CN1910303A - Method for activating surface of metal member - Google Patents
Method for activating surface of metal member Download PDFInfo
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- CN1910303A CN1910303A CNA2005800025506A CN200580002550A CN1910303A CN 1910303 A CN1910303 A CN 1910303A CN A2005800025506 A CNA2005800025506 A CN A2005800025506A CN 200580002550 A CN200580002550 A CN 200580002550A CN 1910303 A CN1910303 A CN 1910303A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
- C23C8/30—Carbo-nitriding
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
- C23C8/30—Carbo-nitriding
- C23C8/32—Carbo-nitriding of ferrous surfaces
Abstract
A method for activating the surface of a metal member, that is, activating a passivated coating film present in the surface of a high alloy steel member, which makes it difficult to effect a diffusion penetration treatment such as a gas nitriding method or a gas carburizing method for forming a nitrided layer, a carburized layer or a carburized and nitrided layer on the surface of a metal member, which method comprises using a gas generally used in a gas heat treatment, forming an HCN gas in a furnace through the utilization of a catalytic action of the surface of a metal to be treated and/or a material of the furnace, to thereby activate the passivated surface of the high alloy steel member. The above method is free from disadvantages such as the formation of deposits in a furnace, the wear of the wall surface in a furnace, and the necessity of the treatment for converting an exhaust gas to a harmless material, which have been problems in the case of a conventional activation treatment using a halogen compound.
Description
Technical field
The present invention relates to that hardware is carried out scattering and permeatings such as nitrogenize and carburizing and handle the pretreatment process that makes metal component surface activatory hardware before.
Background technology
In order to improve mechanical propertiess such as wearability, fatigue strength, form the gas nitriding method of nitride layer or cementation zone and gas carburizing on the surface of hardware and mainly be widely used in the member that constitutes by iron type materials.
When the component surface that is made of steel alloy, particularly high quality steel is carried out these processing, owing to be present in the passive film (oxide compound etc.) of component surface, infiltration diffusion in metal component surface such as nitrogen and carbon is hindered, and has the problem that the processing that above-mentioned member takes place is bad or processing is uneven.Therefore, before these scattering and permeatings are handled, carry out the activation treatment of metal component surface.As this surface activation process, by the most extensive employing is the method that is treated to the use chloride-based compound of representative with the stainless steel surface nitriding.As muriate, use vinyl chloride resin, ammonium chloride, methylene dichloride etc.
Above-mentioned muriate is put into the processing stove with hardware and is heated.By this heating, these muriates decompose generation HCl, and the HCl of this generation destroys (sex change) with the passive film of metal component surface, makes surface active, and scattering and permeatings such as the nitrogenize of assurance subsequent handling and carburizing are handled.
Yet, in the surface active of the muriatic hardware of aforesaid employing, the HCl that decompose to generate is the stove inner-wall surface that is made of brick and metal of loss not only, and in gas nitriding and gas soft nitriding, generate ammonium chloride with ammonia gas react as atmosphere gas, this ammonium chloride savings not only becomes the reason of fault in stove and in the exhaust system, and remains in hardware (workpiece) surface, the erosion resistance that causes this member and decrease of fatigue strength etc.
In recent years, the method for the muriatic method of instead aforementioned use adopts to belong to fluorine cpd (NF haloid equally
3) the activation method of metal component surface be practical (for example, patent documentation 1).Above-mentioned NF
3Generate fluorine by thermal degradation, the fluorine of generation becomes fluoride films with the passive film of metal component surface, and metal component surface is activated.Yet, adopt fluorine cpd (NF
3) the activation method of metal component surface in, contained NF in the waste gas
3With the innoxious processing that needs the degree of depth of HF, this becomes the obstacle that this method is popularized.
In the activation method of the halid metal component surface of aforementioned use, exist savings thing in the stove problem, stove inner-wall surface loss or need the problems such as harmless treatment equipment of waste gas.Consider such background, carried out not using the exploitation of the activation method of halid metal component surface.
The oxide film of metal component surface (MO) is reduced with following formula (2).
The main component of the surface film oxide of High Chrome Alloy Steel component surface is Cr
2O
3,
So CO that generates according to above-mentioned formula (1)～(3) and the ammonia gas react as atmosphere gas generate HCN according to following formula (4).
The HCN that generates by above-mentioned formula (4) reduces by the passive film of following reaction with the High Chrome Alloy Steel component surface.
The Cr (CN) that generates
3C and N be diffused in the High Chrome Alloy Steel component surface, realize carburizing and nitrogenize, do not produce residue in above-mentioned component surface.
