CN102134677A - Iron-based composite material and preparation method thereof - Google Patents
Iron-based composite material and preparation method thereof Download PDFInfo
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- CN102134677A CN102134677A CN 201010617087 CN201010617087A CN102134677A CN 102134677 A CN102134677 A CN 102134677A CN 201010617087 CN201010617087 CN 201010617087 CN 201010617087 A CN201010617087 A CN 201010617087A CN 102134677 A CN102134677 A CN 102134677A
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Abstract
The invention provides an iron-based composite material and a preparation method thereof. The reinforcement phase of the iron-based composite material is carbide solid solution (Nb, V)C synthesized by Nb, V and C atoms in situ. The iron-based composite material comprises the following components in percentage by mass: 2.75 to 6.60 percent of Nb, 1.50 to 3.6 percent of V and a proper amount of C, wherein the C content at least can ensure that both the Nb and the V are completely prepared into carbide, and the rest C content in the iron matrix in a solid solution form is not over 0.5 percent. The NbC and VC carbide solid solution (Nb, V)C is designed as the reinforcement phase of the iron-based composite material, the synergic reinforcement effect of mutual solution strengthening of two carbides is reasonably utilized, the matrix strengthening effect better than that of NbC serving as the reinforcement phase is achieved, and the wear resistance, hardness, casting property and machinability of the iron-based composite material are better considered.
Description
Technical field
The present invention relates to a kind of metal-base composites and preparation method thereof, (Nb, V) C strengthens iron base composite material and preparation method thereof to relate in particular to a kind of original position.
Background technology
MC type carbide strengthens metal-base composites and has high specific strength, high ratio modulus, high-wearing feature and advantage such as high temperature resistant, is a primary study direction of wearing composite material both at home and abroad at present.MC type carbide wild phase in the MC type carbide enhancing metal-base composites is mainly the carbide of IVA～VIA family element, and these carbide Thermodynamically stables have high-melting-point, high rigidity, effectively the reinforced metal matrix.Yet different wild phase elements are widely different to the reinforced effects of different matrix.Present disclosed most of research all is the improvement that are conceived to metal-base composites hardness or wear resistance, and the performance of metal-base composites at aspects such as castability, machinability, plasticity all also is not ideal very, ubiquity fragility is big, be difficult to moulding and be difficult for shortcoming such as machining, and the range of application of metal-base composites and field are greatly limited.
In addition, understand according to the applicant, the preparation method of the foundry goods of metal current based composites has multiple, as casting, powder metallurgic method, self-propagating high-temperature method etc.Generation type by its wild phase mainly contains body method and synthetic two kinds of the body methods that strengthen of original position of strengthening that add, wherein the synthetic enhancing of original position body method is by the original position casting, make the carbide element in high-temperature fusant generation carburizing reagent, thus make have high strength, the wild phase matrix material of high abrasion.Disclosed most of original position casting has just adopted melting, the pouring technology of existing plain carbon stool simply, do not adopt specific technology at the concrete characteristics of designed metal-base composites, the thermal treatment process complexity, thereby, the space that also has improvement and optimize at the selection and the aspects such as proportioning, melting and thermal treatment process of raw material.
Summary of the invention
At the deficiencies in the prior art, it is effective and can take into account the iron base composite material of wear resistance, hardness, castability and machinability that one of purpose of the present invention provides a kind of matrix strengthening, and two of purpose of the present invention provides a kind of preparation method who optimizes improved iron base composite material.
One of purpose of the present invention is achieved through the following technical solutions:
A kind of iron base composite material, the wild phase of described iron base composite material is by Nb, V and C atom original position synthetic carbide sosoloid (Nb, V) C, in mass percent, described iron base composite material contains 2.75%～6.60% Nb and 1.50%～3.6% V and proper C, the content of described C can guarantee to make described Nb and described V all to generate carbide fully at least, and the content of the C of all the other solid solutions in the iron-based body is no more than 0.5%.
Specifically, in mass percent, the C that described iron base composite material is used to generate carbide is 0.75%～1.8%.
Further, wherein Nb is 0.6: 1～1: 0.6 with the atomicity of V than scope, and collaborative enhancement is obvious, can obtain matrix strengthening effect preferably.When the atomicity ratio of Nb and V is 1: 1, and carbide sosoloid (Nb, V) Nb among the C, V atom can be realized displacement solid solution in maximum 1: 1, can produce stronger solution strengthening effect, thus the matrix strengthening effect of acquisition the best.
Further, (Nb, V) percent by volume of C wild phase is 5～12% to described iron base composite material carbide sosoloid.If volume fraction is 5% when following, the carbide wild phase of formation concentrates on the crystal boundary, is interrupted net distribution, is unfavorable for bringing into play the effect of wild phase; When above above 12%, the flowability of molten steel will reduce greatly, and cast is difficulty quite, and foundry goods is difficult to moulding, and the serious gathering of carbide particle is simultaneously grown up, and distributed pole is inhomogeneous, and the fragility of material increases, and wear resisting property also reduces.
Further, (Nb, V) the C wild phase also can comprise the NbC that separates out in the heat treatment process and carbide sosoloid (Nb, V) molecule of C of VC to described carbide sosoloid.
In iron base composite material of the present invention, described iron-based body is that principal element is formed with iron, also can contain an amount of carbon and a spot of alloying element as required, and as molybdenum, chromium, nickel etc., the content of C generally is no more than 0.5%.
Compared with prior art, the beneficial effect of iron base composite material of the present invention is: because the present invention designs the Nb that adopted appropriate level and the V wild phase element as the iron-based body, in the iron-based body, formed the carbide sosoloid (Nb of original position synthetic NbC and VC, V) C wild phase, carbide sosoloid (Nb wherein, V) Nb among the C, V atom can realize replacing solid solution, rationally, effectively utilized the collaborative enhancement of NbC and VC, thereby matrix are effectively strengthened.
