treatment in stove at 1200 DEG C, hardening media is oil, and quenching atmosphere is argon gas, afterwards 550 DEG C to sintering after Steel knot TiCN base cemented carbides carry out double tempering, obtain steel knot TiCN base cemented carbides.
The steel knot TiCN base cemented carbides that the embodiment of the present invention 1 obtains, observe under scanning electron microscope and find：It organizes thin Carbide small, that the alloying element such as W, Mo, V and Cr is formed（Light tone）It is centered around TiCN particles（Black）Around, it act as centre The role of phase, improves hard phase and steel matrix（Grey）Between interface bond strength, steel knot TiCN base cemented carbides sweep Retouch electron microscope（SEM）As shown in Figure 2.The sintered body consistency of acquisition is 99.5%, hardness 1350HV30, and fracture toughness is 11MPa·m1/2, after heat treatment hardness can reach 1695HV30, fracture toughness reaches 15MPam1/2。
Embodiment 2
A kind of steel knot TiCN base cemented carbides, the steel knot TiCN base cemented carbides are using TiCN as hard phase, using steel matrix as bonding Phase, using Fe -20%Ce -8%La intermediate alloys as additive, on the basis of the gross weight of steel knot TiCN base cemented carbides, TiCN Percentage by weight be 30%, the weight hundred that the percentage by weight of steel matrix is 69.5%, Fe -20%Ce -8%La intermediate alloys Divide than being 0.5%, the mass percent that each component of steel matrix accounts for the gross mass of steel knot TiCN base cemented carbides is as follows：3.2%W powder, 2.8%Mo powder, 1%V powder, 1.6%Cr powder, 0.3%Ni powder, 0.3%Cu powder, 0.8% carbon black powder, 12% carbonyl iron dust, 37.4% reduced iron Powder.
The preparation method of above-mentioned steel knot TiCN base cemented carbides comprises the following steps：
Step 1：It is prepared by intermediate alloy, using Fe, Ce, La as raw material, in terms of Fe -20%Ce -8%La intermediate alloy gross masses, Fe -28%Ce -10%La master alloyed powders are that Fe carries out dispensing by weight percentage for 20% Ce, 8% La, surplus, in Fe -20%Ce -8%La intermediate alloy melts are prepared using conventional smelting process in frequency electric induction furnace, then by Fe -20% Fe -20%Ce -8%La intermediate alloy powder is made using conventional water atomization in Ce -8%La intermediate alloy melts；
Step 2：Dispensing, by other raw materials such as intermediate alloy powder and TiCN powder among Fe-20%Ce made from step 1-8%La Dispensing is carried out by weight percentage；It is C/N=1 that purity is higher than 99.9%, Fisher particle size less than 5 μm, mole carbon-nitrogen ratios:1 TiCN powder, purity are less than 10 μm of Fe- rare earth intermediate alloys higher than 99.8%, granularity, and purity is less than 25 μm higher than 99.9%, granularity Tungsten powder, molybdenum powder, chromium powder, vanadium powder, nickel powder, copper powder, carbon black, carbonyl iron dust, and purity is higher than 99.9%, granularity is less than 75 μm Reduced iron powder, dispensing according to the following percentages by weight：30% TiCN powder, 0.5% Fe -28%Ce -10%La master alloyed powders, 3.2%W powder, 2.8%Mo powder, 1%V powder, 1.6%Cr powder, 0.3%Ni powder, 0.3%Cu powder, 0.8% carbon black powder, 12% carbonyl iron dust, 37.4% reduced iron powder.
Step 3：Dispensing in step 2 is subjected to ball milling；In the present embodiment, ball mill is high-energy planetary formula ball mill, The ratio of grinding media to material of ball mill mixing is 8:1, rotating speed 350rpm, Ball-milling Time 10h, milling atmosphere are argon gas；Ball-milling medium is wine Essence, abrasive body are sintered carbide ball.
Step 4：The qualified mixture compression molding that will be obtained in step 3；The composite powder after batch mixing is done It is dry, and pelletized with granulator, in the present embodiment, compression molding is compressing under the pressure of 320Mpa, obtains steel knot TiCN Base cemented carbide pressed compact.
Step 5：The pressed compact obtained in step 4 is sintered；In the present embodiment, vacuum-sintering is sintered to, vacuum is burnt The temperature of knot is that vacuum is less than 0.5Pa, soaking time 70min, and the steel knot TiCN bases after vacuum-sintering are hard at 1450 DEG C Matter alloy furnace cooling.
Step 6：The sintered body obtained in step 5 is heat-treated, first by steel knot TiCN base cemented carbides in horse Not carry out quenching treatment in stove at 1150 DEG C, hardening media is oil, and quenching atmosphere is argon gas, afterwards 540 DEG C to sintering after Steel knot TiCN base cemented carbides carry out double tempering, obtain steel knot TiCN base cemented carbides.
