CN103764313B - Tunicle and manufacture method thereof - Google Patents

Tunicle and manufacture method thereof Download PDF

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Publication number
CN103764313B
CN103764313B CN201180073232.4A CN201180073232A CN103764313B CN 103764313 B CN103764313 B CN 103764313B CN 201180073232 A CN201180073232 A CN 201180073232A CN 103764313 B CN103764313 B CN 103764313B
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China
Prior art keywords
tunicle
initial
metal pattern
carbon
carbon film
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Expired - Fee Related
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CN201180073232.4A
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Chinese (zh)
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CN103764313A (en
Inventor
古川雄一
外崎修司
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Toyota Motor Corp
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Toyota Motor Corp
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/12—Treating moulds or cores, e.g. drying, hardening
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/06—Permanent moulds for shaped castings
    • B22C9/061—Materials which make up the mould
    • 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
    • C23C8/80—After-treatment

Abstract

The invention provides a kind of tunicle and manufacture method thereof that the high strength of deterioration not easily occurs.A kind of manufacturing process (S1) of the tunicle (1) be formed in the forming surface of metal pattern, described manufacturing process (S1) possesses initial tunicle formation process (S11) and intermittent-heating operation (S12), in initial tunicle formation process (S11), the forming surface of described metal pattern is formed initial tunicle (100), wherein, described initial tunicle (100) has: carbon film (140), and it contains nano-sized carbon class (142), and is coated with fullerene (143); Nitride compound layer (120) and sulphide layer (130), described nitride compound layer (120) and sulphide layer (130) are between described carbon film and described iron type materials, in intermittent-heating operation (S12), under nonoxidizing atmosphere, intermittence heating is carried out to the initial tunicle (100) formed in described initial tunicle formation process (S11).