And iron base composite material of the present invention has been taken into account the castability and the machinability of material preferably; Has simultaneously higher intensity, plasticity and hardness again; Avoided in the prior art the ubiquitous fragility of metal-base composites big, be difficult to moulding, castability difference and be difficult for shortcoming such as machining, thereby can on engineering, obtain application more widely, be particularly useful for the preparation of complex-shaped part.
Iron base composite material is further heat-treated,, and suppress matrix grain and grow up, can also further improve the intensity and the plasticity of iron base composite material then because Nb, V can separate out the secondary fine carbide in heat treatment process.
Two of purpose of the present invention is to be achieved through the following technical solutions:
A kind of casting preparation method of above-mentioned iron base composite material may further comprise the steps successively:
Step 1, (Nb, the V) composition of C wild phase calculate and take by weighing ferrocolumbium, ferro-vanadium, graphite carburelant and the iron-based body raw material of required adding according to described carbide sosoloid; Wherein the add-on of graphite carburelant generates NbC, VC, and comprises the scaling loss amount interior to guarantee itself and Nb, V complete reaction at least;
Step 2, heating and melting graphite carburelant, iron-based body raw material, treat that it is ferrocolumbium, the ferro-vanadium of 1～5mm that the molten clear back of whole furnace charges adds granularity, and be warming up to 1520～1560 ℃ of insulation 5～8min, and then be warmed up to 1600～1650 ℃ of cast of coming out of the stove of skimming; Make the iron base composite material foundry goods;
Step 3, the iron base composite material foundry goods that step 2 is made are heat-treated, its thermal treatment process for the iron base composite material foundry goods is heated to 900～950 ℃ and be incubated 1.5～2h after, the naturally cooling of coming out of the stove.
In described step 2, adopt medium-frequency induction furnace heating and melting graphite carburelant, iron-based body raw material, after treating that graphite carburelant, iron-based body raw material all melt clearly, add aluminium deoxidation earlier, leave standstill a moment and skim, adding granularity under the state of induction stirring is ferrocolumbium, the ferro-vanadium of 1～5mm; The add-on of described aluminium is not for adding 0.1～0.15% of ferrocolumbium, the preceding molten steel total mass of ferro-vanadium.
On the one hand can make ferrocolumbium, ferro-vanadium more even in melt, prevent segregation, (Nb, V) C is tiny and be uniformly distributed in the matrix, improves the strengthening effect to matrix to make the original position synthetic on the other hand.After pre-deoxidation, oxygen level in the steel reduces greatly, can avoid the oxidation of niobium, vanadium alloy to greatest extent, reduce the formation of non-metallic inclusion in the molten steel, can guarantee more fully that there is good binding at the interface between generated in-situ carbide particle and the matrix.In addition, carry out the non-metallic inclusion come-up that pre-deoxidation can make molten steel contain earlier, avoid it to remain in the molten steel.
In described step 2, before going out the Shanghai cast, (for example: the FeSiRE26 alloy add rare earth ferrosilicon alloy, or with FeSiRE26 in other suitable ferro-silicon of RE content) go bad to handle or add aluminium and carry out final deoxygenation, the add-on of described rare earth ferrosilicon alloy be ferrocolumbium, ferro-vanadium add back molten steel total mass 0.2%～0.4%; The add-on of described aluminium when final deoxygenation is 0.08～0.10% of ferro-niobium, ferro-vanadium adding back molten steel total mass.
In the described step 2, the graphite carburelant is joined medium-frequency induction furnace, again iron-based body raw material is pressed in energising fusing on the carburelant; Treat furnace charge all molten clear after, add aluminium deoxidation earlier, leave standstill a moment and skim; Be at molten steel then that to add granularity under the state of induction stirring be ferrocolumbium, the ferro-vanadium of 1～5mm, the add-on of described aluminium is not for adding 0.1～0.15% of molten steel total mass before ferrocolumbium, the ferro-vanadium; Add the back and cover liquid level, temperature is raised to 1520～1560 ℃, and is incubated 5～8min with slag former; Temperature is raised to 1600～1650 ℃ then, the adding rare earth ferrosilicon alloy goes bad to handle or add aluminium and carries out final deoxygenation, and the add-on of described rare earth ferrosilicon alloy is 0.2%～0.4% of ferrocolumbium, a ferro-vanadium adding back molten steel total mass; The add-on of described aluminium when final deoxygenation is 0.08～0.10% of ferro-niobium, ferro-vanadium adding back molten steel total mass; The cast of coming out of the stove of skimming then; Make the iron base composite material foundry goods immediately.
The present invention is for original position synthetic carbide particle is difficult for growing up at 1520～1560 ℃ of insulation 5～8min, reduces a large amount of air-breathing and oxidation of molten metal simultaneously; The present invention 1600～1650 ℃ skim come out of the stove the cast be in order to make molten metal have good flowability, to satisfy the moulding requirement.
Further, the add-on of described graphite carburelant generates NbC, VC, and comprises certain scaling loss amount interior to guarantee itself and Nb, V complete reaction at least.
Described iron-based body raw material can be carbon steel, foundry iron or technically pure iron, low alloy steel etc., also can be 2 kinds and above composition according to a certain ratio of above-mentioned raw materials.Among the present invention, from selection angle consideration easily, iron-based body raw material adopts low-carbon waste steel.
The present invention utilizes synthetic wild phase of original position and liquid condition shaping to combine, with low-carbon waste steel, vanadium iron, ferro-niobium, graphite carburelant is raw material, in molten liquid steel, add carbide forming element Nb, V, the disperse of reaction in generation at high temperature is distributed in (Nb, V) the C carbide sosoloid matrix material in the iron-based.(Nb, V) Nb among the C, V atom can be replaced solid solution, and matrix is had certain strengthening effect owing to carbide sosoloid.When the atomicity of Nb and V is 0.6: 1～1: 0.6 than scope, collaborative enhancement is more obvious, matrix has been played strengthening effect preferably, especially when the atomicity ratio of Nb and V is 1: 1, Nb and V can realize displacement in maximum 1: 1, thereby produce stronger solution strengthening effect, obtain best collaborative reinforced effects, make wild phase play better strengthening effect to iron-based, composite property increases significantly.