The sintered body consistency for the steel knot TiCN base cemented carbides that the embodiment of the present invention 2 obtains is 99.4%, and hardness is 1342HV30, fracture toughness 11MPam1/2, after heat treatment hardness can reach 1654HV30, fracture toughness reaches 14MPa·m1/2。
Embodiment 3
A kind of steel knot TiCN base cemented carbides, the steel knot TiCN base cemented carbides are using TiCN as hard phase, using steel matrix as bonding Phase, using Fe -23%Ce -12%La intermediate alloys as additive, on the basis of the gross weight of steel knot TiCN base cemented carbides, The percentage by weight of TiCN is 32%, the percentage by weight of steel matrix is 67.4%, Fe -20%Ce -8%La intermediate alloys Percentage by weight is 0.6%, and the mass percent that each component of steel matrix accounts for the gross mass of steel knot TiCN base cemented carbides is as follows：4% W powder, 3%Mo powder, 1.2%V powder, 2%Cr powder, 0.4%Ni powder, 0.4%Cu powder, 0.65% carbon black powder, 15% carbonyl iron dust, 40.75% also Former iron powder.
The preparation method of above-mentioned steel knot TiCN base cemented carbides comprises the following steps：
Step 1：It is prepared by intermediate alloy, using Fe, Ce, La as raw material, in terms of Fe -23%Ce -12%La intermediate alloy gross masses, Fe -23%Ce -12%La master alloyed powders are that Fe carries out dispensing by weight percentage for 23% Ce, 12% La, surplus, in Intermediate alloy melt is prepared using conventional smelting process in frequency electric induction furnace, then by intermediate alloy melt using conventional water atomization Fe -23%Ce -12%La intermediate alloy powder is made in method；
Step 2：Dispensing, by intermediate alloy powder and TiCN powder etc. among Fe-23%Ce made from step 1-12%La, other are former Material carries out dispensing by weight percentage；It is C/N=1 that purity is higher than 99.9%, Fisher particle size less than 5 μm, mole carbon-nitrogen ratios:1 TiCN powder, purity is higher than 99.8%, granularity is less than 10 μm of Fe- rare earth intermediate alloys, and purity is less than 25 higher than 99.9%, granularity μm tungsten powder, molybdenum powder, chromium powder, vanadium powder, nickel powder, copper powder, carbon black, carbonyl iron dust, and purity is higher than 99.9%, granularity is less than 75 μ The reduced iron powder of m, according to the following percentages by weight dispensing：32% TiCN powder, 0.6% Fe -28%Ce -10%La intermediate alloys Powder, 4%W powder, 3%Mo powder, 1.2%V powder, 2%Cr powder, 0.4%Ni powder, 0.4%Cu powder, 0.65% carbon black powder, 15% carbonyl iron dust, 40.75% reduced iron powder.
Step 3：Dispensing in step 2 is subjected to ball milling；In the present embodiment, ball mill is high-energy planetary formula ball mill, The ratio of grinding media to material of ball mill mixing is 5:1, rotating speed 300rpm, Ball-milling Time 12h, milling atmosphere are argon gas；Ball-milling medium is wine Essence, abrasive body are sintered carbide ball.
Step 4：The qualified mixture compression molding that will be obtained in step 3；After high-energy planetary formula ball mill batch mixing will being used Composite powder be dried, and pelletized with granulator, in the present embodiment, compression molding is suppressed under the pressure of 400Mpa Shaping, obtains steel knot TiCN base cemented carbide pressed compacts.
Step 5：The pressed compact obtained in step 4 is sintered；In the present embodiment, vacuum-sintering is sintered to, vacuum is burnt The temperature of knot is that vacuum is less than 0.5Pa, soaking time 45min, and the steel knot TiCN bases after vacuum-sintering are hard at 1420 DEG C Matter alloy furnace cooling.
Step 6：The sintered body obtained in step 5 is heat-treated, first by steel knot TiCN base cemented carbides in horse Not carry out quenching treatment in stove at 1100 DEG C, hardening media is oil, and quenching atmosphere is argon gas, afterwards 520 DEG C to sintering after Steel knot TiCN base cemented carbides carry out double tempering, obtain steel knot TiCN base cemented carbides.