Description

Tunicle and manufacture method thereof
Technical field
The present invention relates to and be a kind ofly formed on tunicle on the surface of iron type materials and manufacture method thereof.
Background technology
All the time, known one in die casting etc., in order to realize the bad reduction of the demoulding etc. in the upper technology (for example, referring to patent document 1) forming predetermined tunicle of the forming surface (surface of iron type materials) of metal pattern.
Patent Document 1 discloses a kind of by fullerene is coated on the carbon film containing nano-sized carbon classes such as CNTs, thus in the forming surface of metal pattern, form the technology of tunicle.
According to the technology described in patent document 1, by the gap by fullerene landfill carbon film to relax the concavo-convex of the surface of carbon film, thus it is bad to reduce the demoulding.
But, in the technology described in patent document 1, at carbon film and fullerene in conjunction with in incomplete situation, fullerene can be removed due to basic solvent thus make tunicle deterioration.In addition, insufficient by film strength, tunicle easily comes off.
Therefore, the leeway that is improved of the technology described in patent document 1.
At first technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-36194 publication
Summary of the invention
Invent problem to be solved
Problem of the present invention is, provides a kind of tunicle and its manufacture method that the high strength of deterioration not easily occurs.
For solving the method for problem
The manufacture method that the manufacture method of tunicle of the present invention is the tunicle in a kind of forming surface being formed on the metal pattern used in casting, the feature of the manufacture method of described tunicle is, possess initial tunicle formation process and intermittent-heating operation, in initial tunicle formation process, the forming surface of described metal pattern is formed initial tunicle, and wherein, described initial tunicle has: carbon film, it contains nano-sized carbon class, and is coated with fullerene; Nitride compound layer and sulphide layer, described nitride compound layer and sulphide layer are between described carbon film and described metal pattern, in intermittent-heating operation, under nonoxidizing atmosphere, intermittence heating is carried out to the initial tunicle formed in described initial tunicle formation process.In described intermittent-heating operation, be formed under the state that the forming surface of the metal pattern of described initial tunicle is coated with oil-based release agent, using this metal pattern to implement casting repeatedly.
Tunicle of the present invention possesses the carbon film containing nano-sized carbon class, and is formed on the surface of iron type materials, and described tunicle contains hard amorphous carbon, Fe 4n, Fe 3c, martensite and Fe 3o 4, the Sulfur diffusivity in described carbon film is more than 50%.
Be preferably in tunicle of the present invention, the material be identified by X-ray diffraction method is hard amorphous carbon, Fe 4n, Fe 3c, martensite and Fe 3o 4, described Sulfur diffusivity is obtained by the surface analysis in electron microprobe analysis (EPMA).
The effect of invention
According to the present invention, the deterioration of tunicle can be suppressed and come off.
Accompanying drawing explanation
Fig. 1 is the figure of the manufacturing process representing tunicle involved in the present invention.
Fig. 2 is the figure representing initial tunicle.
Fig. 3 is the figure representing tunicle involved in the present invention.
Fig. 4 is the figure of the surface analysis result of the initial tunicle represented in EPMA, and (a) is the figure of the carbon represented in initial tunicle, and (b) is the figure of the Sulfur represented in initial tunicle.
Fig. 5 is the figure of the surface analysis result of the tunicle involved in the present invention represented in EPMA, and (a) be the figure of the carbon represented in tunicle involved in the present invention, and (b) is the figure of the Sulfur in expression tunicle involved in the present invention.
Fig. 6 is the figure of the surface analysis result of the comparison product represented in EPMA, and (a) is the figure representing the carbon compared in product, and (b) is the figure representing the Sulfur compared in product.
Detailed description of the invention
Hereinafter, be described with reference to the manufacturing process S1 of Fig. 1 ~ Fig. 3 to the manufacture method of tunicle involved in the present invention embodiment, tunicle 1.
Tunicle 1 is, is formed on the tunicle in the forming surface of the metal pattern used in die casting etc.
Manufacturing process S1 is, the forming surface of described metal pattern is formed the operation of tunicle 1.
In addition, the metal pattern of present embodiment is, the iron type materials formed by alloy tool steel steel (JISG4404) such as SKD61.
As shown in Figure 1, manufacturing process S1 possesses initial tunicle formation process S11 and intermittent-heating operation S12.
Initial tunicle formation process S11 is the operation forming initial tunicle 100 in the forming surface of described metal pattern.
Initial tunicle formation process S11 is known technology, specifically, is operation disclosed in Japanese Unexamined Patent Publication 2010-36194 publication.Therefore, the detailed description of initial tunicle formation process S11 is omitted.
Fig. 2 illustrates initial tunicle 100 prepared in initial tunicle formation process S11.
As shown in Figure 2, the tunicle of initial tunicle 100 for being prepared by known technology, and possess diffusion layer 110, nitride compound layer 120, sulphide layer 130, carbon film 140.
