NL2032910B1 - Three-stage carbon-nitrogen-boron ternary gas deep co-infiltration method of low-carbon nickel-molybdenum steel - Google Patents
Three-stage carbon-nitrogen-boron ternary gas deep co-infiltration method of low-carbon nickel-molybdenum steel Download PDFInfo
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- 238000001764 infiltration Methods 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 239000010959 steel Substances 0.000 title claims abstract description 23
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 title claims abstract description 12
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000005255 carburizing Methods 0.000 claims abstract description 56
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000008595 infiltration Effects 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000003350 kerosene Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004327 boric acid Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract 2
- 238000005271 boronizing Methods 0.000 claims description 29
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 238000005121 nitriding Methods 0.000 claims description 19
- 238000005256 carbonitriding Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- -1 rare earth lanthanum oxide Chemical class 0.000 claims description 12
- 239000011775 sodium fluoride Substances 0.000 claims description 12
- 235000013024 sodium fluoride Nutrition 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 238000009792 diffusion process Methods 0.000 claims description 9
- 229910052580 B4C Inorganic materials 0.000 claims description 6
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 235000013877 carbamide Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- ZSEYAXRJXUBNLN-UHFFFAOYSA-N [Mo].[Ni].[C] Chemical compound [Mo].[Ni].[C] ZSEYAXRJXUBNLN-UHFFFAOYSA-N 0.000 claims 1
- 229940057952 methanol Drugs 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 238000005553 drilling Methods 0.000 abstract description 8
- 150000004767 nitrides Chemical class 0.000 abstract description 8
- 230000007123 defense Effects 0.000 abstract description 2
- 238000003754 machining Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910000734 martensite Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 48
- 235000019589 hardness Nutrition 0.000 description 19
- 229910052796 boron Inorganic materials 0.000 description 10
- 229960000414 sodium fluoride Drugs 0.000 description 10
- 238000011068 loading method Methods 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- 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
- C23C8/40—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 liquids, e.g. salt baths, liquid suspensions
- C23C8/42—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 liquids, e.g. salt baths, liquid suspensions only one element being applied
-
- 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
- C23C8/40—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 liquids, e.g. salt baths, liquid suspensions
- C23C8/42—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 liquids, e.g. salt baths, liquid suspensions only one element being applied
- C23C8/44—Carburising
- C23C8/46—Carburising of ferrous surfaces
-
- 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
- C23C8/40—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 liquids, e.g. salt baths, liquid suspensions
- C23C8/52—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 liquids, e.g. salt baths, liquid suspensions more than one element being applied in one step
- C23C8/54—Carbo-nitriding
- C23C8/56—Carbo-nitriding of ferrous surfaces
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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
- C23C8/40—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 liquids, e.g. salt baths, liquid suspensions
- C23C8/58—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 liquids, e.g. salt baths, liquid suspensions more than one element being applied in more than one step
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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
- C23C8/80—After-treatment
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- Engineering & Computer Science (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
A three—stage carbon—nitrogen—boron ternary gas deep co— infiltration method for low—carbon nickel—molybdenum steel is disclosed. According to the method, low—carbon nickel—molybdenum steel is placed in a carburizing furnace and a co—infiltration agent composed of kerosene, anhydrous methanol, liquid ammonia, boric acid and lanthanum oxide is added; by using a chemical heat treatment method, with the action of lanthanum oxide and other catalysts, a three—stage ternary gas co—infiltration process is carried out, and finally surface fine needle martensite, nitride and boride are obtained, greatly improving the hardness and wear resistance of parts; the method of the present disclosure is low in cost, simple and controllable in process, provides technical support for the production of high—strength and high—wear— resistant surface—modified drill bits, therefore, this method has broad application prospects in the fields of precision machining, national defense industry, and oil drilling, etc.
Description
P1494 /NLpd
THREE-STAGE CARBON-NITROGEN-BORON TERNARY GAS DEEP CO-INFILTRATION
METHOD OF LOW-CARBON NICKEL-MOLYBDENUM STEEL
The present disclosure relates to the field of new materials, particularly to a three-stage carbon-nitrogen-boron ternary gas deep co-infiltration method of low-carbon nickel-molybdenum steel.