The sintered body consistency for the steel knot TiCN base cemented carbides that the embodiment of the present invention 2 obtains is 99.5%, and hardness is 1319HV30, fracture toughness are 11MPa m1/2, after heat treatment hardness can reach 1628HV30, fracture toughness reaches 14MPa m1/2。
Embodiment 4
A kind of steel knot TiCN base cemented carbides, the steel knot TiCN base cemented carbides are using TiCN as hard phase, using steel matrix as bonding Phase, using Fe -28%Ce -15%La intermediate alloys as additive, on the basis of the gross weight of steel knot TiCN base cemented carbides, The percentage by weight of TiCN is 34%, the percentage by weight of steel matrix is 65.3%, Fe -28%Ce -15%La intermediate alloys Percentage by weight be 0.7%, the mass percent that each component of steel matrix accounts for the gross mass of steel knot TiCN base cemented carbides is as follows： 4.5%W powder, 3.2%Mo powder, 1.5%V powder, 2.6%Cr powder, 0.6%Ni powder, 0.5%Cu powder, 0.7% carbon black powder, 16% carbonyl iron dust, 35.7% reduced iron powder.
The preparation method of above-mentioned steel knot TiCN base cemented carbides comprises the following steps：
Step 1：It is prepared by intermediate alloy, using Fe, Ce, La as raw material, in terms of Fe -28%Ce -15%La intermediate alloy gross masses, Fe -28%Ce -15%La master alloyed powders are that Fe carries out dispensing by weight percentage for 28% Ce, 15% La, surplus, in Intermediate alloy melt is prepared using conventional smelting process in frequency electric induction furnace, then by intermediate alloy melt using conventional water mist Fe -28%Ce -15%La intermediate alloy powder is made in change method；
Step 2：Dispensing, by intermediate alloy powder and TiCN powder etc. among Fe-28%Ce made from step 1-15%La, other are former Material carries out dispensing by weight percentage；It is C/N=1 that purity is higher than 99.9%, Fisher particle size less than 5 μm, mole carbon-nitrogen ratios:1 TiCN powder, purity is higher than 99.8%, granularity is less than 10 μm of Fe- rare earth intermediate alloys, and purity is less than 25 higher than 99.9%, granularity μm tungsten powder, molybdenum powder, chromium powder, vanadium powder, nickel powder, copper powder, carbon black, carbonyl iron dust, and purity is higher than 99.9%, granularity is less than 75 μ The reduced iron powder of m, according to the following percentages by weight dispensing：34% TiCN powder, 0.7% Fe -28%Ce -10%La intermediate alloys Powder, 4.5%W powder, 3.2%Mo powder, 1.5%V powder, 2.6%Cr powder, 0.6%Ni powder, 0.5%Cu powder, 0.7% carbon black powder, 16% carbonyl iron Powder, 35.7% reduced iron powder.
Step 3：Dispensing in step 2 is subjected to ball milling；In the present embodiment, ball mill is high-energy planetary formula ball mill, ball The ratio of grinding media to material for grinding batch mixing is 8:1, rotating speed 340rpm, Ball-milling Time 16h, milling atmosphere are argon gas；Ball-milling medium is alcohol, Abrasive body is sintered carbide ball.
Step 4：The qualified mixture compression molding that will be obtained in step 3；The composite powder after batch mixing is done It is dry, and pelletized with granulator, in the present embodiment, compression molding is compressing under the pressure of 420Mpa, obtains steel knot TiCN Base cemented carbide pressed compact.
Step 5：The pressed compact obtained in step 4 is sintered；In the present embodiment, vacuum-sintering is sintered to, vacuum is burnt The temperature of knot is that vacuum is less than 0.5Pa, soaking time 55min, and the steel knot TiCN bases after vacuum-sintering are hard at 1450 DEG C Matter alloy furnace cooling.
Step 6：The sintered body obtained in step 5 is heat-treated, first by steel knot TiCN base cemented carbides in horse Not carry out quenching treatment in stove at 1180 DEG C, hardening media is oil, and quenching atmosphere is argon gas, afterwards 540 DEG C to sintering after Steel knot TiCN base cemented carbides carry out double tempering, obtain steel knot TiCN base cemented carbides.
The sintered body consistency for the steel knot TiCN base cemented carbides that the embodiment of the present invention 4 obtains is 99.3%, and hardness is 1387HV30, fracture toughness are 12MPa m1/2, after heat treatment hardness can reach 1634HV30, fracture toughness reaches 15MPa m1/2。
Example 5
A kind of steel knot TiCN base cemented carbides, the steel knot TiCN base cemented carbides are using TiCN as hard phase, using steel matrix as bonding Phase, using Fe -26%Ce -18%La intermediate alloys as additive, on the basis of the gross weight of steel knot TiCN base cemented carbides, The percentage by weight of TiCN is 37%, the percentage by weight of steel matrix is 62.4%, Fe -26%Ce -18%La intermediate alloys Percentage by weight be 0.6%, the mass percent that each component of steel matrix accounts for the gross mass of steel knot TiCN base cemented carbides is as follows： 5.0%W powder, 3.0%Mo powder, 1.6%V powder, 3.5%Cr powder, 0.65%Ni powder, 0.42%Cu powder, 1.0% carbon black powder, 17% carbonyl iron dust, 30.23% reduced iron powder.