Diffusion layer 110 is that diffusion has the layer of nitrogen on described metal pattern, and near the forming surface being formed on described metal pattern.
Nitride compound layer 120 is for containing Fe 2n or Fe 3the nitride compounds such as N and Fe 3the layer of C, and be formed on diffusion layer 110.
Sulphide layer 130 is the layer containing vulcanizing compounds such as FeS, and is formed on nitride compound layer 120.
Carbon film 140 is the layer containing nano-sized carbon class, and is positioned at the most surface (topmost of Fig. 2) of initial tunicle 100.
Carbon film 140 is containing hard amorphous carbon 141, nano-sized carbon 142 and fullerene 143.
Hard amorphous carbon 141 is the material of the unformed shape using carbon as main component.Hard amorphous carbon 141 be roughly dispersed in be formed with diffusion layer 110 and nitride compound layer 120 position on.
Nano-sized carbon 142 is the nano-sized carbon classes such as carbon nano-fiber, CNT, carbon nanocoil and carbon nanocoils.The mode that nano-sized carbon 142 extends with the face side (upside of Fig. 2) from hard amorphous carbon 141 to initial tunicle 100 and being formed in a large number.Nano-sized carbon 142 is formed to reach the mode of the position of the most surface of initial tunicle 100.
Fullerene 143 is, with C 60for representative, the carbon bunch that formed by a large amount of carbon atom, and containing being implemented predetermined chemistry and repairing the fullerene derivate of Ornaments.Fullerene 143 is present between nano-sized carbon 142 in a large number.
Thus, initial tunicle 100 has: carbon film 140, and it contains nano-sized carbon 142, and is coated with fullerene 143; Nitride compound layer 120 and sulphide layer 130, described nitride compound layer 120 and sulphide layer 130 are between carbon film 140 and described metal pattern.
In addition, initial tunicle of the present invention, as long as at least containing nano-sized carbon class, and is formed with nitride compound layer and sulphide layer being coated with between the carbon film of fullerene and described metal pattern, and does not limit its manufacture method.
As shown in Figure 1, intermittent-heating operation S12 is, initial tunicle 100 prepared in initial tunicle formation process S11 is carried out to the operation of intermittent heating under nonoxidizing atmosphere.
In intermittent-heating operation S12, by using the metal pattern being formed with initial tunicle 100 in fact to implement repeatedly die casting, thus intermittence heating is carried out to initial tunicle 100.
Specifically, first, mineral oil, artificial oil and plant wet goods oil-based release agent are coated in the forming surface of the metal pattern being formed with initial tunicle 100.Now, the mode covered by described oil-based release agent completely with the forming surface of described metal pattern is to apply this oil-based release agent.Thereby, it is possible to make initial tunicle 100 become the state not contacting water and air, be namely in the state under nonoxidizing atmosphere.
Next, the motlten metals such as the aluminium alloy of high temperature (such as, 600 DEG C) are filled in described metal pattern, and place predetermined time (such as, 5 seconds).Now, the motlten metal of high temperature, by contacting with the forming surface of described metal pattern, and quick refrigeration is to predetermined temperature (such as, 300 DEG C).That is, initial tunicle 100, because of the motlten metal after being just filled in described metal pattern by high-temperature heating, cooled at the temperature of the motlten metal by described metal pattern quick refrigeration afterwards.
Finally, cakey motlten metal (cast thing) is taken out from described metal pattern.
By implementing the above-mentioned process of pre-determined number (such as, adding up to 1000 times), and initial tunicle 100 is made to become tunicle 1.That is, the forming surface of described metal pattern forms tunicle 1.
Thus, in intermittent-heating operation S12, use the metal pattern being formed with initial tunicle 100, and repeatedly implement repeatedly to cast under nonoxidizing atmosphere.Thus, predetermined variations in temperature (heating and cooling) is given repeatedly to initial tunicle 100.That is, initial tunicle 100 intermittence is heated, thus makes the change of initial tunicle 100 become tunicle 1.
In addition, although in the present embodiment, tunicle 1 is formed in the forming surface of metal pattern, can thinks and be not limited in the forming surface of metal pattern, and can to surface applications the present invention of all iron type materials.
In addition, although in the present embodiment, apply oil-based release agent when casting each time, if can maintain initial tunicle 100 be in nonoxidizing atmosphere under state, then do not limit and apply the time point of oil-based release agent.
In addition, although in the present embodiment, by oil-based release agent being coated in the forming surface of described metal pattern, realize initial tunicle 100 be in nonoxidizing atmosphere under state, even but can think by additive method in addition, as long as can realize initial tunicle be in nonoxidizing atmosphere under state, then also can produce tunicle involved in the present invention.
In addition, in the present embodiment, although carrying out intermittence heating by fact repeatedly implementing die casting to initial tunicle 100, can think and laser or ultrasonic etc. also can be used to carry out intermittence heating to initial tunicle 100.
Fig. 3 illustrates the tunicle 1 prepared through manufacturing process S1.
