CN100363529C - Permeation promoter for organic RE chemical heat treatment and its application - Google Patents
Permeation promoter for organic RE chemical heat treatment and its application Download PDFInfo
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- CN100363529C CN100363529C CNB200510010348XA CN200510010348A CN100363529C CN 100363529 C CN100363529 C CN 100363529C CN B200510010348X A CNB200510010348X A CN B200510010348XA CN 200510010348 A CN200510010348 A CN 200510010348A CN 100363529 C CN100363529 C CN 100363529C
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Abstract
The present invention discloses a permeation energizer for chemical heat treatment of organic rare-earth and an application thereof, which relates to a permeation energizer for chemical heat treatment and an application thereof. In order to solve the problem that rare earth chloride easily generates the malfunction of blocking a dropper in use, the present invention is composed of the following ingredients: 8 to 12 % of rare-earth elements, 5 to 8 % of tetrachloroethylene, 1 to 4 % of cyclopentadiene rare-earth, 0 to 30 % of isobutyric acid ammonium, isomerization acid and isomerization alcohol surplus according to weight percentage. The present invention is used for preparing carburizing and carbonitriding energizers. The present invention can be also composed of the following ingredients: 8 to 12 % of rare-earth elements, 5 to 8 % of tetrachloroethylene, 1 to 4 % of cyclopentadiene rare-earth, 20 to 30 % of isobutyric acid ammonium, isomerization acid and isomerization alcohol surplus, and can be used for carburization, nitrocementation, nitridation, nitrocarburizing, or Re, N, C, O, S and B co-cementation. The organic rare-earth of the present invention is easily split in a furnace, and the active rare-earth is analyzed to perform an energizing function. The organic rare-earth does not contain oxygen, and is not easily blocked, and the solubility of the organic rare-earth is better than that of chlorination rare-earth.
Description
Technical field
The present invention relates to a kind of thermo-chemical treatment energizer and application thereof.
Background technology
Carburizing accounts for 80% in the thermo-chemical treatment.Thermo-chemical treatment carburizing is at present generally formed by the carburizing agent of high carbon potential and two kinds of components of thinner of low carbon potential for ease of computer control furnace atmosphere carbon potential.Carburizing agent gas commonly used has Sweet natural gas methane and cracking of oil gas propane; Liquid then is hydrocarbon polymer, as kerosene, benzene, toluene, acetone, ethyl acetate, Virahol, ethanol etc., no matter only fully cracking when being heated to 920 ℃ of which kind of carburizing agent, could carry out controlled carburizing to furnace gas, adopt the fundamental cause of carburizing more than 920 ℃ and 920 ℃ during present conventional carburizing that Here it is.
Rare earth is owing to the singularity of the electronic structure distribution of its atom, and its electronegativity is very low, and chemically reactive is very strong, at the chemical industry catalyzer of doing commonly used.When adding in the stove jointly with carburizing agent, will promote its cracking, 860 ℃ of just fully cracking just can be carried out controlled carburizing at 860 ℃ after therefore adding rare earth, reduce to 860 ℃ by 920 ℃, but saves energy consumption, the minimizing workpiece deformation.In addition, because the activity of rare earth can be removed workpiece surface dirt and passive film, the surface reaction of activation furnace gas and workpiece surface, strengthen cementation process, quicken the infiltration of carbon atom, thereby improved infiltration rate, play the effect of oozing of significantly urging to workpiece surface, facts have proved and to improve infiltration rate 15～30%, look processing condition and difference.
Although its atomic radius of rare earth is more about 40% than iron atom,, thereby can penetrate into the upper layer of steel because the singularity that electronic structure distributes very easily produces polarization or ionization in multicomponent systems such as C, N, H, O.Research is pointed out, rare earth is as product circle, subgrain boundary, dislocation line, room etc. by the defective network in the steel, spread with monatomic or diatomic form, and it is poly-partially at these defective networks, finally in steel, form dilute solid solution, play the microalloying effect, make carbide, nitride and metallographic structure refinement, thereby play the effect that improves diffusion layer organization and performance.
Therefore, rare-earth energizer is different with other chemical energizers, and except that urging the effect of oozing, the effect that improves infiltration layer microtexture and performance is played in the microalloying effect of oozing altogether in addition.This be with other energizer features on basic difference.
Mainly use in the rare earth catalytic cementation technology in the past and be the mixed chlorinated rare earth of main body or La, the Ce rare earth of simple substance with La, Ce.These rare earth chlorides are insoluble to carburizing agents such as kerosene, acetone, ethyl acetate, can only be dissolved in the methyl alcohol and using.In use very easily take place to stop up the dropper fault, be difficult in production practice, promote.Also the someone proposes to use naphthenic acid rare earth, carboxylic acid rare earth as energizer, be dissolved in being mixed with carbon, nitrogen, rare-earth ternary diffusion medium in methyl alcohol, the methane amide, but preparation is complicated, and use range is narrow, is unsuitable for production application.
