CN100434558C - High-boron cast steel containing granular boride and preparing method thereof - Google Patents
High-boron cast steel containing granular boride and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a preparing method of granular boride high-boron cast steel, which comprises the following steps: allocating 0.15%-0.45% C,0.75%-2.70% B, 0.34 %-1.50% Ti, 0.80%-1.20% Cr, 0.50%-1.50% Si, 0.50%-1.50% Mn, 0.04%-0.12% Ce, 0.08%-0.20% Al, 0.03%-0.10% Ca, 0.01%-0.06 N, P<0.05%, S<0.05% and Fe; setting B/C=5.0-6.0, B/Ti=1.8-2.2; adopting electric stove to melt; mixing common scrap steel, pig iron and chromium iron; heating to melt; adding into silicon iron and manganese iron; adding into ferroboron and ferrotitanium before tapping; adjusting furnace-front element to be quality; heating-up; adding into silicon-calcium alloy; pre-deoxidizing; end-deoxidizing with aluminum; micro-alloying; proceeding composite deteriorating process outside of the furnace with cerium and nitrogen; keeping the temperature; proceeding oil-cooling quenching; tempering under the low temperature; getting the product. This invention possesses merits of high hardness and strength and good tenacity and resistance, which can increase the durability of wear resisting part.
Description
Technical field
The invention belongs to antifriction metal material technology field, relate to a kind of high-boron cast steel, particularly a kind of high-boron cast steel that contains granular boride and preparation method thereof.
Background technology
Wearing and tearing are many industrial sector ubiquities such as metallurgy, mine, machinery, electric power, coal, oil, traffic, military project and become a major reason that causes equipment failure or material damage, also be to cause one of maximum problem of financial loss, the development of new wear-resistant material, reduce galling, national economy is had great importance.The wear-resistant material of widespread use at present mainly contains steel alloy and white cast iron, the former good toughness, but have the deficiency that hardness is low and wear no resistance, the latter has high rigidity and high-wearing feature, but exists fragility big, easily peels off in the use even the rimose deficiency.In order to improve white cast iron toughness, Chinese invention patent CN1115339 discloses Cr series white cast iron compound inoculant, and its major technique feature is to have adopted and bred and metamorphic facies bonded technological line.That is: when selecting the C, the Cr that Cr series white cast iron have been solidified inoculation(effect), Fe element for use, add Si, Mg, RE alloying element, in order to changing second phase morphology and distribution, and play metamorphism.Use the present invention and can make chromium white iron impact property improve 60%, fracture toughness property improves 30%, and the crack propagation threshold value improves 100%, and the ballistic work of its medium chrome cast iron reaches 4.5J, and fracture toughness property reaches 32MPa.m
1/2, tensile strength reaches 668MPa.But fragility still can be bigger, uses under heavy duty, gouging abrasion operating mode, and safe reliability is low.
In order to overcome the big deficiency of white cast iron fragility, Chinese invention patent CN86106682 discloses white cast iron and cast steel bimetal composite casting method, it is characterized in that adopting " castingin " and " biliquid " two kinds of composite casting technology methods, white cast iron and cast steel bimetal composite casting are integral, can produce with this technology and both to have required higher impact property, it is good or have the various parts that properties such as good heat resistance, solidity to corrosion are good require simultaneously also to have resistance to abrasion simultaneously.This processing method troublesome poeration, bimetal is prone to casting flaw in conjunction with the position, influences the use properties of material.In order to reduce white cast iron fragility, improve and improve its toughness, Chinese invention patent CN1104562 discloses rolling white cast iron and has been used to make the shot blast machine blade method, and the white cast iron leaf composition of this invention is: C, 2.1～3.0%; Si,＜1.0%; Mn, 0.8～1.5%; Cr, 1.0%; Mo, 0.3～0.8%; Cu, 0.5～1.0%; P,＜0.05%; S,＜0.05%; Available continuous casting is produced the white cast iron strand, and rolling temperature is 750-1100 ℃, rolling deformation rate :≤80%.Its best rolling temperature is 850-1000 ℃, and best rolling deformation rate is 50～60%.Guarantee in the operation of rolling of the present invention that carbide is fully broken, dense structure has high strength, toughness and resistance to abrasion, compares with cast blade, and impelling strength improves 1.85～2.66 times, hardness average out to HRC60, and resistance to abrasion improves 3～5 times.But this method complex process, production efficiency is low, and only is fit to the workpiece of simple shape.