Drill bits are important tools for oil drilling. The drill bits used for oil drilling have the functions of impacting, crush- ing and shearing the formation rock when rotating, and their work- ing performance will directly affect the drilling quality, drill- ing efficiency and drilling cost. The conventional carburization technology has gradually become unsatisfactory.
In recent years, researchers have done a lot of work on the synthesis and preparation of boron-carbon-nitrogen materials, among which there are some reach basis of ternary co-filtration.
As disclosed in the Chinese patent application with publication number CN1442504A “A Boron-carbon-nitrogen Ternary Co-infiltration
Method” (application number: CN02109872.4), a solid boronizing agent is used to place in a carburizing furnace and separated from the workpiece; at the same time, the carbon and nitrogen co- infiltration liquid is dripped into a carburizing furnace respec- tively to form a ternary gas phase co-infiltration of boron, car- bon and nitrogen. The co-infiltration temperature is 750-870 °C, the co-infiltration speed is 0.15-0.2mm/hour, and oil cooling or water cooling is performed after discharge. This patented technol- ogy only considers the shallow co-infiltration technology under low temperature co-infiltration. The thickness of the infiltration layer is only 0.3 mm, mainly carburizing (C) and nitriding (N), and the infiltration of boron (B) at low temperature is seriously insufficient, which affects the impact toughness and other perfor- mance indexes and cannot meet the requirements of high hardness, high wear resistance and high impact resistance, such as oil drilling bits. At present, the carbon-nitride-boron co- infiltration technology of low-carbon nickel-molybdenum steels (for example, 20Ni3Mo, 20Ni4Mo) that can be searched can only ob- tain a co-infiltration layer thickness of less than 0.7 mm. Com- pared with the deep nitriding technology of European and American countries (the co-infiltration layer is about 1mm), Chinese deep nitriding or co-infiltration technology is still poor.
In view of the current situations in the prior art, the ob- ject of the present disclosure is to provide a three-stage carbon- nitrogen-boron ternary gas deep co-infiltration method. For the low-carbon nickel-molybdenum steel, a three-stage ternary co- infiltration method with stepwise control of temperature and time is adopted, to obtain a deep co-infiltration layer. The thickness of the nitriding layer can reach 0.75-1.2 mm, which can signifi- cantly improve the fatigue life and impact toughness of low-carbon nickel-molybdenum steel and satisfy the needs for deep nitriding of oil drill bits and other parts.
In order to achieve the above object, the present disclosure adopts the following technical solutions: (1) preparing boronizing agent, uniformly mixing 2-3% by weight of rare earth lanthanum oxide, 5-15% by weight of boron carbide, 15% by weight of potassium fluoroborate, and the balance of silicon carbide, bonding and drying into solid blocks; mean- while, preparing carbonitriding liquid, wherein the carbonitriding liquid is composed of 50% by weight of carbamide, 40% by weight of sodium carbonate and 10% by weight of sodium chloride; (2) placing the low-carbon nickel-molybdenum steel drill bit workpiece to be treated in a drip-controlled carburizing furnace, heating to 860 °C, and exhausting for 1 hour; (3) carrying out a gas ternary deep co-infiltration process by a three-stage co-infiltration method: 3.1. The first stage is to carry out carburizing mainly, pre- serving heat for 2 h at the initial heating temperature of 860°C before carburizing, wherein the dripping speed of methanol is 40 drops/min, the dripping speed of kerosene is 120-160 drops/min,
the kerosene sulfur content is<0.04%+,the furnace pressure is 25-35 mmHg, the carburazing period is 5-8 hours, the diffusion period is 3-6 hours, and the infiltration rate is 0.18-0.25 mm/hour; 3.2. The second stage is to carry out carburizing and bo- ronizing on the basis of the carburizing in the first stage, add- ing solid boronizing agent prepared in the step 1 and sodium fluo- ride with a mass fraction of 40% to carry out carbon-boronizing in the furnace atmosphere according to the dosage of sodium fluoride at 30 g/h and boronizing agent at 40 g/h, in addition, adding dropwise by 10% mass fraction of boric acid at a dripping speed of 40 drops/min; or adding 50 g-60 g of boric acid solution to each liter of methanol mixture in the first stage according to the dos- age of boric acid between 0.83 g/min and 1g/min, wherein the car- bon-boronizing period is 1 h, then continuing to heat to 920 °C from the original 860°C, and preserving heat for 10 h; 3.3. The third stage is to carry out carburizing and nitrid- ing mainly, lowering the temperature from 920 °C to 870 °C-880 °C in the second stage, preserving heat for 6 h, adding carbonitrid- ing liquid prepared in the step 1 into the furnace atmosphere of the second stage, wherein the dripping speed is 4-6 ml/min, fur- thermore, introducing pure nitrogen N; at a rate of 0.03 m’/h to increase the depth of the co-nitriding layer, or dripping liquid ammonia at a drip rate of 0.09-0.12 liters/h to improve the ni- triding efficiency and the thickness of the co-infiltration layer; (4) performing furnace cooling or air cooling of co- infiltration parts.