The preparation method of above-mentioned steel knot TiCN base cemented carbides comprises the following steps：
Step 1：It is prepared by intermediate alloy, using Fe, Ce, La as raw material, in terms of Fe -26%Ce -18%La intermediate alloy gross masses, Fe -26%Ce -18%La master alloyed powders are that Fe carries out dispensing by weight percentage for 26% Ce, 18% La, surplus, in Intermediate alloy melt is prepared using conventional smelting process in frequency electric induction furnace, then by intermediate alloy melt using conventional water atomization Fe -26%Ce -18%La intermediate alloy powder is made in method；
Step 2：Dispensing, by intermediate alloy powder and TiCN powder etc. among Fe-26%Ce made from step 1-18%La, other are former Material carries out dispensing by weight percentage；It is C/N=1 that purity is higher than 99.9%, Fisher particle size less than 5 μm, mole carbon-nitrogen ratios:1 TiCN powder, purity is higher than 99.8%, granularity is less than 10 μm of Fe- rare earth intermediate alloys, and purity is less than 25 higher than 99.9%, granularity μm tungsten powder, molybdenum powder, chromium powder, vanadium powder, nickel powder, copper powder, carbon black, carbonyl iron dust, and purity is higher than 99.9%, granularity is less than 75 μ The reduced iron powder of m, according to the following percentages by weight dispensing：37% TiCN powder, 0.6% Fe -28%Ce -10%La intermediate alloys Powder, 5.0%W powder, 3.0%Mo powder, 1.6%V powder, 3.5%Cr powder, 0.65%Ni powder, 0.42%Cu powder, 1.0% carbon black powder, 17% carbonyl iron Powder, 30.23% reduced iron powder.
Step 3：Dispensing in step 2 is subjected to ball milling；In the present embodiment, ball mill is high-energy planetary formula ball mill, ball The ratio of grinding media to material for grinding batch mixing is 10:1, rotating speed 360rpm, Ball-milling Time 12h, milling atmosphere are argon gas；Ball-milling medium is wine Essence, abrasive body are sintered carbide ball.
Step 4：The qualified mixture compression molding that will be obtained in step 3；The composite powder after batch mixing is done It is dry, and pelletized with granulator, in the present embodiment, compression molding is compressing under the pressure of 500Mpa, obtains steel knot TiCN Base cemented carbide pressed compact.
Step 5：The pressed compact obtained in step 4 is sintered；In the present embodiment, vacuum-sintering is sintered to, vacuum is burnt The temperature of knot is that vacuum is less than 0.5Pa, soaking time 45min, and the steel knot TiCN bases after vacuum-sintering are hard at 1460 DEG C Matter alloy furnace cooling.
Step 6：The sintered body obtained in step 5 is heat-treated, first by steel knot TiCN base cemented carbides in horse Not carry out quenching treatment in stove at 1250 DEG C, hardening media is oil, and quenching atmosphere is argon gas, afterwards 560 DEG C to sintering after Steel knot TiCN base cemented carbides carry out double tempering, obtain steel knot TiCN base cemented carbides.
The sintered body consistency for the steel knot TiCN base cemented carbides that the embodiment of the present invention 5 obtains is 99.6%, and hardness is 1416HV30, fracture toughness are 12MPa m1/2, and after heat treatment hardness can reach 1645HV30, and fracture toughness reaches 14MPa m1/2。
Example 6
A kind of steel knot TiCN base cemented carbides, the steel knot TiCN base cemented carbides are using TiCN as hard phase, using steel matrix as bonding Phase, using Fe -30%Ce -15%La intermediate alloys as additive, on the basis of the gross weight of steel knot TiCN base cemented carbides, The percentage by weight of TiCN is 40%, the percentage by weight of steel matrix is 59.2%, Fe -30%Ce -15%La intermediate alloys Percentage by weight be 0.8%, the mass percent that each component of steel matrix accounts for the gross mass of steel knot TiCN base cemented carbides is as follows： 3.8%W powder, 4.2%Mo powder, 2.0%V powder, 4.0%Cr powder, 0.3%Ni powder, 0.2%Cu powder, 0.9% carbon black powder, 12% carbonyl iron dust, 31.8% reduced iron powder.