Relatively, the priming reaction of the muriatic High Chrome Alloy Steel component surface of aforementioned employing is represented with following formula (6).
Above-mentioned chromium chloride remains in component surface, becomes the corrosive material that causes member.
Patent documentation 1: Japanese patent laid-open 3-44457 communique
Patent documentation 2: the flat 9-38341 communique of the special hope of Japanese Patent
The announcement of invention
The problem that invention will solve
As mentioned above, aspect the problem of the activation method that solves the muriatic metal component surface of patent documentation 1 described employing from principle, patent documentation 2 described methods are outstanding.Yet patent documentation 2 described methods are used liquid acetone at normal temperatures and pressures, so need to import the device of acetone steam, therefore the flow control difficulty of acetone exists the shortcoming of the hardware of the active surface that is difficult to obtain to have homogeneous.
Solve the method for problem
In order to solve above-mentioned problem, the inventor starts to develop and uses the method that replaces handling last in-problem acetone under the normal temperature and pressure as the compound of gas, and has finished the present invention.
That is of the present invention being constructed as follows.
1. the activation method of metal component surface, it is characterized in that, will with under the normal temperature and pressure be gas for carbon compound and ammonia as the mixed gas of neccessary composition more than process furnace internal heating to 300 ℃, in this heating mixed gas, katalysis by hardware, metal system stove inwall or metal system anchor clamps generates HCN, makes the surface action of the HCN and the hardware of generation.
2. the activation method of aforementioned 1 described metal component surface is characterized in that, is more than one the compound that is selected from acetylene, ethene, propane, butane and carbon monoxide for carbon compound.
3. the activation method of aforementioned 1 described metal component surface is characterized in that, metal system stove inwall or metal system anchor clamps contain more than one the metal that is selected from Fe, Ni, Co, Cu, Cr, Mo, Nb, V, Ti and Zr.
4. the activation method of aforementioned 1 described metal component surface is characterized in that, the concentration of the HCN that generates in stove is at 100mg/m
3More than, the dew point of furnace atmosphere gas is below 5 ℃.
The effect of invention
If adopt the present invention, the activating treatment process of the pretreated metal component surface that can be used as the scattering and permeating processing can be provided, in this method, to generate nitride layer to surface at hardware, the gas nitriding method of cementation zone or carbonitrided case, scattering and permeatings such as gas carburizing are handled the surface passivated membrane of the high quality steel member that causes difficulty, use common gas used in gas thermal treatment, utilize the katalysis of metal to be treated and/or surface of a metal material of the furnace, in stove, generate HCN gas, make the surface active of the high quality steel member of passivation, put aside thing thereby avoid in the past in adopting halid activation treatment, becoming in the stove of problem, the loss of stove inner-wall surface and the disadvantages such as harmless treatment of waste gas.
The best mode that carries out an invention
Below, exemplify the best mode that is used to carry out an invention, the present invention is carried out more specific description.
The inventor infers, the CH that is generated by the thermolysis of acetone
3And HCN (as the CO of another thermolysis resultant and the resultant of reaction of atmosphere gas ammonia) from aforementioned formula (2) and formula (5) be similarly aspect the effect of passive film relatively, CH
3With the existence of HCN be High Chrome Alloy Steel component surface activatory sufficient condition, and be not prerequisite, so be conceived to HCN, the exploitation of the HCN generation method of setting about and adopt the affirmation of activation effect of the metal component surface of HCN in the metallic surface.
With nitriding atmosphere gas (NH
3: N
2=mol ratio 1: 1) is in the retort furnace of SUS310S system with being selected from normal temperature and pressure under that gas for the various carbon compounds of gas imports in the stove, is heated to 550 ℃, the generation of HCN is investigated.Its result confirms can to generate HCN with the combination of ammonia respectively by carbon monoxide, carbonic acid gas, acetylene, ethene, propane, butane.
Relatively, except the inwall with retort furnace changes the stove of brick system into, carry out and above-mentioned same experiment, behind the growing amount of analysis HCN, all do not detect HCN under all as a result situations.Hence one can see that, is prerequisites for the katalysis of the HCN formation reaction metallic surface of adopting ammonia and these gases.
Adopt the HCN formation reaction of ammonia and aforementioned carbon compound can represent with following reaction formula respectively.
Nitriding atmosphere gas (NH
3: N
2=mol ratio 1: 1) in the comparison of the growing amount of the HCN that obtains with the reaction that is selected from the gas of various carbon compounds, with respect to nitriding atmosphere gas (NH
3: N
2=mol ratio 1: 1) contain each carbon compound with equivalence ratio 1% respectively, importing inwall is in the retort furnace of SUS3 10S system, be heated to 550 ℃ 30 minutes, carry out the reaction of aforementioned formula (7)～(12).Its result, the HCN growing amount of various carbon compounds is following order.