Compared with the prior art, the present disclosure has the following advantages:
By using this method, the carbon-nitride-boron co- infiltration layer can be obtained with a thickness of about 0.75- 1.2 mm, and the obtained co-infiltration part has good hardness, wear resistance and fatigue resistance.
The present disclosure adopts a three-stage ternary co- infiltration process. The first stage is mainly carburizing (the mass percentage of carbon content is 0.8-1.6%) to prevent the ap- pearance of carbide mesh; the second stage is mainly carburizing and boronizing (the mass percentage of boron content is 0.02-
0.04%), which greatly improves the impact toughness and bending fatigue strength; the third stage is mainly carburizing and ni- triding (the mass percentage of nitrogen content is 0.3-0.5%), which greatly improves the red hardness. The method is suitable for low-carbon nickel-molybdenum steel wear parts or tool parts that have high requirements on wear resistance and impact tough- ness of hardness testers, and can significantly improve the hard- ness, wear resistance and fatigue life of workpieces; the prepara- tion of penetration agent is simple and the equipment technology is simple.
The above three-stage ternary co-infiltration method can greatly improve the fatigue life of low-carbon nickel-molybdenum steel. Compared with the conventional carburizing process, the service life is increased by more than 2 times, the hardness is increased by more than 3HRC, and the impact toughness is also dou- bled. These drill bits after surface modification by three-stage co-infiltration method have broad application prospects in the fields of precision machining, national defense industry and oil drilling, etc.
The present disclosure is further described in detail below with reference to the specific embodiments.
Example 1
This example comprises the following steps: (1) prepare boronizing agent, uniformly mixing 2% by weight of rare earth lanthanum oxide, 5% by weight of boron carbide, 15% by weight of potassium fluoroborate, and the balance of silicon carbide, bond and dry into solid blocks; meanwhile, prepare car- bonitriding liquid, wherein the carbonitriding liquid is composed of 50% by weight of carbamide, 40% by weight of sodium carbonate and 10% by weight of sodium chloride; (2) place the 20Ni4Mo steel drill bit workpiece to be treated in a drip-controlled carburizing furnace, heat to 860 °C, and ex- haust for 1 hour; (3) carry out a gas ternary deep co-infiltration process by a three-stage co-infiltration method:
3.1. The first stage is to carry out carburizing mainly, pre- serving heat for 2 h at the initial heating temperature of 860 °C before carburizing, wherein the dripping speed of methanol is 40 drops/min, the dripping speed of kerosene is 120 drops/min, the 5 kerosene sulfur content i1s<0.04%, to ensure carburizing quality, the furnace pressure is 25 mmHg; take a 20Nid4Mo steel drill bit workpiece with a diameter less than 200 mm, wherein the carburaz- ing period (tl) is 5-6 hours, the diffusion period (t2) is 3-4 hours (shown in Table 1), and the infiltration rate is 0.18 mm/hour; 3.2. The second stage is to carry out carburizing and bo- ronizing on the basis of the carburizing in the first stage, add solid boronizing agent prepared in the step 1 and sodium fluoride with a mass fraction of 40% to carry out carbon-boronizing in the furnace atmosphere according to the dosage of sodium fluoride at 30 g/h and boronizing agent at 40 g/h, in addition, add dropwise by 10% mass fraction of boric acid at a dripping speed of 40 drops/min, wherein the carbon-boronizing period is 1 h, then con- tinue to heat to 920 °C from the original 860°C, and preserve heat for 10 h; 3.3. The third stage is to carry out carburizing and nitrid- ing mainly, lower the temperature from 920 °C to 870 °C in the second stage, preserving heat for 6 h (t3), add carbonitriding liquid prepared in the step 1 into the furnace atmosphere of the second stage, wherein the dripping speed is 4 ml/min, furthermore, introduce pure nitrogen N, at a rate of 0.03 m’/h to increase the depth of the co-nitriding layer at a drip rate of 0.09 liters/h to improve the nitriding efficiency and the thickness of the co- infiltration layer; (4) perform furnace cooling or air cooling of co- infiltration parts.