In order to obtain to have concurrently the wear-resistant material of good obdurability and wear resistance, Chinese invention patent CN1624180 discloses a kind of high boron foundry iron base anti-wear alloy and heat treating method thereof, the main chemical compositions that it is characterized in that high boron foundry iron base anti-wear alloy is (weight %): C, 0.15～0.70; B, 0.3～1.9; Cr, 0.3～0.8; Si, 0.4～0.8; Mn, 0.6～1.3; Ce, 0.05～0.20; La, 0.02～0.10; Ca, 0.005～0.018; K, 0.04～0.18; Al, 0.08～0.25; S,＜0.04; P,＜0.04; All the other are Fe.Can obtain lath martensite after the thermal treatment and add the complex tissue that the high rigidity boride is formed, make material have better comprehensive performance.But boride is continuous net-shaped distribution, makes the fragility of material bigger.In order to improve high-boron cast alloy toughness, Chinese invention patent CN1804091 discloses the toughening method of casting high-boron wear-resistant alloy, it is characterized in that the chemical ingredients of casting high-boron wear-resistant alloy is: C, 0.30～0.35%; B, 1.0～1.5%; Si, 0.6～0.8%; Mn, 0.8～1.0%; S,＜0.04%; P,＜0.04%; All the other are Fe, Ti and unavoidable impurities element, and wherein Ti is brought into by the alterant ferrotianium.Concrete preparation process is: carry out the molten steel melting earlier, after the aluminium final deoxygenation is finished and is inserted in the molten steel melting, add the processing of going bad of alterant ferro-titanium, treating poured into a mould after skimming clearly, carry out malleableize thermal treatment behind the casting complete, the malleableize thermal treatment temp is 1020-1050 ℃, and soaking time is 2-3 hour, quench or normalizing last tempering then; The consumption of alterant titanium is 0.75～1.0% of a casting high-boron wear-resistant alloy.The eutectic boride of the sand mold casting high-boron wear-resistant alloy after the process patent is isolated shape and is distributed in the matrix.Because boride does not become particulate state, only be big block the distribution, so fragility is bigger, toughness is not too high, is 12.5J only, causes material to use under heavy duty, gouging abrasion operating mode, and safe reliability is poor.
Summary of the invention
The object of the invention is, a kind of high-boron cast steel that contains granular boride and preparation method thereof is provided, after boride in this high-boron cast steel of preparation becomes particulate state, can reduce high-boron cast steel fragility, improve its intensity and toughness, help the safe handling of high-boron cast steel under heavy duty, gouging abrasion operating mode.Its principal feature is to add an amount of titanium in high-boron cast steel, and add a small amount of Ce, Al, Ca and N, make its structure refinement, particularly make the eutectic boride become particulate state, help the high-boron cast steel mechanical property especially toughness increase substantially, cause the raising of high-boron cast steel use properties the most at last.
In order to realize above-mentioned task, the present invention takes following technical measures to realize:
A kind of high-boron cast steel that contains granular boride is characterized in that the chemical composition and the weight percent thereof that make this high-boron cast steel are: C, 0.15%～0.45%; B, 0.75%～2.70%; Ti, 0.34%～1.50%; Cr, 0.80%～1.20%; Si, 0.50%～1.50%; Mn, 0.50%～1.50%; Ce, 0.04%～0.12%; Al, 0.08%～0.20%; Ca, 0.03%～0.10%; N, 0.01%～0.06; P＜0.05%, S＜0.05%, surplus is Fe; Wherein, B/C=5.0～6.0, B/Ti=1.8～2.2.
