CN102912185A - Bismuth and zirconium alloy for environment-friendly high-strength free-cutting steel - Google Patents
Bismuth and zirconium alloy for environment-friendly high-strength free-cutting steel Download PDFInfo
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- CN102912185A CN102912185A CN2012103912819A CN201210391281A CN102912185A CN 102912185 A CN102912185 A CN 102912185A CN 2012103912819 A CN2012103912819 A CN 2012103912819A CN 201210391281 A CN201210391281 A CN 201210391281A CN 102912185 A CN102912185 A CN 102912185A
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Abstract
The invention relates to bismuth and zirconium alloy, particularly relates to bismuth and zirconium alloy for alloying environment-friendly high-strength free-cutting steel, and belongs to the technical field of manufacture of alloy steel (C22C alloy). The bismuth and zirconium alloy comprises, by weight, from 15% to 82% of bismuth, lower than or equal to 1.2% of inevitable impurities and the balance zirconium. The bismuth and zirconium alloy has the advantages that alloying of the high-strength free-cutting steel is feasible, the mechanical property of the steel is improved, bismuth yield is high, and the like. The bismuth and zirconium alloy is suitable to be used as an additive for alloying the environment-friendly high-strength free-cutting steel.
Description
Technical field
The present invention relates to a kind of bismuth zirconium alloy, be specifically related to a kind of bismuth zirconium alloy for environment protection type high-strength free-machining alloy steel Alloying Treatment, belong to steel alloy (C22C alloy) preparing technical field.
Background technology
Bismuth metal (Bi) outward appearance is silvery white in color, strong metalluster is arranged, be fragility, crystalline structure is rhombic system, because bismuth metal is nontoxic, and have low melting point and the high-flexibility close with metallic lead, therefore in the extensive substitute as lead of industrial quilt, bismuth is added in the alloy of cast iron, steel and aluminium, can improve its cutting ability, the bismuth-containing free-machining alloy steel is because its environment amenable characteristic, become modern manufacturing industry in the urgent need to a kind of industrial raw materials.
But the fusing point of bismuth low (271.3 ℃) is given the Alloying Treatment of bismuth free-machining alloy steel and the production of steel alloy, has caused very large difficulty; Therefore, because oxidization burning loss and the evaporation of bismuth, adopting bismuth metal is fully infeasible as the Alloying Treatment additive of described steel alloy, the bismuth manganese alloy can be used as the additive of free-machining alloy steel Alloying Treatment, but because the fusing point lower (1244 ℃) of manganese, and the fusing point of bismuth manganese alloy lower (446 ℃); Therefore, with its additive as the free-machining alloy steel Alloying Treatment, the scaling loss of bismuth element was still very large when the bismuth manganese alloy was added free-machining alloy steel, still be difficult to realize its industrial application, and the Chinese patent result for retrieval shows, Alloying Treatment is feasible, the additive bismuth alloy that is used for the free-machining alloy steel Alloying Treatment that recovery rate is high, except bismuth manganese iron alloy, there is not yet other report, and the fusing point of bismuth ferromanganese is still not high.
Zirconium is a kind of transiting group metal elements, is silvery white in color, and it has intensity and the plasticity coupling that fusing point is high, density is moderate, good.Zirconium is a strong oxide compound, strong nitride forming element, and its compound not only fusing point is high (such as ZrO
2Fusing point is 2677 ℃, and the ZrN fusing point is 3255 ℃), hardness is also high, can suppress Austenite Grain Growth in steel.Contain V, the alloy of Ti and Zr can replace aluminium deoxidation, can greatly reduce non-metallic inclusion to the harmful effect of the use properties of steel; Studies show that, in high-strength low-alloy steel, add the alloying element zirconium and can make size, the form of inclusion and distribute and all obtained obvious improvement, form that particle is tiny, circle or subcircular, be the inclusion that disperse distributes.Inclusion generally is by TiO
2, A1
2O
3, ZrO
2And the complex inclusion of MnS composition, TiO
2, A1
2O
3, ZrO
2Be positioned at the centre of complex inclusion, MnS is positioned at skin.Zirconium-micro-alloyed steel inclusion size, form and distribution are improved, can obviously improve the mechanical property of steel.
