CN115870449A - Protective coating for die, preparation method of protective coating, powder material and die-casting die - Google Patents
Protective coating for die, preparation method of protective coating, powder material and die-casting die Download PDFInfo
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Abstract
In order to solve the problem that high-temperature aluminum liquid erodes a die in the die-casting process, the invention provides a protective coating for the die, which comprises the following element components in percentage by mass: 2-9% of Mn, 15-20% of Cr, 6-12% of B, 1-5% of Si, 44-52% of Mo, 2-32% of Fe and less than 0.1% of other elements. Meanwhile, the invention also discloses a preparation method of the protective coating, a powder material and a die-casting die. The protective coating provided by the invention can effectively avoid the die sticking problem of the aluminum liquid to the die body in the die-casting process, avoids the erosion effect of the aluminum liquid to the die body, and has excellent wear resistance.
Description
Technical Field
The invention belongs to the technical field of metal materials, and particularly relates to a protective coating for a die, a preparation method of the protective coating, a powder material and a die-casting die.
Background
In the process of aluminum alloy die casting, the working environment of the die is harsh, the pouring temperature of molten aluminum alloy is usually 670-790 ℃, the speed of an inner pouring gate is 30-60 m/s, and the pressure is 20-120 Mpa, the surface of a cavity is corroded by high temperature of molten metal and is washed away at high speed, so that the defects of corrosion and falling of the surface of the die, thermal fatigue cracks and the like are caused in the long-period use process, and the die fails.
The existing protective coating for the surface of a mold is prepared by mixing high-entropy alloy and ceramic particles, wherein the ceramic particles are added secondarily, impurities are easily introduced, the distribution is uneven, and the ceramic-metal interface combination is not guaranteed, so that the protective effect of the coating on the mold is further influenced, the composite addition requirement is high in uniformity, and the requirements on equipment and processes are high.
The other alloy material is used as the prior art of the protective coating, however, the alloy protective coating is mainly in an amorphous structure, still has the problem of insufficient impact resistance, and simultaneously fails to avoid the adhesion of aluminum liquid.
Disclosure of Invention
The invention provides a protective coating for a die, a preparation method thereof, a powder material and a die-casting die, aiming at the problem that high-temperature aluminum liquid erodes the die in the die-casting process.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a protective coating for a mold, which comprises the following element components in percentage by mass:
2-9% of Mn, 15-20% of Cr, 6-12% of B, 1-5% of Si, 44-52% of Mo, 2-32% of Fe and less than 0.1% of other elements.
Optionally, the protective coating comprises the following element components in percentage by mass:
4-7% of Mn, 15-20% of Cr, 10-12% of B, 1-3% of Si, 47-50% of Mo, 8-23% of Fe and less than 0.1% of other elements.
Optionally, the protective coating comprises a metal matrix and a ceramic reinforcing phase formed in situ in the metal matrix, the metal matrix comprising a solid solution of Fe, the ceramic reinforcing phase comprising Mo 2 FeB 2 And (MoCrFe) 3 B 2 。
Optionally, the ceramic reinforcing phase further comprises Fe 2 B、Cr 2 B 3 And MoB.
Optionally, cr, mo, and Mn are solid-dissolved in the solid solution of Fe.
Optionally, in the protective coating, the molar ratio of Mo to B is 0.3 to 0.9.
In still another aspect, the present invention provides a powder material for preparing the protective coating for a mold as described above, including a mixture of Fe simple substance and/or Fe alloy powder, mn simple substance and/or Mn alloy powder, cr simple substance and/or Cr alloy powder, B simple substance and/or B alloy powder, si simple substance and/or Si alloy powder, and Mo simple substance and/or Mo alloy powder, wherein each element satisfies the following elemental composition in percentage by mass:
2-9% of Mn, 15-20% of Cr, 6-12% of B, 1-5% of Si, 44-52% of Mo, 2-32% of Fe and less than 0.1% of other elements.
Optionally, the alloy powder comprises Fe powder, ferromolybdenum powder, ferroboron powder, ferrochrome powder, silicon powder and ferromanganese powder.
