CN112538602B - High-nickel cast iron workpiece surface treatment process - Google Patents
High-nickel cast iron workpiece surface treatment process Download PDFInfo
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- CN112538602B CN112538602B CN202011302715.4A CN202011302715A CN112538602B CN 112538602 B CN112538602 B CN 112538602B CN 202011302715 A CN202011302715 A CN 202011302715A CN 112538602 B CN112538602 B CN 112538602B
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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
- C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
- C23C12/02—Diffusion in one step
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Abstract
The invention provides a high nickel cast iron workpiece surface treatment process, which comprises the steps of preparing a penetrating agent, mixing and sealing the workpiece and the penetrating agent, heating to 680-850 ℃ for surface treatment after vacuum heat preservation treatment in a heating furnaceAnd then the high nickel cast iron workpiece with surface treatment is obtained, and the penetrating agent comprises B 4 C、BFe、TiFe、V 2 O 5 、Al、Al 2 O 3 Catalyst and activator, the catalyst and activator specifically comprise rare earth containing Y and NH 4 Cl、NH 4 F、AlF 3 、NaF、NH 4 Br、NH 4 I、KBF 4 One or a mixture of more than one of them. The treatment process can be used for carrying out surface treatment on the high-nickel cast iron workpiece at a lower temperature, and the treated seepage layer is thicker, has better structure and appearance and good physical properties.
Description
Technical Field
The invention relates to the technical field of metal workpiece processing, in particular to a high-nickel cast iron workpiece surface treatment process.
Background
In petroleum exploitation, the petroleum pipeline pump body is used as an important exploitation element, and needs to adapt to various severe exploitation environments, so that the material consumption is particularly high, pump body pipelines, impellers and various accessories are mostly cast by adopting high-nickel cast iron alloy, in order to enable a workpiece to better meet the use requirement, the prior art adopts a surface hardening process to carry out element infiltration on the surface of the high-nickel cast iron, however, the infiltration layer component of the conventional treatment process is too single, the hardness layer of the material is difficult to reach the standard, the infiltration layer thickness is insufficient to meet the requirement, the corrosion resistance is poor, and in the use process, the surface infiltration layer is easy to peel off, and the service life is short.
To achieve better surface treatment effect, more modifying elements are needed to be permeated, so that the surface performance of the metal is improved as a whole, however, the permeation of various elements has higher process requirements on the surface treatment, such as higher permeation treatment temperature and longer treatment time, which can bring about negative effects, such as: the element proportion is improper, so that the metal parts are easy to crack and even peel, the metal parts are deformed at high temperature, and the qualification rate is reduced; the thickness of the permeation layer of the multi-element co-permeation at low temperature is not easy to reach the standard, and the permeation effect of elements is poor. Therefore, the difficulty of the multicomponent infiltration technology is high.
Disclosure of Invention
In view of this, the present invention proposes a surface treatment process of a high nickel cast iron workpiece that can be performed under low temperature conditions.
The technical scheme of the invention is realized as follows: the invention provides a surface treatment process of a high-nickel cast iron workpiece, which comprises the following steps of:
firstly, preparing a penetrating agent, filling the penetrating agent into a heat-resistant sealing tank, putting a high-nickel cast iron workpiece to be treated into the heat-resistant sealing tank, coating the surface of the high-nickel cast iron workpiece with the penetrating agent, and sealing the heat-resistant sealing tank;
step two, hanging the heat-resistant sealing tank subjected to sealing treatment into a heating furnace, and sealing the heating furnace;
step three, vacuumizing the heating furnace, introducing inert gas to replace the gas in the heating furnace, and keeping the pressure in the heating furnace at 101.325 x 1.5-101.325 x 2kPa;
step four, heating the heating furnace to 400-600 ℃, and carrying out heat preservation treatment for 1-3h;
and fifthly, after the treatment is finished, heating the heating furnace to 680-850 ℃, and preserving heat for 8-12 hours to obtain the high-nickel cast iron workpiece with the surface treated.