After adding bismuth element in the steel, although can improve its cutting ability, the mechanical property of steel descends to some extent.For this reason, provide a kind of Alloying Treatment feasible, not only can improve steel mechanical property, but also can improve the described environment protection type high-strength free-machining alloy steel Alloying Treatment additive of the recovery rate of bismuth element, just become pursuing a goal of Metallurgical Industry.
Summary of the invention
It is feasible that the present invention aims to provide a kind of Alloying Treatment, can improve the mechanical property of steel, again the bismuth zirconium alloy of higher recovery rate be arranged, and satisfies the environment protection type high-strength free-cutting steel and smelt the demand of producing.
The present invention realizes that the technical scheme of its purpose is:
A kind of bismuth zirconium alloy is characterized in that: the component of described bismuth zirconium alloy by weight percentage composition calculating is respectively: bismuth: 15 ~ 82%; Inevitable impurity :≤1.2%; Zirconium: surplus.
A kind of typical technical scheme of the present invention is:
A kind of bismuth zirconium alloy is characterized in that: the component of described bismuth zirconium alloy by weight percentage composition calculating is respectively: bismuth: 45% ~ 75%; Inevitable impurity :≤1.2%; Zirconium: surplus.
It is block that bismuth zirconium alloy of the present invention is, and its lumpiness is in 10 ~ 50mm scope; Perhaps in pelletized form, its particle diameter is in 1.0～10mm scope.
Inevitable impurity of the present invention, refer in the preparation process of bismuth zirconium alloy, metallic element and the non-metallic element that can not thoroughly remove, inevitable impurity of the present invention, mainly refer to hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen, wherein the weight percentage of iron+chromium≤0.2%.
After technique scheme was implemented, because the weight percentage of bismuth of the present invention reaches as high as 82%, and described fusing point of the present invention is higher, and (the BiZr fusing point was 1302 ℃, Bi
2Zr
3Fusing point is 1497 ℃), and its proportion and iron phase when or be slightly larger than the proportion of iron, thereby to adopt bismuth zirconium alloy of the present invention to carry out the stokehold Alloying Treatment be feasible, the adding of alloy and mix all very convenient; Because the fusing point of bismuth zirconium alloy is higher, so the recovery rate of bismuth is very high, can reach more than 95%; In addition, zr element can play deoxidation and improve the effect of size, form and the distribution of steel inclusion, and is very favourable to the mechanical property that improves steel, so the present invention can satisfy the environment protection type easy Cutting Steel with the requirement of alloy addition.
Embodiment
Embodiment 1: a kind of bismuth zirconium alloy, and the weight percentage of its component and each component is (%): bismuth 20, inevitably the summation of impurity hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen is 1.0%, surplus is zirconium; It is block that its product is, and lumpiness is 20mm.
Embodiment 2: a kind of bismuth zirconium alloy, and the weight percentage of its component and each component is (%): bismuth 35, inevitably the summation of impurity hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen is 1.2%, surplus is zirconium; Its product in pelletized form, particle diameter is in 1.0 ~ 10mm scope.
Embodiment 3: a kind of bismuth zirconium alloy, and the weight percentage of its component and each component is (%): bismuth 50, inevitably the summation of impurity hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen is 0.8%, surplus is zirconium; It is block that its product is, and lumpiness is 35mm.
Embodiment 4: a kind of bismuth zirconium alloy, and the weight percentage of its component and each component is (%): bismuth 65, inevitably the summation of impurity hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen is 1.0%, surplus is zirconium; Its product in pelletized form, particle diameter is in 1.0～10mm scope.
Embodiment 5: a kind of bismuth zirconium alloy, and the weight percentage of its component and each component is (%): bismuth 80, inevitably the summation of impurity hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen is 1.0%, surplus is zirconium; It is block that its product is, and lumpiness is 48mm.
Because bismuth zirconium alloy of the present invention belongs to compound between friable metal, can be prepared into easily little lumpiness or be prepared into required granular alloy product.
Preparation method's of the present invention concise and to the point description is:
Adopt a step remelting process or infiltration reaction method to implement the present invention, a step remelting process namely adopts fusion casting directly to prepare bismuth zirconium master alloy, and its preparation method has two kinds, and a kind of method is first melting bismuth, adds industrial pure zirconium (zirconium sponge) again; Another kind method is first melting industrial pure zirconium, adds bismuth again.