C
2H
2＞CO＞C
2H
4＞C
4H
10＞C
3H
8＞CO
2
Use SUS304 sheet material the initial stage at nitriding treatment is imported in process furnace whether have activation evaluation with these compounds respectively for having confirmed by generating these carbon compounds of HCN with the reaction of nitriding atmosphere gas.Its result finds C
2H
2, CO, C
2H
2, C
4H
10And C
3H
8Compare with the contrast nitriding treatment that does not import carbon compound, in the above-mentioned SUS304 sheet material, the weight increase that produces for nitrogenize homogeneity and nitriding has positive effect.Relatively, use CO
2Situation under, aspect the weight increase of nitrogenize homogeneity and test film all with the contrast nitriding treatment as broad as long, for CO
2There is not the activation of discovery to above-mentioned SUS304 plate surface.
In stove, though pass through CO
2Importing generate HCN, but not have to obtain activation to above-mentioned SUS304 plate surface, infer that this is the by product O owing to the HCN formation reaction of aforementioned formula (8)
2And H
2The reoxidation of the above-mentioned SUS304 plate surface that the oxygenizement of O causes.For CO, generate HCN as mentioned above, but this thinks that not by the phenomenon contradiction of homogeneous nitrogenize this contradiction is owing to following reason with having ammonia and contain under the gas soft nitriding atmosphere of RX gas of CO stainless steel.Wherein, RX gas is meant that hydrocarbon gas (for example propane gas, butane gas, Sweet natural gas) and air mix with about equally chemical equivalent, decomposes in remaining on 1000 ℃ Catalytic Layer, with CO, H
2(N
2) be main component, contain a spot of CO
2And H
2The gas of O is the gas that is widely used as carburizing gas.
The representativeness of gas soft nitriding is formed NH
3: contained CO is expressed as about 10% with volume ratio in RX gas=mol ratio 1: 1.Therefore, infer in the nitempering furnace to exist enough metal component surfaces to activate necessary HCN, but have the H of a great deal of in the uncontrolled RX gas of dew point
2CO about O (about 2 capacity %) and 0.5 capacity %
2So, infer oxygenizement owing to them, the surface of the above-mentioned SUS304 sheet material that is activated again be oxidized, and hinders the infiltration of nitrogen in above-mentioned plate surface.
Therefore, when selecting the conduct of CO gas to be used for the metal component surface activatory, better be to use independent CO gas for carbon compound, rather than RX gas.Yet the essential injection rate of the CO gas among the present invention is about 1/10 (capacity) of gas soft nitriding atmosphere, thereby the H in the RX gas
2O and CO
2Influence little, can utilize the situation of RX gas so also have as the CO source.
Right formula according to previous reaction formula (7)～(12) judges to have in these compounds of cyanogen nucleus formation CO
2Situation under the oxygenizement of by product the strongest, be CO secondly, hydrocarbon compound all generates the hydrogen of reductibility.Therefore, in order to prevent reoxidation, better be to select hydrocarbon compound as supplying carbon compound.
The activation of steel alloy component surface of the present invention is produced by HCN.Above-mentioned activation effect depends on the HCN concentration in the furnace atmosphere.Be used to obtain the suitable concentration of the HCN of satisfied activation at 100～30000mg/m
3Scope in.The concentration of HCN is less than 100mg/m
3The time, can't expect above-mentioned activation.On the other hand, the concentration of HCN surpasses 30000mg/m
3The time, above-mentioned activation effect is saturated, and is not only unfavorable on cost, and causes carbon deposit (carbon in the stove generates) for the thermolysis of carbon compound, so be unfavorable.
In addition, the dew point of furnace atmosphere gas better is below 5 ℃.Above-mentioned dew point is if be higher than 5 ℃, then by the metallic surface of HCN gas activation by the H in the atmosphere
2O reoxidation, passivation again.
As illustrated ground in previous reaction formula (5), the advantage of the environment aspect of the inventive method is, give metal component surface activatory HCN and enter into component surface, help nitrogenize, the carburizing of member, do not stay residue in component surface, have neither part nor lot in reaction simultaneously and can easily burn innoxiously as the HCN that waste gas is discharged from, do not need new optional equipment by the ammonia combustion unit that is attached to the nitrogenize device.
Another advantage of the present invention be in the nitriding treatment process smoothly operation carry out shortening time of nitriding treatment.The gas nitriding of hardware is undertaken by following program usually.