On the basis of the technical scheme, preferably, the penetrating agent comprises B 4 C、BFe、TiFe、V 2 O 5 、Al、Al 2 O 3 A catalyst and an activator.
The surface comprehensive performance of cast iron workpiece and alloy structure co-infiltrated by boron, titanium, vanadium and aluminum is enhanced, the diffusion layer has special metallurgical needle structure, and in the case of single infiltration B, the infiltration layer is formed by FeB and Fe 2 B composition containing a certain concentration of V 2 O 5 Under the action of high temperature, the superfine Al powder and the Y-containing catalyst have a diffusion layer containing FeB and Fe 2 B, (Fe, V, ti) 2 B,(Fe,V,Ti) 3 C,(Fe,V,Ti) 7 C 3 The alpha solid solution layer of FeBTiVAl+C is formed in the concentration range of 8-16% Al; VTi particles are uniformly distributed in Fe after the V penetration of the part 2 B or (Fe) 2 V) 2 B, the seepage layer is continuous, compact and has no gap; especially, after the part is infiltrated with Ti, titanium carbide is formed on the surface, the hardness and the wear resistance of the titanium carbide are superior to those of the infiltrated V layer and the infiltrated B layer, the infiltrated Ti layer also has higher corrosion resistance, and the corrosion resistance is superior to that of other metal layers; the structure of the boron-titanium-vanadium infiltration layer aluminum alloying infiltration layer is stable, and the infiltration layer thickness and elasticity are good; comprehensive performance after infiltration: the thickness of the seepage layer is more than 40 mu m, and the highest hardness can reach HV0.2 1900.
Based on the technical proposal, preferably, the weight percentage is 100 percentThe penetrating agent comprises 10-20% B 4 C、25-35％BFe、6-10％TiFe、2-8％V 2 O 5 、8-16％Al、20-30％Al 2 O 3 3-5% of catalyst and 1-2% of activator.
In the actual working of chemical heat treatment, the infiltration temperature of Ti, V and Al is basically greater than 900 ℃, and the low-temperature co-infiltration by Ti, V, al and other elements is difficult to realize, and the invention research proves that the activator such as NH is a certain proportion 4 Cl、AlF 3 、NaF、KBF 4 After heating, containing Y rare earth and the like, the alloy can contain Al and V 2 O 5 The active gas phase compound is formed by decomposition in the medium of the penetrating agent, the active gas phase compound plays an obvious activation role in the thermal reaction of the penetrating agent, the energy change of a crystal boundary is caused by the interaction of elements, the penetrating part and FeB and FeTi materials can be subjected to serious decarburization at high temperature, the chemical property of the materials is changed by decarburization, however, the atmosphere is provided with a carbon supplementing process for the materials under the high-temperature infiltration accelerating environment, the surface layer structure of the materials is rearranged and combined, the atmosphere of catalyst decomposition not only accelerates the chemical heat treatment process of powder in the gas phase medium, but also can greatly reduce the infiltration reaction temperature to 680-850 ℃, the deformation of the parts is reduced, and the added activating agent can greatly improve the activation of Ti, V and Al in the metal penetrating agent and improve the infiltration speed. The high-temperature multi-component co-permeation of boron, titanium, vanadium and aluminum is mainly based on boronizing, and a plurality of elements generate boron, titanium and vanadium atoms and oxidize and consume the contradictions of the boron, titanium, vanadium and aluminum atoms under the high-temperature environment, so that the contradictions can be overcome by correctly adjusting the proportion of various raw materials according to the characteristic that the penetrant has certain oxidability. The process principle adds excessive Al element, and Al is used as a reducing agent for the infiltration of excessive Al participating materials and can consume a small amount of oxygen atoms generated in the reaction to generate Al 2 O 3 And emits heat, thus further enhancing the material infiltration reaction. Preferably, the ratio of the boron, titanium, vanadium and aluminum penetrating agent is (8-12): (2-4): (1-3): (3-7).