One step of the first remelting process prepares the present invention: bismuth metal and industrial pure zirconium are pressed preparation proportion ingredient required for the present invention, deposite metal bismuth in advance, add again industrial pure zirconium and stir, so that zirconium fully is dissolved in the bismuth liquid, in this process, along with the continuous adding of zirconium, alloy liquid slowly heats up, until industrial pure zirconium dissolves fully and evenly after the mixing aluminium alloy is poured into fast cooling in the ingot mould, namely make bismuth zirconium alloy ingot of the present invention.
One step of the second remelting process prepares the present invention: bismuth metal and industrial pure zirconium are pressed preparation proportion ingredient required for the present invention, melt industrial pure zirconium in advance, again bismuth metal is dropped in the metal zirconium liquid and stir, so that bismuth fully is dissolved in the zirconium liquid, in this process, along with the continuous adding of bismuth metal, alloy liquid carries out slow cooling to be processed, until bismuth metal dissolves fully and evenly after the mixing aluminium alloy is poured into fast cooling in the ingot mould, namely make bismuth zirconium alloy ingot of the present invention.
Because bismuth zirconium alloy of the present invention belongs to intermetallic compound, more crisp, if need more short grained when of the present invention, can be to the invention process artificial or machinery morcel heat up and the cooling processing because the present invention adopts in fusion process, can effectively reduce the loss of bismuth.
The infiltration reaction method:
At first be that 200 purpose zirconium powders are put into cast-iron pot and the top is floating with granularity, again the bismuth metal piece be placed in equably the zirconium powder top; Place well formula resistance furnace to be heated to 800 ℃ the cast-iron pot that fills zirconium powder and bismuth metal, insulation is infiltrated in the zirconium powder bismuth liquid under this temperature, bismuth and zirconium are reacted form the bismuth zirconium compounds, after bismuth metal infiltrates zirconium powder fully, cut off the electricity supply and cast-iron pot is taken out, when treating that it is cooled to 50 ℃ in air the bismuth zirconium alloy is taken out from cast-iron pot, then it is broken into desired size, make required bismuth zirconium alloy.
The bismuth zirconium alloy that adopts the present invention to produce is done result's demonstration of stokehold Alloying Treatment, and its adding method is simple and feasible; The recovery rate of Alloying Treatment bismuth can reach more than 95%.
Embodiment 6: because the Q235 composition of steel near the free-cutting steel of bismuth-containing zirconium, therefore selects the Q235 steel as the Alloying Treatment object; The Q235 steel is carried out melting in vacuum induction furnace, melt rear adding bismuth zirconium alloy 1 of the present invention fully and kept 5 minutes until it, this alloying constituent is (%): bismuth 20, and inevitably the summation of impurity hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen is 1.0, surplus is zirconium; It is block that its product is, lumpiness is 20mm, alloy addition calculates according to this formula: Bi element recovery rate 95% in Bi constituent content 20% * alloy in alloy addition 4.474g=steel quality 500g * (Bi constituent content 0% in the object element Bi content 0.17%-steel)/alloy, the control molten steel temperature is poured into a mould at 1600 ℃, be cast for the pole sample, the sample that cast is good carries out conventional thermal treatment, carries out subsequently the experiment of cutting experiment and mechanical property.
Embodiment 7: select the Q235 steel as the Alloying Treatment object.The Q235 steel is carried out melting in vacuum induction furnace, melt rear adding bismuth zirconium alloy 2 of the present invention fully and kept 5 minutes until it, this alloying constituent is (%): bismuth 35, and inevitably the summation of impurity hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen is 1.2, surplus is zirconium; Its product in pelletized form, particle diameter is in 1.0 ~ 10mm scope, alloy addition calculates according to this formula: Bi element recovery rate 95% in Bi constituent content 35% * alloy in alloy addition 2.556g=steel quality 500g * (Bi constituent content 0% in the object element Bi content 0.17%-steel)/alloy, the control molten steel temperature is poured into a mould at 1600 ℃, be cast for the pole sample, the sample that cast is good carries out conventional thermal treatment, carries out subsequently the experiment of cutting experiment and mechanical property.
