CN1876877A - Nano composite ceramic additive for thermostable steel and preparation process thereof - Google Patents
Nano composite ceramic additive for thermostable steel and preparation process thereof Download PDFInfo
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- CN1876877A CN1876877A CN 200610046522 CN200610046522A CN1876877A CN 1876877 A CN1876877 A CN 1876877A CN 200610046522 CN200610046522 CN 200610046522 CN 200610046522 A CN200610046522 A CN 200610046522A CN 1876877 A CN1876877 A CN 1876877A
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Abstract
The invention relates to a nanometer composite ceramic additive used in refractory steel and its preparation technology, in which the said additive is prepared with ceramic powder, low-melting point metal and highdensity metal; in which the ceramic powder consists of nano aluminum oxide, titanium oxide and other metallic oxides and their total weight is 10-25 % of the total additive weight; the low-melting point metal consists of one of aluminium, titanium and magnesium or multiple elements mixed according to any ratio by weight and the low-melting point metal weight is 5-18 % of the total additive weight; the highdensity metal consists of one of chromium, manganese, plumbum and zinc or multiple elements mixed according to any ratio by weight and the low-melting point metal weight is 57-85 % of the total additive weight. The preparation technology is as follows: dispersing the nano ceramic powder into single grain layer state and adding them into absolute ethyl alcohol solution to prepare slip, adding the low-melting point metal and the highdensity metal into the slip and evenly stirring with agitator, burning after dehumidification, finally obtaining the additive. It can substitute noble-metal- nickel to prepare heat resisting steel.
Description
One, technical field: the present invention relates to a kind of nano composite ceramic additive and preparation technology thereof that high temperature steel is used that prepare, particularly a kind of high temperature steel, the new additive agent that substitutes original precious metal nickel and its preparation method of being used for.
Two, background technology: the high temperature steel foundry goods plays an important role in fields such as thermal power plant boiler, high-temperature electric resistance furnaces.Heat resisting cast steel all needs to add the nickel metal of 6～35% (weight percents).Nickel is the aircraft engine strategic resource, and non-renewable, and a large amount of uses of civilian industry will be accelerated the spending rate of nickel resources; And because nickel metal price costliness (about 160,000 yuan/ton), be used in and cause cost to increase on the civilian industry, enterprise profit significantly reduces.
Three, summary of the invention:
1, goal of the invention: the invention provides a kind of nano composite ceramic additive for thermostable steel and preparation technology thereof, its objective is and solve the nickel metal that traditional high temperature steel foundry goods need add 6～35% weight percents, but nickel metal price costliness has increased the cost of product, also accelerates the problem of aspects such as the spending rate existence of nickel resources.
2, technical scheme: the present invention is achieved through the following technical solutions:
A kind of nano composite ceramic additive for thermostable steel is characterized in that: this additive is formed by ceramic powder, low melting point metal, high desnity metal combined preparation; Wherein ceramic powder is by nano level Al
2O
3, TiO
2And other metal oxide forms, their weight and account for 10～25% of additive gross weight; Low melting point metal is that one or more elements in aluminium, titanium, the magnesium mix by any part by weight, and the weight of low melting point metal accounts for 5～18% of additive gross weight; High desnity metal is mixed by any part by weight by one or more elements in chromium, manganese, lead, the zinc, and the weight of high desnity metal accounts for 57～85% of additive gross weight.
Nano level Al in the ceramic powder
2O
3And TiO
2The weight sum account for 6～21% of ceramic powder gross weight; Other metal oxide is MgO, Cr
2O
3And ZrO
2, to press arbitrary proportion between the three and mix, its gross weight accounts for 79～94% of ceramic powder gross weight.
The density that makes additive is 5.03～6.19g/cm
3, fusing point is 1450～15lO ℃.
A kind of preparation technology of nano composite ceramic additive for thermostable steel is characterized in that: this preparation technology is undertaken by following step: get each raw material according to the above ratio, at first with the nano level Al in the ceramic powder
2O
3, TiO
2Be dispersed into the single particle state, join together with other metal oxide and to be prepared into slip in the ethanol solution, low melting point metal is joined in the slip of preparation, add high desnity metal again, stir with stirrer then, churning time 6～24 hours, dry back sintering promptly gets nano composite ceramic additive for thermostable steel of the present invention.