The reaction formula at high temperature of the invention comprises:
on the basis of the technical scheme, preferably, the catalyst is ammonium halide.
Still more preferably, the catalyst is NH 4 F、NH 4 Cl、NH 4 Br and NH 4 One or a mixture of several of I.
On the basis of the technical scheme, preferably, the activator comprises Y-containing rare earth.
On the basis of the technical scheme, preferably, the activator further comprises NH 4 Cl、AlF 3 、NaF、KBF 4 One or a mixture of more than one of them.
On the basis of the technical scheme, preferably, the Y-containing rare earth is cerium carbonate and/or lanthanum carbonate.
On the basis of the technical scheme, preferably, the first step further comprises adding carbon powder into the sealing tank, wherein the mass ratio of the carbon powder to the penetrating agent is 2-7:100.
on the basis of the technical scheme, preferably, the high-nickel cast iron workpiece is an oil extraction pump impeller and accessories thereof.
Compared with the prior art, the surface treatment process of the high nickel cast iron workpiece has the following beneficial effects:
(1) Under the condition of boronizing the surface of a workpiece, the invention utilizes the interaction of the penetrating agent containing vanadium, titanium, aluminum and the catalyst containing Y to lead the penetrating layer to have (Fe, V, ti) B, (Fe, V, ti) at a certain temperature 2 B、(Fe,V,Ti) 3 C and (F)e,V,Ti) 7 C 3 The FeBTiVAl+C infiltration layer is continuous and compact, has no gap, good wear resistance and corrosion resistance, stable in structure, thick in infiltration layer, good in elasticity and not easy to crack and fall off;
(2) Because the conventional infiltration temperature is higher and the structural shape of a workpiece is easy to damage, the invention adopts specific active agent components, an active gas phase compound is formed after heating, the active gas phase compound plays an activating role in the thermal reaction of the infiltration agent, the temperature of the infiltration agent is increased through the replacement exothermic reaction of element interaction, the energy change of grain boundaries is caused, the atmosphere generated by the decomposition of the active agent components accelerates the chemical heat treatment process of powder in a gas phase medium, the temperature range of the infiltration reaction is greatly reduced, and the deformation of parts is reduced.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Example 1
10 parts of B are weighed respectively 4 C. 35 parts of BFe, 10 parts of TiFe and 5 parts of V 2 O 5 8 parts of Al, 25 parts of Al 2 O 3 3 parts of NH 4 F. 2 parts of KBF 4 And 2 parts of cerium carbonate powder, and uniformly mixing to obtain the penetrating agent.
100 parts of penetrating agent powder is filled in a heat-resistant sealing tank, a petroleum pump impeller cast by high-nickel cast iron to be treated is placed in the heat-resistant sealing tank, the surface of the petroleum pump impeller is coated by the penetrating agent, the heat-resistant sealing tank is sealed, the sealed heat-resistant sealing tank is hung into a heating furnace, the heating furnace is sealed, the heating furnace is vacuumized, then argon is injected to replace air in the heating furnace, the pressure in the heating furnace is kept to be 101.325 x 1.5kPa, then the heating furnace is heated to 400 ℃, the temperature in the heating furnace is kept for 3 hours, then the temperature is increased to 680 ℃, the heat preservation is carried out for 12 hours, after the treatment is completed and the temperature is reduced to room temperature, the sealing tank is taken out from the heating furnace, and the petroleum pump impeller cast by the high-nickel cast iron is taken out from the sealing tank.
Example 2
Respectively weighing 20 parts of B 4 C. 25 parts of BFe, 6 parts of TiFe and 8 parts of V 2 O 5 16 parts of Al, 20 parts of Al 2 O 3 3 parts of NH 4 Cl, 0.5 part of lanthanum carbonate, 1 part of KBF 4 And 0.5 part AlF 3 Is uniformly mixed to obtain the penetrating agent.