For the better above-mentioned matrix material of obtained performance, preparation method of the present invention is also optimizing aspect melting technology and the thermal treatment process.
At first, be the ferro-niobium of 1～5mm and the method that ferro-vanadium evenly joins molten steel by adopting granularity, (Nb, V) C is even and tiny, helps improving the uniform distribution of wild phase in matrix, improves the strengthening effect to matrix to make the original position synthetic.If granularity is too big, not only fusing is difficult more, and is not easy uniform distribution in molten steel, and easily local gathering of the carbide particle of generation grows up, and performance of composites is had bigger disadvantageous effect.
Secondly, add behind ferro-niobium and the ferro-vanadium and temperature to be controlled at 1520～1560 ℃ and be incubated 5～8min earlier, mainly be to make fully carrying out of reaction in, also limited seriously growing up of carbide simultaneously, reduce a large amount of air-breathing and oxidation of molten metal by induction stirring.And then be warmed up to 1600～1650 ℃ and come out of the stove, mainly be to guarantee that molten steel has good casting.
In addition, preparation method of the present invention has also taked multiple innovative approachs such as pre-deoxidation and rotten processing aspect melting technology, and effective utilization of above-mentioned measure has further improved the strengthening effect of wild phase to matrix.
The employing of pre-deoxidation measure can reduce the oxidation of niobium, vanadium alloy and help the come-up of deoxidation products in the molten steel.
With the rare earth ferrosilicon alloy processing of going bad mainly is the oxygen level that further reduces in the molten steel, the distribution and the form of rare earth ferrosilicon rotten processing can also improvement non-metallic inclusion in the molten steel in addition, play the effect that reduces sulphur in the molten steel, help the raising of composite property.In addition, also played the effect of final deoxygenation.
As not adopting the rare earth ferrosilicon alloy processing of going bad, also can adopt reductor aluminium to carry out final deoxygenation, also can play similar effect.
At last, matrix material has been carried out suitable thermal treatment.Made full use of the effect of Nb, V element microalloying in steel, i.e. Nb, V element and the C tool strong avidity of solid solution in matrix in heat treatment process, generate MC type proeutectoid carbide, disperse is distributed in the matrix, be spherical and size mostly below micron order, matrix is played the effect of dispersion-strengthened, secondary MC type carbide can also suppress growing up of austenite crystal simultaneously, further the refinement matrix grain improves the intensity of matrix material, plasticity greatly.
Preparation method of the present invention is by further optimizing melting technology and suitable thermal treatment, given full play to the carbide sosoloid (Nb of NbC and VC, V) strengthening effect of C wild phase in matrix material, make carbide sosoloid (Nb than low volume fraction, V) matrix material of C wild phase still has higher intensity, plasticity and good processing properties, thereby has expanded the practical ranges of matrix material greatly.Can be used to make the part that locomotive, automobile etc. need good abrasion resistance and complicated shape.
Description of drawings
Fig. 1: (Nb, V) C volume fraction 5% and Nb and V atomicity ratio are 1: 1 matrix material metallographic structure (500 times) to the original position that makes for the embodiment of the invention 1.Wherein, matrix is the perlite of ferrite and minute quantity, and (Nb, V) the C wild phase is short strip shape or spot distribution in matrix.
Fig. 2: the original position that makes for the embodiment of the invention 2 (Nb, V) C volume fraction 8% and Nb and V atomicity ratio be 1: 1 matrix material metallographic structure (500 times).Wherein, matrix is ferrite and a spot of perlite, (Nb, V) C is the homogeneous granules shape and is distributed in the matrix, and the proeutectoid carbide particle that has a large amount of disperses to distribute in ferrite matrix is very tiny.
Fig. 3: (Nb, V) the atomicity ratio of C volume fraction 8% and Nb and V is 0.6: 1 matrix material metallographic structure (500 times) to the original position that makes for the embodiment of the invention 3.Wherein, matrix is a ferrite, (Nb, V) C is particulate state and strip is distributed in the matrix, and the proeutectoid carbide particle that distributes in matrix is very tiny.
Fig. 4: (Nb, V) the atomicity ratio of C volume fraction 8% and Nb and V is 1: 0.6 matrix material metallographic structure (500 times) to the original position that makes for the embodiment of the invention 4.Wherein, matrix is the perlite of ferrite and minute quantity, and (Nb, V) C is big bulk, sheet or particulate state distribution, and inhomogeneous.In ferrite matrix, be distributed with the secondary fine carbide particle.
Fig. 5: (Nb, V) C volume fraction 12% and Nb and V atomicity ratio are 1: 1 matrix material metallographic structure (500 times) to the original position that makes for the embodiment of the invention 5.Wherein, matrix is the perlite of ferrite and minute quantity, and (Nb, V) C is particulate state and is distributed in the matrix, but particle size is obviously thicker and inhomogeneous, and a large amount of disperses gray proeutectoid carbide particle that distributes is arranged in the matrix, and is very tiny.
Fig. 6: the matrix material metallographic structure (500 times) of the original position NbC volume fraction 8% that makes for Comparative Examples of the present invention.Wherein, matrix is a point-like carbide on ferrite and its, and NbC is particulate state and is distributed in the matrix, the obviously thicker and skewness of particle size.
Embodiment
Used raw material form, commercial specification etc. only are the example explanations among the following embodiment, do not limit protection scope of the present invention.Below the present invention is described in detail by various embodiments of the present invention.
