EP3192887A1 - Matériau à base d'acier et de céramique et son procédé de préparation - Google Patents

Matériau à base d'acier et de céramique et son procédé de préparation Download PDF

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Publication number
EP3192887A1
EP3192887A1 EP14833447.7A EP14833447A EP3192887A1 EP 3192887 A1 EP3192887 A1 EP 3192887A1 EP 14833447 A EP14833447 A EP 14833447A EP 3192887 A1 EP3192887 A1 EP 3192887A1
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EP
European Patent Office
Prior art keywords
materials
cerasteel
metal
phase
kinds
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.)
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Application number
EP14833447.7A
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German (de)
English (en)
Inventor
Jialin YAN
Yanbin Zhang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bright Time (hubei) Industrial Ltd
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Bright Time (hubei) Industrial Ltd
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Publication of EP3192887A1 publication Critical patent/EP3192887A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/14—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Definitions

  • the invention belongs to the technical field of composites, in particular to Cerasteel materials and their preparation method.
  • Knives, cutting tools as one of the necessary equipment of kitchen, are perennially in the water, water vapor, salt, acid and other environment, this is a big challenge for corrosion resistance of materials; meanwhile, knives, cutting tools are used for cutting or cutting food, hence, the demand for strength and hardness of materials are increasing.
  • the common materials used for manufacturing knives and cutting tools on the market are usually those materials such as stainless steel, ceramics and so on.
  • Stainless steel is well accepted due to its properties such as high toughness and corrosion resistance since the advent of it in 1913, which lays a foundation of the development of modern industry and improvement of technology. Therefore, it plays an important role in the production of knives and cutting tools.
  • the blade is easy to be blunt and not sharp during use due to its low hardness, poor wear resistance, stainless steel usually needs frequent grinding.
  • Zirconium ceramic knife and cutting tool is one of the new knives and cutting tools developed in recent years, which have properties of high hardness, wear resistance and high temperature resistance.
  • zirconium ceramic knife and cutting tool have some fatal flaws: High brittleness, poor impact resistance, thin edge of knife and cutting tool, easily chipping during use, which affects the useful life of zirconium ceramic knives and cutting tools. Therefore, in order to better meet people's daily needs, the researchers are keen to research a kind of composite materials which have properties of high hardness, excellent wear resistance, corrosion resistance and high temperature resistance.
  • this invention intends to provide Cerasteel materials and their preparation method, which have properties of high hardness, excellent wear resistance, corrosion resistance, high temperature resistance and good toughness.
  • Cerasteel materials in this invention are composed of ceramic phase and metal phase.
  • said ceramic phase is the boride consisted of Fe, Co, Ni, and one or more metal elements of IVB, VB and VIB of the fourth, fifth and sixth periodic metals.
  • said metal phase is an alloy composed of Mo and one or more metal elements of Fe, Co, Ni.
  • said Cerasteel materials further contain a few additives, said additives are C and one or more elements of V, Cr, Mn, Cu.
  • the weight percentage of each chemical component is: B 5 ⁇ 10 wt.%, Ti 0 ⁇ 50 wt.%, V 0 ⁇ 50 wt.%, Cr 0 ⁇ 50 wt.%, Zr 0 ⁇ 50 wt.%, Nb 0 ⁇ 50 wt.%, Mo 20 ⁇ 60 wt.%, Fe 10 ⁇ 40 wt.%, Ni 0 ⁇ 15 wt.%, Co 0 ⁇ 20 wt.%.
  • Element contents in said additives are no more than 5 wt.%.
  • Means for solving the other technical problems by the invention is to provide a preparation method of Cerasteel materials, characterized in that: Said preparation method of Cerasteel materials comprises the following steps of:
  • the said milling medium described above is one of the following materials: anhydrous ethanol, gasoline, acetone, hexane, carbon tetrachloride and benzene.
  • the said forming agent described above is one of the following materials: paraffin composed of n-alkanes, zinc stearate, polyvinyl butyral anhydrous ethanol solution and rubber oil solution.
  • the said drying method described above is one of the following methods: vacuum drying, vapor drying and spray drying.
  • the said sintering described above is one of the vacuum sintering, hot isostatic pressing sintering, activated sintering and spark plasma sintering.
  • the Cerasteel materials in this invention are composed of ceramic phase and metal phase.
  • ceramic phase is the boride consisted of Fe, Co, Ni, and one or more metal elements of IVB, VB and VIB of the fourth, fifth and sixth periodic metals.
  • Metal phase is an alloy composed of Mo and one or more metal elements of Fe, Co, Ni. Cerasteel materials in this invention have properties of high hardness, excellent wear resistance, corrosion resistance and high temperature resistance and can be used for producing knives, cutting tools, and all kinds of wear resistant, corrosion resistant, high temperature resistant materials and all kinds of structural components composed of them.
  • Cerasteel materials have good weldability with steel and other metal materials, which can meet people's daily needs and application in industry, agriculture, machining and medical apparatus and instruments and so on. Moreover, the invention provides a method for preparing Cerasteel materials.
  • the raw material reacted during sintering, boride and multiple boride were produced by in situ, which provides high hardness for Cerasteel materials using the above preparation method.
  • Fig. 1 shows the microstructure of Cerasteel materials observed under a scanning electron microscope.
  • ceramic phase of the Cerasteel materials is the boride consisted of Fe, Co, Ni, and one or more metal elements of IVB, VB and VIB of the fourth, fifth and sixth periodic metals.
  • Metal phase is an alloy composed of Mo and one or more metal elements of Fe, Co, Ni.
  • the Cerasteel materials further contain a few additives, the additives are C and one or more elements of V, Cr, Mn, Cu.
