CN1024689C - Composite additive of anticorrosion, antiwear cast iron - Google Patents

Composite additive of anticorrosion, antiwear cast iron Download PDF

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Publication number
CN1024689C
CN1024689C CN 90106133 CN90106133A CN1024689C CN 1024689 C CN1024689 C CN 1024689C CN 90106133 CN90106133 CN 90106133 CN 90106133 A CN90106133 A CN 90106133A CN 1024689 C CN1024689 C CN 1024689C
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China
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iron
cast iron
corrosion
antimony
rare earth
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CN 90106133
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CN1062005A (en
Inventor
韩绍昌
龚建森
盛志云
洪首宗
朱士鎏
刘东初
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Xiangdong chemical machinery factory
Hunan University
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Xiangdong chemical machinery factory
Hunan University
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Abstract

The present invention relates to a composite additive for corrosion resistant and wear resistant cast iron, which is composed of antimony, tin, copper, rare earth (mainly cerium), barium, calcium, silicon, iron, etc. 0.8 to 1.6% of compound additive is added to molten cast iron, and iron castings with performance of corrosion resistance and wear resistance can be produced. The use of the present invention is convenient, and the present invention is suitable for producing pump valves, pipelines, and other equipment components, which have the advantages of corrosion resistance and wear resistance.