The parameters in the above steps are selected from the lower values within the range of parameters. The co-infiltration temper- ature of the third stage is 870 ° C to obtain a deeper ternary co- infiltration layer with a carbon content of 0.81%, a nitrogen con- tent of 0.177% and a boron content of 0.034%. According to the method, the obtained ternary co-infiltration layer has a thickness of about 0.95-1.15 mm. The hardness of the surface layer is meas- ured to be 1,000-1,150 HV under the above process, and the hard- ness of the infiltration layer at a thickness of 1 mm is still as high as 950 HV, and the wear resistance is about 2.8-3 times high- er than that of the first stage of carburization, at this time, the dispersion degree of carbide is higher. In addition, a ternary co-infiltration layer with a high thickness is obtained, and the nitride and boride are dispersed. The thickness of the nitride layer is increased to 1.06 mm, the fatigue life is increased by 18-20 times, and the comprehensive performance is greatly im- proved.
Table 1
Serial | Speci- | Com- Loading | tl ofthe | t2 ofthe | t3 ofthe | Qutermost | Thickness
No. fica- ponent | capacity | first second third layer hard- | of co- tion clear- stage stage stage ness HV infiltration ance (hour) {hour} {hour}) layer (mm)
Tem ew [wo [v3 Jo [wem wn ee efor sem fen wo Jos]
I i il ll
Note: Under the above loading capacity, a ®80mm ventilating duct is reserved in the center of the charging basket.
Example 2
This example comprises the following steps: (1) prepare boronizing agent, uniformly mixing 2% by weight of rare earth lanthanum oxide, 5% by weight of boron carbide, 15% by weight of potassium fluoroborate, and the balance of silicon carbide, bond and dry into solid blocks; meanwhile, prepare car- bonitriding liquid, wherein the carbonitriding liquid is composed of 50% by weight of carbamide, 40% by weight of sodium carbonate and 10% by weight of sodium chloride; {2} place the 20Ni4Mo steel drill bit workpiece to be treated in a drip-controlled carburizing furnace, heat to 860 °C, and ex- haust for 1 hour; {3) carry out a gas ternary deep co-infiltration process by a three-stage co-infiltration method: 3.1. The first stage is to carry out carburizing mainly, pre- serving heat for 2 h at the initial heating temperature of 860 °C before carburizing, wherein the dripping speed of methanol is 40 drops/min, the dripping speed of kerosene is 120 drops/min, the kerosene sulfur content is<0.04%, to ensure carburizing quality, the furnace pressure is 25 mmHg; take a 20Ni4Mo steel drill bit workpiece with a diameter less than 200 mm, wherein the carburaz- ing period (tl) is 5-6 hours, the diffusion period (t2) is 3-4 hours (shown in Table 2}, and the infiltration rate is 0.18 mm/ hour; 3.2. The second stage is to carry out carburizing and bo- ronizing on the basis of the carburizing in the first stage, add solid boronizing agent prepared in the step 1 and sodium fluoride with a mass fraction of 40% to carry out carbon-boronizing in the furnace atmosphere according to the dosage of sodium fluoride at 30 g/h and boronizing agent at 40 g/h, in addition, in the first stage, add 50 g of boric acid solution to per liter of methanol mixture to control the amount of boric acid of 0.83 g/min, wherein the carbon-boronizing period is 1 h, then continue to heat to 920 °C from the original 860°C, and preserve heat for 10 h; 3.3. The third stage is to carry out carburizing and nitrid- ing mainly, lower the temperature from 920 °C te 870 °C in the second stage, preserving heat for 6 h (t3), add carbonitriding liquid prepared in the step 1 into the furnace atmosphere of the second stage, wherein the dripping speed is 4 ml/min, furthermore, introduce liquid ammonia at a drip rate of 0.09 liters/h to im- prove the nitriding efficiency and the thickness of the co- infiltration layer; {4) perform furnace cooling or air cooling of co-infiltration parts.