Hardware is placed in the stove, behind purification of the atmospheric vacuum in the stove or nitrogen replacement, per hour imports the nitriding atmosphere gas (NH of 1～10 times of amount of furnace volume
3+ N
2), be warming up to the nitriding treatment temperature of hardware simultaneously after, maintain constant temp.In the processing, press in the stove to maintain about normal atmosphere+0.5kPa by pressure pump, the waste gas of extrusion is by the waste gas burner combustion decomposition.
Embodiment as No. 2501925 specification sheets of Japanese Patent puts down in writing, the method of the employing fluorine type gas shown in the aforementioned patent document 1 need import nitriding atmosphere gas in stove after class gas is fluoridized in discharge after importing is fluoridized class gas and carried out the activation treatment of member.
Relatively, among the present invention hardware is warming up in the step of nitriding treatment temperature, can in nitriding atmosphere gas, imports, generate HCN activated metal component surface, then by stopping directly to enter into nitriding step for the importing of carbon compound for carbon compound.Thus, the treatment time that significantly shortens nitriding step, when activation entered nitriding step, the reoxidation phenomenon that becomes the metal component surface of problem in the processing in the past also can be eliminated from principle.
Technical characterictic of the present invention and effect are as mentioned above.Below, the preferred embodiment of the present invention is described.Processing stove used in the present invention better is that inwall is metal, even but inwall is not the catalyzer that metal, processed hardware becomes HCN, perhaps keeping the anchor clamps of hardware in stove is metal getting final product.As the metal that constitutes above-mentioned metal system inwall, hardware, anchor clamps, better be to contain more than one the metal that for example is selected from Fe, Ni, Co, Cu, Cr, Mo, Nb, V, Ti and Zr.
As the hardware that is carried out surface activation process in the method for the present invention, can exemplify cold die steel, mold heat steel, mould of plastics steel, rapid tool steel, powder rapid tool steel, chromemolybdenum steel, maraging steel (maraging steel), austenitic stainless steel, ferritic stainless steel with excellent formability, martensite class stainless steel, martensite class high temperature steel, austenitic type high temperature steel and nickel based super alloy etc., these hardwares are placed according to the usual method carrying by suitable anchor clamps in the aforementioned processing stove, carry out surface activation process.
Surface treatment gas in the aforesaid supply stove is to be the confession carbon compound and the ammonia of gas under the normal temperature and pressure, and the high-pressure gas cylinder from special use supplies in the stove respectively.About these gas, hardware is being placed in the stove, with the purification of the atmospheric vacuum in the stove or with behind the nitrogen replacement, in stove, import nitriding atmosphere gas (independent ammonia, ammonia+nitrogen or ammonia+nitrogen+hydrogen), begin to heat up after establishing reducing atmosphere, import of the present invention for carbon compound.Ammonia and confession carbon compound are heated in stove more than 300 ℃, and then the katalysis by the metallic surface generates HCN.Should be located at as the ratio for the flow of carbon compound of the flow of the ammonia of nitriding atmosphere gas and importing in 1: 0.0001～1: 0.1 the scope.Be lower than for the throughput ratio of carbon compound under 1: 0.0001 the situation,, therefore can't obtain activation effect because the growing amount of HCN is low.Throughput ratio for carbon compound surpasses at 1: 0.1 o'clock, and activation effect is saturated, and is unfavorable on cost.
As previously mentioned, be more than one the gaseous compound that selects Baiyi alkynes, ethene, propane, butane and carbon monoxide for carbon compound, also can in handling stove, supply with simultaneously with the gas that contains ammonia as previously mentioned.The importing that the aforementioned interior temperature of stove that contains the gas of ammonia begins for carbon compound when reaching about 300 ℃ is preferred in efficient utilization aspect carbon compound, but for the treatment time that makes for carbon compound concentration of improving as early as possible in the furnace atmosphere shortens, better be when beginning to heat up, to import, just realize the generation of HCN from initial stage for carbon compound.
Embodiment
Below, exemplify embodiment and comparative example, the present invention is carried out more specific description.The processing stove that following embodiment and comparative example use structure shown in Figure 1 carries out.Among Fig. 1,1 is retort furnace, and 2 is its shell, and 3 is well heater, 4 is inner vessels (retort), and 5 is gas introduction tube, and 6 is vapor pipe, and 7 is electric motor, 8 is fan, and 9 are metal system anchor clamps, and 10 is the gas guide barrel, 11 is heat shield panel, and 12 is vacuum pump, and 13 is waste gas burner, 14 for supplying carbon compound gas high-pressure gas cylinder, and 15 is the ammonia high-pressure gas cylinder, and 16 is the nitrogen high-pressure gas cylinder, 17 is the hydrogen high-pressure gas cylinder, and 18 is under meter, and 19 is the control pump of gas.