Summary of the invention
At the problem that prior art exists, the present invention develops a kind of permeation promoter for organic RE chemical heat treatment and application thereof, and it can solve rare earth chloride dropper fault, the problem that is difficult to promote in production practice in use very easily take place to stop up.Permeation promoter for organic RE chemical heat treatment of the present invention can have following two kinds of composition proportion:
First kind of composition proportion is: permeation promoter for organic RE chemical heat treatment is made up of according to weight percent following compositions: 8～12% rare earth elements, 5～8% zellons, 1～4% luxuriant rare earth, isomeric acid and isomery alcohol surplus; This energizer is dissolved in kerosene, benzene, toluene, is used to prepare carburizing and carbonitriding energizer.
Second kind of composition proportion is: permeation promoter for organic RE chemical heat treatment is made up of according to weight percent following compositions: 8～12% rare earth elements, 5～8% zellons, 1～4% luxuriant rare earth, isopropylformic acid ammonium 20～30%, isomeric acid and isomery alcohol surplus; When this energizer is dissolved in kerosene, ethyl acetate, acetone or Virahol, be used as carburizing, carbonitriding, nitriding, carbonitriding or Re, N, C, O, S, B multiple permeation respectively.
The present invention still adopts based on the La of the mixed chlorinated rare earth of La, Ce or simple substance or Ce rare earth chloride salt and makes raw material, adopt isomeric acid such as isocaprylic acid and naphthenic acid and isooctyl alcohol to be mixed with extraction agent by a certain percentage, adopt the hyperconcentration abstraction technique, under certain extraction process condition, make and contain La and Ce is the norium (ratio of mixture depends on starting material) of main body or the organic RE solution of pure La or Ce, wherein contain pure rare earth 8～12wt%.
Energizer of the present invention is formed by sponsoring agent organic RE, secondary energizer zellon and luxuriant rare earth and solubility promoter, is divided into three kinds of situations according to using difference in producing, and is divided into three models, division following (its composition is all represented with weight percentage wt%):
YF-I type rare earth chemistry thermal treatment energizer:
Adopt the extraction agent of isooctyl alcohol, naphthenic acid, isooctyl alcohol preparation, the organic RE solution that makes by the hyperconcentration technology adds 5～8% zellons in every liter, 1～4% luxuriant rare earth is formulated, wherein contains pure rare earth amount 8～12%.This energizer is dissolved in kerosene, benzene, toluene, is used to prepare carburizing and carbonitriding energizer, is applicable to instillation formula pit carburizing furnace.
YF-II type thermo-chemical treatment energizer:
Adopt isocaprylic acid, isooctyl alcohol to be mixed with extraction agent, the organic RE solution of producing by the hyperconcentration technology, add zellon 5～8%, 1～4% luxuriant rare earth in every liter, and solubility promoter 20～30% isopropylformic acid ammoniums are formulated, wherein contain pure rare earth amount 8～12%, this penetration enhancer is dissolved in carburizing agents such as kerosene, ethyl acetate, acetone, Virahol, is used for carburizing and energizer is made in carbonitriding.Can be used for pit carburizing furnace, how with sealed-box type furnace and continous way cementing furnace.
YF-II type thermo-chemical treatment energizer also can be used for gas nitriding, gas nitriding carbon oozes (soft carbonization) or multiple permeation (RE, N, C, O, S, B etc.) altogether, can be used for handling the speedy steel cutting-tool and the various mould of the various trades mark when being dissolved in acetone.
The easier cracking in stove of organic RE of the present invention decomposites active rare earth atom and works the effect of oozing of urging, and oxygen-free, can constitute a kind of effective rare earth catalytic cementation agent material, and is better than the solubility of rare earth chloride, and is difficult for producing obstruction, has following characteristics:
1, in organic rare-earth energizer, adds luxuriant rare earth and help catalytic material, can further improve the cleavage rate of organic carburizing agent, further reduce the generation of carbon black in cementation process, improve carburizing speed, the carburization process that does not more add rare-earth energizer improves carburizing speed 15～30%;
2, in organic rare-earth energizer, add solubility promoter, make that the suitability of this organic rare-earth energizer is wide, can be dissolved in kerosene, acetone, ethyl acetate, toluene, benzene, Virahol isotonic agent;
3, the inorganic rare earth energizer that has overcome present use stops up the disadvantage of dropper fault easily, makes rare earth urge the application of the technology of oozing altogether in carburization process to become possibility.