Uniformly mixing 100 parts of penetrating agent powder and 2 parts of carbon powder, filling the mixture into a heat-resistant sealing tank, putting a petroleum pump impeller cast by high-nickel cast iron to be treated into the heat-resistant sealing tank, coating the surface of the petroleum pump impeller by the penetrating agent and the carbon powder, sealing the heat-resistant sealing tank, hanging the sealed heat-resistant sealing tank into a heating furnace, sealing the heating furnace, vacuumizing the heating furnace, injecting argon to replace air in the heating furnace, keeping the pressure in the heating furnace at 101.325 x 2kPa, heating the heating furnace to 450 ℃, carrying out heat preservation treatment for 2 hours, then heating to 700 ℃, carrying out heat preservation treatment for 11 hours, taking out the sealing tank from the heating furnace after cooling to room temperature, and taking out the petroleum pump impeller cast by the high-nickel cast iron from the sealing tank.
Example 3
13 parts of B are weighed respectively 4 C. 32 parts of BFe, 7 parts of TiFe and 6 parts of V 2 O 5 10 parts of Al, 26 parts of Al 2 O 3 4 parts of NH 4 Br, 0.5 part of cerium carbonate, 1 part of KBF 4 And 0.5 part of lanthanum carbonate powder, and uniformly mixing to obtain the penetrating agent.
Uniformly mixing 100 parts of penetrating agent powder and 4 parts of carbon powder, filling the mixture into a heat-resistant sealing tank, putting a petroleum pump impeller cast by high-nickel cast iron to be treated into the heat-resistant sealing tank, coating the surface of the petroleum pump impeller by the penetrating agent and the carbon powder, sealing the heat-resistant sealing tank, hanging the sealed heat-resistant sealing tank into a heating furnace, sealing the heating furnace, vacuumizing the heating furnace, injecting argon to replace air in the heating furnace, keeping the pressure in the heating furnace at 101.325 x 1.5kPa, heating the heating furnace to 500 ℃, carrying out heat preservation treatment for 2 hours, then heating to 750 ℃, carrying out heat preservation treatment for 10 hours, taking out the sealing tank from the heating furnace after cooling to room temperature, and taking out the petroleum pump impeller cast by the high-nickel cast iron from the sealing tank.
Example 4
Respectively weighing 18 parts of B 4 C. 27 parts of BFe, 9 parts of TiFe and 5 parts of V 2 O 5 12 parts of Al, 22 parts of Al 2 O 3 5 parts of NH 4 I. 1 part of cerium carbonate, 0.5 part of NH 4 Powder of Cl and 0.5 part of NaF are uniformly mixed to obtain the penetrating agent.
100 parts of penetrating agent powder and 6 parts of carbon powder are uniformly mixed and then filled in a heat-resistant sealing tank, a petroleum pump impeller cast by high-nickel cast iron to be treated is placed in the heat-resistant sealing tank, the surface of the petroleum pump impeller is coated by the penetrating agent and the carbon powder, the heat-resistant sealing tank is subjected to sealing treatment, the sealed heat-resistant sealing tank is hung into a heating furnace, the heating furnace is sealed, the heating furnace is vacuumized, then argon is injected to replace air in the heating furnace, the pressure in the heating furnace is kept to be 101.325 x 2kPa, then the heating furnace is heated to the temperature of 550 ℃, the temperature is kept for 2 hours, then the temperature is kept to be 800 ℃, the temperature is kept for 9 hours, after the treatment is completed, the sealing tank is taken out from the heating furnace, and the petroleum pump impeller cast by the high-nickel cast iron is taken out from the sealing tank.
Example 5
Respectively weighing 15 parts of B 4 C. 30 parts of BFe, 8 parts of TiFe and 4 parts of V 2 O 5 13 parts of Al, 25 parts of Al 2 O 3 2 parts of NH 4 F. 2 parts of NH 4 I. 0.5 part lanthanum carbonate and 0.5 part KBF 4 And (5) uniformly mixing the powder to obtain the penetrating agent.