The high-boron cast steel that contains granular boride of the present invention adopts electrosmelting, and its manufacturing technology steps is:
1. with ordinary scrap steel, the pig iron and the fusing of ferrochrome Hybrid Heating, the molten clear back of molten steel adds ferrosilicon and ferromanganese, adds ferro-boron and ferrotianium before coming out of the stove;
2. the stokehold is adjusted to branch and temperature is risen to 1580 ℃～1640 ℃ after qualified, adds silicon-calcium alloy pre-deoxidation, then uses aluminium final deoxygenation and microalloying, comes out of the stove then;
3. cerium base rare earth and nitrogenous substances are crushed to the fritter of granularity less than 12mm, after oven dry below 200 ℃, place the casting ladle bottom, with the method that pours in the bag molten steel is carried out composite inoculating and handle;
4. molten steel directly pours into casting mold, 1450 ℃～1480 ℃ of pouring molten steel temperature;
5. foundry goods quenches in oily temperature is lower than 150 ℃ oil sump behind 880 ℃～920 ℃ insulation 1h～3h, and then at 180 ℃～250 ℃ insulation 3h～8h, air cooling or stove are chilled to room temperature.
The high-boron cast steel that the present invention contains granular boride compared with prior art has following advantage:
High-boron cast steel of the present invention is to be evenly distributed on the martensitic matrix by granular boride, have hardness and intensity height, good toughness, high abrasion resistance does not rupture in the use, and use properties obviously is better than high mangaenese steel and chromium molybdenum copper steel alloy, production technique is simple, quenching temperature is low, does not contain valuable alloying element, and production cost is low.Use the high-boron cast steel that contains granular boride of the present invention can significantly improve the work-ing life of wear resisting part, prolong the wear resisting part life cycle, alleviate labor strength, have good economic and social benefit.
Description of drawings
Fig. 1 is the high-boron cast steel microstructure picture that the present invention contains granular boride.
The present invention is described in further detail below in conjunction with embodiment that principle and contriver provide.
Embodiment
The performance of alloy material is determined by metallographic structure, and certain tissue depends on chemical ingredients and thermal treatment process, the high-boron cast steel that contains granular boride of the present invention, the chemical ingredients composition and the weight percent thereof that make this high-boron cast steel are: C, 0.15%～0.45%; B, 0.75%～2.70%; Ti, 0.34%～1.50%; Cr, 0.80%～1.20%; Si, 0.50%～1.50%; Mn, 0.50%～1.50%; Ce, 0.04%～0.12%; Al, 0.08%～0.20%; Ca, 0.03%～0.10%; N, 0.01%～0.06; P＜0.05%, S＜0.05%, surplus is Fe; Wherein, B/C=5.0～6.0, B/Ti=1.8～2.2.
This theoretical foundation that contains the high-boron cast steel chemical ingredients of granular boride is to determine like this:
The main effect of C:C in high-boron cast steel be solid solution in matrix, improve hardenability, the hardening capacity of matrix, improve the wear resistance of cast steel.C content is low excessively, is prone to the perlite and the ferrite of soft in the quenching structure, and the C too high levels is prone to the bigger high carbon martensite of fragility, selects C content 0.15%～0.45%, and the back of quenching easily obtains obdurability and the good lath martensite tissue of wear resistance.Therefore C content is controlled at 0.15%～0.45% in the cast steel.
B:B is the main alloy element in the high-boron cast steel, mainly is in order to obtain the boride of high rigidity, to improve the cast steel wear resistance.In addition, a small amount of B solid solution can improve the hardenability and the hardening capacity of cast steel in matrix.The B add-on is very few, and boride quantity is few in the cast steel, wears no resistance, and add-on is too much, and boride quantity obviously increases, and cast steel fragility increases, and takes all factors into consideration B content is controlled at 0.75%～2.70%.
Ti:Ti adds in the high-boron cast steel, and Ti+2B=TiB takes place
2Reaction forms blocky TiB
2, the improvement that promotes iron boron compound form and distribution is had a significant effect, help improving the mechanical property of high-boron cast steel.The Ti add-on is too much, will thick block TiB occur
2, reduce the intensity and the toughness of high-boron cast steel on the contrary, take all factors into consideration Ti content is controlled at 0.34%～1.50%.
Cr:Cr part in high-boron cast steel enters boride, part enters matrix, improve the hardening capacity and the temper resistance of cast steel, the Cr add-on very little, and is not obvious to the high-boron cast steel influence, add-on is too much, can occur containing the Cr carbide, matrix C content is reduced, reduce the hardening capacity and the hardenability of matrix, take all factors into consideration, Cr content is controlled at 0.8%～1.2%.