Slip after above-mentioned the stirring is sloughed partial solvent make mud cake, dry back sintering; Or, be pressed into block back sintering with dry-pressing formed method directly with the slip oven dry; Finish under the gas shield condition during sintering, the gas of protection usefulness is argon gas or nitrogen, and sintering temperature is 1000～1350 ℃, is incubated 30～240 minutes.3, advantage and effect: by the enforcement of technical solution of the present invention, can solve the nickel metal that traditional high temperature steel foundry goods need add 6～35% weight percents well, but nickel metal price costliness has increased the cost of product, also accelerates the problem of aspects such as the spending rate existence of nickel resources.
The present invention adopts cheap material to make additive, and the precious metal nickel that adds during its alternative preparation high temperature steel both can be saved strategic resource, can be the high temperature steel castings production producer increase benefit that reduces cost again.The present invention utilizes ceramic powders such as nano aluminium oxide, zirconium white, magnesium oxide, titanium oxide and chromic oxide, carries out compoundly with other metal powder materials, makes nano composite ceramic additive and adds in the high temperature steel, substitutes precious metal nickel.
Confirm that by experiment prepared additive is used on the heat-resistant casting steel, the thermotolerance of steel casting surpasses the workpiece that added nickel originally, and welding property is good, and the thermotolerance of commissure is identical with the thermotolerance of mother metal, save rare metal resources, reduced the high temperature steel product cost.
Four, embodiment:
The objective of the invention is to study a kind of nano composite ceramic additive material, make it to have fusing point and the density close with high temperature steel.After molten steel fusing, this additive is added and be fused in the high temperature steel, can cast subsequently.Precious metal nickel with in the additive replacement high temperature steel had both kept the original resistance toheat of high temperature steel, had greatly reduced the cost of high temperature steel again, saved rare metal resources.In research process, must solve three major issues: the one, the fusing point of additive must be close with the fusing point of high temperature steel, if fusing point difference is excessive, additive can't fully fuse, and will form component segregation, and is unfavorable to improving thermotolerance.The 2nd, the density of additive must be close with the density of high temperature steel, if density has big difference, additive floats at molten steel surface, is difficult to fuse in the molten steel, can't play and improve stable on heating effect.The 3rd, all constituent elements of additive all can not influence the processing performance of high temperature steel, if melting or casting cycle are produced detrimentally affect, high temperature steel manufacturer just is unwilling to use, and will influence the popularization of this product.
The present invention is a kind of nano composite ceramic additive for thermostable steel, and this additive is formed by ceramic powder, low melting point metal, high desnity metal combined preparation; The Al that wherein comprises nano level or submicron order in the ceramic powder
2O
3, TiO
2With other metal oxide, their weight sum accounts for 10～25% of additive gross weight, nano level Al in the ceramic powder
2O
3And TiO
2The weight sum account for 6～21% of ceramic powder gross weight, metal oxide is MgO, Cr
2O
3And ZrO
2Combine their weight and account for 79～94% of ceramic powder gross weight by any weight ratio; Low melting point metal is mixed by any part by weight by one or more elements in aluminium, titanium, the magnesium, and the weight of low melting point metal accounts for 5～18% of additive gross weight; High desnity metal is mixed by any part by weight by one or more elements in chromium, manganese, lead, the zinc, and the weight of high desnity metal accounts for 57～85% of additive gross weight.
The preparation technology of nano composite ceramic additive for thermostable steel of the present invention, this preparation technology is undertaken by following step: get each raw material according to the above ratio, at first with the nano level Al in the ceramic powder
2O
3And TiO
2Be dispersed into single particle state and other metal oxide and join together and be prepared into slip in the ethanol solution, low melting point metal is joined in the slip of preparation, add high desnity metal again, stir churning time 6～21 hours, dry back sintering then with stirrer; Finish under the gas shield condition of argon gas or nitrogen during sintering, sintering temperature is 1000～1350 ℃, is incubated 30～240 minutes, promptly gets nano composite ceramic additive for thermostable steel of the present invention.Slip after above-mentioned the stirring can be sloughed partial solvent and make mud cake, dry back sintering; Also can be pressed into block back sintering with dry-pressing formed method directly with the slip oven dry.