Embodiment 8: select the Q235 steel as the Alloying Treatment object.The Q235 steel is carried out melting in vacuum induction furnace, melt rear adding bismuth zirconium alloy 3 of the present invention fully and kept 5 minutes until it, this alloying constituent is (%): bismuth 50, and inevitably the summation of impurity hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen is 1.2, surplus is zirconium; It is block that its product is, lumpiness is 35mm, alloy addition calculates according to this formula: Bi element recovery rate 95% in Bi constituent content 50% * alloy in alloy addition 1.789g=steel quality 500g * (Bi constituent content 0% in the object element Bi content 0.17%-steel)/alloy, the control molten steel temperature is poured into a mould at 1600 ℃, be cast for the pole sample, the sample that cast is good carries out conventional thermal treatment, carries out subsequently the experiment of cutting experiment and mechanical property.
Embodiment 9: select the Q235 steel as the Alloying Treatment object.The Q235 steel is carried out melting in vacuum induction furnace, melt rear adding bismuth zirconium alloy 4 of the present invention fully and kept 5 minutes until it, this alloying constituent is (%): bismuth 65, inevitably impurity, the summation of hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen is 1.0, and surplus is zirconium; Its product in pelletized form, particle diameter is in 1.0 ~ 10mm scope, alloy addition calculates according to this formula: Bi element recovery rate 95% in Bi constituent content 65% * alloy in alloy addition 1.377g=steel quality 500g * (Bi constituent content 0% in the object element Bi content 0.17%-steel)/alloy, the control molten steel temperature is poured into a mould at 1600 ℃, be cast for the pole sample, the sample that cast is good carries out conventional thermal treatment, carries out subsequently the experiment of cutting experiment and mechanical property.
Embodiment 10: select the Q235 steel as the Alloying Treatment object.The Q235 steel is carried out melting in vacuum induction furnace, melt rear adding bismuth zirconium alloy 5 of the present invention fully and kept 5 minutes until it, this alloying constituent is (%): bismuth 80, inevitably impurity, the summation of hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen is 1.0, and surplus is zirconium; It is block that its product is, lumpiness is 48mm, alloy addition calculates according to this formula: Bi element recovery rate 95% in Bi constituent content 80% * alloy in alloy addition 1.118g=steel quality 500g * (Bi element residual content 0% in the object element Bi content 0.17%-steel)/alloy, the control molten steel temperature is poured into a mould at 1600 ℃, be cast for the pole sample, the sample that cast is good carries out conventional thermal treatment, carries out subsequently the experiment of cutting experiment and mechanical property.
The free cutting property of steel is mainly evaluated indirectly by the cutter life of Cutting Steel, the cutting ability of the 12L14 free-cutting steel close with published cutting ability is compared, after the bismuth zirconium alloy of five kinds of different bi contents of use was processed the Q235 steel alloying, the bismuth zirconium free-cutting steel of acquisition had reached the cutting ability requirement of free-cutting steel.
Table 1 is the mechanical property of the bismuth zirconium free-cutting steel that obtains behind the bismuth zirconium alloy Alloying Treatment Q235 steel of the present invention, and as seen, the mechanical property of steel all is in the middle upper limit of standard.
The mechanical property of the bismuth zirconium free-cutting steel that obtains behind the table 1 bismuth zirconium alloy Alloying Treatment Q235 steel
Range of application of the present invention, the restriction that not described by its specification sheets.
Claims (8)
1. bismuth zirconium alloy is characterized in that: the component of described bismuth zirconium alloy by weight percentage composition is calculated and is respectively: bismuth: 15 ~ 82%; Inevitable impurity :≤1.2%; Zirconium: surplus.
2. a kind of bismuth zirconium alloy as claimed in claim 1 is characterized in that: the component of described bismuth zirconium alloy by weight percentage composition is calculated and is respectively: bismuth: 45% ~ 75%; Inevitable impurity :≤1.2%; Zirconium: surplus.
3. a kind of bismuth zirconium alloy as claimed in claim 1 is characterized in that: described bismuth zirconium alloy is block, and its lumpiness is in 10 ~ 50mm scope; Perhaps in pelletized form, its particle diameter is in 1.0～10mm scope.
4. a kind of bismuth zirconium alloy as claimed in claim 1, it is characterized in that: described inevitable impurity, refer in the preparation process of bismuth zirconium alloy, metallic element and the non-metallic element that can not thoroughly remove, mainly refer to hafnium, iron, chromium, carbon, nitrogen, hydrogen and oxygen, wherein the weight percentage of iron+chromium≤0.2%.