The preparation method of above-mentioned steel knot TiCN base cemented carbides comprises the following steps：
Step 1：It is prepared by intermediate alloy, using Fe, Ce, La as raw material, in terms of Fe -30%Ce -15%La intermediate alloy gross masses, Fe -30%Ce -15%La master alloyed powders are that Fe carries out dispensing by weight percentage for 30% Ce, 15% La, surplus, in Intermediate alloy melt is prepared using conventional smelting process in frequency electric induction furnace, then by intermediate alloy melt using conventional water mist Fe -30%Ce -15%La intermediate alloy powder is made in change method；
Step 2：Dispensing, by intermediate alloy powder and TiCN powder etc. among Fe-30%Ce made from step 1-15%La, other are former Material carries out dispensing by weight percentage；It is C/N=1 that purity is higher than 99.9%, Fisher particle size less than 5 μm, mole carbon-nitrogen ratios:1 TiCN powder, purity is higher than 99.8%, granularity is less than 10 μm of Fe- rare earth intermediate alloys, and purity is less than 25 higher than 99.9%, granularity μm tungsten powder, molybdenum powder, chromium powder, vanadium powder, nickel powder, copper powder, carbon black, carbonyl iron dust, and purity is higher than 99.9%, granularity is less than 75 μ The reduced iron powder of m, according to the following percentages by weight dispensing：40% TiCN powder, 0.8% Fe -28%Ce -10%La intermediate alloys Powder, 3.8%W powder, 4.2%Mo powder, 2.0%V powder, 4.0%Cr powder, 0.3%Ni powder, 0.2%Cu powder, 0.9% carbon black powder, 12% carbonyl iron Powder, 31.8% reduced iron powder.
Step 3：Dispensing in step 2 is subjected to ball milling；In the present embodiment, ball mill is high-energy planetary formula ball mill, The ratio of grinding media to material of ball mill mixing is 9:1, rotating speed 380rpm, Ball-milling Time 10h, milling atmosphere are argon gas；Ball-milling medium is wine Essence, abrasive body are sintered carbide ball.
Step 4：The qualified mixture compression molding that will be obtained in step 3；After high-energy planetary formula ball mill batch mixing will being used Composite powder be dried, and pelletized with granulator, in the present embodiment, compression molding is suppressed under the pressure of 650Mpa Shaping, obtains steel knot TiCN base cemented carbide pressed compacts.
Step 5：The pressed compact obtained in step 4 is sintered；In the present embodiment, vacuum-sintering is sintered to, vacuum is burnt The temperature of knot is that vacuum is less than 0.5Pa, soaking time 65min, and the steel knot TiCN bases after vacuum-sintering are hard at 1450 DEG C Matter alloy furnace cooling.
Step 6：The sintered body obtained in step 5 is heat-treated, first by steel knot TiCN base cemented carbides in horse Not carry out quenching treatment in stove at 1220 DEG C, hardening media is oil, and quenching atmosphere is argon gas, afterwards 570 DEG C to sintering after Steel knot TiCN base cemented carbides carry out double tempering, obtain steel knot TiCN base cemented carbides.
The sintered body consistency for the steel knot TiCN base cemented carbides that the embodiment of the present invention 6 obtains is 99.5%, and hardness is 1422HV30, fracture toughness are 12MPa m1/2, and after heat treatment hardness can reach 1672HV30, and fracture toughness reaches 14MPa m1/2。
Embodiment 7
A kind of steel knot TiCN base cemented carbides, the steel knot TiCN base cemented carbides are using TiCN as hard phase, using steel matrix as bonding Phase, using Fe -28%Ce -10%La intermediate alloys as additive, on the basis of the gross weight of steel knot TiCN base cemented carbides, The percentage by weight of TiCN is 35%, the percentage by weight of steel matrix is 64.3%, Fe -28%Ce -10%La intermediate alloys Percentage by weight be 0.7%, the mass percent that each component of steel matrix accounts for the gross mass of steel knot TiCN base cemented carbides is as follows： 3.0%W powder, 2.5%Mo powder, 1.4%V powder, 2.5%Cr powder, 0.8%Ni powder, 0.6%Cu powder, 1.2% carbon black powder, 18% carbonyl iron dust, 34.5% reduced iron powder.