In still another aspect, the present invention provides a die casting mold, including a mold body and the protective coating for a mold as described above, the protective coating being formed on a surface of the mold body.
Optionally, the die-casting mold is a steel mold.
Optionally, the die-casting die is an aluminum alloy die-casting die.
In a further aspect, the present invention provides a method for preparing a protective coating for a mold as described above, comprising the operations of:
respectively preparing elementary substances and/or Fe alloys, elementary substances and/or Mn alloys, elementary substances and/or Cr alloys, elementary substances and/or B alloys, elementary substances and/or Si alloys and elementary substances and/or Mo alloys containing Fe, elementary substances and/or Mn alloys containing Mn, elementary substances containing Cr and/or Cr alloys containing Cr, elementary substances containing B and/or B alloys containing Si, elementary substances containing Mo and/or Mo alloys containing Mo, respectively preparing the obtained mixture into powder, and mixing the powder to obtain powder materials;
the powder material comprises the following element components in percentage by mass:
2-9% of Mn, 15-20% of Cr, 6-12% of B, 1-5% of Si, 44-52% of Mo, 2-32% of Fe and less than 0.1% of other elements;
and melting and covering the powder material on the die body, forming a solid solution by using the Fe element in the melting and covering process, synthesizing a ceramic reinforcing phase in situ in the solid solution by using the B element, fe, mo and Gr, and cooling to obtain the protective coating.
Optionally, the powder material is prepared by an atomization method.
Optionally, the powder material is melted and covered on the die body by a plasma cladding or laser cladding method to form a protective coating.
According to the protective coating for the die, the Fe element is used as the matrix, and the protective coating with high compatibility with the steel die body can be formed when the surface of the die is subjected to melt coating through the adjustment and the matching of the elements, so that the bonding strength of the protective coating and the die body is ensured, and the protective coating has good impact resistance and wear resistance; when the protective coating contacts with the aluminum liquid, the protective coating has better erosion resistance to the dynamic aluminum liquid, no additional ceramic powder is needed, the reinforcing phase formed by the protective coating has lower wettability with the aluminum liquid, the die sticking problem of the aluminum liquid to the die body in the die casting process is effectively avoided, and the erosion effect of the aluminum liquid to the die body is avoided.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
An embodiment of the invention provides a protective coating for a mold, which comprises the following element components in percentage by mass:
2-9% of Mn, 15-20% of Cr, 6-12% of B, 1-5% of Si, 44-52% of Mo, 2-32% of Fe and less than 0.1% of other elements.
In a preferred embodiment, the protective coating comprises the following elemental components in percentage by mass:
4-7% of Mn, 15-20% of Cr, 10-12% of B, 1-3% of Si, 47-50% of Mo, 8-23% of Fe and less than 0.1% of other elements.
In particular embodiments, the Mn content may be selected from 2%, 2.2%, 2.4%, 2.7%, 3.1%, 3.3%, 3.7%, 4%, 4.3%, 4.8%, 5.1%, 5.5%, 5.7%, 6%, 6.4%, 6.9%, 7%, 7.5%, 8%, 8.2%, 8.6%, or 9%; the content of Cr can be selected from 15%, 16%, 17%, 18%, 19% or 20%; the content of B may be selected from 6%, 6.4%, 6.9%, 7%, 7.5%, 8%, 8.2%, 8.6%, 9%, 9.5%, 10%, 10.3%, 10.9%, 11%, 11.2%, 11.4%, 11.7% or 12%; the content of Si may be selected from 1%, 1.3%, 1.9%, 2.1%, 2.2%, 2.4%, 2.7%, 3%, 3.3%, 3.7%, 4%, 4.3%, 4.8% or 5%; the content of Mo can be selected from 44-52%
The protective coating for the die adopts Fe element as a matrix, and can form a protective coating with high compatibility with a steel die body when the surface of the die is subjected to melt coating through the adjustment and the matching of the elements, so that the bonding strength of the protective coating and the die body is ensured, and the protective coating has good impact resistance and has wear resistance; when the protective coating is contacted with the aluminum liquid, the protective coating has better erosion resistance to the dynamic aluminum liquid, no ceramic powder is required to be additionally added, a reinforcing phase formed by the protective coating has lower wettability with the aluminum liquid, the die sticking problem of the aluminum liquid to the die body in the die-casting process is effectively avoided, and the erosion effect of the aluminum liquid to the die body is avoided.