  • Alloy powders, compound powders and elementary powders can be selected as raw materials to prepare Cerasteel. After exactly weighing raw materials powder (ceramic phase and metal phase raw materials), mixtures were processed by wet-ball-milled by one of cemented carbide ball, stainless steel ball and corundum ball, with milling media for 20 ⁇ 100h, 2 ⁇ 6 wt.% of forming agent were added, the ball-to-powder mass ratio was (3-10):1; Mixed slurries were dried, sieved through 200 to 400 mesh, and then compressed under a pressure of 100 ⁇ 400 MPa.
  • the raw material reacted during sintering, boride and multiple boride were produced by in situ, which provides high hardness for Cerasteel materials using the above preparation method.
  • the ceramic phase and metal phase precipitated in situ have high bonding strength, so the Cerasteel had high toughness. Therefore, the Cerasteel has excellent mechanical properties.
  • the hardness of the Cerasteel in the present invention can be up to 50 ⁇ 75 HRC, comparable to zirconium ceramic, while flexural strength can be up to 1200 ⁇ 2300 MPa, much higher than zirconium ceramic.
  • Cerasteel has higher hardness, more than doubled wear resistance.
  • Cerasteel has excellent chemical stability. Therefore, Cerasteel is suitable for preparing knives, cutting tools, and all kinds of wear resistant, corrosion resistant, high temperature resistant materials and all kinds of structural components composed of them, which are supposed to be used perennially in the water, water vapor, salt, acid, alkali and other work environment.
  • Cerasteel has good weldability with steel, hence, it is possible to prepare Cerasteel knives, cutting tools and all kinds of wear resistant, corrosion resistant, high temperature resistant materials and all kinds of structural components composed of them at low costs and easier to achieve large-scale promotion with only a few Cerasteel welding to the stainless steel.
  • Cerasteel materials of this invention have properties of high hardness, excellent wear resistance, corrosion resistance and high temperature resistance and can be used for producing knives, cutting tools, and all kinds of wear resistant, corrosion resistant, high temperature resistant materials and all kinds of structural components composed of them. Moreover, Cerasteel materials have good weldability with steel and other metal materials, which can meet people's daily needs, and are suitable for application in industry, agriculture, machining and medical apparatus and instruments and so on.
  • Cerasteel materials in this invention are composed of ceramic phase and metal phase.
  • ceramic phase is the boride consisted of Fe, Co, Ni, and one or more metal elements of IVB, VB and VIB of the fourth, fifth and sixth periodic metals.
  • Metal phase is an alloy composed of Mo and one or more metal elements of Fe, Co, Ni.
  • Alloy powders, compound powders and elementary powders can be selected as raw materials to prepare Cerasteel. After exactly weighing raw materials powder, mixtures were processed by ball milling, drying, sieving, pressing and sintering. Then, Cerasteel materials were obtained.
  • Knives and cutting tools made of Cerasteel materials have the advantages of stainless steel knives and cutting tools and zirconium ceramic knives and cutting tools without their shortcomings. Therefore, Cerasteel knives and cutting tools can be used to replace existing stainless steel knives and cutting tools and zirconium ceramic knives and cutting tools, which are not only durable, but also cost-effective and easy to realize promotion in application on a large scale.
  • Example 1 A preparation method of Cerasteel materials: 20 wt.% of NiB, 40 wt.% of Mo, 5 wt.% of Cr, 10 wt.% of Ni, 1 wt.% of C and Fe powder (the balance), and 2.5 wt.% of paraffin were wet-milled in a ball milling machine for 100h.
  • the slurry mixtures were vacuum dried for 7h at the temperature of 70°C, sieved through 325 mesh, and then compressed.
  • Example 2 A preparation method of Cerasteel materials: 20 wt.% of FeB, 60 wt.% of Mo, 5 wt.% of Cr, 10 wt.% of Ni, 1 wt.% of C and Fe powder (the balance), and 2.2 wt.% of paraffin were wet-milled in a ball milling machine for 85h.
  • Example 3 A preparation method of Cerasteel materials: 20 wt.% of CoB, 40 wt.% of W, 20 wt.% of Co, 10 wt.% of Ni, 1 wt.% of C and Fe powder (the balance), and 2 wt.% of rubber oil solution were wet-milled in a ball milling machine for 65h.
  • the stainless steel ball-to-powder: (CoB, W, Co, Ni, C and Fe powder) mass ratio was 5:1, hexane were added as milling media.
  • the slurry mixtures were vacuum dried for 10h at the temperature of 60°C, sieved through 300 mesh, and then compressed. Finally, Cerasteel materials were obtained after hot isostatic pressing sintering at 1280°C for 12h.
  • Example 4 A preparation method of Cerasteel materials: 50 wt.% of TiB 2 , 20 wt.% of Mo, 5 wt.% of Cr, 15 wt.% of Ni, 1 wt.% of C and Fe powder (the balance), and 2.5 wt.% of rubber oil solution were wet-milled in a ball milling machine for 80h.
  • the slurry mixtures were spray dried for 8h at the temperature of 90°C, sieved through 200 mesh, and then compressed.
  • Example 5 A preparation method of Cerasteel materials: 50 wt.% of ZrB 2 , 20 wt.% of Mo, 5 wt.% of Cr, 15 wt.% of Ni, 1 wt.% of C and Fe powder (the balance), and 3 wt.% of zinc stearate were wet-milled in a ball milling machine for 90h.
  • the corundum ball-to-powder: (ZrB 2 , Mo, Cr, Ni, C, and Fe powder) mass ratio was 5:1, benzene were added as milling media.
  • Example 6 A preparation method of Cerasteel materials: 50 wt.% of NbB 2 , 20 wt.% of Mo, 5 wt.% of Cr, 15 wt.% of Ni, 1 wt.% of C and Fe powder (the balance), and 3 wt.% of polyvinyl butyral anhydrous ethanol solution were wet-milled in a ball milling machine for 75h.
  • the corundum ball-to-powder: (NbB 2 , Mo, Cr, Ni, C and Fe powder) mass ratio was 5:1, gasoline were added as milling media.
  • the slurry mixtures were vapor dried for 8h at the temperature of 90°C, sieved through 400 mesh, and then compressed. Finally, Cerasteel materials were obtained after activated sintering at 1250°C for 15h.
  • Example 7 A preparation method of Cerasteel materials: 25 wt.% of FeB, 35 wt.% of Mo, 10 wt.% of Cr, 5 wt.% of Ni, 0.6 wt.% of C, 2 wt.% of V, 5 wt.% of Cu and Fe powder (the balance), and 3 wt.% of paraffin were wet-milled in a ball milling machine for 60h.
  • the corundum ball-to-powder: (FeB, Mo, Cr, Ni, C, V, Cu and Fe powder) mass ratio was 6:1, gasoline were added as milling media.
  • the slurry mixtures were vacuum dried for 8h at the temperature of 90°C, sieved through 400 mesh, and then compressed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
EP14833447.7A 2014-12-23 2014-12-23 Matériau à base d'acier et de céramique et son procédé de préparation Withdrawn EP3192887A1 (fr)