As shown in Figure 3, tunicle 1 possesses diffusion layer 10, nitride compound layer 20, sulphide layer 30, carbon film 40.
The diffusion layer 110 of diffusion layer 10 for being formed through intermittent-heating operation S12, and near the forming surface being formed on described metal pattern.
The nitride compound layer 120 of nitride compound layer 20 for being formed through intermittent-heating operation S12, and be formed on diffusion layer 10.
Nitride compound layer 20 is for containing Fe 4the nitride compounds such as N and Fe 3the layer of C.That is, nitride compound layer 20 is containing Fe 4the aspect of N, different with the nitride compound layer 120 of initial tunicle 100.Because of through intermittent-heating operation S12, and make Fe contained in the nitride compound layer 120 of initial tunicle 100 2n or Fe 3n is to Fe 4n changes.
At this, Fe 4n and Fe 2n or Fe 3n compares has finer and close structure.
Therefore, have containing Fe 4the tunicle 1 of the nitride compound layer 20 of N, and has containing Fe 2n or Fe 3the intensity that comes off (pressure when coming off from described metal pattern) with about 1.5 times compared by the initial tunicle 100 of the nitride compound layer 120 of N.
Therefore, according to the present invention, tunicle 1 can be set to high strength.
The sulphide layer 130 of sulphide layer 30 for being formed through intermittent-heating operation S12, and be formed on nitride compound layer 20.Sulphide layer 30 is formed to reach the mode of the position of the most surface of tunicle 1.
The carbon film 140 of carbon film 40 for being formed through intermittent-heating operation S12.
In carbon film 40, entirety is formed with sulphide layer 30.That is, in carbon film 40, Sulfur is the state spread on the whole.
Thus, in initial tunicle 100, sulphur is concentrated in root (bottom of Fig. 2) place of carbon film 140, and in tunicle 1, in carbon film 40, diffusion has Sulfur on the whole.
Therefore, tunicle 1 has less coefficient of friction compared with initial tunicle 100.
Therefore, according to the present invention, the demoulding that can reduce tunicle 1 is bad.
Carbon film 40 is containing hard amorphous carbon 41, nano-sized carbon 42 and fullerene 43.
The hard amorphous carbon 141 of hard amorphous carbon 41 for being formed through intermittent-heating operation S12.
Hard amorphous carbon 41 is formed in the following way, that is, through intermittent-heating operation S12 but not the fullerene 143 of a part for crystal qualitative makes hard amorphous carbon 141 densified.Thus, hard amorphous carbon 41 has finer and close structure compared with the hard amorphous carbon 141 of initial tunicle 100.
The nano-sized carbon 142 of nano-sized carbon 42 for being formed through intermittent-heating operation S12.The mode that nano-sized carbon 42 extends with the face side (upside of Fig. 3) to tunicle 1 from hard amorphous carbon 41 and being formed in a large number.Nano-sized carbon 42, is formed to arrive the mode of the position of the most surface of tunicle 1.
The fullerene 143 of fullerene 43 for being formed through intermittent-heating operation S12.
Fullerene 43 combines with nano-sized carbon 42 and makes the structure that carbon film 40 becomes finer and close.
Therefore, fullerene 43 can not be removed due to basic solvent.
Therefore, according to the present invention, the deterioration of tunicle 1 can be prevented.
In addition, till fullerene 43 diffuses to nitride compound layer 20 and diffusion layer 10.
As mentioned above, although in tunicle 1, in carbon film 40, overall diffusion has Sulfur, can infer, and this is because fullerene 43 soaks into reason to diffusion layer 10.
Specifically, through intermittent-heating operation S12, and make the fullerene 143 in the more face side being present in carbon film 140, produce with the phase counterdiffusion of the Sulfur on the more root being present in carbon film 140, be accompanied by this, can infer that overall diffusion in carbon film 40 has Sulfur.
In addition, owing to being easy to diffusion under the condition of fullerene generally more than 240 DEG C, the lower limit of the temperature (having the temperature of cooled motlten metal by contacting with the forming surface of described metal pattern) when therefore initial tunicle 100 is cooled in intermittent-heating operation S12 is preferably 240 DEG C.
And when the carbon film 140 of initial tunicle 100 is more than 600 DEG C, then have the possibility of oxidative degradation, therefore in intermittent-heating operation S12, initial tunicle 100 is preferably 600 DEG C by the upper limit of the temperature (initial temperature of motlten metal) during heating.
Hereinafter, be described with reference to the characteristic of Fig. 4 ~ Fig. 6 to tunicle involved in the present invention according to embodiment and comparative example.
First, before the operation implementing embodiment and comparative example, EPMA(ElectronProbeMicroAnalyser is implemented to initial tunicle 100: electron probe microanalysis (EPMA)) in surface analysis.Implementing the section of surface analysis is, the face that direction is internally cut-off along the surface from initial tunicle 100.
Fig. 4 illustrates the surface analysis result of the initial tunicle 100 in EPMA.Fig. 4 (a) is for representing the figure of the surface analysis result of the carbon in the initial tunicle 100 in EPMA, and Fig. 4 (b) is the figure of the surface analysis result of the Sulfur represented in the initial tunicle 100 in EPMA.
The Sulfur diffusivity in the carbon film of tunicle is obtained by this surface analysis result.
At this, the Sulfur diffusivity in carbon film refers to, implements in the section of the surface analysis in EPMA, the Sulfur ratio relative to carbon film.Such as, in the whole region of carbon film, diffusion has a Sulfur, Sulfur diffusivity is judged as 100%.