In the material, fe is used as a main element in the protective coating, is a group of the protective coating, supports a hard and brittle ceramic reinforcing phase in the protective coating, and ensures the toughness of the protective coating and the bonding strength of the protective coating and a steel die body.
Mn enables acicular FeAl 3 Conversion to flocculent (Fe, mn) Al 3 The aluminum alloy has the function of modification and improves the erosion of the coating by the Al liquid.
Cr fills up Fe to a certain extent 2 Al 5 The crystallography vacancy of (2) hinders the mutual diffusion between Fe atoms in the Fe matrix and Al atoms in the molten aluminum, and improves the high-temperature oxidation resistance, but when the content of Cr is excessive, the matrix can generate excessive brittle phases which are distributed on the matrix in a net shape, so that the toughness of the matrix is poor.
Si is used for reducing the melting point of the alloy powder and is easy to clad; can occupy Fe 2 Al 5 The crystallographic vacancy in the coating hinders the interdiffusion of Fe and Al, improves the Al liquid erosion resistance, but the coating is more brittle due to excessive Si.
B is used for reducing the melting point of the alloy powder; is a main element for forming boride ceramic phase, and a part of the boride forms ternary boride M 3 B 2 A part forming M 2 B, the B content can determine the amount of the ceramic reinforcing phase in the cladding.
When the content of B is too low, the ceramic strengthening phase in the protective coating is less, the hardness of the protective coating is lower, and the wear resistance of the coating is insufficient.
When the content of B is too high, the ceramic strengthening phase in the protective coating is deviated, so that the performance of the protective coating is uneven, and the part where the ceramic strengthening phase is concentrated is easy to be stripped from the die body in the using process because the periphery of the part is lack of the protection of the metal base.
Mo is used to form the ceramic reinforcing phase. When the content of Mo is too low, the number and the size of the ceramic reinforcing phase in the protective coating are small, so that the protective coating is difficult to reinforce; excessive Mo increases the melting point of the powder and is not favorable for melting the powder, and excessive Mo increases the size of the ceramic reinforcing phase, but rather deteriorates the strengthening effect, and the protective coating is easy to crack.
It should be noted that, in the protective coating, each element does not act alone, but there is an associated action, and an increase or decrease of any element may cause a change in the action effect of other elements, and further cause a change in the overall performance of the protective coating, and the relationship between the elements in the present invention is further described by the following specific examples:
in some embodiments, the protective coating includes a metal matrix including a solid solution of Fe and a ceramic reinforcing phase formed in-situ in the metal matrix including Mo 2 FeB 2 And (MoCrFe) 3 B 2 。
Wherein, mo 2 FeB 2 Being a hard ceramic reinforcing phase, (MoCrFe) 3 B 2 Is in Mo 2 FeB 2 Compared with amorphous alloy, the two ceramic reinforced phases can effectively improve the hardness of the protective coating, enhance the wear resistance of the protective coating, reduce the wettability of the protective coating and aluminum liquid and do not have infiltration reaction with the aluminum liquid; compared with the form of doping ceramic powder in the alloy, the ceramic reinforcing phase in the protective coating is a thermodynamic stable phase formed by in-situ nucleation and growth of each element in the coating, so that the problem of poor compatibility with the die body can be avoided, and the adhesion strength of the protective coating on the surface of the die body is ensured.
The solid solution of Fe is used as a metal base, so that the ceramic reinforcing phase with higher hardness can be supported, and the toughness requirement of die casting on a die body is met; and the Fe matrix and the die steel have similar thermal expansion coefficients, so that thermal fatigue cracks generated by cyclic stress are not easy to generate at the interface of the protective coating and the die body in the using process of the protective coating, and the service life of the protective coating is prolonged.
In some embodiments, the ceramic reinforcing phase further comprises Fe 2 B、Cr 2 B 3 And MoB.
Fe 2 B、Cr 2 B 3 And MoB is a binary boride for improving the erosion resistance of the protective coating to the molten aluminum.