5. the preparation method of a kind of bismuth zirconium alloy as claimed in claim 1, it is characterized in that: bismuth metal and industrial pure zirconium are pressed required proportion ingredient, deposite metal bismuth in advance, add again industrial pure zirconium and stir, so that zirconium fully is dissolved in the bismuth liquid, in this process, continuous adding along with zirconium, alloy liquid slowly heats up, until industrial pure zirconium dissolves fully and evenly after the mixing aluminium alloy is poured into fast cooling in the ingot mould, namely makes bismuth zirconium alloy ingot.
6. the preparation method of a kind of bismuth zirconium alloy as claimed in claim 1, it is characterized in that: bismuth metal and industrial pure zirconium are pressed required proportion ingredient, melt industrial pure zirconium in advance, again bismuth metal is dropped in the metal zirconium liquid and stir, so that bismuth fully is dissolved in the zirconium liquid, in this process, continuous adding along with bismuth metal, alloy liquid carries out slow cooling to be processed, until bismuth metal dissolves fully and evenly after the mixing aluminium alloy is poured into fast cooling in the ingot mould, namely make bismuth zirconium alloy ingot.
7. the preparation method of a kind of bismuth zirconium alloy as claimed in claim 1 is characterized in that: at first be that 200 purpose zirconium powders are put into cast-iron pot and the top is floating with granularity, the bismuth metal piece be placed in equably the zirconium powder top again; Place well formula resistance furnace to be heated to 800 ℃ the cast-iron pot that fills zirconium powder and bismuth metal, insulation is infiltrated in the zirconium powder bismuth liquid under this temperature, bismuth and zirconium are reacted form the bismuth zirconium compounds, after bismuth metal infiltrates zirconium powder fully, cut off the electricity supply and cast-iron pot is taken out, when treating that it is cooled to 50 ℃ in air the bismuth zirconium alloy is taken out from cast-iron pot, then it is broken into desired size, make the bismuth zirconium alloy.
8. a kind of bismuth zirconium alloy as claimed in claim 1 is in the purposes of high-strength simple-cutting steel alloying processing, it is characterized in that: free-cutting steel is carried out melting in vacuum induction furnace, melt rear adding bismuth zirconium alloy fully and kept 5 minutes until free-cutting steel, bismuth zirconium alloy add-on is calculated according to this formula: Bi element recovery rate in Bi constituent content * alloy in alloy addition=steel quality * (Bi constituent content in object element Bi content-steel)/alloy, the control molten steel temperature is poured into a mould at 1600 ℃, is cast for the pole sample.
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Cited By (3)
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| CN103667592A (en) * | 2013-12-09 | 2014-03-26 | 武汉钢铁(集团)公司 | Method used for realizing dispersion uniform distribution of bismuth element in alloy steel containing bismuth |
| CN107245662A (en) * | 2017-05-05 | 2017-10-13 | 重庆大学 | It is a kind of while improving the sulfide denaturation method of sulphur system's easy-to-cut structural steel mechanical performance and cutting ability |
| CN110282975A (en) * | 2019-07-08 | 2019-09-27 | 先导薄膜材料（广东）有限公司 | A kind of Germanium selenide target and preparation method thereof |
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Cited By (4)
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| CN103667592A (en) * | 2013-12-09 | 2014-03-26 | 武汉钢铁(集团)公司 | Method used for realizing dispersion uniform distribution of bismuth element in alloy steel containing bismuth |
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| CN107245662B (en) * | 2017-05-05 | 2019-03-01 | 重庆大学 | Sulfide denaturation method that is a kind of while improving sulphur system easy-to-cut structural steel mechanical performance and cutting ability |
| CN110282975A (en) * | 2019-07-08 | 2019-09-27 | 先导薄膜材料（广东）有限公司 | A kind of Germanium selenide target and preparation method thereof |
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Date of cancellation: 20230912 Granted publication date: 20160504 Pledgee: Zaozhuang rural commercial bank Limited by Share Ltd. Yicheng sub branch Pledgor: Shandong Xuedi Aluminum Technology Co.,Ltd. Registration number: Y2022980016328 |