The parameters in the above steps are selected from the lower values within the range of parameters. The co-infiltration temper- ature of the third stage is 870 ° C to obtain a deeper ternary co- infiltration layer with a carbon content of 0.80%, a nitrogen con- tent of 0.175% and a boron content of 0.03%. According to the method, the obtained ternary co-infiltration layer has a thickness of about 0.75-1.1 mm. The hardness of the surface layer is meas- ured to be 1,000-1,100 HV under the above process, and the hard- ness of the infiltration layer at a thickness of 1 mm is still as high as 925 HV, and the wear resistance is about 2.5-3 times high- er than that of the first stage of carburization, at this time, the dispersion degree of carbide is higher. In addition, a ternary co-infiltration layer with a high thickness is obtained, and the nitride and boride are dispersed. The thickness of the nitride layer is increased to 1.05 mm, the fatigue life is increased by 17-20 times, and the comprehensive performance is greatly im- proved.
Table 2
Serial | Speci- | Com- Loading | tl ofthe | t2 ofthe | t3 ofthe | Outermost Thickness
No. fica- ponent | capacity | first second third layer hard- | of co- tion clear- stage stage stage ness HY infiltration ance {hour) {hour) (hour) layer (mm) offs forme a 3 ®230 | 6-10 8 8 |6 6 | 1000-1100 | 0.85-1.1 fence ee
Note: Under the above loading capacity, a ®80mm ventilating duct is reserved in the center of the charging basket.
Example 3
This example comprises the following steps: (1) prepare boronizing agent, uniformly mixing 2.5% by weight of rare earth lanthanum oxide, 10% by weight of boron carbide, 155 by weight of potassium fluoroborate, and the balance of silicon carbide, bond and dry into solid blocks; meanwhile, prepare car- bonitriding liquid, wherein the carbonitriding liquid is composed of 50% by weight of carbamide, 40% by weight of sodium carbonate and 10% by weight of sodium chloride; {2} place the 20Ni4Mo steel drill bit workpiece to be treated in a drip-controlled carburizing furnace, heat to 860 °C, and ex- haust for 1 hour; {3) carry out a gas ternary deep co-infiltration process by a three-stage co-infiltration method: 3.1. The first stage is to carry out carburizing mainly, pre- serving heat for 2 h at the initial heating temperature of 860 °C before carburizing, wherein the dripping speed of methanol is 40 drops/min, the dripping speed of kerosene is 140 drops/min, the kerosene sulfur content is<0.04%, to ensure carburizing quality, the furnace pressure is 30 mmHg; take a 20Ni4Mo steel drill bit workpiece with a diameter less than 200 mm, wherein the carburaz- ing period (tl) is 5-6 hours, the diffusion period (t2) is 3-4 hours (shown in Table 3}, and the infiltration rate is 0.21 mm/ hour; 3.2. The second stage is to carry out carburizing and bo- ronizing on the basis of the carburizing in the first stage, add solid boronizing agent prepared in the step 1 and sodium fluoride with a mass fraction of 40% to carry out carbon-boronizing in the furnace atmosphere according to the dosage of sodium fluoride at 30 g/h and boronizing agent at 40 g/h, in addition, add dropwise by 10% mass fraction of boric acid at a dripping speed of 40 drops/min, wherein the carbon-boronizing period is 1 h, then con- tinue to heat to 920 °C from the original 860°C, and preserve heat for 10 h; 3.3. The third stage is to carry out carburizing and nitrid- ing mainly, lower the temperature from 920 °C te 870 °C in the second stage, preserving heat for 6 h (t3), add carbonitriding liquid prepared in the step 1 into the furnace atmosphere of the second stage, wherein the dripping speed is 5 ml/min, furthermore, introduce liquid ammonia at a drip rate of 0.105 liters/h to im- prove the nitriding efficiency and the thickness of the co- infiltration layer; {4) perform furnace cooling or air cooling of co-infiltration parts.