In some embodiments, the solid solution of Fe has Cr, mo, and Mn solid dissolved therein.
Cr, mo and Mn are dissolved in Fe in a solid solution manner, so that the strength of a metal matrix is improved, and the aluminum liquid has a certain erosion resistance effect.
In some embodiments, the molar ratio of Mo to B in the protective coating is 0.3 to 0.9.
Through further experiments, the inventor finds that Mo and B have strong correlation effect, and Mo and B are more favorable for being combined with each other to form Mo under the condition that the Mo and the B are in the molar ratio 2 FeB 2 Ternary boride ceramic phase M 3 B 2 (part of Mo element can be replaced by Fe and Cr), which is beneficial to further enhancing the wear resistance and erosion resistance of the protective coating.
Another embodiment of the present invention provides a powder material for preparing the protective coating for a mold as described above, including a mixture of Fe simple substance and/or Fe alloy powder, mn simple substance and/or Mn alloy powder, cr simple substance and/or Cr alloy powder, B simple substance and/or B alloy powder, si simple substance and/or Si alloy powder, and Mo simple substance and/or Mo alloy powder, wherein each element satisfies the following element components in percentage by mass:
2-9% of Mn, 15-20% of Cr, 6-12% of B, 1-5% of Si, 44-52% of Mo, 2-32% of Fe and less than 0.1% of other elements.
In a preferred embodiment, the powder materials include Fe powder, ferromolybdenum powder, ferroboron powder, ferrochrome powder, silicon powder, and ferromanganese powder.
Another embodiment of the present invention provides a die casting mold including a mold body and the protective coating for a mold as described above, the protective coating being formed on a surface of the mold body.
In some embodiments, the die casting mold is a steel mold.
The protective coating has better compatibility with the steel mould and consistent thermal expansion coefficient, and has better bonding strength and abrasion resistance when applied to the steel mould.
In some embodiments, the die casting mold is an aluminum alloy die casting mold.
The wettability of the protective coating and the Al liquid is poor, and the corrosion of the Al liquid to the die body can be effectively avoided.
Another embodiment of the present invention provides a method for preparing the protective coating for a mold as described above, comprising the operations of:
respectively preparing elementary substances and/or Fe alloys, elementary substances and/or Mn alloys, elementary substances and/or Cr alloys, elementary substances and/or B alloys, elementary substances and/or Si alloys and elementary substances and/or Mo alloys containing Fe, elementary substances and/or Mn alloys containing Mn, elementary substances containing Cr and/or Cr alloys containing Cr, elementary substances containing B and/or B alloys containing Si, elementary substances containing Mo and/or Mo alloys containing Mo, respectively preparing the obtained mixture into powder, and mixing the powder to obtain powder materials;
the powder material comprises the following element components in percentage by mass:
2-9% of Mn, 15-20% of Cr, 6-12% of B, 1-5% of Si, 44-52% of Mo, 2-32% of Fe and less than 0.1% of other elements;
and cladding the surface of the powder material on the die body, wherein in the cladding process, fe element forms a solid solution, B element, fe, mo and Gr are synthesized into a ceramic reinforcing phase in the solid solution in situ, and the protective coating is obtained after cooling.
In some embodiments, the powder material may be prepared in a conventional manner.
Specifically, the powder material may be prepared by a mechanical method or a physicochemical method.
The mechanical method is a processing method for crushing metal into powder with required particle size by means of mechanical external force, and the chemical components of the material are basically unchanged in the preparation process of the method, and the method comprises a ball milling method, a grinding method and an atomization method.
The ball milling method is mainly divided into a rolling ball method and a vibration ball milling method, and the method utilizes the mechanism that metal particles generate strain at different strain rates to be crushed and refined.
The grinding method is that compressed gas is sprayed to a grinding area after passing through a special nozzle, so that materials in the grinding area are driven to collide with each other and are rubbed into powder; after the gas flow is expanded, the gas flow rises along with the materials and enters a grading area, the materials reaching the granularity are sorted out by a turbine type classifier, and the rest coarse powder returns to a grinding area to be continuously ground until the required granularity is separated.