The preparation method of above-mentioned steel knot TiCN base cemented carbides comprises the following steps：
Step 1：It is prepared by intermediate alloy, using Fe, Ce, La as raw material, in terms of Fe -28%Ce -10%La intermediate alloy gross masses, Fe -28%Ce -10%La master alloyed powders are that Fe carries out dispensing by weight percentage for 28% Ce, 10% La, surplus, in Fe -28%Ce -10%La intermediate alloy melts are prepared using conventional smelting process in frequency electric induction furnace, then by Fe -28% Fe -28%Ce -10%La intermediate alloy powder is made using conventional water atomization in Ce -10%La intermediate alloy melts.Step 2： Dispensing, by other raw materials such as intermediate alloy powder and TiCN powder by weight hundred among Fe-28%Ce made from step 1-10%La Divide than carrying out dispensing；It is C/N=1 that purity is higher than 99.9%, Fisher particle size less than 5 μm, mole carbon-nitrogen ratios:1 TiCN powder is pure Degree is less than 10 μm of Fe- rare earth intermediate alloys higher than 99.8%, granularity, and purity is higher than tungsten powder of the 99.9%, granularity less than 25 μm, molybdenum Powder, chromium powder, vanadium powder, nickel powder, copper powder, carbon black, carbonyl iron dust, and purity are less than 75 μm of reduced iron higher than 99.9%, granularity Powder, according to the following percentages by weight dispensing：35% TiCN powder, 0.6% Fe -28%Ce -10%La master alloyed powders, 3.0%W powder, 2.5%Mo powder, 1.4%V powder, 2.5%Cr powder, 0.8%Ni powder, 0.6%Cu powder, 1.2% carbon black powder, 18% carbonyl iron dust, 34.5% reduction Iron powder.
Step 3：Dispensing in step 2 is subjected to ball milling；In the present embodiment, ball mill is high-energy planetary formula ball mill, The ratio of grinding media to material of ball mill mixing is 10:1, rotating speed 270rpm, Ball-milling Time 8h, milling atmosphere are argon gas；Ball-milling medium is wine Essence, abrasive body are sintered carbide ball.Step 4：The qualified mixture compression molding that will be obtained in step 3；I.e. by answering after batch mixing Close powder to be dried, and pelletized with granulator, in the present embodiment, compression molding be it is compressing under the pressure of 200Mpa, Obtain steel knot TiCN base cemented carbide pressed compacts.
Step 5：The pressed compact obtained in step 4 is sintered；In the present embodiment, vacuum-sintering, vacuum-sintering are sintered to Temperature be 1380 DEG C at, vacuum is less than 0.5Pa, soaking time 60min, the steel knot TiCN base hard after vacuum-sintering Alloy furnace cooling.
Step 6：The sintered body obtained in step 5 is heat-treated, first by steel knot TiCN base cemented carbides in horse Not carry out quenching treatment in stove at 1200 DEG C, hardening media is oil, and quenching atmosphere is argon gas, afterwards 550 DEG C to sintering after Steel knot TiCN base cemented carbides carry out double tempering, obtain steel knot TiCN base cemented carbides.
The steel knot TiCN base cemented carbides that the embodiment of the present invention 7 obtains, observe under scanning electron microscope and find：It organizes thin Carbide small, that the alloying element such as W, Mo, V and Cr is formed（Light tone）It is centered around TiCN particles（Black）Around, it act as centre The role of phase, improves hard phase and steel matrix（Grey）Between interface bond strength, steel knot TiCN base cemented carbides sweep Retouch electron microscope（SEM）As shown in Figure 2.The sintered body consistency of acquisition is 99.5%, hardness 1386HV30, and fracture toughness is 12MPa·m1/2, after heat treatment hardness can reach 1669HV30, fracture toughness reaches 15MPam1/2。
Embodiment 8
A kind of steel knot TiCN base cemented carbides, the steel knot TiCN base cemented carbides are using TiCN as hard phase, using steel matrix as bonding Phase, using Fe -28%Ce -10%La intermediate alloys as additive, on the basis of the gross weight of steel knot TiCN base cemented carbides, The percentage by weight of TiCN is 35%, the percentage by weight of steel matrix is 64.3%, Fe -28%Ce -10%La intermediate alloys Percentage by weight be 0.7%, the mass percent that each component of steel matrix accounts for the gross mass of steel knot TiCN base cemented carbides is as follows： 6.0%W powder, 3.5%Mo powder, 1.4%V powder, 2.5%Cr powder, 0.5%Ni powder, 0.4%Cu powder, 0.6% carbon black powder, 14% carbonyl iron dust, 34.4% reduced iron powder.
The preparation method of above-mentioned steel knot TiCN base cemented carbides comprises the following steps：
Step 1：It is prepared by intermediate alloy, using Fe, Ce, La as raw material, in terms of Fe -28%Ce -10%La intermediate alloy gross masses, Fe -28%Ce -10%La master alloyed powders are that Fe carries out dispensing by weight percentage for 28% Ce, 10% La, surplus, in Fe -28%Ce -10%La intermediate alloy melts are prepared using conventional smelting process in frequency electric induction furnace, then by Fe -28% Fe -28%Ce -10%La intermediate alloy powder is made using conventional water atomization in Ce -10%La intermediate alloy melts.Step 2： Dispensing, by other raw materials such as intermediate alloy powder and TiCN powder by weight hundred among Fe-28%Ce made from step 1-10%La Divide than carrying out dispensing；It is C/N=1 that purity is higher than 99.9%, Fisher particle size less than 5 μm, mole carbon-nitrogen ratios:1 TiCN powder is pure Degree is less than 10 μm of Fe- rare earth intermediate alloys higher than 99.8%, granularity, and purity is higher than tungsten powder of the 99.9%, granularity less than 25 μm, molybdenum Powder, chromium powder, vanadium powder, nickel powder, copper powder, carbon black, carbonyl iron dust, and purity are less than 75 μm of reduced iron higher than 99.9%, granularity Powder, according to the following percentages by weight dispensing：35% TiCN powder, 0.6% Fe -28%Ce -10%La master alloyed powders, 6.0%W powder, 3.5%Mo powder, 1.4%V powder, 2.5%Cr powder, 0.5%Ni powder, 0.4%Cu powder, 0.6% carbon black powder, 14% carbonyl iron dust, 34.4% reduction Iron powder.
