CN114150260B - Laser surface carburizing method for low-carbon steel - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910001209 Low-carbon steel Inorganic materials 0.000 title claims abstract description 25
- 238000005255 carburizing Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 109
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 42
- 239000012188 paraffin wax Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000000084 colloidal system Substances 0.000 claims abstract description 20
- 229940057995 liquid paraffin Drugs 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005237 degreasing agent Methods 0.000 claims description 3
- 239000013527 degreasing agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 23
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000005728 strengthening Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 8
- 229910000734 martensite Inorganic materials 0.000 description 6
- 239000000110 cooling liquid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- C23C8/60—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 solids, e.g. powders, pastes
- C23C8/62—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 solids, e.g. powders, pastes only one element being applied
- C23C8/64—Carburising
- C23C8/66—Carburising of ferrous surfaces
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
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Abstract
The invention discloses a low-carbon steel laser surface carburizing method, which comprises the following steps: 1) preparing a colloid mixture of liquid paraffin and carbon powder, wherein the content of the carbon powder is 65-70%; 2) preparing a paraffin and carbon powder composite film on the surface to be coated with carbon, wherein the thickness of the composite film is 2.5-3 mm; 3) the surface of the low carbon steel is subjected to laser scanning in an atmosphere having an oxygen content of 1ppm or less to perform carburization. The invention utilizes the laser surface carburization technology to carry out carburization treatment on the low-carbon steel, and can improve the surface hardness and the fatigue property of parts. The invention adopts a special carbon coating mode, presets carbon powder with high efficiency, and simultaneously realizes the recycling of the carbon powder and paraffin. Therefore, a simple, efficient, green and environment-friendly novel treatment method can be provided for surface strengthening of the low-carbon steel metal parts, and the service life of the metal parts is prolonged.
Description
Technical Field
The invention relates to the technical field of heat treatment strengthening of low-carbon steel, in particular to a laser surface carburizing method for low-carbon steel.
Background
Low carbon steel cannot obtain a high-strength and high-hardness martensite structure after quenching because of low carbon content, and generally needs to be subjected to carburizing treatment. The conventional carburization treatment has long heat preservation time and low cooling speed, is easy to generate coarse martensite structures and carbide phases, and is extremely unfavorable for the toughness and the fatigue strength of parts.
The laser surface carburizing technology is that laser beam with energy density is utilized to scan metal part fast to raise the surface temperature of the part fast to over austenite phase transition temperature and below melting point, carbon element is diffused fast into the surface of the part, and when the laser beam leaves the surface, the metal part has fast heat exchange between the surface and the substrate to convert the austenite structure into martensite. The laser surface carburizing technology can greatly refine martensite and carbide and improve toughness and fatigue performance.
However, if the carbon powder is preset by adopting a traditional direct powder spreading or physical deposition mode, the carbon powder is easily combined with the base material poorly, holes are more in the carbon powder layer, and oxygen, moisture and the like are remained in the gaps between the carbon powder, so that the whole laser surface carburization process is influenced. Especially for the nano-scale carbon powder with high activity, the nano-scale carbon powder is easy to agglomerate and bond and is difficult to spread.
Disclosure of Invention
The invention aims to adopt a laser surface carburization strengthening method to carry out surface treatment on low-carbon steel and carry out carburization in a mode of presetting carbon powder.
The technical scheme of the invention is specifically that the low-carbon steel laser surface carburizing method is characterized by comprising the following steps:
1) preparing a colloid mixture of liquid paraffin and carbon powder, wherein the content of the carbon powder is 65-70%;
2) preparing a paraffin and carbon powder composite film on the surface to be coated with carbon, wherein the thickness of the composite film is 2.5-3 mm;
3) the surface of the low carbon steel is subjected to laser scanning in an atmosphere having an oxygen content of 1ppm or less to perform carburization.
Further preferably, the preparation of the colloid mixture of liquid paraffin and carbon powder comprises the steps of putting solid paraffin into a container, and heating in a water bath at 70-90 ℃; after the paraffin is completely melted, adding carbon powder into the flask for a few times, and continuously mixing and stirring; after the carbon powder is completely added, stirring is continued for 5-15 minutes to form a completely dispersed colloid mixture.
Further preferably, the preparation of the paraffin and carbon powder composite film on the surface to be carbon-coated is specifically that firstly, the surface to be carbon-coated is cleaned, and the cleaning method comprises the following steps: removing oil stains on the surface by using a chemical degreasing agent → hot water cleaning → running water cleaning → absolute ethyl alcohol cleaning → drying; pouring the prepared colloid mixture on the surface to be coated with carbon, and naturally cooling and solidifying in air; scraping redundant parts by using a knife to obtain the paraffin and carbon powder composite film with the thickness of 2.5-3 mm.