The atomization method generally uses high-pressure gas, high-pressure liquid or high-speed rotating blades to break the molten metal or alloy into fine droplets, and then the fine droplets are condensed in a collector to obtain ultrafine metal powder, which is not chemically changed. Atomization methods include double-flow atomization, centrifugal atomization, multi-stage atomization, ultrasonic atomization, close-coupled atomization, high-pressure gas atomization, laminar atomization, ultrasonic close-coupled atomization, and hot gas atomization.
The physical-chemical method refers to a production method for obtaining ultrafine powder by changing chemical components or aggregation states of raw materials during the preparation of powder. They can be classified into reduction, electrolysis and chemical displacement according to their chemical principles.
In some embodiments, the powder material is prepared using an atomization process.
In some embodiments, the powder material is melted and coated on the die body by plasma cladding or laser cladding to form the protective coating.
When the protective coating is prepared by plasma cladding, a powder material is instantaneously heated and accelerated to form particle rays after entering a plasma beam, the particle rays are in a molten or semi-molten state, and are sprayed to a die body to be processed, and physical and chemical changes such as melting, mixing, solidification and the like are generated on the surface of the die body, and finally the surface of the die body is metallurgically bonded.
The laser cladding is that selected powder materials are placed on the surface of a die body in different material adding modes, and are simultaneously melted with a thin layer on the surface of the die body through laser irradiation, and the powder materials are rapidly solidified to form a surface coating which has extremely low dilution and is metallurgically combined with the die body.
The present invention will be further illustrated by the following examples.
TABLE 1
Example 1
This embodiment is used to illustrate the protective coating, the die casting mold and the preparation method thereof disclosed by the present invention, and includes the following operations:
step 1: respectively weighing Fe powder, ferromolybdenum alloy powder, ferroboron powder, ferrochrome powder, silicon powder and ferromanganese alloy powder according to the mass content shown in Table 1, wherein the mass content of each element is as follows: 5% of Mn, 17% of Cr, 11% of B, 2% of Si, 48% of Mo and the balance of Fe, wherein the mass of the required various master alloys or simple substances is calculated according to the mass content of the elements, and the balance is Fe powder and inevitable impurities, and the content of the impurities is less than 0.1%.
And 2, step: mixing Fe powder, ferromolybdenum alloy powder, ferroboron powder, ferrochromium alloy powder, silicon powder and ferromanganese alloy powder, and uniformly stirring to form a powder material.
And step 3: and feeding the powder material into a plasma cladding machine, carrying and cladding the powder material on the surface of a steel die for die-casting aluminum through plasma, and obtaining the die-casting die with the protective coating formed on the surface.
Examples 2 to 18
Examples 2-18, which are provided to illustrate the protective coating, die casting mold and method of making the same disclosed in the present invention, include most of the operating steps of example 1, with the following differences:
the elemental compositions shown in examples 2 to 18 in Table 1 were used, and the other operation steps were the same as in example 1.
Comparative examples 1 to 10
Comparative examples 1 to 10 are for comparative illustration of the protective coating, die casting mold and method for manufacturing the same disclosed in the present invention, including most of the operating steps in example 1, except that:
the elemental compositions shown in comparative examples 1 to 10 in Table 1 were used, and the other operation steps were the same as in example 1.
Comparative example 11
Comparative example 11 is a comparative illustration of the protective coating, die casting mold and method of making the same disclosed in the present invention, including most of the operating steps of example 1, except that:
boron in the powder material being provided by Mo 2 FeB 2 Adding ceramic powder, specifically, fe powder, ferro-molybdenum alloy powder and Mo 2 FeB 2 Mixing the ceramic powder, the ferrochrome powder, the silicon powder and the ferromanganese powder, and uniformly stirring to form a powder material.
Performance test
The die casting die prepared by the method is subjected to the following performance tests:
erosion testing: weighing the die-casting die to record the initial weight M1, placing the die-casting die in aluminum liquid for soaking and rotating at the rotating speed of 300r/min, the temperature of the aluminum liquid is 710 ℃, the soaking time is 10min, taking out the die-casting die, soaking the die-casting die in NaOH solution, weighing and recording the weight M2 after erosion, and calculating the residual mass ratio of the die after erosion according to the following formula:
and (3) hardness testing: and (4) taking several positions on the surface of the die casting mould to test the Vickers hardness, and calculating to obtain the average value of the Vickers hardness of the surface.
