CN104325135B - Nanometer iron powder sintered body containing nanometer iron sesquioxide and preparation method thereof - Google Patents

Nanometer iron powder sintered body containing nanometer iron sesquioxide and preparation method thereof Download PDF

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CN104325135B
CN104325135B CN201410648712.4A CN201410648712A CN104325135B CN 104325135 B CN104325135 B CN 104325135B CN 201410648712 A CN201410648712 A CN 201410648712A CN 104325135 B CN104325135 B CN 104325135B
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powder
nanometer
nanometer iron
preparation
ferric oxide
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CN104325135A (en
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何明生
骆忠汉
薛改凤
彭守军
刘孟
邹龙
张敬
吴常久
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Wuhan Iron and Steel Co Ltd
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Wuhan Iron and Steel Group Corp
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Abstract

The invention discloses a kind of nanometer iron powder sintered body containing nanometer iron sesquioxide and preparation method thereof.Nanometer iron powder sintered body is formed by following preparation of raw material by mass percentage: nanometer ferric oxide powder 80~100%, additive powder 0~20%, described additive powder is containing a kind of powder in C, Al, Si, Mn, Sn, Ni, Co, Cr, Mo, Sb, Bi element or two kinds and two or more composite powders.Its preparation method is, is sufficiently mixed by raw material, then carries out molding, isostatic pressed or vibration moulding, finally in the mixed atmosphere of high-purity hydrogen or high-purity hydrogen and nitrogen, is sintered at 700~1000 DEG C, is incubated 30~600 minutes.Invented technology is simple, realizes the sintering of quick ferrum system composite powder, can manufacture antifriction alloy, high temperature alloy, silicon steel, automobile high-strength parts and other steel for special purposes products, low production cost under relatively low low temperature.