Description

Composite additive of anticorrosion, antiwear cast iron
The present invention is relevant a kind of corrosion-proof wear cast iron composite additive.
At present, one of most effectual way of making anticorrosive wear-resistant damage ironcasting is to add alloying element in cast iron.Use maximum alloying elements that chromium, nickel, molybdenum, nitrogen, vanadium, copper, tungsten, aluminium, zirconium, silicon etc. are arranged.These element majorities can form the compound of high rigidity with the carbon in the cast iron, thereby improve wear resisting property; The chemical property that then improves cast iron that has or form fine and close protective membrane in Iron Casting Surface, thus corrosion resistance nature improved.As European patent EP 0272788A 1, promptly in hypoeutectic cast iron solution, add titanium, vanadium or the molybdenum of 0.3-0.8%, improve the abrasion resistance and the comprehensive mechanical performance of cast iron.This method mainly forms carbide by titanium, vanadium or molybdenum, and must heat-treat, but can not improve the corrosion resistance nature of foundry goods.European patent EP 0141966A and for example 1Then be before cast or when cast adds the powdered alloy of being made up of nickel 85%, silicon 10%, copper 3% or nickel 94%, boron 3% and silicon 3% in molten iron, form anti-corrosion layer in Iron Casting Surface, this kind method only is applicable to spun cast pipe, otherwise is difficult to obtain promising result.1988 the 15th volume second phases of Hunan University's journal have been delivered one piece of " elements such as antimony, tin are to iron machine and effect on corrosion " paper.It is the acid medium-frequency induction furnace melting base iron of 150kg that this article has been reported with capacity, comes out of the stove for 1480 ℃, and the stokehold also adds in the casting ladle after toasting with the quantitative molten iron of platform scale, alloying element weighing.The alloying element that adds is tin, antimony and copper, rare earth, and antimony and copper adopt the form of master alloy to add, and they add respectively in the molten iron, investigate single-element then to the machinery of cast iron and the influence of corrosion resisting property.The composition of base iron is a carbon 3.61%, silicon 1.17%, and manganese 0.61%, sulphur 0.03%, phosphorus 0.037%, surplus is an iron.Wherein, tin content is lower than at 0.4% o'clock, promotes the generation of cast iron Medium pearlite and improves mechanical property, can significantly reduce cast iron at H 2SO 4, the corrosion speed in HCl and the NaOH medium, and high more its effect of tin content is remarkable more.Antimony is the strongest to the influence of the mechanical property of cast iron and corrosion resisting property, and along with the increase of antimony content, cast iron is in acid, alkaline media, and particularly the corrosion resisting property in the HCl of different concns solution significantly improves, but the intensity of cast iron then linearly descends.Antimony content is higher than after 0.1%, every increase 0.1%Sb, and the bending strength value of cast iron just reduces 30MPa.Copper can improve the mechanical property and the corrosion resisting property of cast iron, and the disadvantageous effect that suppresses antimony weakening cast iron intensity is had certain effect.When the residual quantity of cast iron middle-weight rare earths was lower than 0.014% threshold value, the mechanical property and the corrosion resisting property of cast iron improved.The 15th volume third phase of Hunan University's journal has been delivered another piece of writing " experimental study of New Type Low-Alloy Corrosion Resistant Cast Iron " paper, this article is on above-mentioned basis to single alloying element test, select No. one rare earth, aluminium, four factors of tin and copper and antimony alloy, add in the casting ladle in advance together, the molten iron tapping temperature is 1450~1500 ℃, teeming temperature is 1320~1350 ℃, the cast alloy iron that is obtained is based on metallic element antimony, be aided with copper, element such as tin and rare earth carries out composite alloying and forms, excellent corrosion-proof performance not only, and can stablize the acquisition higher mechanical properties.It is abundant to produce the employed alloy element resource of this kind cast alloy iron simultaneously, and consumption is few, and production technique is easy, and starting material are not had particular requirement, easily applies.But when producing this cast alloy iron, each alloying element all is after accurate weighing, adds respectively in the casting ladle again, and formality is loaded down with trivial details, and does not provide the content range of each alloying element in this article, therefore, is restricted when practical application.
The object of the present invention is to provide a kind of corrosion-proof wear cast iron composite additive, when producing ironcasting,, can obtain excellent corrosion-proof performance as long as certain quantity of additive is joined in the molten iron, the corrosion-proof wear cast iron that mechanical property is higher, and use very convenient.
Feature of the present invention is to comprise copper 25.0-38.0%, tin 15.0-24.0%, antimony 9.5-19.0%, rare earth 2.6-5.0%, silicon 10.0-25.0%, and surplus is iron and unavoidable impurities element.It is characterized in that also comprising barium 0.0-1.6%, calcium 0.0-0.5%.It is characterized in that rare earth selects that to contain the light rare earths cerium be main for use, its total amount is lower than 25% rare earth 24 or 1 #Rare earth alloy.Implement when of the present invention, must choose the raw material of each alloying element, copper adopts electrolytic copper, No. three or No. four standard coppers; Antimony and Xi Ze select for use respectively No. three or No. four industrial antimony and tin (be Sb-3, Sb-4, Sn-3, Sn-4); Rare earth selects that to contain the light rare earths cerium be main for use: its total amount is lower than 25% rare earth 24 or 1 #Rare earth alloy; Barium and calcium are selected the Ba-Ca alloy that contains of domestic ferroalloy works production for use, as HB type Ba-Ca alloy; Silicon and iron is because of containing in rare earth and the Ba-Ca alloy, and can guarantee its content requirement, therefore do not need other adding.During melting, choose smelting furnace earlier, as cokew-fired crucible furnace, fuel oil crucible oven, electrical crucible etc.Preferably select induction furnace for use, its easy to operate, easy control.After determining the fusing stove and accessory, prepare the consumption of each alloying element by the composition scope, earlier copper is placed the fusing that heats up in the stove, treat that copper is molten clear and heat up after the alloy of baric calcium is added, add antimony and tin then, add rare earth alloy at last and stir, after treating that temperature rises to 1050-1100 ℃, left standstill 5-8 minute, and took the oxidation sludge on the liquid level off, pour into strip or block getting final product.
When the present invention was used for making the corrosion-proof wear ironcasting, the chemical ingredients that base iron is suitable is: carbon 2.9-3.8%, silicon 1.4-2.4%, manganese≤0.8%, sulphur≤0.15%, phosphorus≤0.20%, surplus were iron, and control molten iron tapping temperature is higher than 1380 ℃.Molten iron temperature is low excessively, will be unfavorable for that the dissolving of additive absorbs, and too highly will increase unnecessary energy consumption.The consumption of additive is for handling the 0.8-1.6% of iron water amount, and is not remarkable to the effect that improves foundry goods corrosion-proof wear performance when consumption is lower than 0.8%, is higher than 1.6%, though favourable to the corrosion-proof wear performance that improves foundry goods, may damage the comprehensive mechanical performance of foundry goods.The method of handling molten iron is: earlier additive is broken into the particle of diameter 3-10 millimeter, and is baked to 200-400 ℃ and removes moisture content, go out molten iron before, additive is added casting ladle bottom, gone out molten iron after, need not stir, leave standstill a little, take off removing dross, add that thermal-insulating covering agent is promptly pourable.