The results of the tests obtained are filled in table 2.
TABLE 2
The test results in table 2 show that the protective coating provided by the invention can protect the die body in the aluminum die-casting process, and the protective coating has better wear resistance and erosion resistance, so that the service life of the die-casting die is effectively prolonged.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (12)
1. The protective coating for the mold is characterized by comprising the following element components in percentage by mass:
2-9% of Mn, 15-20% of Cr, 6-12% of B, 1-5% of Si, 44-52% of Mo, 2-32% of Fe and less than 0.1% of other elements.
2. The protective coating for a mold according to claim 1, comprising the following elemental compositions in mass percent:
4-7% of Mn, 15-20% of Cr, 10-12% of B, 1-3% of Si, 47-50% of Mo, 8-23% of Fe, and the total amount of other elements is less than 0.1%.
3. The protective coating for a mold of claim 1, wherein the protective coating comprises a metal matrix comprising a solid solution of Fe and a ceramic reinforcing phase formed in-situ in the metal matrix, the ceramic reinforcing phase comprising Mo 2 FeB 2 And (MoCrFe) 3 B 2 。
4. The protective coating for a mold of claim 3, wherein the ceramic reinforcing phase further comprises Fe 2 B、Cr 2 B 3 And MoB, in which Cr, mo and Mn are solid-dissolved in a solid solution of Fe.
5. The protective coating for a mold according to claim 1, wherein a molar ratio of Mo to B in the protective coating is 0.3 to 0.9:1.
6. the powder material for preparing the protective coating for the mold according to any one of claims 1 to 5, comprising a mixture of elemental Fe and/or Fe alloy powder, elemental Mn and/or Mn alloy powder, elemental Cr and/or Cr alloy powder, elemental B and/or B alloy powder, elemental Si and/or Si alloy powder, elemental Mo and/or Mo alloy powder, wherein each element satisfies the following element components in percentage by mass:
2-9% of Mn, 15-20% of Cr, 6-12% of B, 1-5% of Si, 44-52% of Mo, 2-32% of Fe and less than 0.1% of other elements.
7. A powdered material according to claim 6, characterised by comprising Fe powder, ferromolybdenum powder, ferroboron powder, ferrochrome powder, silicon powder and ferromanganese powder.
8. A die casting mold comprising a mold body and the protective coating for mold according to any one of claims 1 to 5, the protective coating being formed on a surface of the mold body.
9. The die casting mold according to claim 8, wherein the die casting mold is a steel mold and/or an aluminum alloy die casting mold.
10. The process for the preparation of a protective coating for moulds according to any of claims 1 to 5, comprising the following operations:
respectively preparing elementary substances and/or Fe alloys, elementary substances and/or Mn alloys, elementary substances and/or Cr alloys, elementary substances and/or B alloys, elementary substances and/or Si alloys and elementary substances and/or Mo alloys containing Fe, elementary substances and/or Mn alloys containing Mn, elementary substances containing Cr and/or Cr alloys containing Cr, elementary substances containing B and/or B alloys containing Si, elementary substances containing Mo and/or Mo alloys containing Mo, respectively preparing the obtained mixture into powder, and mixing the powder to obtain powder materials;
the powder material comprises the following element components in percentage by mass:
2-9% of Mn, 15-20% of Cr, 6-12% of B, 1-5% of Si, 44-52% of Mo, 2-32% of Fe and less than 0.1% of other elements;
and cladding the surface of the powder material on the die body, wherein in the cladding process, fe element forms a solid solution, B element, fe, mo and Gr are synthesized into a ceramic reinforcing phase in the solid solution in situ, and the protective coating is obtained after cooling.
11. The method of claim 10, wherein the powder material is produced by atomization.
12. The method for preparing the ceramic mold according to the claim 10, wherein the powder material is melted and coated on the mold body by a plasma cladding or laser cladding method to form a protective coating.
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