Description of drawings
Fig. 1 is infiltration layer metallographic structure figure behind the adding rare-earth energizer, Fig. 2 is the kinetics of carburising curve, the non-martensite microstructure figure that Fig. 3 produces for the carburization process that does not add rare earth, Fig. 4 is non-martensite microstructure figure behind the adding rare earth, Fig. 5 is not for adding the surface hardness distribution plan of re carburizing product, and Fig. 6 is the surface hardness distribution plan of the carburizing product behind the adding rare earth.
Embodiment
Embodiment one: the permeation promoter for organic RE chemical heat treatment of present embodiment is made up of according to weight percent following compositions: 8～12% rare earth elements, 5～8% zellons, 1～4% luxuriant rare earth, isomeric acid and isomery alcohol surplus.
In the present embodiment, described rare earth element is norium, simple substance La or simple substance Ce rare earth metal based on La and Ce; Described isomeric acid is isocaprylic acid and naphthenic acid; Described isomery alcohol is isooctyl alcohol.This energizer is dissolved in kerosene, benzene, toluene, is used to prepare carburizing and carbonitriding energizer.
Embodiment two: present embodiment is achieved through the following technical solutions its goal of the invention:
One, test conditions:
1,105KW pit carburizing furnace is furnished with the microcomputer self-control system that Beijing remittance Expway makes;
2, main penetration enhancer: kerosene, carrier gas: methyl alcohol;
3, workpiece material: 20CrMnTi; Workpiece is that M6 is with lower gear;
4, organic rare-earth energizer: YF-I type, isocaprylic acid, naphthenic acid, isooctyl alcohol are 2:1 according to weight ratio: 1 is mixed with extraction agent, after pressing 70% ammonification of acidity value, adopt the hyperconcentration abstraction technique to make organic RE solution, add 5～8% zellons, 1～4% luxuriant rare earth in every liter of organic RE solution, wherein contain pure rare earth amount 8～12%, press different ratios and mix with kerosene;
5, batch: adopt conventional shove charge suspender and batch.
Two, test-results:
1, metallographic structure: as Fig. 1;
2, kinetic curve and carburizing speed:
Add the visible Fig. 2 of kinetic curve situation under the different organic RE situations.According to test-results as can be seen, adopt same process, add organic RE and do not add rare earth obviously raising on carburizing speed, when 880 ℃ of carburizings, can improve 30%; When 920 ℃ of carburizings, can improve 29%,, can save the heating and cooling time though 880 ℃ of carburizing speeds that add rare earth are lower than 920 ℃ infiltration rate, make that always accounting for the stove time shortens, reduce power consumption, and reduce the distortion of workpiece, very big comprehensive benefit is arranged.
Embodiment three: the permeation promoter for organic RE chemical heat treatment of present embodiment is made up of according to weight percent following compositions: 8～12% rare earth elements, 5～8% zellons, 1～4% luxuriant rare earth, isopropylformic acid ammonium 20～30%, isomeric acid and isomery alcohol surplus.
In the present embodiment, described rare earth element is norium, simple substance La or simple substance Ce rare earth metal based on La and Ce; Described isomeric acid is isocaprylic acid and naphthenic acid; Described isomery alcohol is isooctyl alcohol.
When permeation promoter for organic RE chemical heat treatment is dissolved in different solvents (kerosene, ethyl acetate, acetone or Virahol), can be used for various objectives: carburizing, carbonitriding, nitriding, carbonitriding or multiple permeation (Re, N, C, O, S, B).
Embodiment four: present embodiment is achieved through the following technical solutions its goal of the invention:
Test conditions:
1,105KW pit carburizing furnace, oxygen probe control;
2, main penetration enhancer: kerosene+air, air flow quantity: 0.2L/ branch;
3, workpiece material: 20CrMnTi; Workpiece is that M6 is with lower gear;
4, organic rare-earth energizer: YF-II type, isocaprylic acid and isooctyl alcohol are to be mixed with extraction agent at 4: 1 according to weight ratio, after pressing 70% ammonification of acidity value, adopt the hyperconcentration abstraction technique to make organic RE solution, add 5～8% zellons, 1～4% luxuriant rare earth, 20～30% isopropylformic acid ammoniums in every liter of organic RE solution, wherein contain pure rare earth amount 8～12%, mix with kerosene in 7% ratio;
5, batch: adopt conventional shove charge suspender and batch.