Description

Nanometer iron powder sintered body containing nanometer iron sesquioxide and preparation method thereof
Technical field
The present invention relates to nanometer iron powder sintered body, contain nanometer three in particular to one and aoxidize two Nanometer iron powder sintered body of ferrum and preparation method thereof.
Background technology
In field of powder metallurgy, metal powder is pressurizeed in metal pattern, after molding, enters The sintered body that row sinters and makes, can manufacture the Machinery Ministry of complicated shape well with precision Part.Therefore, require the automobile component of high dimensional accuracy, antifriction alloy, high temperature alloy with And in the manufacture of other specific use parts, sintered body can be applied widely.
The Chinese invention patent of Publication No. CN101772389A discloses " powder used in metallurgy Ferrum system mixed-powder and iron powder sintering body ", it is with containing iron-based powder, graphite powder, copper powder It is raw material with composite oxides, sinters 1000 DEG C of implemented below.Publication No. The Chinese invention patent of CN101733400A disclose " high-strength composition iron powder and use it Sintered component ", be with iron powder primary raw material, add a certain amount of Mn, Fe-Mn (grain Less than 45 microns of footpath), Cu and powdered graphite, more than the fusing point of Cu, 1300 DEG C with Sintering is realized in lower temperature range.The Chinese utility model of Publication No. CN201141401Y Patent disclosure " bimetallic bearing of a kind of copper-clad iron powder sintering ", on the surface of steel plate Upper sintering has the wearing layer of copper-clad iron powder, forms the composite of stacking, and uses this composite wood Material makes axle sleeve or flat board, and sintering has the rubbing surface that surface is bearing of copper-clad iron powder.
In sum, the research of ferrum system composite powder sintered body, it is concentrated mainly on employing fusing point Relatively low copper powder is as sintering aid aspect, it is impossible to meet high intensity parts and its The use of his steel for special purposes product needs.
Summary of the invention
Present invention aim to the deficiency overcome existing for prior art, it is provided that Yi Zhongna Nanometer iron powder sintered body of meter Han You nanometer iron sesquioxide and preparation method thereof.
The fusing point of general material is, under a certain pressure, the solid-state of pure material and liquid are in flat Temperature during weighing apparatus, say, that under this pressure and melting temperature, pure material is solid-state Chemical potential and the chemical potential being in a liquid state are equal.For block pure object, its chemical potential is simply The function of temperature and pressure.
And nano-particle is little due to particle diameter, specific surface free energy is high, therefore its chemical potential ratio is identical Under the conditions of blocks of solid much higher, result cause its fusing point and sintering temperature be significantly less than with The blocks of solid of sample material, and the particle diameter of granule is the least, its fusing point and sintering temperature are the lowest. Such as, the fusing point of bulk Pb is 600K, and the fusing point of 20 nanometer spherical Pb granules reduces 288K, and nano-Ag particles is starting fusing less than 373K, and the fusing point of conventional Ag is high Reach 1273K.
We are found by experimental study, when the particle diameter of nanometer iron powder is less than 100 nanometer, Its fusing point can reduce, meanwhile, high-purity hydrogen or high-purity hydrogen and the spy of nitrogen mixture atmosphere Under the conditions of Shu, after metal-oxide is reduced into simple substance granule, its activity is higher, it is easier to it His metal or oxide reaction, sintering.Utilize this principle to design, produce multiple gold Belong to sintered powder, to meet high intensity parts and the use of other steel for special purposes products Need.
For achieving the above object, the nanometer containing nanometer iron sesquioxide designed by the present invention Iron powder sintering body, it forms by following preparation of raw material by mass percentage: nanometer three aoxidizes Two iron powder 80~100%, additive powder 0~20%, described additive powder is for containing A kind of powder in C, Al, Si, Mn, Sn, Ni, Co, Cr, Mo, Sb, Bi element End or two kinds and two or more composite powders.
Preferably, the nanometer iron powder sintered body containing nanometer iron sesquioxide by following by quality The preparation of raw material of percentage ratio forms: nanometer ferric oxide powder 90~95%, graphite powder 0.05~0.5%, Al powder 1.0~5.0%, Si powder 1.0~5.0%, Mn powder 1.0~4.5%.
Preferably, the nanometer iron powder sintered body containing nanometer iron sesquioxide by following by quality The preparation of raw material of percentage ratio forms: nanometer ferric oxide powder 80~93%, Ni powder 5~ 15%, Co powder 2~10%.
Preferably, the nanometer iron powder sintered body containing nanometer iron sesquioxide by following by quality The preparation of raw material of percentage ratio forms: nanometer ferric oxide powder 80~90%, Ni powder 5~ 15%, Cr powder 5~10%, Mn powder 0~5%.
Preferably, the nanometer iron powder sintered body containing nanometer iron sesquioxide by following by quality The preparation of raw material of percentage ratio forms: nanometer ferric oxide powder 90~95%, Al powder 1.0~ 1.5%, Si powder 2.0~5.0%, Mn powder 1.0~3.5%, Sn powder 0.1~1.0%, Sb Powder 0.2~0.8%, Bi powder 0.1~0.5%.
Preferably, the nanometer iron powder sintered body containing nanometer iron sesquioxide by following by quality The preparation of raw material of percentage ratio forms: nanometer ferric oxide powder 80~90%, graphite powder 0.1~0.5%, Mn powder 1.0~3.5%, Cr powder 5~15%, Mo powder 2~8%.
In the present invention, the mean diameter of described nanometer ferric oxide powder is less than 100 nanometers, Purity more than 98%.
In the present invention, the mean diameter of described additive powder is less than 10 microns, purity 99% Above.
The preparation method of the above-mentioned nanometer iron powder sintered body containing nanometer iron sesquioxide: first Raw material is sufficiently mixed, then carries out molding, isostatic pressed or vibration moulding, finally high-purity In the mixed atmosphere of hydrogen or high-purity hydrogen and nitrogen, at sintering temperature 700~1000 DEG C It is sintered, is incubated 30~600 minutes.
In the mixed atmosphere of the present invention, hydrogen volume percent concentration is 30~99%, nitrogen Concentration of volume percent is 1~70%.
Found by experimental study, when the particle diameter of nanometer ferric oxide powder is received less than 100 Meter Shi, its fusing point can reduce, meanwhile, in high-purity hydrogen or high-purity hydrogen and the mixing of nitrogen Under the specific condition of atmosphere, nanometer ferric oxide powder be reduced into fe after its activity relatively , even there is liquid phase in height, it is easier to reacts with other metals or oxide, sinters, profit Can design by this principle, produce various metals sintered powder.
The beneficial effects of the present invention is: use technique scheme, present invention process is simple, Under relatively low low temperature, realize the sintering of quick ferrum system composite powder, antifriction alloy, height can be manufactured Temperature alloy, silicon steel, automobile high-strength parts and other steel for special purposes products, produce With low cost.
Detailed description of the invention