(embodiment 1)
Use the SUS310S retort furnace of internal volume 100L shown in Figure 1, in this stove, place SUS304 sheet material, send into NH with the flow velocity of 200L/h respectively
3Gas and N
2Gas was warming up to 550 ℃ with 75 minutes from room temperature.Beginning is injected acetylene gas with 2L/h (to heat up beginning certainly after 18 minutes) when atmosphere temperature reaches 100 ℃ midway.After being warming up to 550 ℃, kept atmosphere temperature 2 hours, at this moment stop the injection of acetylene gas, continue simultaneously to import NH down at 550 ℃
3Gas and N
2After gas carried out nitrogenize in 4 hours, stop heating, only continue to import N
2Gas cools off stove, and atmosphere temperature reaches back below 100 ℃ and takes out the interior test film of stove.
In addition, will a part of waste gas be absorbed the 2 quality % caustic soda aqueous solution, and carry out HCN and analyze from the shunting of the waste gas in the stove.According to the analytical results of HCN absorption liquid, the average HCN concentration in the furnace atmosphere of acetylene gas injection period is 8000mg/m
3After the weightening finish before and after the nitriding treatment of mensuration SUS304 test film, the result is 20g/m
2The SUS304 test film is cut off and grinds, corrode,, find the nitride layer (microphotograph of representing 500 times of multiplying powers among Fig. 2) of the homogeneous thickness of formation 50 μ m by the observation by light microscope cut surface with copper sulfate hcl corrosion liquid.Measure on the above-mentioned test film 5 surface hardness with Vickers hardness tester, all values all is distributed in the scope of Hv=1200～1250 as a result.
(embodiment 2)
Place SUS304 sheet material in the retort furnace that in embodiment 1, uses, send into NH with the flow velocity of 200L/h respectively
3Gas and N
2Gas was warming up to 550 ℃ with 75 minutes from room temperature.Beginning is injected propane gas with 5L/h (to heat up beginning certainly after 18 minutes) when atmosphere temperature reaches 100 ℃ midway.After being warming up to 550 ℃, kept atmosphere temperature 2 hours, at this moment stop the injection of propane gas, continue simultaneously to import NH down at 550 ℃
3Gas and N
2After gas carried out nitrogenize in 4 hours, stop heating, only continue to import N
2Gas cools off stove, and atmosphere temperature reaches back below 100 ℃ and takes out the interior test film of stove.
In addition, will a part of waste gas be absorbed the 2 quality % caustic soda aqueous solution, and carry out HCN and analyze from the shunting of the waste gas in the stove.According to the analytical results of HCN absorption liquid, the average HCN concentration in the furnace atmosphere of propane gas injection period is 400mg/m
3After the weightening finish before and after the nitriding treatment of mensuration SUS304 test film, the result is 18g/m
2The SUS304 test film is cut off and grinds, corrode,, find the nitride layer of the homogeneous thickness of formation 45 μ m by the observation by light microscope cut surface with copper sulfate hcl corrosion liquid.Measure on the above-mentioned test film 5 surface hardness with Vickers hardness tester, all values all is distributed in the scope of Hv=1200～1250 as a result.
(embodiment 3)
Place SUS304 sheet material in the retort furnace that in embodiment 1, uses, send into NH with the flow velocity of 200L/h respectively
3Gas and N
2Gas was warming up to 550 ℃ with 75 minutes from room temperature.Beginning is injected CO gas with 5L/h (to heat up beginning certainly after 18 minutes) when atmosphere temperature reaches 100 ℃ midway.After being warming up to 550 ℃, kept atmosphere temperature 2 hours, at this moment stop the injection of CO gas, continue simultaneously to import NH down at 550 ℃
3Gas and N
2After gas carried out nitrogenize in 4 hours, stop heating, only continue to import N
2Gas cools off stove, and atmosphere temperature reaches back below 100 ℃ and takes out the interior test film of stove.
In addition, will a part of waste gas be absorbed the 2 quality % caustic soda aqueous solution, and carry out HCN and analyze from the shunting of the waste gas in the stove.According to the analytical results of HCN absorption liquid, the average HCN concentration in the furnace atmosphere of CO gas injection period is 1000mg/m
3After the weightening finish before and after the nitriding treatment of mensuration SUS304 test film, the result is 18g/m
2The SUS304 test film is cut off and grinds, corrode,, find the nitride layer of the homogeneous thickness of formation 45 μ m by the observation by light microscope cut surface with copper sulfate hcl corrosion liquid.Measure on the above-mentioned test film 5 surface hardness with Vickers hardness tester, all values all is distributed in the scope of Hv=1200～1250 as a result.