Embodiment 1:
A kind of (Nb, V) C strengthens iron base composite material, its wild phase is by Nb, V and C atom original position synthetic carbide sosoloid (Nb, V) C, in mass percent, described iron base composite material contains 2.75%～6.60% Nb and 1.50%～3.6% V and proper C, and the content of described C can guarantee to make described Nb and described V all to generate carbide fully at least, and the content of the C of all the other solid solutions in the iron-based body is no more than 0.5%.
In this example, contain niobium (Nb), vanadium (V), carbon (C), iron (Fe) etc. in the original position synthetic system of selecting for use, in mass percent, main component is:
Niobium (Nb) 2.75%;
Vanadium (V) 1.50%;
Carbon (C) 0.75%;
Iron-based body (Fe) all the other;
Wherein the atomicity of Nb, V ratio is 1: 1, and C content generates NbC, VC in assurance and Nb, V complete reaction.Other minor element (as the Si in the iron-based body, Mn, P, S) and auxiliary element (as the Al in the reductor, the RE in the alterant etc.) are ignored because content is extremely low.
In the composition of mentioned component, the adding form of Nb is FeNb60 alloy (containing the Nb amount is 65%), and the adding form of V is FeV50 alloy (V content is 52%), and C adds with the form of graphite carburelant.Iron-based body (Fe) adds with the form of soft steel (carbon content 0.2%).
In addition, used reductor adds with the form of fine aluminium in the preparation method; Alterant adds with the form of FeSiRE26.
Concrete preparation method:
A, take by weighing required starting material by table 1, wherein ferrocolumbium, ferro-vanadium are broken for granularity 1～5mm;
The actual weighing proportioning of table 1 (wt%)
Annotate: the scaling loss amount of above-mentioned carburelant is in 5%-10%, and the scaling loss of other alloy is disregarded; Al accounts for the percentage ratio that does not add molten steel total mass before ferro-niobium, the ferro-vanadium by it, and FeSiRE26 accounts for the percentage ratio that adds molten steel total mass behind ferro-niobium, the ferro-vanadium by it.
B, fusion process: the graphite carburelant is joined medium-frequency induction furnace, again soft steel is pressed in energising fusing on the graphite carburelant.The whole molten clear back addings of furnace charge account for the Al deoxidation that does not add ferro-niobium, the preceding molten steel total mass 0.1% of ferro-vanadium, skim after static 1 minute.Evenly add ferrocolumbium and ferro-vanadium subsequently, add the back and cover liquid level with slag former, temperature is raised to 1520～1560 ℃ rapidly, and be incubated 5～8min, then temperature is raised to 1600～1650 ℃ rapidly, add the pre-prepd rare earth ferrosilicon alloy FeSiRE26 that accounts for ferro-niobium, ferro-vanadium adding back molten steel total mass 0.25%, skimming then comes out of the stove pours into a mould in sand mold; Make the iron base composite material foundry goods;
C, heat treatment process: in chamber type electric resistance furnace, the above-mentioned iron base composite material foundry goods that makes is warmed up to 900～950 ℃, the air cooling of coming out of the stove behind the insulation 2h.
The tensile strength of this iron base composite material foundry goods is 525Mpa, and unit elongation is 3.0%, and hardness is 25HRC.(Nb, V) percent by volume of C wild phase is 5% to this iron base composite material carbide sosoloid.
Embodiment 2:
A kind of (Nb, V) C strengthens iron base composite material, its wild phase is by Nb, V and C atom original position synthetic carbide sosoloid (Nb, V) C, in mass percent, described iron base composite material contains 2.75%～6.60% Nb and 1.50%～3.6% V and proper C, and the content of described C can guarantee to make described Nb and described V all to generate carbide fully at least, and the content of the C of all the other solid solutions in the iron-based body is no more than 0.5%.
In this example, contain niobium (Nb), vanadium (V), carbon (C), iron (Fe) etc. in the original position synthetic system of selecting for use,
Main component is counted with mass percent:
Niobium (Nb) 4.40%;
Vanadium (V) 2.40%;
Carbon (C) 1.20%;
Iron-based body (Fe) all the other;
Wherein the atomicity of Nb, V ratio is 1: 1, and C content is to generate NbC, VC with Nb, V complete reaction.Other minor element (as the Si in the iron-based body, Mn, P, S) and auxiliary element (as the Al in the reductor, the RE in the alterant etc.) are ignored because content is extremely low.
In the composition of mentioned component, the adding form of Nb is FeNb60 alloy (containing the Nb amount is 65%), and the adding form of V is FeV50 alloy (V content is 52%), and C adds with the form of graphite carburelant.Iron-based body (Fe) adds with the form of low-carbon waste steel (carbon content 0.2%).
In addition, used reductor adds with the form of fine aluminium in the preparation method.Alterant adds with the form of FeSiRE26.
Its preparation method is such:
A, take by weighing starting material by above-mentioned composition, its proportioning is as shown in table 2, and wherein ferrocolumbium, ferro-vanadium are broken for granularity 1～5mm;
The actual weighing proportioning of table 2 (wt%)
Annotate: the scaling loss amount of above-mentioned carburelant is in 5%-10%, and the scaling loss of other alloy is disregarded; Al accounts for the percentage ratio that does not add molten steel total mass before ferro-niobium, the ferro-vanadium by it, and FeSiRE26 accounts for the percentage ratio that adds molten steel total mass behind ferro-niobium, the ferro-vanadium by it.