In order to preferably explain the present invention, below in conjunction with specific embodiment, the present invention is made into one The detailed description of step, but they do not constitute restriction to the present invention.
Embodiment 1
The composition of raw materials of the nanometer iron powder sintered body containing nanometer iron sesquioxide, by quality hundred Proportion by subtraction is: nanometer ferric oxide powder 90%, additive powder 10%;Wherein, add Thing powder is graphite powder 0.5%, Al powder 1.0%, Si powder 5.0%, Mn powder 3.5%.
The preparation method of the nanometer iron powder sintered body containing nanometer iron sesquioxide: first will receive Rice ferric oxide powder is sufficiently mixed with additive powder, is then molded into Type, finally in high-purity hydrogen atmosphere, is sintered, temperature retention time 60 at 850 DEG C Minute.
Embodiment 2
The composition of raw materials of the nanometer iron powder sintered body containing nanometer iron sesquioxide, by quality hundred Proportion by subtraction is: nanometer ferric oxide powder 95%, additive powder 5%;Wherein, add Thing powder is graphite powder 0.1%, Al powder 2.0%, Si powder 1.4%, Mn powder 1.5%.
The preparation method of the nanometer iron powder sintered body containing nanometer iron sesquioxide: first will receive Rice ferric oxide powder is sufficiently mixed with additive powder, is then molded into Type, finally in high-purity hydrogen atmosphere, is sintered, temperature retention time 30 at 900 DEG C Minute.
Embodiment 3
The composition of raw materials of the nanometer iron powder sintered body containing nanometer iron sesquioxide, by quality hundred Proportion by subtraction is: nanometer ferric oxide powder 93%, additive powder 7%;Wherein, add Thing powder is graphite powder 0.3%, Al powder 2.0%, Si powder 2.2%, Mn powder 2.5%.
The preparation method of the nanometer iron powder sintered body containing nanometer iron sesquioxide: first will receive Rice ferric oxide powder is sufficiently mixed with additive powder, is then molded into Type, finally in high-purity hydrogen and nitrogen mixture atmosphere, hydrogen volume percent concentration is 90%, nitrogen concentration of volume percent is 10%, is sintered, during insulation at 850 DEG C Between 30 minutes.
Embodiment 4
The raw material of the nanometer iron powder sintered body containing nanometer iron sesquioxide is 100% nanometer three Aoxidize two iron powder.
The preparation method of the nanometer iron powder sintered body containing nanometer iron sesquioxide: by nanometer three Aoxidize two iron powder and carry out compression molding, in high-purity hydrogen atmosphere, carry out at 750 DEG C Sintering, temperature retention time 60 minutes.
Embodiment 5
The raw material of the nanometer iron powder sintered body containing nanometer iron sesquioxide is 100% nanometer three Aoxidize two iron powder.
The preparation method of the nanometer iron powder sintered body containing nanometer iron sesquioxide: by nanometer three Aoxidize two iron powder and carry out compression molding, in high-purity hydrogen and nitrogen mixture atmosphere, hydrogen Concentration of volume percent is 70%, and nitrogen concentration of volume percent is 30%, at 850 DEG C It is sintered, temperature retention time 120 minutes.
Embodiment 6
The composition of raw materials of the nanometer iron powder sintered body containing nanometer iron sesquioxide, by quality hundred Proportion by subtraction is: nanometer ferric oxide powder 83%, additive powder 17%;Wherein, add Thing powder is Ni powder 15%, Co powder 2%.
The preparation method of the nanometer iron powder sintered body containing nanometer iron sesquioxide: first will receive Rice ferric oxide powder is sufficiently mixed with additive powder, then vibrates into Type, finally in high-purity hydrogen, is sintered at 950 DEG C, temperature retention time 300 minutes.
Embodiment 7
The composition of raw materials of the nanometer iron powder sintered body containing nanometer iron sesquioxide, by quality hundred Proportion by subtraction is: nanometer ferric oxide powder 85%, additive powder 15%;Wherein, add Thing powder is Ni powder 15%.
The preparation method of the nanometer iron powder sintered body containing nanometer iron sesquioxide: first will receive Rice ferric oxide powder is sufficiently mixed with additive powder, then carries out isostatic pressed one-tenth Type, finally in high-purity hydrogen, is sintered at 900 DEG C, temperature retention time 600 minutes.
Embodiment 8
The composition of raw materials of the nanometer iron powder sintered body containing nanometer iron sesquioxide, by quality hundred Proportion by subtraction is: nanometer ferric oxide powder 80%, additive powder 20%;Wherein, add Thing powder is Ni powder 10%, Co powder 10%.
The preparation method of the nanometer iron powder sintered body containing nanometer iron sesquioxide: first will receive Rice ferric oxide powder is sufficiently mixed with additive powder, is then molded into Type, finally in high-purity hydrogen and nitrogen mixture atmosphere, hydrogen volume percent concentration is 50%, nitrogen concentration of volume percent is 50%, is sintered, during insulation at 980 DEG C Between 120 minutes.
Embodiment 9
The composition of raw materials of the nanometer iron powder sintered body containing nanometer iron sesquioxide, by quality hundred Proportion by subtraction is: nanometer ferric oxide powder 80%, additive powder 20%;Wherein, add Thing powder is Ni powder 15%, Cr powder 5%, Mn powder 5%.
The preparation method of the nanometer iron powder sintered body containing nanometer iron sesquioxide: first will receive Rice ferric oxide powder is sufficiently mixed with additive powder, is then molded into Type, finally in high-purity hydrogen atmosphere, is sintered, temperature retention time 120 at 930 DEG C Minute.
Embodiment 10
The composition of raw materials of the nanometer iron powder sintered body containing nanometer iron sesquioxide, by quality hundred Proportion by subtraction is: nanometer ferric oxide powder 80%, additive powder 20%;Wherein, add Thing powder is Ni powder 10%, Cr powder 10%.
The preparation method of the nanometer iron powder sintered body containing nanometer iron sesquioxide: first will receive Rice ferric oxide powder is sufficiently mixed with additive powder, then vibrates into Type, in high-purity hydrogen and nitrogen mixture atmosphere, hydrogen volume percent concentration is 40%, Nitrogen concentration of volume percent is 60%, is sintered at 960 DEG C, is incubated 120 minutes.
Embodiment 11
The composition of raw materials of the nanometer iron powder sintered body containing nanometer iron sesquioxide, by quality hundred Proportion by subtraction is: nanometer ferric oxide powder 95%, additive powder 5%;Wherein, add Thing powder is Al powder 1.0%, Si powder 2.0%, Mn powder 1.0%, Sn powder 0.5%, Sb powder 0.2%, Bi powder 0.3%.
The preparation method of the nanometer iron powder sintered body containing nanometer iron sesquioxide: first will receive Rice ferric oxide powder is sufficiently mixed with additive powder, is then molded into Type, finally in high-purity hydrogen atmosphere, is sintered at sintering temperature 950 DEG C, insulation 120 minutes time.
Embodiment 12
The composition of raw materials of the nanometer iron powder sintered body containing nanometer iron sesquioxide, by quality hundred Proportion by subtraction is: nanometer ferric oxide powder 81%, additive powder 19%;Wherein, add Thing powder is graphite powder 0.5%, Mn powder 1.0%, Cr powder 15%, Mo powder 2.5%.
Preparation technology is: first nanometer ferric oxide powder and additive powder are carried out fully Mixing, then carries out compression molding, finally in high-purity hydrogen atmosphere, in sintering temperature 980 It is sintered at DEG C, temperature retention time 300 minutes.