Embodiment 1:
A kind of nano composite ceramic additive for thermostable steel, this additive is formed by ceramic powder, low melting point metal, high desnity metal combined preparation; Wherein ceramic powder comprises nano level Al
2O
3, TiO
2With metal oxide MgO, Cr
2O
3, ZrO
2The weight sum be 500g; Al wherein
2O
3150g, TiO
2150g, MgO 80g, Cr
2O
370g, ZrO
270g; Low melting point metal is mixed by any part by weight by aluminium, titanium, each element of magnesium, and the weight of low melting point metal is 900g; High desnity metal is mixed by any part by weight by chromium, manganese, lead, each element of zinc, and the weight of high desnity metal is 3600g.
A kind of preparation technology of nano composite ceramic additive for thermostable steel is undertaken by following step: get each raw material by above-mentioned weight, at first with nano level Al in the ceramic powder
2O
3And TiO
2Be dispersed into single particle state and other metal oxide MgO, Cr
2O
3And ZrO
2Join together and be prepared into slip in the ethanol solution, successively low melting point metal aluminium, titanium, magnesium are joined in the slip of preparation, add high desnity metal chromium, manganese, lead, zinc again, stir with stirrer then, churning time 6～24 hours, dry back sintering; Sintering is finished under the gas shield condition of argon gas or nitrogen, and sintering temperature is 1000～1350 ℃, is incubated 30～240 minutes, promptly gets nano composite ceramic additive for thermostable steel of the present invention.
Embodiment 2:
A kind of nano composite ceramic additive for thermostable steel, this additive is formed by ceramic powder, low melting point metal, high desnity metal combined preparation; Nano level Al in the ceramic powder wherein
2O
3, TiO
2With metal oxide MgO, Cr
2O
3, ZrO
2The weight sum be 750g; Al wherein
2O
3200g, TiO
2200g, MgO 150g, Cr
2O
3100g, ZrO
2100g; Low melting point metal is mixed by any part by weight by aluminium, titanium, each element of magnesium, and the weight of low melting point metal is 500g; High desnity metal is mixed by any part by weight by chromium, manganese, lead, each element of zinc, and the weight of high desnity metal is 3750g.
A kind of preparation technology of nano composite ceramic additive for thermostable steel is undertaken by following step: get each raw material by above-mentioned weight, at first with nano level Al in the ceramic powder
2O
3And TiO
2Be dispersed into single particle state and other metal oxide MgO, Cr
2O
3And ZrO
2Join together and be prepared into slip in the ethanol solution, successively low melting point metal aluminium, titanium, magnesium are joined in the slip of preparation, add high desnity metal chromium, manganese, lead, zinc again, stir with stirrer then, churning time 6～24 hours, slip is sloughed partial solvent make mud cake, dry back sintering; Drying process keeps negative pressure, and sintering is finished under the gas shield condition of argon gas or nitrogen, and sintering temperature is 1000～1350 ℃, is incubated 30～240 minutes, promptly gets nano composite ceramic additive for thermostable steel of the present invention.
Embodiment 3:
A kind of nano composite ceramic additive for thermostable steel, this additive is formed by ceramic powder, low melting point metal, high desnity metal combined preparation; Nano level Al in the ceramic powder wherein
2O
3, TiO
2With metal oxide MgO, Cr
2O
3, ZrO
2The weight sum be 1250g; Al wherein
2O
3500g, TiO
2500g, MgO 100g, Cr
2O
375g, ZrO
275g; Low melting point metal is mixed by any part by weight by aluminium, titanium, each element of magnesium, and the weight of low melting point metal is 500g; High desnity metal is mixed by any part by weight by chromium, manganese, lead, each element of zinc, and the weight of high desnity metal is 3250g.
A kind of preparation technology of nano composite ceramic additive for thermostable steel is undertaken by following step: get each raw material by above-mentioned weight, at first with nano level Al in the ceramic powder
2O
3And TiO
2Be dispersed into single particle state and other metal oxide MgO, Cr
2O
3And ZrO
2Join together and be prepared into slip in the ethanol solution, successively low melting point metal aluminium, titanium, magnesium are joined in the slip of preparation, add high desnity metal chromium, manganese, lead, zinc again, stir with stirrer then, churning time 6～24 hours is pressed into block back sintering with dry-pressing formed method; Sintering is finished under the gas shield condition of argon gas or nitrogen, and sintering temperature is 1000～1350 ℃, is incubated 30～240 minutes, promptly gets nano composite ceramic additive for thermostable steel of the present invention.