(embodiment 4)
Place SUS304 sheet material in the retort furnace that in embodiment 1, uses, send into NH with the flow velocity of 200L/h respectively
3Gas and N
2Gas was warming up to 550 ℃ with 75 minutes from room temperature.Beginning is injected C with 5L/h (to heat up beginning certainly after 18 minutes) when atmosphere temperature reaches 100 ℃ midway
2H
4Gas.After being warming up to 550 ℃, keep atmosphere temperature 2 hours, at this moment stop C
2H
4The injection of gas continues to import NH down at 550 ℃ simultaneously
3Gas and N
2After gas carried out nitrogenize in 4 hours, stop heating, only continue to import N
2Gas cools off stove, and atmosphere temperature reaches back below 100 ℃ and takes out the interior test film of stove.
In addition, will a part of waste gas be absorbed the 2 quality % caustic soda aqueous solution, and carry out HCN and analyze from the shunting of the waste gas in the stove.According to the analytical results of HCN absorption liquid, C
2H
4Average HCN concentration in the furnace atmosphere of gas injection period is 1200mg/m
3After the weightening finish before and after the nitriding treatment of mensuration SUS304 test film, the result is 18g/m
2The SUS304 test film is cut off and grinds, corrode,, find the nitride layer of the homogeneous thickness of formation 45 μ m by the observation by light microscope cut surface with copper sulfate hcl corrosion liquid.Measure on the above-mentioned test film 5 surface hardness with Vickers hardness tester, all values all is distributed in the scope of Hv=1200～1250 as a result.
(embodiment 5)
Place SUS304 sheet material in the retort furnace that in embodiment 1, uses, send into NH with the flow velocity of 200L/h respectively
3Gas and N
2Gas was warming up to 550 ℃ with 75 minutes from room temperature.Beginning is injected C with 5L/h (to heat up beginning certainly after 18 minutes) when atmosphere temperature reaches 100 ℃ midway
4H
10Gas.After being warming up to 550 ℃, keep atmosphere temperature 2 hours, at this moment stop C
4H
10The injection of gas continues to import NH down at 550 ℃ simultaneously
3Gas and N
2After gas carried out nitrogenize in 4 hours, stop heating, only continue to import N
2Gas cools off stove, and atmosphere temperature reaches back below 100 ℃ and takes out the interior test film of stove.
In addition, will a part of waste gas be absorbed the 2 quality % caustic soda aqueous solution, and carry out HCN and analyze from the shunting of the waste gas in the stove.According to the analytical results of HCN absorption liquid, C
4H
10Average HCN concentration in the furnace atmosphere of gas injection period is 600mg/m
3After the weightening finish before and after the nitriding treatment of mensuration SUS304 test film, the result is 18g/m
2The SUS304 test film is cut off and grinds, corrode,, find the nitride layer of the homogeneous thickness of formation 45 μ m by the observation by light microscope cut surface with copper sulfate hcl corrosion liquid.Measure on the above-mentioned test film 5 surface hardness with Vickers hardness tester, all values all is distributed in the scope of Hv=1200～1250 as a result.
(comparative example 1)
Place SUS304 sheet material in the retort furnace that in embodiment 1, uses, send into NH with the flow velocity of 200L/h respectively
3Gas and N
2Gas was warming up to 550 ℃ with 75 minutes from room temperature.After being warming up to 550 ℃, keep atmosphere temperature 6 hours, continue to import NH
3Gas and N
2After gas carries out nitrogenize, stop heating, only continue to import N
2Gas cools off stove, and atmosphere temperature reaches back below 100 ℃ and takes out the interior test film of stove.
To a part of waste gas be absorbed the 2 quality % caustic soda aqueous solution from the shunting of the waste gas in the stove, and carry out HCN and analyze.In the analytical results of HCN absorption liquid, do not detect HCN fully, confirm not have HCN fully in the furnace atmosphere.After the weightening finish before and after the nitriding treatment of mensuration SUS304 test film, the result is 10g/m
2The SUS304 test film is cut off and grinds, corrode,, find the nitride layer (microphotograph of representing 500 times of multiplying powers among Fig. 3) of the heterogeneity thickness of formation 8～18 μ m by the observation by light microscope cut surface with copper sulfate hcl corrosion liquid.Measure on the above-mentioned test film 5 surface hardness with Vickers hardness tester, the result changes in the scope of Hv=500～1100 significantly, and absolute value also shows the value lower than embodiment.