The contained alloying element of the present invention role in cast iron can be divided into two classes.One class is to promote the cast iron perlite to form strongly, makes cast iron obtain the fine and closely woven pearlite matrix of homogeneous under as-cast condition, and simultaneously, they are dissolved in the matrix, and the corrosion resistance nature that improves ironcasting is played conclusive effect, and this dvielement has antimony, tin, copper.
Antimony is a kind of ferocious perlite stablizer, and its effect is stronger one times than tin, and is then stronger 100 times than copper, and this is because during eutectoid transformation, antimony has stoped carbon atom further separating out on graphite crystal nucleus.Antimony is because the effect of high chemical stability of self and raising foundry goods overpotential of hydrogen evolution improves the acidproof seawater corrosion resistance ability of ironcasting greatly.But when antimony content is higher in the cast iron, may seriously undermine intercrystalline bonding force, ironcasting fragility is increased, mechanical property descends; Antimony content is low excessively, does not then have the effect that improves ironcasting corrosion-proof wear performance.Therefore, antimony content is controlled to be 9.5-19.0% in the additive.
Tin has antimony and similarly acts on.Tin is when eutectic solidification, and expanding equilibrium and non-equilibrium eutecticum transition temperature interval help graphite and form, and during eutectoid transformation, hinders then that carbon spreads on graphite in the austenite, promotes perlite to generate.In the certain limit, there is not the problem that the foundry goods mechanical property is descended in tin, so the content of tin can be above the content of antimony in the foundry goods, therefore, the content of tin is 15.0-24.0% in the additive.
Copper is dissolved in the cast iron matrix, has both improved mechanical property, improve anticorrosive wear-resistant again and decrease performance, and copper also have in and antimony effect that ironcasting is had a negative impact.Therefore the content of copper is 25.0-38.0% in the additive.
In addition, in strong corrosive medium, antimony, tin and copper all have in cast(ing) surface deposition, the effect that corrosion mitigation takes place.
Another kind of element of the present invention is rare earth cerium, barium, calcium and silicon, and this dvielement mainly plays rotten and purifying molten iron.
Cerium in the rare earth can with the impurity element chemical combination such as sulphur in the molten iron, generation contains the compound of cerium, remove the detrimental impurity in the molten iron on the one hand, on the other hand, these compounds also may play graphite nuclei, improve the tissue of cast iron, improve mechanical property, therefore, the content of additive middle-weight rare earths is 2.5-5.0%.
Barium and calcium have the identical effect of cerium in the rare earth.As barium, when calcium exists, the effect of cerium is strengthened, and the content of cerium can reduce.Cerium, barium and calcium all have and overcome antimony produces harmful effect to foundry goods effect.The content of this dvielement is unsuitable too high in the foundry goods, otherwise also can destroy the mechanical property and the corrosion resisting property of foundry goods.Therefore, the content of additive middle-weight rare earths is no more than 5.0%, and the content of barium and calcium is respectively 0.0-1.6% and 0.0-0.5%.
Silicon is a main inoculation(effect) in cast iron, also works to adjust additive component simultaneously.Therefore, the content of silicon is 10.0-25.0% in the additive.
The abundant raw material of the alloying element that the present invention is selected, Additive Production technology is easy, and consumption is few.When particularly producing anticorrosive wear-resistant damage ironcasting with composite additive, the cast iron melting work simplification neither needs the adding of back stove batching time control alloyage element, has also removed numerous and diverse operation of forehearth weighing respectively, fragmentation, baking and the various alloying elements of adding from.During use, only need in proportion with the additive fragmentation, suitably once to add in the casting ladle after the baking and just can finish, needn't worry the dissolving and the absorption of additive according to handling what of iron water amount.Like this, the operation of forehearth and back stove is all greatly simplified, and uses very convenient.And the ironcasting of producing, stable mechanical performance not only, simultaneously, also have excellent anticorrosive wear-resistant and decrease performance, and can be widely used in the equipment unit of working under pump, valve, pipeline and other the corrosion and the abrasive conditions of media such as contact high-concentration sulfuric acid, city and industrial sewage, pit water, seawater.
Embodiment 1: for guaranteeing that the contained alloying element of additive in specialized range, adopts 8.5 kilograms of electrolytic coppers, and 3 kilograms in No. three antimony, 6.5 kilograms in No. four tin, 7.0 kilograms of rare earth alloies, 4.0 kilograms of HB type Ba-Ca alloys.Adopt the fuel oil crucible oven, No. 50 plumbago crucible fusings.Earlier crucible is cleaned out and preheating, put into electrolytic copper intensification fusing subsequently, the molten clear follow-up temperature of continuing rising of copper.Add Ba-Ca alloy then, stir and to make it evenly to add antimony and tin, a rare earth with fragmentation and preheating adds at last, fully stirs, and continues to heat up up to all molten clear, leaves standstill about 5 minutes, takes off removing dross, comes out of the stove to pour into ingot bar and get final product.
Embodiment 2: adopt 50 kilograms of electrolytic coppers, 25 kilograms of No. four antimony and Xi Ge, 20 kilograms of rare earth alloies (R24), 20 kilograms of HB type Ba-Ca alloys.The fuel oil crucible oven, No. 200 plumbago crucible fusings.Elder generation cleans out crucible and preheating, subsequently electrolytic copper is put into crucible intensification fusing, after copper melts clearly, continue to heat up, add Ba-Ca alloy then, stir and make it evenly adding antimony and tin, the rare earth alloy that will be broken into 10 millimeter and preheating at last adds, fully stir, when being warming up to 1100 ℃, left standstill 5 minutes, take off removing dross, coming out of the stove pours into strip and bulk.
Embodiment 3: processed molten iron chemical ingredients is: carbon 3.46%, and silicon 1.98%, manganese 0.77%, phosphorus 0.19%, sulphur 0.10%, surplus is an iron.Get composite additive of the present invention by above-mentioned process operations by 1.45% of processing weight of molten iron.Every performance comparison of cast iron is as follows before and after handling:
Project mechanical property corrosion resistance nature (corrosion rate g/m 2H)
Tensile strength hardness
50℃,65%H 2SO 420℃,3%NaCl
State (MPa) (HB)
Handle preceding 188 209 2.988 0.1732
Handle back 219 229 1.719 0.0988
Embodiment 4: when using the present invention to make the charcoal ink factory with the suction bend pipe, adopt 1.5T/h four joint stove molten iron to make.1390 ℃ of molten iron tapping temperatures, the molten iron chemical ingredients is: carbon 3.41%, silicon 2.10%, manganese 0.78%, sulphur 0.15%, phosphorus 0.14%, surplus is an iron, handles 500 kilograms of iron water amounts, green casting with 5 kilograms of composite additives of the present invention, is broken into diameter 3-10 mm granules, moisture content is removed in preheating, puts into casting ladle bottom, gone out molten iron after, leave standstill a little, take off removing dross, add the perlite powder insulation, 1300 ℃ of cast were produced the suction bend pipe cycle of operation above 1 year, exceeded more than one times than former weldless steel tube.