B, fusion process: the graphite carburelant is joined medium-frequency induction furnace, again low-carbon waste steel is pressed in energising fusing on the graphite carburelant.The whole molten clear back addings of furnace charge account for the Al deoxidation that does not add ferro-niobium, the preceding molten steel total mass 0.1% of ferro-vanadium, skim after static 1 minute, evenly add ferrocolumbium and ferro-vanadium subsequently, add the back and cover liquid level with slag former, temperature is raised to 1520～1560 ℃ rapidly, and is incubated 5～8min, then temperature is raised to 1600～1650 ℃ rapidly, add the pre-prepd FeSiRE26 alloy modification that accounts for ferro-niobium, ferro-vanadium adding back molten steel total mass 0.3%, the cast of coming out of the stove of skimming then; Make the iron base composite material foundry goods;
C, heat treatment process: in chamber type electric resistance furnace, the above-mentioned iron base composite material foundry goods that makes is heated to 900～950 ℃, the air cooling of coming out of the stove behind the insulation 2h.
The tensile strength of this iron base composite material foundry goods is 660Mpa, and unit elongation is 3.0%, and hardness is 30HRC.(Nb, V) percent by volume of C wild phase is 8% to this iron base composite material carbide sosoloid.
Embodiment 3:
A kind of (Nb, V) C strengthens iron base composite material, its wild phase is by Nb, V and C atom original position synthetic carbide sosoloid (Nb, V) C, in mass percent, described iron base composite material contains 2.75%～6.60% Nb and 1.50%～3.6% V and proper C, and the content of described C can guarantee to make described Nb and described V all to generate carbide fully at least, and the content of the C of all the other solid solutions in the iron-based body is no more than 0.5%.
In this example, contain niobium (Nb), vanadium (V), carbon (C), iron (Fe) etc. in the original position synthetic system of selecting for use, main component is counted with mass percent:
Niobium (Nb) 3.50%;
Vanadium (V) 3.25%;
Carbon (C) 1.25%;
Iron-based body (Fe) all the other;
Wherein the atomicity of Nb, V ratio is 0.6: 1, and C content is to generate NbC, VC with Nb, V complete reaction.Other minor element (as the Si in the iron-based body, Mn, P, S) and auxiliary element (as the Al in the reductor, the RE in the alterant etc.) are ignored because content is extremely low.
In the composition of mentioned component, the adding form of Nb is FeNb60 alloy (containing the Nb amount is 65%), and the adding form of V is FeV50 alloy (V content is 52%), and C adds with the form of graphite carburelant.Iron-based body (Fe) adds with the form of soft steel (carbon content 0.2%).
In addition, used reductor adds with the form of fine aluminium in the preparation method.Alterant adds with the form of FeSiRE26.
Its preparation method is such:
A, take by weighing starting material by above-mentioned composition, its proportioning is as shown in table 3, and wherein ferrocolumbium, ferro-vanadium are broken for granularity 1～5mm;
The actual weighing proportioning of table 3 (wt%)
Annotate: the scaling loss amount of above-mentioned carburelant is in 5%-10%, and the scaling loss of other alloy is disregarded; Al accounts for the percentage ratio that does not add molten steel total mass before ferro-niobium, the ferro-vanadium by it, and FeSiRE26 accounts for the percentage ratio that adds molten steel total mass behind ferro-niobium, the ferro-vanadium by it.
B, fusion process: the graphite carburelant is joined medium-frequency induction furnace, again soft steel is pressed in energising fusing on the graphite carburelant.The whole molten clear back addings of furnace charge account for the Al deoxidation that does not add ferro-niobium, the preceding molten steel total mass 0.1% of ferro-vanadium, skim after static 1 minute, evenly add ferrocolumbium and ferro-vanadium subsequently, add the back and cover liquid level with slag former, temperature is raised to 1520～1560 ℃ rapidly, and is incubated 5～8min, then temperature is raised to 1600～1650 ℃ rapidly, add the pre-prepd FeSiRE26 alloy modification that accounts for ferro-niobium, ferro-vanadium adding back molten steel total mass 0.3%, the cast of coming out of the stove of skimming then; Make the iron base composite material foundry goods;
C, heat treatment process: in chamber type electric resistance furnace, the above-mentioned iron base composite material foundry goods that makes is heated to 900～950 ℃, the air cooling of coming out of the stove behind the insulation 2h.
The tensile strength of this iron base composite material foundry goods is 495Mpa, and unit elongation is 3.0%, and hardness is 24HRC.(Nb, V) percent by volume of C wild phase is 8% to this iron base composite material carbide sosoloid.
Embodiment 4:
A kind of (Nb, V) C strengthens iron base composite material, its wild phase is by Nb, V and C atom original position synthetic carbide sosoloid (Nb, V) C, in mass percent, described iron base composite material contains 2.75%～6.60% Nb and 1.50%～3.6% V and proper C, and the content of described C can guarantee to make described Nb and described V all to generate carbide fully at least, and the content of the C of all the other solid solutions in the iron-based body is no more than 0.5%.
In this example, contain niobium (Nb), vanadium (V), carbon (C), iron (Fe) etc. in the original position synthetic system of selecting for use, main component consists of in mass percent:
Niobium (Nb) 5.20%;
Vanadium (V) 1.70%;
Carbon (C) 1.11%;
Iron-based body (Fe) all the other;
Wherein the atomicity of Nb, V ratio is 1: 0.6, and C content is to generate NbC, VC with Nb, V complete reaction.Other minor element (as the Si in the iron-based body, Mn, P, S) and auxiliary element (as the Al in the reductor, the RE in the alterant etc.) are ignored because content is extremely low.
In the composition of mentioned component, the adding form of Nb is FeNb60 alloy (containing the Nb amount is 65%), and the adding form of V is FeV50 alloy (V content is 52%), and C adds with the form of graphite carburelant.Iron-based body (Fe) adds with the form of low-carbon waste steel (carbon content 0.2%).
In addition, used reductor adds with the form of fine aluminium in the preparation method.Alterant adds with the form of FeSiRE26.