Si:Si is non-carbide and boride forming element, mainly dissolves in matrix in high-boron cast steel, has the effect of the matrix of reinforcement, and the Si add-on is too much, and matrix is become fragile, and therefore its content is controlled at 0.50%～1.50%.
Mn:Mn is the element that enlarges the γ phase region, Mn enters the boride except part in high-boron cast steel, mainly be dissolved in matrix, obviously improve high-boron cast steel hardening capacity, when the Mn add-on was too much, retained austenite obviously increased in the quenching structure, reduced the high-boron cast steel wear resistance on the contrary, take all factors into consideration, Mn content is controlled at 0.50%～1.50%.
Ce:Ce easily with molten steel in remaining oxygen reaction, formation CeO
2, CeO
2Fusing point is up to 2397 ℃, (001)
γ-Fe 
Forming core dot matrix mismatch is low on the face, CeO
2Heterogeneous core during as the austenite crystallization is effective, promotes the austenite forming core, refinement primary austenite and eutectic austenite.When causing eutectic reaction, the growth of boride is suppressed, and the suspension that promotes boride is with isolated.In addition, Ce is a surface active element, easily be enriched in the process of setting boride around, stop boride to be grown up along crystal boundary, make the boride refinement, suitable add-on is 0.04%～0.12%.
Al:Al is a kind of active element, and easy and Ce and oxygen reaction generate CeAlO
3CeAlO
3Fusing point is up to 2050 ℃, (001)
γ-Fe 
Forming core dot matrix mismatch is low on the face, CeAlO
3Heterogeneous core during as the austenite crystallization is effective, promotes the austenite forming core, refinement primary austenite and eutectic austenite.When causing eutectic reaction, the growth of boride is suppressed, and the suspension that promotes boride is with isolated, and suitable add-on is 0.08%～0.20%.
Ca:Ca easily with steel in remaining sulphur combine generation CaS.The CaS fusing point is up to 2525 ℃, and CaS is effective as the heterogeneous core of eutectic boride, and boride depends on CaS symbiosis growth, promotes the formation of boride particle.Suitable add-on is 0.03%～0.10%.
N:N adds in the high-boron cast steel easily and the Ti chemical combination in the steel generates dystectic TiN, and has very low mismatch between TiN and γ-Fe lattice, therefore intensive promotes forming core, can become crystallization nuclei, make the as cast condition grain refining, the refinement and being evenly distributed that help boride, suitable add-on is 0.01%～0.06%.
Inevitably trace impurity is to bring in the raw material, and P and S are wherein arranged, and all is harmful elements, and intensity, toughness and wear resistance in order to guarantee high-boron cast steel are controlled at P content below 0.05%, and S content is controlled at below 0.05%.
The thermal treatment of high-boron cast steel mainly is in order to obtain the good martensitic matrix of wear resistance, and high-temperature heat treatment also helps promoting the granulating of boride.
The quenching temperature of high-boron cast steel of the present invention is chosen in 880 ℃～920 ℃.Quenching temperature is low excessively, the homogeneity that element such as the few and carbon of elements such as dissolved boron, chromium, manganese, chromium distributes in austenite in the high temperature austenite is relatively poor, austenitic whole hardening capacity is low, has the pearlitic structure of part soft in the quenching structure, reduces the high-boron cast steel wear resistance.Quenching temperature is too high, and the high temperature austenite alligatoring causes quenching structure thick.And quenching temperature is too high, also is prone to the retained austenite of soft in the quenching structure.In addition, quenching temperature is too high, and the thermal treatment energy consumption increases, and heat treatment cycle prolongs, and the heat treatment heating furnace lost of life causes the thermal treatment cost of high-boron cast steel to increase.After high-boron cast steel is selected 880 ℃～920 ℃ insulation 1-3h, in oily temperature is lower than 150 ℃ oil sump, quench, can obtain to inlay on the martensitic matrix complex tissue of granular boride, make material have good obdurability and wear resistance.After high-boron cast steel quenched, at 180-250 ℃ of insulation 3-8h, air cooling or stove were chilled to room temperature, mainly are for stabilizing tissue, eliminate quenching stress subsequently.