As shown in Fig. 4 (a) and Fig. 4 (b), can confirm as, in the carbon film 140 in initial tunicle 100, not be distributed with Sulfur on the whole, but more have Sulfur at root (bottom of Fig. 4 (b)) place.Now, can judge that the Sulfur diffusivity in the carbon film 140 in initial tunicle 100 is 50%.
In addition, known when X-ray diffraction implemented to initial tunicle 100, in initial tunicle 100, containing hard amorphous carbon, Fe 4n, Fe 3c, martensite and Fe 3o 4.
Embodiment
First, described oil-based release agent is coated in the forming surface of the metal pattern being formed with initial tunicle 100, and the state under initial tunicle 100 being become be in nonoxidizing atmosphere.
Next, the motlten metal of the aluminium alloy of 600 DEG C is filled in described metal pattern, and at heat transfer coefficient 6000W/m 2k(600 DEG C of 50MPa) heat transfer interface (forming surface of described metal pattern) on, initial tunicle 100 is implemented to the 4000kcal/m in 5 seconds 2enter heat.
Finally, cakey motlten metal (cast thing) is taken out from described metal pattern.
Tunicle 1 is prepared in the above-mentioned process that enforcement total is 1000 times.
Identical with initial tunicle 100, tunicle 1 is implemented to the surface analysis in EPMA.
Fig. 5 is the surface analysis result of the tunicle 1 represented in EPMA.Fig. 5 (a) is for representing the figure of the surface analysis result of the carbon in the tunicle 1 in EPMA, and Fig. 5 (b) is the figure of the surface analysis result of the Sulfur represented in the tunicle 1 in EPMA.
As shown in Fig. 5 (a) and Fig. 5 (b), can confirm as, in the carbon film 40 in tunicle 1, be distributed with Sulfur on the whole, even and if near surface (top of Fig. 5 (the b)) place of tunicle 1 also general equalization have Sulfur.Now, can judge that the Sulfur diffusivity in the carbon film 40 in tunicle 1 is 100%.
Thus, the Sulfur diffusivity of tunicle 1 compared with initial tunicle 100 in carbon film is larger.Therefore, as mentioned above, tunicle 1 has less coefficient of friction compared with initial tunicle 100, and the demoulding is bad compared with initial tunicle 100 diminishes.
In addition, although the Sulfur diffusivity in carbon film 40 in tunicle 1 is 100%, as long as the coefficient of friction of tunicle at least involved in the present invention diminishes compared with the coefficient of friction of initial tunicle.That is, as long as the Sulfur diffusivity in the carbon film in tunicle involved in the present invention is more than 50%.
In addition, known when X-ray diffraction implemented to tunicle 1, containing hard amorphous carbon, Fe in tunicle 1 4n, Fe 3c, martensite and Fe 3o 4.
As mentioned above, owing to containing Fe in tunicle 1 4n, described Fe 4n has and Fe 2n compares and finer and close structure, and therefore tunicle 1 is high strength compared with initial tunicle 100.
Comparative example
Using except water-soluble mold-release agent except replacing described oil-based release agent, implementing the operation identical with the above embodiments, thus prepare tunicle (following, to be stated as " comparing product ").
At this, water-soluble mold-release agent is different from oil-based release agent, can not prevent initial tunicle 100 from contacting with water and air.
That is, compare product to prepare by carrying out intermittence heating to initial tunicle 100 under oxidizing atmosphere.
Identical with tunicle 1, to the surface analysis compared in product enforcement EPMA.
Fig. 6 is the surface analysis result of the comparison product represented in EPMA.Fig. 6 (a) is for representing the figure of the surface analysis result of the carbon in the comparison product in EPMA, and Fig. 6 (b) is the figure of the surface analysis result of the Sulfur represented in the comparison product in EPMA.
As shown in Fig. 6 (a) and Fig. 6 (b), can confirm as, in the carbon film in relatively product, only have a few part to be distributed with Sulfur.Now, can be judged as, the Sulfur diffusivity in the carbon film in relatively product is 5%.
Thus, compare the Sulfur diffusivity of product compared with initial tunicle 100 in carbon film and diminish, and there is coefficient of friction larger compared with initial tunicle 100.That is, compare product the demoulding is bad compared with initial tunicle 100 and uprise.
As mentioned above, known tunicle involved in the present invention is prepared by carrying out intermittence heating to initial tunicle under nonoxidizing atmosphere.
And known tunicle involved in the present invention contains hard amorphous carbon, Fe 4n, Fe 3c, martensite and Fe 3o 4, and the Sulfur diffusivity in described carbon film is more than 50%.
In addition, although implement the surface analysis in EPMA during Sulfur diffusivity in the carbon film obtaining tunicle, as long as the Sulfur diffusivity in the carbon film of tunicle can be obtained, then its method is not limited.
In addition, although when differentiating material contained in tunicle, X-ray diffraction method is used, as long as carrying out mirror method for distinguishing to material contained in tunicle, then do not limit its method.
Utilizability in industry
The present invention can tunicle on the surface being formed on iron type materials and manufacture method in utilize.
Symbol description
1 tunicle
10 diffusion layers
20 nitride compound layers
30 sulphide layers
40 carbon films
41 hard amorphous carbons
42 nano-sized carbon
43 fullerenes
100 initial tunicles
110 diffusion layers
120 nitride compound layers
130 sulphide layers
140 carbon films
141 hard amorphous carbons
142 nano-sized carbon
143 fullerenes