Further preferably, the atmosphere is an inert gas atmosphere, and is realized by introducing an inert protective gas or a mixed gas of methane and the inert protective gas before the carburizing treatment.
Further preferably, in the carburizing treatment, the low carbon steel to be treated is placed in a cooling liquid.
Further preferably, the effective energy per unit area E of the laser light is controlled by the following formula,
wherein P is the laser power, v is the scanning speed, and l is the spot diameter.
Further preferably, the carbon content is controlled by the following formula,
wherein w' is the surface carbon content, w0The original carbon content before carburization, d is the carburized layer thickness, and w is the carbon content at the distance h calculated according to the formula.
Further preferably, the number of times of laser scanning on the surface of the low carbon steel is 3-4.
Compared with the prior art, the method utilizes the laser surface carburization technology to perform carburization treatment on the low-carbon steel, can improve the surface hardness and fatigue performance of parts, adopts a special carbon coating mode, presets carbon powder with high efficiency, and simultaneously realizes the recycling of the carbon powder and paraffin. Therefore, a simple, efficient, green and environment-friendly novel treatment method can be provided for surface strengthening of the low-carbon steel metal parts, and the service life of the metal parts is prolonged.
Drawings
FIG. 1a is a schematic view of the water bath heating process before adding carbon powder in the preparation of the colloid mixture of paraffin and carbon powder of the present invention.
FIG. 1b is a schematic view of the colloidal mixture of paraffin and carbon powder of the present invention prepared by adding carbon powder and stirring.
FIG. 1c is a schematic view of the mixture formed by adding carbon powder and then continuously mixing and stirring the mixture when the colloid mixture of paraffin and carbon powder is prepared.
FIG. 2a is a schematic view of pouring a colloid mixture on the surface of a metal part when a composite film of paraffin and carbon powder is prepared on the surface to be coated with carbon according to the present invention.
FIG. 2b is a schematic view showing the cooling and solidification of the colloid mixture when the composite film of paraffin and carbon powder is prepared on the surface to be coated with carbon.
FIG. 2c is a schematic view of the present invention, when a composite film of paraffin and carbon powder is prepared on the surface to be coated with carbon, the colloid mixture is completely solidified and then the excess part is scraped off by a knife.
Fig. 2d is a schematic diagram of a composite film of paraffin and carbon powder with a given thickness finally obtained when the composite film of paraffin and carbon powder is prepared on the surface to be coated with carbon.
FIG. 3 is a schematic view of the carburizing process of the present invention.
FIG. 4 is a macro topography of low carbon steel after carburization in accordance with an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described below with reference to the drawings in the embodiments of the present invention.
Specifically, the low-carbon steel laser surface carburizing method mainly comprises the following steps:
1. preparation of colloidal mixture of liquid paraffin and carbon powder
In the step, the ratio of the paraffin to the carbon powder is the key for preparing the colloid mixture, and if the content of the carbon powder is too high, the carbon powder is easy to agglomerate and cannot be uniformly dispersed in the liquid paraffin; if the content of the carbon powder is too low, the carbon content in the paraffin and carbon powder mixed film is not enough, and an ideal carburizing effect cannot be achieved, and an ideal colloid mixture can be obtained when the carbon powder content is preferably 65-70%.
The preparation process of the colloid mixture of liquid paraffin and carbon powder is specifically shown in fig. 1 a-1 c. First, paraffin wax was placed in a flask and heated in a water bath at 80 ℃ (see fig. 1 a). After the paraffin was completely melted, carbon powder was added to the flask. The carbon powder is added in small amount and the mixture is stirred continuously by a stirrer to prevent the carbon powder from agglomerating (as shown in figure 1 b). After the carbon powder was added completely, stirring was continued for 10 minutes to form a completely dispersed liquid paraffin + carbon powder colloid mixture (see fig. 1 c).
2. Preparation of composite film of paraffin and carbon powder
The preparation process of the composite film of paraffin and carbon powder is shown in fig. 2 a-2 d. Firstly, cleaning the surface of a low-carbon steel metal part to be coated with carbon, wherein the cleaning method comprises the following steps: removing oil stains on the surface by using a chemical degreasing agent → washing with hot water → washing with running water → washing with absolute ethyl alcohol → drying. Pouring the prepared colloid mixture of liquid paraffin and carbon powder on the surface of the metal part (shown in figure 2 a), and naturally cooling and solidifying in air (shown in figure 2 b). After the colloidal mixture of paraffin and carbon powder was completely solidified, the excess was scraped off with a knife (shown in fig. 2 c) to obtain a composite film of paraffin and carbon powder of a given thickness (shown in fig. 2 d). The thickness of the paraffin and carbon powder composite film is generally 2.5-3mm, when the thickness is too small, the carburizing amount is insufficient, and when the thickness is too large, the carbon elements in the paraffin and carbon powder on the upper part of the film cannot effectively enter the surface layer of the part, so that waste is caused. The mixture of the paraffin and the carbon powder scraped by the knife can be recovered and then continuously used as a raw material to prepare liquid paraffin and carbon powder colloid.