Below be the specific embodiment that the contriver provides:
Embodiment 1:
The high-boron cast steel that the present invention contains granular boride is with 500 kilograms of acid medium-frequency induction furnace meltings, and its manufacturing technology steps is:
1. with ordinary scrap steel, the pig iron and the fusing of ferrochrome Hybrid Heating, the molten clear back of molten steel adds ferrosilicon and ferromanganese, adds ferro-boron and ferrotianium before coming out of the stove;
2. the stokehold is adjusted to branch and temperature is risen to 1620 ℃ after qualified, adds silicon-calcium alloy pre-deoxidation, then uses aluminium final deoxygenation and microalloying, comes out of the stove then;
3. cerium base rare earth and nitrogenous substances are crushed to the fritter of granularity less than 12mm, after oven dry below 200 ℃, place the casting ladle bottom, with the method that pours in the bag molten steel is carried out composite inoculating and handle;
4. molten steel directly pours into casting mold, 1465 ℃ of pouring molten steel temperature;
5. foundry goods quenches in oily temperature is lower than 150 ℃ oil sump behind 900 ℃ of insulation 2h, and then at 230 ℃ of insulation 5h, air cooling is to room temperature.
The chemical composition that the present invention contains the high-boron cast steel of granular boride sees Table 1, and its mechanical property sees Table 2.
Table 1 high-boron cast steel chemical ingredients (weight %)
| Element | C | B | Ti | Cr | Si | Mn | Ce | Al |
| Composition | 0.22 | 1.26 | 0.59 | 1.15 | 0.78 | 1.20 | 0.08 | 0.11 |
| Element | Ca | N | P | S | B/C | B/Ti | Fe | |
| Composition | 0.07 | 0.04 | 0.037 | 0.025 | 5.73 | 2.14 | Surplus |
Table 2 high-boron cast steel mechanical property
| Hardness HRC | Tensile strength MPa | Impelling strength kJ/m 2 | Fracture toughness property MPa.m 1/2 |
| 56.7 | 1104.5 | 273.2 | 41.6 |
Embodiment 2:
The high-boron cast steel that the present invention contains granular boride is with 1000 kilograms of alkaline medium-frequency induction furnace meltings, and its manufacturing technology steps is:
1. with ordinary scrap steel, the pig iron and the fusing of ferrochrome Hybrid Heating, the molten clear back of molten steel adds ferrosilicon and ferromanganese, adds ferro-boron and ferrotianium before coming out of the stove;
2. the stokehold is adjusted to branch and temperature is risen to 1593 ℃ after qualified, adds silicon-calcium alloy pre-deoxidation, then uses aluminium final deoxygenation and microalloying, comes out of the stove then;
3. cerium base rare earth and nitrogenous substances are crushed to the fritter of granularity less than 12mm, after oven dry below 200 ℃, place the casting ladle bottom, with the method that pours in the bag molten steel is carried out composite inoculating and handle;
4. molten steel directly pours into casting mold, 1458 ℃ of pouring molten steel temperature;
5. foundry goods quenches in oily temperature is lower than 150 ℃ oil sump behind 890 ℃ of insulation 2.5h, and then at 190 ℃ of insulation 7h, stove is chilled to room temperature.
The chemical composition that the present invention contains the high-boron cast steel of granular boride sees Table 3, and its mechanical property sees Table 4.
Table 3 high-boron cast steel chemical ingredients (weight %)
| Element | C | B | Ti | Cr | Si | Mn | Ce | Al |
| Composition | 0.38 | 1.97 | 1.04 | 0.86 | 1.23 | 0.79 | 0.11 | 0.18 |
| Element | Ca | N | P | S | B/C | B/Ti | Fe | |
| Composition | 0.09 | 0.02 | 0.040 | 0.028 | 5.18 | 1.89 | Surplus |
Table 4 high-boron cast steel mechanical property
| Hardness HRC | Tensile strength MPa | Impelling strength kJ/m 2 | Fracture toughness property MPa.m 1/2 |
| 58.6 | 1072.8 | 266.4 | 38.7 |
The present invention contains the microstructure of the high-boron cast steel of granular boride and sees Fig. 1, and its granular boride is evenly distributed on the martensitic matrix.PEL1000 impact breaker beater plate and Φ 3.8m ball grinding machine lining board have been made with the present invention, the former is used for broken cement slurry, and the latter is used to grind thermal power plant's coal dust, and is safe in utilization, reliable, improve 3-5 doubly than high mangaenese steel beater plate work-ing life, improves 2-3 doubly than chromium molybdenum copper steel alloy liner plate.