Its preparation method is such:
A, take by weighing starting material by above-mentioned composition, its proportioning is as shown in table 4, and wherein ferrocolumbium, ferro-vanadium are broken for granularity 1～5mm;
The actual weighing proportioning of table 4 (wt%)
Annotate: the scaling loss amount of above-mentioned carburelant is in 5%-10%, and the scaling loss of other alloy is disregarded; Al accounts for the percentage ratio that does not add molten steel total mass before ferro-niobium, the ferro-vanadium by it, and FeSiRE26 accounts for the percentage ratio that adds molten steel total mass behind ferro-niobium, the ferro-vanadium by it.
B, fusion process: the graphite carburelant is joined medium-frequency induction furnace, again low-carbon waste steel is pressed in energising fusing on the graphite carburelant.The whole molten clear back addings of furnace charge account for the Al deoxidation that does not add ferro-niobium, the preceding molten steel total mass 0.1% of ferro-vanadium, skim after static 1 minute, evenly add ferrocolumbium and ferro-vanadium subsequently, add the back and cover liquid level with slag former, temperature is raised to 1520～1560 ℃ rapidly, and is incubated 5～8min, then temperature is raised to 1600～1650 ℃ rapidly, add the pre-prepd FeSiRE26 alloy modification that accounts for ferro-niobium, ferro-vanadium adding back molten steel total mass 0.35%, the cast of coming out of the stove of skimming then; Make the iron base composite material foundry goods;
C, heat treatment process: in chamber type electric resistance furnace, the above-mentioned iron base composite material foundry goods that makes is heated to 900～950 ℃, the air cooling of coming out of the stove behind the insulation 2h.
The tensile strength of this iron base composite material foundry goods is 485Mpa, and unit elongation is 4.0%, and hardness is 22HRC.(Nb, V) percent by volume of C wild phase is 8% to this iron base composite material carbide sosoloid.
Embodiment 5:
A kind of (Nb, V) C strengthens iron base composite material, its wild phase is by Nb, V and C atom original position synthetic carbide sosoloid (Nb, V) C, in mass percent, described iron base composite material contains 2.75%～6.60% Nb and 1.50%～3.6% V and proper C, and the content of described C can guarantee to make described Nb and described V all to generate carbide fully at least, and the content of the C of all the other solid solutions in the iron-based body is no more than 0.5%.
In this example, contain niobium (Nb), vanadium (V), carbon (C) in the original position synthetic system of selecting for use, iron (Fe) etc.
Main component consists of with mass percent:
Niobium (Nb) 6.60%;
Vanadium (V) 3.60%;
Carbon (C) 1.80%;
Iron-based body (Fe) all the other;
Wherein the atomicity of Nb, V ratio is 1: 1, and C content is to generate NbC, VC with Nb, V complete reaction.Other minor element (as the Si in the iron-based body, Mn, P, S) and auxiliary element (as the Al in the reductor, the RE in the alterant etc.) are ignored because content is extremely low.
In the composition of mentioned component, the adding form of Nb is FeNb60 alloy (containing the Nb amount is 65%), and the adding form of V is FeV50 alloy (V content is 52%), and C adds with the form of graphite carburelant.Iron-based body (Fe) adds with the form of soft steel (carbon content 0.2%).
In addition, used reductor is the form adding of fine aluminium in the preparation method.Alterant adds with the form of FeSiRE26.
Its preparation method is such:
A, take by weighing starting material by above-mentioned composition, its proportioning is as shown in table 5, and wherein ferrocolumbium, ferro-vanadium are broken for granularity 1～5mm;
The actual weighing proportioning of table 5 (wt%)
Annotate: the scaling loss amount of above-mentioned carburelant is in 5%-10%, and the scaling loss of other alloy is disregarded; Al accounts for the percentage ratio that does not add molten steel total mass before ferro-niobium, the ferro-vanadium by it, and FeSiRE26 accounts for the percentage ratio that adds molten steel total mass behind ferro-niobium, the ferro-vanadium by it.
B, fusion process: the graphite carburelant is joined medium-frequency induction furnace, again soft steel is pressed in energising fusing on the carburelant.The whole molten clear back addings of furnace charge account for the Al deoxidation that does not add ferro-niobium, the preceding molten steel total mass 0.15% of ferro-vanadium, static 1 minute and skim, evenly add ferrocolumbium and ferro-vanadium subsequently, add the back and cover liquid level with slag former, temperature is raised to 1520～1560 ℃ rapidly, and be incubated 5～8min, then temperature is raised to 1600～1650 ℃ rapidly, add pre-prepd account for rare earth ferrosilicon alloy FeSiRE26 that ferro-niobium, ferro-vanadium add back molten steel total mass 0.35% processing of going bad, the cast of coming out of the stove of skimming then;
C, heat treatment process: in chamber type electric resistance furnace, matrix material is heated to 900～950 ℃, the air cooling of coming out of the stove behind the insulation 2h.
The tensile strength of this composite castings is 525Mpa, and unit elongation is 4.0%, and hardness is 24HRC.(Nb, V) percent by volume of C wild phase is 12% to this iron base composite material carbide sosoloid.
Comparative Examples:
A kind of NbC strengthens iron base composite material, contains niobium (Nb), carbon (C), iron (Fe) etc. in the original position synthetic system of selecting for use.Main component is counted with mass percent:
Niobium (Nb) 7.20%;
Carbon (C) 0.92%;
Iron-based body (Fe) all the other;
Other minor element (as the Si in the iron-based body, Mn, P, S) and auxiliary element (as the A l in the reductor, the RE in the alterant etc.) are ignored because content is extremely low.
In the composition of mentioned component, the adding form of Nb is FeNb60 alloy (containing the Nb amount is 65%), and C adds with the form of graphite carburelant.Iron-based body (Fe) adds with the form of low-carbon waste steel (carbon content 0.2%).
In addition, used reductor is the form adding of fine aluminium in the preparation method; Alterant adds with the FeSiRE26 form.