The possibility of utilizing on the industry
If employing the present invention, the activating treatment method of the pretreated metal component surface that can be used as the scattering and permeating processing can be provided, in the method, will be to process the surface passivated membrane of the high-alloy steel member that causes difficulty at scattering and permeatings such as the gas nitriding method of Surface Creation nitration case, carburized layer or the carbonitrided case of hardware, gas carbonizing methods, use usually used gas in air heat is processed, utilize the catalytic action of metal to be treated and/or surface of a metal material of the furnace, in stove, generate HCN gas, make the surface active of the high-alloy steel member of passivation, put aside the loss of thing, stove internal face and the disadvantages such as harmless treatment of waste gas thereby avoid in the past in adopting halid activation process, becoming in the stove of problem.
The simple declaration of accompanying drawing
Fig. 1 is the synoptic diagram of the structure of the processing stove that uses among the present invention.
Fig. 2 is the Photomicrograph of cut surface of the test film of embodiment 1.
Fig. 3 is the Photomicrograph of cut surface of the test film of comparative example 1.
The explanation of symbol
1: retort furnace
2: shell
3: well heater
4: inner vessels (retort)
5: gas introduction tube
6: vapor pipe
7: electric motor
8: fan
9: metal system anchor clamps
10: the gas guide barrel
11: heat shield panel
12: vacuum pump
13: waste gas burner
14: for carbon compound gas high-pressure gas cylinder
15: the ammonia high-pressure gas cylinder
16: the nitrogen high-pressure gas cylinder
17: the hydrogen high-pressure gas cylinder
18: under meter
19: the control pump of gas
Claims (4)
1. the activation method of metal component surface, it is characterized in that, will with under the normal temperature and pressure be gas for carbon compound and ammonia as the mixed gas of neccessary composition more than process furnace internal heating to 300 ℃, in this heating mixed gas, katalysis by hardware, metal system stove inwall or metal system anchor clamps generates HCN, makes the surface action of the HCN and the hardware of generation.
2. the activation method of the described metal component surface of claim 1 is characterized in that, is more than one the compound that is selected from acetylene, ethene, propane, butane and carbon monoxide for carbon compound.
3. the activation method of the described metal component surface of claim 1 is characterized in that, metal system stove inwall or metal system anchor clamps contain more than one the metal that is selected from Fe, Ni, Co, Cu, Cr, Mo, Nb, V, Ti and Zr.
4. the activation method of the described metal component surface of claim 1 is characterized in that, the concentration of the HCN that generates in stove is at 100mg/m
3More than, the dew point of furnace atmosphere gas is below 5 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004012328 | 2004-01-20 | ||
| JP012328/2004 | 2004-01-20 | ||
| PCT/JP2005/000607 WO2005068679A1 (en) | 2004-01-20 | 2005-01-19 | Method for activating surface of metal member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1910303A true CN1910303A (en) | 2007-02-07 |
| CN1910303B CN1910303B (en) | 2010-05-12 |
Family
ID=34792370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800025506A Active CN1910303B (en) | 2004-01-20 | 2005-01-19 | Method for activating surface of metal member |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20070204934A1 (en) |
| EP (1) | EP1707646B1 (en) |
| JP (1) | JP4861703B2 (en) |
| KR (1) | KR100858598B1 (en) |
| CN (1) | CN1910303B (en) |
| DE (1) | DE602005015934D1 (en) |
| WO (1) | WO2005068679A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI548778B (en) * | 2014-02-11 | 2016-09-11 | 國立臺灣大學 | Method for treating stainless steel surface and stainless steel treating system |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006233261A (en) * | 2005-02-24 | 2006-09-07 | Nippon Techno:Kk | Gas nitriding method |
| KR100902169B1 (en) * | 2007-07-24 | 2009-06-10 | 쳉-시엔 리우 | Method for improvement of hardness of martensite type stainless surface |