Embodiment 4
The additive formulations of the present invention's preparation is as follows:
(1) add low melting point metal: aluminium, titanium, magnesium, add-on is controlled at 5～18%;
(2) add the high metal of density as chromium, manganese, lead, zinc, total add-on is 57～85%; Wherein low melting point metal total amount plumbous and zinc is 0.5～3.5%, has good thermotolerance to guarantee high temperature steel.
(3) nano-ceramic powder: Al
2O
3, TiO
2, MgO, Cr
2O
3, and ZrO
2(5Y-PSZ promptly contains 5mol Y
2O
3PSZ).Amounting to add-on is 10～25%.Wherein: Al
2O
3, Cr
2O
3Two sums are 6～21%.
Preparation technology:
According to listed moiety, utilize ultrasonic wave with nano level Al
2O
3And TiO
2After ceramic powder fully disperses, add in the PVB-ethanol solution for preparing in advance, utilize stirrer to stir, add low melting point metal aluminium, titanium, magnesium successively simultaneously, add high desnity metal chromium, manganese, lead, zinc again.Restir 6～24 hours, dry in vacuum drying oven then, drying process keeps negative pressure.Ball milling sieves then, is pressed into bulk with hydropress and particular manufacturing craft again, and sintering 90min under 1000～1350 ℃, argon shield condition promptly gets additive of the present invention.
The additive performance of the present invention that makes with above-mentioned prescription is as follows:
The acquisition additive density is 5.03～6.19g/cm
3The fusing point of additive: 1450～1510 ℃.
Join embodiment in the steel casting about additive
The using method of castingprocesses additive: in the induction furnace of 200kg, cast experiment.Other compositions of Heat resisting cast steel are identical with 1Cr33Ni9TiRe, just add additive 9%, cancelled original 9% precious metal nickel.Addition means adopts following two kinds of experiments:
Experiment one: according to normal process molten steel is melted, then additive of the present invention is added in the molten steel, through about about 5 minutes, additive melted, and molten steel is poured in the ladle cast; Sample number into spectrum is A1.
Experiment two: according to normal process molten steel is melted, the additive of the present invention after will smashing is added to the ladle bottom, then molten steel is poured in the ladle, and the additive fusing was waited for about 1 minute and can be cast this moment.Sample number into spectrum is A2.
Because casting technique remains unchanged, and satisfies the requirement of cast steel technology.
High temperature steel thermotolerance embodiment:
The experiment sample:
Three, be respectively A1, A2 and 1Cr33Ni9TiRe high temperature steel (are called for short: B).
Thermotolerance experiment: adopt following two schemes:
Test one: 1250 ℃ of oxidation 72 hours.Test two: 1300 ℃ of oxidations 36 hours.
Rate of weight loss is as shown in table 1.
The rate of weight loss of sample under two kinds of experiment conditions of table 1
| Sample | Test one rate of weight loss/% | Test two rate of weight loss/% |
| A1 | 0.7786 | 0.4657 |
| A2 | 1.2461 | 1.0208 |
| B | 3.1665 | 2.0197 |
From weightless result, the high temperature steel oxidation-resistance that adds additive is better than adding originally the high temperature steel of nickel.
Add the high temperature steel weldability EXPERIMENTAL EXAMPLE that the present invention makes additive
To use the high temperature steel sample of additive to weld experiment, adopt the argon arc welding respectively and adopt two kinds of schemes of stainless steel electrode welding.
The argon arc welding result: welding process does not ftracture, and postwelding was placed 48 hours, and cracking is not heated to 1300 ℃ and kept 36 hours, not cracking.
The stainless steel electrode welding: welding process does not ftracture, and postwelding was placed 48 hours, and cracking is not heated to 1300 ℃ and kept 36 hours, not cracking.
Therefore the additive that makes of the present invention fully alternative metals nickel as the additive use of preparation high temperature steel, the various performances of the high temperature steel that makes with it all are better than preparing high temperature steel with metallic nickel, greatly reduce the cost of high temperature steel, reduced the consumption of metallic nickel resource.