Its preparation method is such:
A, take by weighing starting material by above-mentioned composition, its proportioning is as shown in table 6, and wherein ferrocolumbium is broken for granularity 1～5mm;
The actual weighing proportioning of table 6 (wt%)
Annotate: the scaling loss amount of above-mentioned carburelant is in 5%-10%, and the scaling loss of other alloy is disregarded; Al accounts for the percentage ratio that does not add molten steel total mass before the ferrocolumbium by it, and FeSiRE26 accounts for the percentage ratio that adds molten steel total mass behind the ferrocolumbium by it.
B, fusion process: the graphite carburelant is joined medium-frequency induction furnace, again low-carbon waste steel is pressed in energising fusing on the carburelant.The whole molten clear back addings of furnace charge account for the Al deoxidation that does not add the preceding molten steel total mass 0.1% of ferrocolumbium, skim after static 1 minute, evenly add ferrocolumbium subsequently, add the back and cover liquid level with slag former, temperature is raised to 1520～1560 ℃ rapidly, and is incubated 5～8min, then temperature is raised to 1620 ℃ rapidly, add the pre-prepd rare earth ferrosilicon alloy FeSiRE26 that accounts for ferrocolumbium adding back molten steel total mass 0.3% and go bad the cast of coming out of the stove of skimming then;
C, heat treatment process: in chamber type electric resistance furnace, matrix material is heated to 900～950 ℃, the air cooling of coming out of the stove behind the insulation 2h.
Tensile strength to the foundry goods that adopts the matrix material that above-mentioned castmethod makes is 420Mpa, and unit elongation is 3.5%, and hardness is 20HRC.The percent by volume of this iron base composite material carbide sosoloid NbC wild phase is 8%.
Among the present invention, the various performances of the composite castings that embodiment 1～5 and Comparative Examples prepare all are that sample detects with the separately cast test bar.Wherein GB/T228-2002 " metallic substance tensile test at room temperature method " execution is pressed in the test of tensile strength and unit elongation, and the test of hardness is pressed GB/T230.1-2009 " metallic substance Rockwell hardness test first part: test method " and carried out.Slag former in the present embodiment adopts the poly-slag agent of the JF-3 type cast steel of Zhengzhou Jin Naiyuan company.Certainly, can also select other slag former for use, this need be selected according to the character of electric furnace: if acid lined furnace, and just can be with above-mentioned poly-slag agent; If basic furnace just can adopt slag making materialses such as lime; If neutral stove can be used slag making materialses such as high alumina matter.So-called acid lined furnace and basic furnace are meant the material difference of furnace lining, and this is common practise in the industry, does not repeat them here.
Among the embodiment 1～5, the rare earth ferrosilicon alloy that adds before the cast of coming out of the stove also can replace with aluminium, and the add-on of described aluminium when final deoxygenation is 0.08～0.10% of ferro-niobium, ferro-vanadium adding back molten steel total mass.
Used rare earth ferrosilicon alloy is FeSiRE26 among the embodiment 1～5, also can adopt with FeSiRE26 in other suitable ferro-silicons of RE content.
Used ferrocolumbium and ferro-vanadium also can contain the alloy form of niobium or baric with other in embodiment 1～5 and the Comparative Examples except that the form that adopts FeNb60 and FeV50 alloy.
From embodiment 1～5 and Comparative Examples more as can be seen, embodiment 1～5 prepared composite property is better than Comparative Examples.Therefore, the present invention is with respect to the main advantage of prior art:
1, the Nb of appropriate level scope and the V wild phase element as the iron-based body has been adopted in iron base composite material of the present invention design, sufficiently and reasonably utilize NbC, VC wild phase collaborative enhancement to matrix, make iron base composite material of the present invention under the not high situation of wild phase percent by volume, both had higher intensity and wear resistance, possessed good casting and machinability again.So iron base composite material of the present invention is applicable to wear resisting property requirement height, have the component of higher-strength requirement simultaneously, be particularly useful for preparing comparatively complicated parts of shape, opened up the new range of application and the field of iron base composite material.
2, aspect melting technology, optimize, further improve the performance of iron base composite material.
The first, the adding granularity of ferro-niobium and ferro-vanadium is controlled at 1～5mm, and takes evenly to add the mode of molten steel, make it even as adopting the medium-frequency induction furnace induction stirring among the embodiment, mainly be generated in-situ (Nb, V) the even tiny distribution of C in order to make.
The second, add behind ferro-niobium and the ferro-vanadium and temperature to be controlled at 1520～1560 ℃ and be incubated 5～8min earlier, mainly be to make fully carrying out of reaction in by induction stirring, also limited seriously growing up of carbide simultaneously.And then be warmed up to 1600～1650 ℃ and come out of the stove, mainly be to guarantee that molten steel has good casting.
Further optimizing technology is to carry out pre-deoxidation with the Al reductor before adding ferro-niobium and ferro-vanadium, thereby can prevent the severe oxidation after alloying element adds.Last optimization technology is to adopt rare earth ferrosilicon alloy that molten steel is carried out deoxidation and rotten the processing before the cast of coming out of the stove, mainly play further deoxidation and reduce S in the molten steel, change the form and the distribution of non-metallic inclusion simultaneously, further improve the mechanical property of material.
3, the present invention is in order further to improve the over-all properties of material, improve when particularly taking into account the intensity of material and plasticity simultaneously, matrix material has been carried out thermal treatment optimization, further brought into play Nb, the V microalloying effect in steel, make it in heat treatment process, separate out tiny NbC, VC particle and the sosoloid thereof that is uniformly distributed in the matrix, not only can further improve the volume fraction of wild phase, refinement simultaneously iron-based crystal grain, intensity, the plasticity of material also are greatly improved.