100 parts of penetrating agent powder and 7 parts of carbon powder are filled in a heat-resistant sealing tank, a petroleum pump impeller cast by high-nickel cast iron to be treated is placed in the heat-resistant sealing tank, the surface of the petroleum pump impeller is coated by the penetrating agent and the carbon powder, the heat-resistant sealing tank is subjected to sealing treatment, the sealed heat-resistant sealing tank is hung into a heating furnace, the heating furnace is sealed, the heating furnace is vacuumized, then inert gas is injected to replace air in the heating furnace, the pressure in the heating furnace is kept to be 101.325 x 1.5kPa, the heating furnace is heated to 600 ℃, the temperature is kept for 1h, then the temperature is kept at 850 ℃ for 8h, after the treatment is completed, the sealing tank is taken out from the heating furnace, and the petroleum pump impeller cast by the high-nickel cast iron is taken out from the sealing tank.
Comparative example 1
Respectively weighing 25 parts of B 4 C. 35 parts of BFe, 5 parts of TiFe, 6 parts of Al and 25 parts of Al 2 O 3 2 parts of NH 4 F. 2 parts of NH 4 And (3) mixing the Cl powder uniformly to obtain the penetrating agent.
Filling a penetrating agent into a heat-resistant sealing tank, putting a petroleum pump impeller cast by high-nickel cast iron to be treated into the heat-resistant sealing tank, coating the surface of the petroleum pump impeller by the penetrating agent and carbon powder, sealing the heat-resistant sealing tank, hanging the sealed heat-resistant sealing tank into a heating furnace, sealing the heating furnace, vacuumizing the heating furnace, injecting inert gas to replace air in the heating furnace, keeping the pressure in the heating furnace to be 101.325 x 1.5kPa, heating the heating furnace to 600 ℃, preserving heat for 1h, then heating to 850 ℃, preserving heat for 8h, taking out the sealing tank from the heating furnace after cooling to room temperature, and taking out the petroleum pump impeller cast by high-nickel cast iron from the sealing tank.
Comparative example 2
Respectively weighing 35 parts of B 4 C. 25 parts BFe, 5 parts V 2 O 5 5 parts of Al, 25 parts of Al 2 O 3 3 parts of NH 4 F. 2 parts of NH 4 And (I) uniformly mixing the powder to obtain the penetrating agent.
Filling a penetrating agent into a heat-resistant sealing tank, putting a petroleum pump impeller cast by high-nickel cast iron to be treated into the heat-resistant sealing tank, coating the surface of the petroleum pump impeller by the penetrating agent and carbon powder, sealing the heat-resistant sealing tank, hanging the sealed heat-resistant sealing tank into a heating furnace, sealing the heating furnace, vacuumizing the heating furnace, injecting inert gas to replace air in the heating furnace, keeping the pressure in the heating furnace to be 101.325 x 1.5kPa, heating the heating furnace to 600 ℃, preserving heat for 1h, then heating to 950 ℃, preserving heat for 8h, taking out the sealing tank from the heating furnace after cooling to room temperature, and taking out the petroleum pump impeller cast by high-nickel cast iron from the sealing tank.