Step 3：Dispensing in step 2 is subjected to ball milling；In the present embodiment, ball mill is high-energy planetary formula ball mill, The ratio of grinding media to material of ball mill mixing is 10:1, rotating speed 300rpm, Ball-milling Time 20h, milling atmosphere are argon gas；Ball-milling medium is wine Essence, abrasive body are sintered carbide ball.Step 4：The qualified mixture compression molding that will be obtained in step 3；I.e. by answering after batch mixing Close powder to be dried, and pelletized with granulator, in the present embodiment, compression molding be it is compressing under the pressure of 520Mpa, Obtain steel knot TiCN base cemented carbide pressed compacts.
Step 5：The pressed compact obtained in step 4 is sintered；In the present embodiment, vacuum-sintering is sintered to, vacuum is burnt The temperature of knot is that vacuum is less than 0.5Pa, soaking time 60min, and the steel knot TiCN bases after vacuum-sintering are hard at 1400 DEG C Matter alloy furnace cooling.
Step 6：The sintered body obtained in step 5 is heat-treated, first by steel knot TiCN base cemented carbides in horse Not carry out quenching treatment in stove at 1200 DEG C, hardening media is oil, and quenching atmosphere is argon gas, afterwards 550 DEG C to sintering after Steel knot TiCN base cemented carbides carry out double tempering, obtain steel knot TiCN base cemented carbides.
The steel knot TiCN base cemented carbides that the embodiment of the present invention 8 obtains, observe under scanning electron microscope and find：It organizes thin Carbide small, that the alloying element such as W, Mo, V and Cr is formed（Light tone）It is centered around TiCN particles（Black）Around, it act as centre The role of phase, improves hard phase and steel matrix（Grey）Between interface bond strength, steel knot TiCN base cemented carbides sweep Retouch electron microscope（SEM）As shown in Figure 2.The sintered body consistency of acquisition is 99.4%, hardness 1392HV30, and fracture toughness is 11MPa·m1/2, after heat treatment hardness can reach 1657HV30, fracture toughness reaches 15MPam1/2。
Comparative example 1
The TiCN powder of comparative example 1, the component of prealloy powder and percentage by weight, preparation technology parameter are all same as Example 1, The addition form of only rare earth element is different, i.e., with rare earth oxide La2O3Form add, content 0.6%.The sintered body of acquisition Consistency is 98.5%, hardness 1294HV30, fracture toughness 9MPam1/2, after heat treatment hardness can reach 1596HV30, fracture toughness reach 11MPam1/2。
Comparative example 2
Prepared composition be WC-10Co hard alloy, it is raw materials used be 1 μm tungsten carbide powder, 1 μm of cobalt powder.（1）Dispensing：Press Following weight percents dispensing, 90% WC, 10% Co；（2）High-energy ball milling batch mixing：Ball-milling medium is alcohol, and abrasive body is hard Matter alloying pellet, ratio of grinding media to material 10:1, when Ball-milling Time is 12 small, using argon gas as protective gas；（3）Shaping：Will be through ball milling, dry Qualified mixture 200MPa pressure compression moldings after dry, granulation.（4）Sintering, the vacuum-sintering at 1450 DEG C, vacuum are low In 0.5Pa, soaking time is 60 minutes, then furnace cooling.The alloy consistency that the comparative example 2 is obtained is 94.2%, hardness For 1587HV30, fracture toughness 14MPam1/2。
The main preparation technology parameter of embodiment 1,2,3,4,5,6,7,8 and comparative example 1,2, and its physical property contrast are detailed It is shown in Table 1.
Performance test
1st, microstructure
Steel knot TiCN base cemented carbide materials are observed using the HITACHI S-2500 types scanning electron microscope of Hitachi, Japan Expect the microstructure of sample 1, its scanning electron microscope (SEM) photograph（SEM）See Fig. 2.
