CN110629123A - Method for improving thermal fatigue resistance of alloy steel casting - Google Patents
Method for improving thermal fatigue resistance of alloy steel casting Download PDFInfo
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- CN110629123A CN110629123A CN201911087138.9A CN201911087138A CN110629123A CN 110629123 A CN110629123 A CN 110629123A CN 201911087138 A CN201911087138 A CN 201911087138A CN 110629123 A CN110629123 A CN 110629123A
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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Abstract
The invention relates to the technical field of new materials, and discloses a method for improving the thermal fatigue resistance of an alloy steel casting, which solves the problem that the fatigue resistance of the casting is sharply reduced due to the addition of various elements for improving the additional performance in the processing of the existing alloy steel casting by researching the alloy steel material and the thermal fatigue principle; because the ceramic alloy material has strong affinity with iron, a regular lamellar structure is formed, stress concentration is not easy to generate in the process of cold and hot circulation, a crack source cannot be caused, crack propagation cannot be accelerated even if cracks are generated under the action of external force, and the fatigue resistance of the alloy steel casting is obviously improved.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a method for improving thermal fatigue resistance of an alloy steel casting.
Background
The alloy steel is formed by adding a proper amount of one or more alloy elements on the basis of common carbon steel. When operating under high temperature conditions, the ambient temperature is not constant, but may be rapidly and repeatedly changed. When the expansion and contraction caused by this is restrained, thermal stress (also called temperature difference stress) is generated in the part. The temperature changes repeatedly, and the thermal stress changes repeatedly, so that the material is subjected to fatigue damage.
In order to improve the mechanical strength of steel castings, various functional elements are often added, so that the properties of high strength, high toughness, wear resistance, corrosion resistance and the like are obtained. However, the added element simple substance cannot be perfectly fused with the steel structure, and the more the inclusion elements are, the more difficult the shape and size of the steel are to be controlled. Particularly, in the process of cold and hot circulation, stress concentration is easily generated due to the difference between thermodynamic coefficients such as thermal expansion coefficients, thermal conductivity coefficients and the like of various elements, the stress concentration becomes an unstable factor for forming cracks, after the cracks are formed, the expansion speed is higher than that of pure carbon steel, and the heat fatigue resistance of the alloy steel casting is further increased.
Disclosure of Invention
The invention aims to provide a method for improving the thermal fatigue resistance of an alloy steel casting against the existing problems, which can not initiate a crack source, can not accelerate crack propagation even if cracks are generated under the action of external force, and obviously improves the fatigue resistance of the alloy steel casting.
The invention is realized by the following technical scheme:
a method for improving the thermal fatigue resistance of an alloy steel casting is characterized in that in the preparation of the alloy steel casting, the thermal fatigue resistance of the alloy steel casting is improved by adding prepared ceramic alloy powder and mixing.
The preparation method of the ceramic alloy powder comprises the following steps: weighing 30-32 g of kaolin powder and silicon carbide according to the mass ratio of 3-4:1, placing the kaolin powder and the silicon carbide into a mortar, adding 20-25 ml of abietic alcohol solution, mixing and continuously grinding for 2-3 hours, placing the ground material into a vibration mill, adding 13-15 g of boron oxide and 7-8 g of alumina powder, mixing for 2-3 hours, adding 50-60 ml of 18-20% polyvinyl alcohol aqueous solution with mass concentration into the obtained mixed powder, continuously mixing for 40-50 minutes in a high-speed mixing mill at the mixing speed of 3500-4000 turns/minute, placing the mixed material into a drying box with the temperature of 200-210 ℃ for drying for 4-5 hours, then heating to 400-420 ℃, preserving the temperature for 3-4 hours, removing overflow liquid, placing the rest material into a tubular furnace for sintering, under the protection of argon, heating to 1850-; the ceramic alloy powder prepared by the method has small density, large specific surface area and strong affinity with iron element, forms uniformly dispersed lamellar nucleation, inhibits the growth of crystal grains, promotes balanced solidification, obviously reduces heat sensitivity, has the functions of refining the crystal grains and strengthening, and has important influence on the heat stability of alloy steel castings.
The mass ratio of the rosin to the ethanol solvent in the rosin alcohol solution is 1.7-1.9: 5-6;
the alloy steel comprises the following elements in percentage by mass: 0.30-0.34 percent of silicon, 0.20-0.23 percent of carbon, 0.30-0.35 percent of chromium, 1.20-1.30 percent of nickel, 0.45-0.55 percent of molybdenum, 0.10-0.12 percent of vanadium, 0.01-0.02 percent of yttrium, 0.010-0.015 percent of phosphorus, 0.008-0.010 percent of sulfur and the balance of iron.