The impellers of examples 1 to 5 and comparative examples were each examined for appearance, morphology of a surface-permeated layer, thickness of a permeated layer, and hardness, and the results were as follows:
the results show that the treatment process provided by the invention can be matched with a specific penetrating agent to effectively reduce the temperature in the treatment process, so that the influence on the performance of the workpiece at high temperature is avoided, and meanwhile, the performance of the high-nickel cast iron workpiece treated at low temperature is good.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (5)
1. The surface treatment process of the high-nickel cast iron workpiece is characterized by comprising the following steps of:
firstly, preparing a penetrating agent, filling the penetrating agent into a heat-resistant sealing tank, putting a high-nickel cast iron workpiece to be treated into the heat-resistant sealing tank, coating the surface of the high-nickel cast iron workpiece with the penetrating agent, and sealing the heat-resistant sealing tank;
step two, hanging the heat-resistant sealing tank subjected to sealing treatment into a heating furnace, and sealing the heating furnace;
step three, vacuumizing the heating furnace, introducing inert gas to replace the gas in the heating furnace, and keeping the pressure in the heating furnace at 101.325 multiplied by 1.5-101.325 multiplied by 2kPa;
step four, heating the heating furnace to 400-600 ℃, and carrying out heat preservation treatment for 1-3h;
step five, after the treatment is finished, heating the heating furnace to 680-850 ℃, and preserving heat for 8-12 hours to obtain a high-nickel cast iron workpiece with the surface treated;
the penetrating agent comprises B 4 C、BFe、TiFe、V 2 O 5 、Al、Al 2 O 3 A catalyst and an activator; the penetrating agent comprises 10 to 20 percent of B by mass percent 4 C、25-35%BFe、6-10%TiFe、2-8%V 2 O 5 、8-16%Al、20-30%Al 2 O 3 3-5% of catalyst and 1-2% of activator;
the activator comprises cerium carbonate and/or lanthanum carbonate and/or NaF;
the first step also comprises the step of adding carbon powder into the sealed tank, wherein the mass ratio of the carbon powder to the penetrating agent is 2-7:100.
2. the process for treating the surface of a high nickel cast iron workpiece according to claim 1, wherein the catalyst is ammonium halide.
3. The surface treatment process for high nickel cast iron workpiece according to claim 2, wherein the catalyst is NH 4 F、NH 4 Cl、NH 4 Br and NH 4 One or a mixture of several of I.
4. The surface treatment process for high nickel cast iron workpieces according to claim 1, wherein said activator further comprises NH 4 Cl、AlF 3 Or KBF 4 One or a mixture of more than one of them.
5. The use of the high nickel cast iron workpiece surface treatment process according to claim 1 in the surface treatment of oil extraction pump impellers and accessories thereof.
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| US3870569A (en) * | 1972-05-25 | 1975-03-11 | Degussa | Process for boriding refractory metals and their alloys |
| JPH08176792A (en) * | 1994-12-20 | 1996-07-09 | Tawara Yoshiaki | Method for thickly penetrating aluminum and boron into iron and steel materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU885341A1 (en) * | 1979-09-03 | 1981-11-30 | Восточно-Сибирский технологический институт | Composition for boron-aluminizing of steel articles |
| CN1005853B (en) * | 1987-07-01 | 1989-11-22 | 西南石油学院 | Powder process for surface hardening of steel parts |
| CN102071394A (en) * | 2009-11-20 | 2011-05-25 | 缪建良 | Process method for metal surface boronisation |
| CN102268635A (en) * | 2011-08-12 | 2011-12-07 | 李华平 | Rare earth-boron-vanadium carburizing agent |
| CN102330053B (en) * | 2011-10-20 | 2013-05-22 | 陈唯明 | B-Al-Ti infiltration process for low-chromium multi-element alloy cast grinding ball |
| CN102494057B (en) * | 2011-11-29 | 2013-08-28 | 宁波精磊汽车零部件有限公司 | Automobile brake disc and manufacturing method thereof |
| CN107201495B (en) * | 2017-06-12 | 2019-11-22 | 武汉力盾新材料科技有限公司 | A kind of high abrasion boride coating fabrication method for hard sealed valve sealing surface |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870569A (en) * | 1972-05-25 | 1975-03-11 | Degussa | Process for boriding refractory metals and their alloys |
| JPH08176792A (en) * | 1994-12-20 | 1996-07-09 | Tawara Yoshiaki | Method for thickly penetrating aluminum and boron into iron and steel materials |
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