3. Laser surface carburization
The laser surface carburizing treatment is shown in fig. 3, and the whole process is performed in the inert atmosphere forming chamber 4. Before laser surface carburization, inert gas is filled into the inert atmosphere forming cavity 4 for protection, or inert gas containing methane is filled into the inert atmosphere forming cavity for auxiliary carburization. Oxygen can cause decarburization and its content must be strictly controlled to ensure that the oxygen content is below 1 ppm. The metal part 2 coated with the composite film 3 of paraffin and carbon powder on the surface is placed on the table 1 and can be placed in the cooling liquid 6 (such as water), so that the cooling speed can be further increased, the generation of coarse martensite structures and carbides can be avoided, the fatigue strength of the metal part 2 can be improved, and particularly, the cooling liquid is preferably kept flowing as shown in fig. 3.
When the laser 5 is used for scanning carburization treatment, two process parameters are mainly regulated and controlled: energy input per unit area, number of scans. Wherein, the unit area energy input E is controlled by the following formula:
in the formula, P is laser power, v is scanning speed, l is spot diameter, and if the energy input per unit area is too small, the temperature cannot reach high enough, and the expected carburization effect cannot be achieved; excessive energy input per unit area results in melting of the metal parts, which can damage the parts. The energy input per unit area is generally 35 to 40 J.mm-2. Meanwhile, the scanning speed should be selected as large as possible, so that the surface of the metal part is heated to a high temperature instantly and then cooled rapidly to obtain a finer structure.
The number of scans will affect the carburized layer thickness and the carbon content after carburization. The thickness of the carburized layer increases along with the increase of the scanning times, and after 3 times of scanning, the thickness of the carburized layer does not increase basically and is 0.7-0.75mm at most. The carbon content of the surface of the metal part is increased along with the increase of the scanning times, after the metal part is scanned for 3 times, the carbon content of the surface of the metal part reaches 0.6-0.67%, after the metal part is scanned for 4 times, the carbon content of the surface of the metal part is 0.75-0.8%, and after the carbon content is more than 0.8%, the martensite structure of the surface of the metal part has larger brittleness, and the fatigue strength of the metal part is influenced. Therefore, the number of scanning is preferably 3 to 4. The greater the distance from the surface, the lower the carbon content, and the empirical formula for the carbon content w and the distance h from the surface is:
wherein w' is the surface carbon content, w0The original carbon content before carburization, d is the thickness of the carburized layer, and w is the carbon content at the position h away from the surface calculated according to a formula, so that the carbon content w at the depth h away from the surface can be calculated and estimated by monitoring the carbon content w' of the surface in real time, and whether the carburization requirement is met or not is judged.
4. Post-treatment
And measuring the surface roughness of the metal part by using a surface profile measuring instrument, and detecting surface defects by using methods such as surface permeability detection and the like. If the surface roughness meets the manufacturing requirements and the defects such as cracks do not exist, the method can be used in a deliverable way.
The specific embodiment parameters of the invention are set as follows:
the steel 18CrMnTi for the gear shaft is subjected to laser surface carburization, the laser power is 4000W, the scanning speed is 1.2mm/s, the spot diameter is 10mm, the thickness of a paraffin and carbon powder composite film is 2.5mm, and the scanning times are 4 times.
After laser surface carburization treatment in an inert gas protective atmosphere, a carburized layer with the thickness of 0.725mm is obtained, the surface hardness reaches about 800HV, and the surface hardness is improved by more than 1.6 times compared with an untreated sample (300 HV). Tests show that the surface carbon content is 0.77%, the surface roughness is Ra1.2, and the manufacturing requirements of the gear shaft are met. The macroscopic topography of the carburized layer is shown in fig. 4.