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PCT/CN2014/094719 WO2016101156A1 (fr) 2014-12-23 2014-12-23 Matériau à base d'acier et de céramique et son procédé de préparation

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EP3192887A1 true EP3192887A1 (fr) 2017-07-19

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US (1) US20160348219A1 (fr)
EP (1) EP3192887A1 (fr)
CN (1) CN105917014A (fr)
WO (1) WO2016101156A1 (fr)

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CN106521283A (zh) * 2016-12-04 2017-03-22 丹阳市宸兴环保设备有限公司 一种耐磨陶瓷钢管复合材料

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JPS4995810A (fr) * 1973-01-18 1974-09-11
US3999952A (en) * 1975-02-28 1976-12-28 Toyo Kohan Co., Ltd. Sintered hard alloy of multiple boride containing iron
US4194900A (en) * 1978-10-05 1980-03-25 Toyo Kohan Co., Ltd. Hard alloyed powder and method of making the same
JPS58217656A (ja) * 1982-06-08 1983-12-17 Hitachi Metals Ltd 超硬質合金の製造方法
CN1046316C (zh) * 1994-12-13 1999-11-10 北京科技大学 一种用反应烧结法制取钢结硬质合金的方法
US5708956A (en) * 1995-10-02 1998-01-13 The Dow Chemical Company Single step synthesis and densification of ceramic-ceramic and ceramic-metal composite materials
US5993978A (en) * 1997-06-21 1999-11-30 Volvo Construction Equipment Korea Co., Ltd. Engine tappet of high abrasion resistance and method for manufacturing the same
CN1502714A (zh) * 2002-11-26 2004-06-09 山东大学 三元硼化物基金属陶瓷覆层材料及其制备工艺
JP2014141691A (ja) * 2011-03-30 2014-08-07 Toyo Kohan Co Ltd 硬質焼結合金
CN103890204B (zh) * 2011-10-17 2016-11-16 山特维克知识产权股份有限公司 通过使用共振声混合器制造硬质合金或金属陶瓷粉末的方法
CN102787267A (zh) * 2012-09-04 2012-11-21 四川大学 基于高熵合金粘结剂的多元硼化物金属陶瓷及其制备方法
CN103468994B (zh) * 2013-09-17 2015-04-08 北京科技大学 一种钼镍铬硼多元硼化物基金属陶瓷的制备方法

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US20160348219A1 (en) 2016-12-01
CN105917014A (zh) 2016-08-31

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