Test objective: solve the non-martensite microstructure problem that in carburizing, produces
Test-results: owing to add rare earth, can obviously improve non-martensite microstructure, the non-martensite microstructure situation is basically eliminate, improves surface hardness, the visible Fig. 3 of result～6.Evidence because the effect of rare earth can obviously improve and eliminate the non-martensite microstructure problem, improves surface hardness, and surface hardness can reach 61～64CHR.
Embodiment five: the permeation promoter for organic RE chemical heat treatment of present embodiment is made up of rare earth element, zellon, luxuriant rare earth, isomeric acid and isomery alcohol, and the weight percent of each composition sees Table 1.
Table 1
| Sequence number | Rare earth element | Zellon | Luxuriant rare earth | Isocaprylic acid | Naphthenic acid | Isooctyl alcohol | The isopropylformic acid ammonium | ||
| La | Ce | Other elements | |||||||
| 1 | 8 | - | - | 7 | 2 | 43 | 20 | 20 | - |
| 2 | - | 10 | - | 6 | 4 | 40 | 30 | 10 | - |
| 3 | 4 | 5 | 3 | 5 | 3 | 20 | 20 | 40 | - |
| 4 | 5 | 4 | - | 8 | 1 | 30 | 40 | 12 | - |
| 5 | 3 | 7 | 1 | 8 | 2 | 20 | 29 | 30 | - |
| 6 | 8 | - | - | 7 | 4 | 32 | - | 29 | 20 |
| 7 | - | 10 | - | 8 | 2 | 46 | - | 12 | 22 |
| 8 | 4 | 5 | 3 | 6 | 1 | 28 | - | 28 | 25 |
| 9 | 5 | 4 | - | 5 | 3 | 40 | - | 16 | 27 |
| 10 | 3 | 7 | 1 | 6 | 4 | 40 | - | 10 | 29 |
Claims (4)
1. permeation promoter for organic RE chemical heat treatment is characterized in that it is made up of according to weight percent following compositions: 8～12% rare earth elements, 5～8% zellons, 1～4% luxuriant rare earth, isomeric acid and isomery alcohol surplus; Wherein said rare earth element is norium, simple substance La or simple substance Ce rare earth metal based on La and Ce; Described isomeric acid is isocaprylic acid and naphthenic acid; Described isomery alcohol is isooctyl alcohol.
2. the application of the described permeation promoter for organic RE chemical heat treatment of claim 1 when it is characterized in that permeation promoter for organic RE chemical heat treatment is dissolved in kerosene, benzene or toluene, is used to prepare the carburizing or carbonitriding energizer.
3. permeation promoter for organic RE chemical heat treatment is characterized in that it is made up of according to weight percent following compositions: 8～12% rare earth elements, 5～8% zellons, 1～4% luxuriant rare earth, 20～30% isopropylformic acid ammoniums, isomeric acid and isomery alcohol surplus; Wherein said rare earth element is norium, simple substance La or simple substance Ce rare earth metal based on La and Ce; Described isomeric acid is an isocaprylic acid; Described isomery alcohol is isooctyl alcohol.
4. the application of the described permeation promoter for organic RE chemical heat treatment of claim 3, when it is characterized in that permeation promoter for organic RE chemical heat treatment is dissolved in kerosene, ethyl acetate, acetone or Virahol, be used as carburizing, carbonitriding, nitriding, carbonitriding or Re, N, C, O, S, B multiple permeation respectively.
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| CN1039069A (en) * | 1988-07-05 | 1990-01-24 | 哈尔滨工业大学 | Solid-liquid rare earth chemistry thermal treatment energizer and compound method |
| CN1072733A (en) * | 1991-11-23 | 1993-06-02 | 山东工业大学 | Ionic nitridation technology with rare earth catalytic permeating |
| CN1206051A (en) * | 1997-07-18 | 1999-01-27 | 刘志儒 | Application of rare earths in gaseous nitridation and nitrogen-carbon cocementing process |
| US20030124267A1 (en) * | 2001-12-29 | 2003-07-03 | Younsoo Kim | Method for manufacturing metal film having high purity |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039069A (en) * | 1988-07-05 | 1990-01-24 | 哈尔滨工业大学 | Solid-liquid rare earth chemistry thermal treatment energizer and compound method |
| CN1072733A (en) * | 1991-11-23 | 1993-06-02 | 山东工业大学 | Ionic nitridation technology with rare earth catalytic permeating |
| CN1206051A (en) * | 1997-07-18 | 1999-01-27 | 刘志儒 | Application of rare earths in gaseous nitridation and nitrogen-carbon cocementing process |
| US20030124267A1 (en) * | 2001-12-29 | 2003-07-03 | Younsoo Kim | Method for manufacturing metal film having high purity |
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