Claims (4)

1. the nanometer iron powder sintered body containing nanometer iron sesquioxide, it is characterised in that It is formed by following preparation of raw material by mass percentage:
Nanometer ferric oxide powder 90~95%, graphite powder 0.05~0.5%, Al powder 1.0~ 5.0%, Si powder 1.0~5.0%, Mn powder 1.0~4.5%;
Or, nanometer ferric oxide powder 80~95%, Ni powder 5~15%, Co powder 0~ 10%;
Or, nanometer ferric oxide powder 80~90%, Ni powder 5~15%, Cr powder 5~ 10%, Mn powder 0~5%;
Or, nanometer ferric oxide powder 90~95%, Al powder 1.0~1.5%, Si powder 2.0~ 5.0%, Mn powder 1.0~3.5%, Sn powder 0.1~1.0%, Sb powder 0.2~0.8%, Bi Powder 0.1~0.5%;
Or, nanometer ferric oxide powder 80~90%, graphite powder 0.1~0.5%, Mn Powder 1.0~3.5%, Cr powder 5~15%, Mo powder 2~8%.
Nanometer iron powder containing nanometer iron sesquioxide the most according to claim 1 burns Knot body, it is characterised in that: the mean diameter of described nanometer ferric oxide powder is less than 100 Nanometer, purity more than 98%.
3. the Nanoscale Iron containing nanometer iron sesquioxide according to claim 1 The preparation method of compact, it is characterised in that: first raw material is sufficiently mixed, then enters Row molds, isostatic pressed or vibration moulding, finally at high-purity hydrogen or high-purity hydrogen and nitrogen In mixed atmosphere, it is sintered at sintering temperature 700~1000 DEG C, is incubated 30~600 Minute.
Nanometer iron powder containing nanometer iron sesquioxide the most according to claim 3 burns The preparation method of knot body, it is characterised in that: in described mixed atmosphere, hydrogen volume percentage ratio Concentration is 30~99%, and nitrogen concentration of volume percent is 1~70%.
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