The parameters in the above steps are selected from the in- termediate values within the range of parameters. The co- infiltration temperature of the third stage is 875 ° C to obtain a deeper ternary co-infiltration layer with a carbon content of 0.81%, a nitrogen content of 0.178% and a boron content of 0.034%.
According to the method, the obtained ternary co-infiltration lay-
er has a thickness of about 1.0-1.2 mm. The hardness of the sur- face layer is measured to be 1,000-1,150 HV under the above pro- cess, and the hardness of the infiltration layer at a thickness of 1 mm is still as high as 965 HV, and the wear resistance is about 2.5-3 times higher than that of the first stage of carburization, at this time, the dispersion degree of carbide is higher. In addi- tion, a ternary co-infiltration layer with a high thickness is ob- tained, and the nitride and boride are dispersed. The thickness of the nitride layer is increased to 1.06 mm, the fatigue life is in- creased by 18-20 times, and the comprehensive performance is greatly improved.
Table 3
Serial | Speci- | Com- Loading | tl ofthe | t2 ofthe | t3 ofthe | Outermost Thickness
No. fica- ponent | capacity | first second third layer hard- | of co- tion clear- stage stage stage ness HY infiltration ance {hour) {hour) (hour) layer (mm) ese ef fer i 3 ®170 | 6-10 14 6 3 6 | 1000-1150 | 1.0-1.2 foe a a
Note: Under the above loading capacity, a ®80mm ventilating duct is reserved in the center of the charging basket.
Example 4
This example comprises the following steps: (1) prepare boronizing agent, uniformly mixing 3% by weight of rare earth lanthanum oxide, 15% by weight of boron carbide, 155 by weight of potassium fluoroborate, and the balance of silicon carbide, bond and dry into solid blocks; meanwhile, prepare car- bonitriding liquid, wherein the carbonitriding liquid is composed of 50% by weight of carbamide, 40% by weight of sodium carbonate and 10% by weight of sodium chloride; {2} place the 20Ni4Mo steel drill bit workpiece to be treated in a drip-controlled carburizing furnace, heat to 860 °C, and ex- haust for 1 hour; {3) carry out a gas ternary deep co-infiltration process by a three-stage co-infiltration method: 3.1. The first stage is to carry out carburizing mainly, pre- serving heat for 2 h at the initial heating temperature of 860 °C before carburizing, wherein the dripping speed of methanol is 40 drops/min, the dripping speed of kerosene is 160 drops/min, the kerosene sulfur content is<0.04%, to ensure carburizing quality, the furnace pressure is 35 mmHg, take a 20Ni4Mo steel drill bit workpiece with a diameter of 200 mm-300 mm, wherein the carburaz- ing period (tl) is 8 hours, the diffusion period (t2) is 5-6 hours (shown in Table 4), and the infiltration rate is 0.25 mm/hour; 3.2. The second stage is to carry out carburizing and bo- ronizing on the basis of the carburizing in the first stage, add solid boronizing agent prepared in the step 1 and sodium fluoride with a mass fraction of 40% to carry out carbon-boronizing in the furnace atmosphere according to the dosage of sodium fluoride at 30 g/h and boronizing agent at 40 g/h, in addition, in the first stage, add 60 g of boric acid solution to per liter of methanol mixture to control the amount of boric acid of 1 g/min, wherein the carbon-boronizing period is 1 h, then continue to heat to 920 °C from the original 860°C, and preserve heat for 10 h; 3.3. The third stage is to carry out carburizing and nitrid- ing mainly, lower the temperature from 920 °C to 880 °C in the second stage, preserving heat for 6 h (t3), add carbonitriding liquid prepared in the step 1 into the furnace atmosphere of the second stage, wherein the dripping speed is 5 ml/min, furthermore, introduce pure nitrogen N, at a rate of 0.03 m’/h to increase the depth of the co-nitriding layer at a drip rate of 0.12 liters/h to improve the nitriding efficiency and the thickness of the co- infiltration layer; (4) perform furnace cooling or air cooling of co-infiltration parts.