Claims (3)

1, a kind of corrosion-proof wear cast iron composite additive is characterized in that comprising copper 25.0-38.0%, tin 15.0-24.0%, antimony 9.5-19.0%, rare earth 2.6-5.0%, silicon 10.0-25.0%, and surplus is iron and unavoidable impurities element.
2, a kind of corrosion-proof wear cast iron composite additive according to claim 1 is characterized in that also comprising barium 0.0-1.6%, calcium 0.0-0.5%.
3, according to claim 1 or 2 described a kind of corrosion-proof wear cast iron composite additives, it is characterized in that rare earth selects that to contain the light rare earths cerium be main for use, its total amount is lower than 25% rare earth 24 or 1 #Rare earth alloy.
CN 90106133 1990-12-07 1990-12-07 Composite additive of anticorrosion, antiwear cast iron Expired - Fee Related CN1024689C (en)

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Application Number Priority Date Filing Date Title
CN 90106133 CN1024689C (en) 1990-12-07 1990-12-07 Composite additive of anticorrosion, antiwear cast iron

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Application Number Priority Date Filing Date Title
CN 90106133 CN1024689C (en) 1990-12-07 1990-12-07 Composite additive of anticorrosion, antiwear cast iron

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CN1062005A CN1062005A (en) 1992-06-17
CN1024689C true CN1024689C (en) 1994-05-25

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100365149C (en) * 2005-07-25 2008-01-30 河南禹王水工机械有限公司 Seawater corrosion resistant alloy cast iron

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115069968B (en) * 2021-03-10 2023-05-23 西南科技大学 Green casting sand, environment-friendly carbonaceous additive and preparation process thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100365149C (en) * 2005-07-25 2008-01-30 河南禹王水工机械有限公司 Seawater corrosion resistant alloy cast iron

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