Claims (5)
1, a kind of nano composite ceramic additive for thermostable steel is characterized in that: this additive is formed by ceramic powder, low melting point metal, high desnity metal combined preparation; Wherein ceramic powder is by nano level Al
2O
3, TiO
2And other metal oxide composition, their weight sum accounts for 10～25% of additive gross weight; Low melting point metal is that one or more elements in aluminium, titanium, the magnesium mix by any part by weight, and the weight of low melting point metal accounts for 5～18% of additive gross weight; High desnity metal is mixed by any part by weight by one or more elements in chromium, manganese, iron, lead, the zinc, and the weight of high desnity metal accounts for 57～85% of additive gross weight.
2, nano composite ceramic additive for thermostable steel according to claim 1 is characterized in that: the nano level Al in the ceramic powder
2O
3And TiO
2The weight sum account for 6～21% of ceramic powder gross weight; Other metal oxide is MgO, Cr
2O
3And ZrO
2, to press arbitrary proportion between the three and mix, its gross weight accounts for 79～94% of ceramic powder gross weight.
3, nano composite ceramic additive for thermostable steel according to claim 1 is characterized in that: the density that makes additive is 5.03～6.19g/cm
3, fusing point is 1450～1510 ℃.
4, a kind of preparation technology of nano composite ceramic additive for thermostable steel is characterized in that: this preparation technology is undertaken by following step: get each raw material according to the above ratio, at first with the nano level Al in the ceramic powder
2O
3, TiO
2Be dispersed into the single particle state, join together with other metal oxide and to be prepared into slip in the ethanol solution, low melting point metal is joined in the slip of preparation, add high desnity metal again, stir with stirrer then, churning time 6～24 hours, dry back sintering promptly gets nano composite ceramic additive for thermostable steel of the present invention.
5, the preparation technology of nano composite ceramic additive for thermostable steel according to claim 4 is characterized in that: the slip after above-mentioned the stirring is sloughed partial solvent make mud cake, dry back sintering; Or, be pressed into block back sintering with dry-pressing formed method directly with the slip oven dry; Finish under the gas shield condition during sintering, the gas of protection usefulness is argon gas or nitrogen, and sintering temperature is 1000～1350 ℃, is incubated 30～240 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610046522 CN1876877A (en) | 2006-05-09 | 2006-05-09 | Nano composite ceramic additive for thermostable steel and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610046522 CN1876877A (en) | 2006-05-09 | 2006-05-09 | Nano composite ceramic additive for thermostable steel and preparation process thereof |
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| CN1876877A true CN1876877A (en) | 2006-12-13 |
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|---|---|---|---|
| CN 200610046522 Pending CN1876877A (en) | 2006-05-09 | 2006-05-09 | Nano composite ceramic additive for thermostable steel and preparation process thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732740A (en) * | 2012-06-27 | 2012-10-17 | 北京京奥泰尔新材料科技有限公司 | Nano-material interalloy modifier and preparation method thereof, and alloy preparation method |
| CN103088265A (en) * | 2011-10-28 | 2013-05-08 | 曲德毅 | High-temperature heat-resistant alloy and preparation method thereof |
| CN104264029A (en) * | 2014-10-13 | 2015-01-07 | 沈阳工业大学 | Nano composite abrasion-resistant alloy for abrasion-resistant steel and preparation technology for nano composite abrasion-resistant alloy |
-
2006
- 2006-05-09 CN CN 200610046522 patent/CN1876877A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088265A (en) * | 2011-10-28 | 2013-05-08 | 曲德毅 | High-temperature heat-resistant alloy and preparation method thereof |
| CN103088265B (en) * | 2011-10-28 | 2015-05-06 | 曲德毅 | High-temperature heat-resistant alloy and preparation method thereof |
| CN102732740A (en) * | 2012-06-27 | 2012-10-17 | 北京京奥泰尔新材料科技有限公司 | Nano-material interalloy modifier and preparation method thereof, and alloy preparation method |
| CN104264029A (en) * | 2014-10-13 | 2015-01-07 | 沈阳工业大学 | Nano composite abrasion-resistant alloy for abrasion-resistant steel and preparation technology for nano composite abrasion-resistant alloy |
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