The parameters in the above steps are selected from the high- est values within the range of parameters. The co-infiltration temperature of the third stage is 880 ° C to obtain a deeper ter- nary co-infiltration layer with a carbon content of 0.81%, a ni- trogen content of 0.177% and a boron content of 0.033%. According to the method, the obtained ternary co-infiltration layer has a thickness of about 0.95-1.1 mm. The hardness of the surface layer is measured to be 1,000-1,150 HV under the above process, and the hardness of the infiltration layer at a thickness of 1 mm is still as high as 965 HV, and the wear resistance is about 2.5-3 times higher than that of the first stage of carburization, at this time, the dispersion degree of carbide is higher. In addition, a ternary co-infiltration layer with a high thickness is obtained, and the nitride and boride are dispersed. The thickness of the ni- tride layer is increased to 1.05 mm, the fatigue life is increased by 18-20 times, and the comprehensive performance is greatly im- proved.
Table 4
Serial | Speci- | Com- Load- | tl ofthe | t2 ofthe | t3 ofthe | Outermost Thickness
No. fica- ponent | ing first second third layer hard- | of co- tion clear- ca- stage stage stage ness HV infiltration ance pacity | {hour} (hour) {hour)) layer (mm) ae aa
Ee foi come = 5
Note: Under the above loading capacity, a ®80mm ventilating duct is reserved in the center of the charging basket.
Comparative example:
This comparative example comprises the following steps: (1) place the 20Ni4Mo steel drill bit workpiece with @100 mm-5200 mm and 20Ni3Mo steel drill bit workpiece with ®200 mm-®300 mm to be treated in a drip-controlled carburizing furnace, heat to 860 °C, and exhaust for 1 hour; (2) continuously drip the co-penetrating agent composed of kerosene (CnH2n, etc.), anhydrous methanol (CH30H), liquid ammonia (NH3), etc. (wherein the kerosene sulfur content is less than 0.04% to ensure the carburizing quality) into a carburizing fur- nace; when the carbon active atoms generated by the decomposition of heat reach a certain atomic concentration, charge and carry out carburizing treatment on the surface of the drill bit;
(3) carry out carburizing only, preserve heat for 2 h at the initial heating temperature of 860 °C before carburizing, wherein the dripping speed of methanol is 40 drops/min, the dripping speed of kerosene is 140 drops/min (the kerosene sulfur content 1s<0.04%, to ensure the carburizing quality), the furnace pressure is 30 mmHg, for the 20Ni4Mo drill bits, the carburazing period (t 1) is 5-6 hours, the diffusion period (t 2 ) is 3-4 hours; for the 20Ni3Mo drill bits, the carburazing period (t 1) is 8 hours, the diffusion period (t 2 } is 5-6 hours (shown in Table 5), and the infiltration rate is 0.21 mm/hour; (4) perform furnace cooling or air cooling of co- infiltration parts after the above steps are completed.
After the end of the above steps, the obtained co- infiltration layer has a carbon content of about 1.2%, and a car- burized layer thickness of about 1.2-2.1 mm. After measurement, the surface hardness in this step is only 880-890HV, and the hard- ness of the infiltration layer when the distance from the surface thickness is 0.5mm is about 600 HV, and the hardness of the infil- tration layer when the distance from the surface thickness is 1mm is about 400HV. After carburizing, the wear resistance is in- creased by about 1 time and the carbides are distributed in a net- work.
Table 5
Serial | Specification | Component | Loading | Carburizing | Diffusion | Outermost | Thickness
No. clearance capacity | period t; period layer of co- (hour) 12 {hour} | hardness infiltration
HV layer (mm) fewer im 3 6-10 140 880-890 lef fe ee on
Jen pe RF EO pee coe 9 EE ee
Note: Under the above loading capacity, a @®80mm ventilating duct is reserved in the center of the charging basket.
Therefore, compared with the comparative example, the present disclosure has the advantages as follows:
By using this method, the carbon-nitride-boron co- infiltration layer can be obtained with a thickness of about 0.75- 1.2 mm, and the obtained co-infiltration part has good hardness, wear resistance and fatigue resistance.
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