In conclusion, the laser surface carburization technology is utilized to perform carburization treatment on the low-carbon steel, so that the surface hardness and the fatigue property of the part can be improved. The invention adopts a special carbon coating mode, presets carbon powder with high efficiency, and simultaneously realizes the recycling of the carbon powder and paraffin. Therefore, a simple, efficient, green and environment-friendly novel treatment method can be provided for surface strengthening of the low-carbon steel metal parts, and the service life of the metal parts is prolonged.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (6)
1. The laser surface carburizing method for the low-carbon steel is characterized by comprising the following steps of:
1) preparing a colloid mixture of liquid paraffin and carbon powder, wherein the content of the carbon powder is 65-70%; the preparation of the colloid mixture of the liquid paraffin and the carbon powder comprises the steps of putting the solid paraffin into a container, and heating in a water bath at 70-90 ℃; after the paraffin is completely melted, adding carbon powder into the flask for a few times, and continuously mixing and stirring; after the carbon powder is completely added, continuously stirring for 5-15 minutes to form a completely dispersed colloid mixture;
2) preparing a paraffin and carbon powder composite film on the surface to be coated with carbon, wherein the thickness of the composite film is 2.5-3 mm; the preparation of the paraffin and carbon powder composite film on the surface to be coated with carbon comprises the following steps of firstly, cleaning the surface to be coated with carbon, wherein the cleaning method comprises the following steps: removing oil stains on the surface by using a chemical degreasing agent → hot water cleaning → running water cleaning → absolute ethyl alcohol cleaning → drying; pouring the prepared colloid mixture on the surface to be coated with carbon, and naturally cooling and solidifying in air; scraping redundant parts by using a knife to obtain a paraffin and carbon powder composite film with the thickness of 2.5-3 mm;
3) the surface of the low carbon steel is subjected to laser scanning in an atmosphere having an oxygen content of 1ppm or less to perform carburization.
2. The method according to claim 1, wherein the atmosphere is an inert gas atmosphere by introducing an inert gas atmosphere or a mixed gas of methane and an inert gas atmosphere before the carburizing treatment.
3. The method of claim 1, wherein the low carbon steel to be treated is placed in a coolant during the carburizing treatment.
4. The method of claim 1, wherein the effective energy per unit area E of the laser is controlled by the following formula,
wherein P is the laser power, v is the scanning speed, and l is the spot diameter.
5. The method according to claim 1, wherein the carbon content is controlled by the following formula,
wherein w' is the surface carbon content, w0The original carbon content before carburization, d is the carburized layer thickness, and w is the carbon content at the distance h calculated according to the formula.
6. The method of claim 1, wherein the laser scanning the surface of the mild steel is performed 3-4 times.
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|---|---|---|---|---|
| GB570971A (en) * | 1943-10-21 | 1945-07-31 | Sydney Charles Caddy | Improvements in or relating to case-hardening of iron and steel |
| JPS59179776A (en) * | 1983-03-29 | 1984-10-12 | Shinko Electric Co Ltd | Surface hardening method by carburization hardening of pure iron and low carbon steel by laser |
| JPH0941125A (en) * | 1995-07-28 | 1997-02-10 | Hitachi Seiki Co Ltd | Method for hardening metallic surface |
| CN103526152A (en) * | 2012-07-03 | 2014-01-22 | 山东科技大学 | Nitriding catalyst |
| CN108796425A (en) * | 2017-04-28 | 2018-11-13 | 陈兴月 | A kind of New Kind of Anti-Carburizing Paint |
| CN108914051A (en) * | 2018-06-21 | 2018-11-30 | 北京煜鼎增材制造研究院有限公司 | Metal material laser surface carburization process and its painting carbon device |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB570971A (en) * | 1943-10-21 | 1945-07-31 | Sydney Charles Caddy | Improvements in or relating to case-hardening of iron and steel |
| JPS59179776A (en) * | 1983-03-29 | 1984-10-12 | Shinko Electric Co Ltd | Surface hardening method by carburization hardening of pure iron and low carbon steel by laser |
| JPH0941125A (en) * | 1995-07-28 | 1997-02-10 | Hitachi Seiki Co Ltd | Method for hardening metallic surface |
| CN103526152A (en) * | 2012-07-03 | 2014-01-22 | 山东科技大学 | Nitriding catalyst |
| CN108796425A (en) * | 2017-04-28 | 2018-11-13 | 陈兴月 | A kind of New Kind of Anti-Carburizing Paint |
| CN108914051A (en) * | 2018-06-21 | 2018-11-30 | 北京煜鼎增材制造研究院有限公司 | Metal material laser surface carburization process and its painting carbon device |
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Address after: No. 1205, 1f, building 12, neijian Middle Road, Xisanqi building materials City, Haidian District, Beijing 100096 Patentee after: Beijing Yuding Additive Manufacturing Research Institute Co.,Ltd. Address before: No. 1205, 1f, building 12, neijian Middle Road, Xisanqi building materials City, Haidian District, Beijing 100096 Patentee before: BEIJING YUDING ZENGCAI MANUFACTURE RESEARCH INSTITUTE Co.,Ltd. |
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