Claims (3)

1. a manufacture method for tunicle, described tunicle is formed in the forming surface of the metal pattern used in casting,
The feature of the manufacture method of described tunicle is, possesses following operation:
Initial tunicle formation process, the forming surface of described metal pattern is formed initial tunicle, and wherein, described initial tunicle has: carbon film, and it contains nano-sized carbon class, and is coated with fullerene; Nitride compound layer and sulphide layer, described nitride compound layer and sulphide layer between described carbon film and described metal pattern,
Intermittent-heating operation, carries out intermittence heating to the initial tunicle formed in described initial tunicle formation process under nonoxidizing atmosphere,
In described intermittent-heating operation, be formed under the state that the forming surface of the metal pattern of described initial tunicle is coated with oil-based release agent, using this metal pattern to implement casting repeatedly.
2. a tunicle, its tunicle prepared for the manufacture method by tunicle according to claim 1, described tunicle has the carbon film containing nano-sized carbon class, and is formed on the surface of iron type materials,
The feature of described tunicle is,
Containing hard amorphous carbon, Fe 4n, Fe 3c, martensite and Fe 30 4,
Sulfur diffusivity in described carbon film is more than 50%.
3. tunicle as claimed in claim 2, is characterized in that,
The material be identified by X-ray diffraction method is hard amorphous carbon, Fe 4n, Fe 3c, martensite and Fe 30 4,
Described Sulfur diffusivity is obtained by the surface analysis in electron microprobe analysis.
CN201180073232.4A 2011-09-13 2011-09-13 Tunicle and manufacture method thereof Expired - Fee Related CN103764313B (en)

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Application Number Priority Date Filing Date Title
PCT/JP2011/070859 WO2013038503A1 (en) 2011-09-13 2011-09-13 Film and method for manufacturing same

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Publication Number Publication Date
CN103764313A CN103764313A (en) 2014-04-30
CN103764313B true CN103764313B (en) 2015-11-25

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US (1) US20140212689A1 (en)
JP (1) JP5660221B2 (en)
CN (1) CN103764313B (en)
DE (1) DE112011105613T5 (en)
WO (1) WO2013038503A1 (en)

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