Claims (10)
1. iron base composite material, the wild phase of described iron base composite material is by Nb, V and C atom original position synthetic carbide sosoloid (Nb, V) C, it is characterized in that: in mass percent, described iron base composite material contains 2.75%～6.60% Nb and 1.50%～3.6% V and proper C, the content of described C can guarantee to make described Nb and described V all to generate carbide fully at least, and the content of the C of all the other solid solutions in the iron-based body is no more than 0.5%.
2. iron base composite material as claimed in claim 1 is characterized in that: in mass percent, the C that described iron base composite material is used to generate carbide is 0.75%～1.8%.
3. iron base composite material as claimed in claim 1 is characterized in that: wherein Nb is 0.6: 1～1: 0.6 with the atomicity of V than scope.
4. iron base composite material as claimed in claim 1 is characterized in that: wherein Nb is 1: 1 with the atomicity ratio of V.
5. iron base composite material as claimed in claim 1 is characterized in that: (Nb, V) percent by volume of C wild phase is 5～12% to the carbide sosoloid of described iron base composite material.
6. the preparation method as the described iron base composite material of claim 1～5 is characterized in that, may further comprise the steps:
Step 1, (Nb, the V) composition of C wild phase calculate and take by weighing ferrocolumbium, ferro-vanadium, graphite carburelant and the iron-based body raw material of required adding according to described carbide sosoloid; Wherein the add-on of graphite carburelant generates NbC, VC, and comprises the scaling loss amount interior to guarantee itself and Nb, V complete reaction at least;
Step 2, heating and melting iron-based body raw material are treated that it is ferrocolumbium, the ferro-vanadium of 1～5mm that all molten clear back of furnace charge adds granularity, and are warming up to 1520～1560 ℃ of insulation 5～8min, and then be warmed up to 1600～1650 ℃ of cast of coming out of the stove of skimming; Make the iron base composite material foundry goods;
Step 3, the iron base composite material foundry goods that step 2 is made are heat-treated, its thermal treatment process for the iron base composite material foundry goods is heated to 900～950 ℃ and be incubated 1.5～2h after, the naturally cooling of coming out of the stove.
7. the preparation method of iron base composite material as claimed in claim 6, it is characterized in that: in described step 2, adopt medium-frequency induction furnace heating and melting graphite carburelant, iron-based body raw material, after treating that graphite carburelant, iron-based body raw material all melt clearly, add aluminium deoxidation earlier, leave standstill a moment and skim, adding granularity then under the state of induction stirring is ferrocolumbium, the ferro-vanadium of 1～5mm; The add-on of described aluminium is not for adding 0.1～0.15% of ferrocolumbium, the preceding molten steel total mass of ferro-vanadium.
8. the preparation method of iron base composite material as claimed in claim 7, it is characterized in that: in described step 2, before going out the Shanghai cast, the adding rare earth ferrosilicon alloy goes bad to handle or add aluminium and carries out final deoxygenation, and the add-on of described rare earth ferrosilicon alloy is 0.2%～0.4% of ferrocolumbium, a ferro-vanadium adding back molten steel total mass; The add-on of described aluminium when final deoxygenation is 0.08～0.10% of ferro-niobium, ferro-vanadium adding back molten steel total mass.
9. the preparation method of iron base composite material as claimed in claim 8 is characterized in that: described rare earth ferrosilicon alloy be FeSiRE26 or with FeSiRE26 in other suitable ferro-silicons of RE content.
10. the preparation method of iron base composite material as claimed in claim 6 is characterized in that: in the described step 2, the graphite carburelant is joined medium-frequency induction furnace, iron-based body raw material is pressed in energising fusing on the graphite carburelant again;
Treat furnace charge all molten clear after, add aluminium deoxidation earlier, leave standstill a moment and skim; Be at molten steel then that to add granularity under the state of induction stirring be ferrocolumbium, the ferro-vanadium of 1～5mm, the add-on of described aluminium is not for adding 0.1～0.15% of molten steel total mass before ferrocolumbium, the ferro-vanadium;
Add the back and cover liquid level, temperature is raised to 1520～1560 ℃, and is incubated 5～8min with slag former;
Temperature is raised to 1600～1650 ℃ then, the adding rare earth ferrosilicon alloy goes bad to handle or add aluminium and carries out final deoxygenation, and the add-on of described rare earth ferrosilicon alloy is 0.2%～0.4% of ferrocolumbium, a ferro-vanadium adding back molten steel total mass; The add-on of described aluminium when final deoxygenation is 0.08～0.10% of ferro-niobium, ferro-vanadium adding back molten steel total mass;
The cast of coming out of the stove of skimming then; Make the iron base composite material foundry goods.
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| CN102350824A (en) * | 2011-08-25 | 2012-02-15 | 深圳市和胜金属技术有限公司 | Vanadium carbide rare-earth ceramic composite material based on metal matrix and method |
| CN102383128A (en) * | 2011-08-25 | 2012-03-21 | 深圳市和胜金属技术有限公司 | Metal matrix based niobium carbide rare earth ceramic composite material and method |
| CN106756584A (en) * | 2016-12-05 | 2017-05-31 | 常州轻工职业技术学院 | Iron base composite material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102350824A (en) * | 2011-08-25 | 2012-02-15 | 深圳市和胜金属技术有限公司 | Vanadium carbide rare-earth ceramic composite material based on metal matrix and method |
| CN102383128A (en) * | 2011-08-25 | 2012-03-21 | 深圳市和胜金属技术有限公司 | Metal matrix based niobium carbide rare earth ceramic composite material and method |
| CN102383128B (en) * | 2011-08-25 | 2014-04-09 | 深圳市和胜金属技术有限公司 | Metal matrix based niobium carbide rare earth ceramic composite material and method |
| CN106756584A (en) * | 2016-12-05 | 2017-05-31 | 常州轻工职业技术学院 | Iron base composite material and preparation method thereof |
| CN106756584B (en) * | 2016-12-05 | 2018-07-20 | 常州轻工职业技术学院 | Iron base composite material and preparation method thereof |
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