| EP2278038A1 (en) | 2009-07-20 | 2011-01-26 | Danmarks Tekniske Universitet (DTU) | A method of activating an article of passive ferrous or non-ferrous metal prior to carburizing, nitriding and/or nitrocarburizing |
| CA2771090C (en) * | 2009-08-07 | 2017-07-11 | Swagelok Company | Low temperature carburization under soft vacuum |
| US8961711B2 (en) | 2010-05-24 | 2015-02-24 | Air Products And Chemicals, Inc. | Method and apparatus for nitriding metal articles |
| CN102168269A (en) * | 2011-03-16 | 2011-08-31 | 广州有色金属研究院 | Method for preparing accelerated carburizing plasma nitrocarburizing and titanium carbonitride composite membrane layer |
| KR101245564B1 (en) * | 2011-05-06 | 2013-03-20 | 주식회사 삼락열처리 | Gas Nitriding Heat Treatment of the Stainless steel, Heat resisting steel and High alloy steel |
| CA2861180A1 (en) | 2012-01-20 | 2013-07-25 | Swagelok Company | Concurrent flow of activating gas in low temperature carburization |
| JP6357042B2 (en) * | 2014-07-18 | 2018-07-11 | 株式会社日本テクノ | Gas soft nitriding method and gas soft nitriding apparatus |
| JP6516238B2 (en) * | 2015-03-30 | 2019-05-22 | 日鉄ステンレス株式会社 | Austenitic stainless steel and method for producing the same |
| TWI798885B (en) | 2020-11-18 | 2023-04-11 | 日商帕卡熱處理工業股份有限公司 | Metal component processing method and processing device |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1984411A (en) * | 1933-06-08 | 1934-12-18 | Du Pont | Method of case hardening |
| US2095565A (en) * | 1936-11-18 | 1937-10-12 | Electro Alloys Company | Carburizing box |
| DE851810C (en) * | 1943-06-19 | 1952-10-09 | Bergwerksverband Zur Verwertun | Cementing of objects made of iron, steel and their alloys |
| US2404060A (en) * | 1944-02-03 | 1946-07-16 | Westinghouse Electric Corp | High temperature furnace |
| US3281517A (en) * | 1963-11-19 | 1966-10-25 | Melpar Inc | Vacuum furnace |
| CA933073A (en) * | 1969-06-25 | 1973-09-04 | H. Podgurski Harry | Method for maintaining nitriding atmosphere |
| JPS51105938A (en) * | 1975-02-28 | 1976-09-20 | Fujikoshi Kk | Ko chutetsuno teionshintanchitsukashorihoho |
| JPS52145344A (en) * | 1976-05-31 | 1977-12-03 | Daido Steel Co Ltd | Method of preparing atmosphere gas for soft nitriding |
| US4145232A (en) * | 1977-06-03 | 1979-03-20 | Union Carbide Corporation | Process for carburizing steel |
| US4175986A (en) * | 1978-10-19 | 1979-11-27 | Trw Inc. | Inert carrier gas heat treating control process |
| US4406714A (en) * | 1980-05-02 | 1983-09-27 | Bowes Robert G | Heat treatment of metals |
| JPH05202464A (en) * | 1992-01-27 | 1993-08-10 | Parker Netsushiyori Kogyo Kk | Method for partially nitriding parts |
| KR100277156B1 (en) * | 1995-03-29 | 2001-01-15 | 스기야마 미 찌오 | Method and Equipment for Vacuum Carburization and Products of Carburization |
| JPH10219418A (en) * | 1997-02-06 | 1998-08-18 | Nippon Bell Parts Kk | Method for nitriding high-chromium alloy steel with gaseous ammonia |
| JP3960697B2 (en) * | 1998-12-10 | 2007-08-15 | 株式会社日本テクノ | Carburizing and carbonitriding methods |
-
2005
- 2005-01-19 JP JP2005517113A patent/JP4861703B2/en active Active
- 2005-01-19 DE DE602005015934T patent/DE602005015934D1/en active Active
- 2005-01-19 EP EP05703844A patent/EP1707646B1/en not_active Expired - Fee Related
- 2005-01-19 WO PCT/JP2005/000607 patent/WO2005068679A1/en active Application Filing
- 2005-01-19 KR KR1020067016535A patent/KR100858598B1/en active IP Right Grant
- 2005-01-19 CN CN2005800025506A patent/CN1910303B/en active Active
- 2005-01-19 US US10/586,626 patent/US20070204934A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI548778B (en) * | 2014-02-11 | 2016-09-11 | 國立臺灣大學 | Method for treating stainless steel surface and stainless steel treating system |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20060114368A (en) | 2006-11-06 |
| EP1707646A4 (en) | 2008-09-03 |
| DE602005015934D1 (en) | 2009-09-24 |
| WO2005068679A1 (en) | 2005-07-28 |
| US20070204934A1 (en) | 2007-09-06 |
| KR100858598B1 (en) | 2008-09-17 |
| JPWO2005068679A1 (en) | 2007-12-27 |
| JP4861703B2 (en) | 2012-01-25 |
| CN1910303B (en) | 2010-05-12 |
| EP1707646B1 (en) | 2009-08-12 |
| EP1707646A1 (en) | 2006-10-04 |
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