2nd, hardness test
According to hard alloy Vickers hardness test method（GB/T 7997-2014）The hardness of each sample is tested, the results are shown in Table 1.
3rd, density measurement
The close of each sample is tested according to dense sintering metal material and hard alloy density measurement method (GB/T 3850-1983) Degree, the results are shown in Table 1.
4th, fracture toughness test
According to hard alloy Vickers hardness indentation method come the fracture strength of test material, impression load is 3878 standards of ISO It is recommended that 30kgf（294.2N）, guarantor's lotus time is 10 ~ 15s.The fracture toughness test of each sample the results are shown in Table 1.
In conclusion compared with Example 1, the primary alloy constituent of comparative example 1, preparation process is identical, only rare earth is first The addition form of element is different, i.e., embodiment 1 is added in the form of rare earth intermediate alloy, and comparative example 1 is in the form of rare earth oxide Add.The two physical property contrast is understood, consistency, hardness, the fracture toughness index of the alloy of comparative example 1, which are all less than, to be implemented The alloy of example 1, embodies the superiority that rare earth intermediate alloy powder is added in steel knot TiCN base cemented carbides.
Comparative example 2 is traditional WC/Co hard alloy, its hole is more, and consistency is only 96.2%.And its proportion is about 2 times of steel knot TiCN base cemented carbides prepared by the present invention, the important physical properties such as hardness, fracture toughness be below or with this hair It is bright suitable.
Above-mentioned performance indicator shows that the steel matrix in the present invention is using iron as primary raw material, it is in fact i.e. using iron as bonding Phase, the i.e. present invention are successfully realized with cheap iron instead of cobalt as main raw material(s), significantly reduce cost of material, National grand strategy resource is saved.In short, the present invention, Nai Zhichao close with WC/Co series hard alloy materials in material property On the premise of more, declining to a great extent for production cost is realized, its production cost is only WC/Co series hard alloy material production costs Half, it is even lower, there is high cost performance.
The steel knot TiCN base cemented carbides of the present invention are suitable for requiring higher hardness, wearability, toughness and high temperature red The various tool materials of hardness.More specifically, present invention is suitably applied to wear part and high-speed cutting instrument, such as roll Roller, CNC milling cutter, cutting tool and punching tool etc..
For example, the steel knot TiCN base cemented carbides that the embodiment of the present invention 1 is obtained are made roll, proved through using, with High-speed steel roll is compared, its wearability is greatly improved, and service life is 6 ~ 10 times of common high-speed steel roll.
The foregoing is merely a prefered embodiment of the invention, is not intended to limit the invention, it is all the present invention spirit and All any modification, equivalent and improvement made within principle etc., should all be included in the protection scope of the present invention.
Main preparation technology parameter and the physical and mechanical property contrast of 1 embodiment of table, comparative example

Claims (3)

  1. A kind of 1. steel knot TiCN base cemented carbides, it is characterised in that：The steel knot TiCN base cemented carbides are using TiCN as hard Phase, using steel matrix as Binder Phase, using Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloys as additive, with steel knot TiCN bases On the basis of the gross weight of hard alloy, the percentage by weight of the TiCN is 30 ~ 40%, percentage by weight of the steel matrix For 59.2 ~ 69.5%, the percentage by weight of the Fe-(20 ~ 30%) Ce-(8 ~ 20%) La intermediate alloys is 0.5 ~ 0.8%, institute Stating the material composition of steel matrix includes W powder, Mo powder, V powder, Cr powder, Ni powder, Cu powder, carbon black powder, carbonyl iron dust, reduced iron powder.
  2. 2. steel knot TiCN base cemented carbides according to claim 1, it is characterised in that：The material composition of the steel matrix And each component account for alloy gross mass mass percent it is as follows：3.0 ~ 6.0%W powder, 2.5 ~ 4.2%Mo powder, 0.8 ~ 2.0%V powder, 1.6 ~ 4.0%Cr powder, 0.3 ~ 0.8%Ni powder, 0.2 ~ 0.6%Cu powder, 0.6 ~ 1.2% carbon black powder, 12 ~ 18% carbonyl iron dusts, surplus are reduction Iron powder.
  3. 3. the steel knot TiCN base cemented carbides described in claim 1 or 2, in high speed cutting tool, hot forming tool and wear-resisting The application in part field.
CN201711443017.4A 2017-12-27 2017-12-27 A kind of steel knot TiCN base cemented carbides and application Pending CN108034881A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110144512A (en) * 2019-05-15 2019-08-20 株洲精工硬质合金有限公司 Non-magnetic iron-base cemented carbide material and preparation method thereof, application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110144512A (en) * 2019-05-15 2019-08-20 株洲精工硬质合金有限公司 Non-magnetic iron-base cemented carbide material and preparation method thereof, application

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