The high-boron cast steel that contains granular boride of the present invention is compared with existing high-boron cast steel following technique effect:
1. the boride that contains in the granular boride high-boron cast steel of the present invention is graininess and is evenly distributed on the good martensitic matrix of obdurability, and not only intensity and hardness are high to make high-boron cast steel, and have good toughness and wearability.
2. the granular boride high-boron cast steel that contains of the present invention distributes owing to boride becomes graininess, cause the high-boron cast steel mechanical property to increase substantially, hardness remains on 56～59HRC basis, and tensile strength reaches 1050MPa～1130MPa, and impact flexibility reaches 250～280kJ/m2, fracture toughness reaches 38～42MPa.m1/2。
3. of the present invention to contain granular boride high-boron cast steel quenching temperature low, can reduce the heat treatment energy consumption, the shortening heat treatment cycle.
4. the granular boride high-boron cast steel that contains of the present invention does not contain the precious alloy element, melting, casting and Technology for Heating Processing are easy, low production cost, for the manufacture of the anti impact wear-proof parts, such as impact breaker beater plate, ball grinding machine lining board etc., safe and reliable, obviously improve than materials such as potassium steel commonly used, low-alloy steel service life.
Claims (2)
1. a high-boron cast steel that contains granular boride is characterized in that the chemical ingredients composition and the weight percent thereof that make this high-boron cast steel are: C, 0.15%～0.45%; B, 0.75%～2.70%; Ti, 0.34%～1.50%; Cr, 0.80%～1.20%; Si, 0.50%～1.50%; Mn, 0.50%～1.50%; Ce, 0.04%～0.12%; Al, 0.08%～0.20%; Ca, 0.03%～0.10%; N, 0.01%～0.06%; P＜0.05%, S＜0.05%, surplus is Fe; Wherein, B/C=5.0～6.0, B/Ti=1.8～2.2.
2. the described manufacture method that contains the high-boron cast steel of granular boride of claim 1 adopts electric furnace production, it is characterized in that its processing step comprises:
1. with ordinary scrap steel, the pig iron and the fusing of ferrochrome Hybrid Heating, the molten clear back of molten steel adds ferrosilicon and ferromanganese, adds ferro-boron and ferrotianium before coming out of the stove;
2. the stokehold is adjusted to branch and temperature is risen to 1580 ℃～1640 ℃ after qualified, adds silicon-calcium alloy pre-deoxidation, then uses aluminium final deoxygenation and microalloying, comes out of the stove then;
3. cerium base rare earth and nitrogenous substances are crushed to the fritter of granularity less than 12mm, after oven dry below 200 ℃, place the casting ladle bottom, with the method that pours in the bag molten steel is carried out composite inoculating and handle;
4. molten steel directly pours into casting mold, and the pouring molten steel temperature is 1450 ℃～1480 ℃;
5. foundry goods quenches in oily temperature is lower than 150 ℃ oil sump behind 880 ℃～920 ℃ insulation 1h～3h, and then at 180 ℃～250 ℃ insulation 3h～8h, air cooling or stove are chilled to room temperature and get final product.
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| CA2997367C (en) | 2015-09-04 | 2023-10-03 | Scoperta, Inc. | Chromium free and low-chromium wear resistant alloys |
| CN107653422B (en) * | 2017-09-04 | 2019-12-24 | 西安交通大学 | High-boron iron-based wear-resistant alloy layer and method for preparing composite wear-resistant part |
| AU2019363613A1 (en) | 2018-10-26 | 2021-05-20 | Oerlikon Metco (Us) Inc. | Corrosion and wear resistant nickel based alloys |
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| RU2068020C1 (en) * | 1992-08-10 | 1996-10-20 | Юлия Алексеевна Щепочкина | Cast alloy having high content of boron |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2068020C1 (en) * | 1992-08-10 | 1996-10-20 | Юлия Алексеевна Щепочкина | Cast alloy having high content of boron |
| CN1624180A (en) * | 2004-12-15 | 2005-06-08 | 宁波浙东精密铸造有限公司 | High boron foundry iron base anti-wear alloy and its heat treatment method |
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