The preparation method of the alloy steel casting comprises the following steps: the preparation method comprises the following steps of (1) preparing materials according to the components and content of alloy steel, carrying out alloy smelting by adopting a non-oxidation smelting process, adding the prepared ceramic alloy powder into molten steel when the temperature of the alloy steel reaches 1500-; degassing, removing impurities and refining the melt, injecting the melt obtained by refining into a preheated mold cavity from a feed inlet, naturally cooling to the temperature of 360-380 ℃ after the mold cavity is filled, opening the mold to obtain a molded casting, and further performing heat treatment; the heat treatment is divided into two steps: the first step is as follows: the quenching and tempering treatment is that the temperature of the formed casting is raised to 920-930 ℃ at the speed of 8-10 ℃/min, and after the temperature is kept for 40-45 min, the formed casting is cooled for 3-4 h by oil quenching; the second step is as follows: after the first step of treatment, the casting is sent into a furnace, the temperature is raised to 710 ℃ and 720 ℃ at the speed of 7.0-7.5 ℃/min, the temperature is kept for 1.5-2.0 hours, and the casting is cooled to the room temperature by air.
In the preparation method of the alloy steel casting, the addition amount of the ceramic alloy powder is 0.07-0.10 percent of the mass of the molten steel.
In the preparation method of the alloy steel casting, the preheating temperature of the die cavity is 340-350 ℃.
Compared with the prior art, the invention has the following advantages: the ceramic alloy powder prepared by adding the ceramic alloy powder has small density and large specific surface area, forms uniformly dispersed lamellar nucleation effect, inhibits the growth of crystal grains, promotes balanced solidification, obviously reduces heat sensitivity, has the functions of refining the crystal grains and strengthening the crystal grains, and has important influence on the heat stability of the alloy steel casting; because the ceramic alloy material has strong affinity with iron, a regular lamellar structure is formed, stress concentration is not easy to generate in the process of cold and hot circulation, a crack source cannot be caused, even if cracks are generated under the action of external force, crack expansion cannot be accelerated, and the fatigue resistance of the alloy steel casting is obviously improved; interface reaction does not exist, the structure is refined, the crack propagation speed is reduced, the number of cold and hot circulation times at the temperature of 0-650 ℃ is 0-5000 times, and the maximum value of the propagation speed of the main crack is only 0.05 micron/time; the invention effectively solves the problem of poor thermal fatigue resistance of the alloy steel casting caused by element inclusion, has the characteristics of low cost, low energy consumption and good economy, greatly prolongs the service life of the alloy steel casting, can realize the practical significance of enhancing the service performance of the alloy steel casting and improving the market competitiveness, has higher value for the research of alloy thermal fatigue performance, obviously promotes the rapid development and the sustainable development of resources of the modern alloy casting industry, and is a technical scheme which is extremely worthy of popularization and use.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is further described with reference to specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the present invention and are not used for limiting the technical solutions provided by the present invention.
Example 1
A method for improving the thermal fatigue resistance of an alloy steel casting is characterized in that in the preparation of the alloy steel casting, the thermal fatigue resistance of the alloy steel casting is improved by adding prepared ceramic alloy powder and mixing.
The preparation method of the ceramic alloy powder comprises the following steps: weighing 30 g of kaolin powder and silicon carbide according to the mass ratio of 3:1, placing the kaolin powder and the silicon carbide into a mortar, adding 20 ml of abietic alcohol solution, mixing and continuously grinding for 2 hours, placing the ground material into a vibration mill, adding 13 g of boron oxide and 7 g of alumina powder, mixing for 2 hours, adding 50 ml of polyvinyl alcohol aqueous solution with the mass concentration of 18% into the obtained mixed powder, continuously mixing for 40 minutes in a high-speed mixing mill at the mixing speed of 3500 rpm, placing the mixed material into a drying oven at 200 ℃ for drying for 4 hours, then heating to 400 ℃, keeping the temperature for 3 hours, removing overflow liquid, placing the rest material into a tubular furnace for sintering, heating to 1850 ℃ at the speed of 12 ℃/minute under the protection of argon, keeping the temperature for 70 minutes, naturally cooling to room temperature along with the furnace, placing into an oven at 110 ℃ for drying for 3 hours, grinding to obtain powder with the particle size of 1-10 microns, namely the ceramic alloy powder.
The mass ratio of the rosin to the ethanol solvent in the rosin alcohol solution is 1.7: 5;
the alloy steel comprises the following elements in percentage by mass: 0.30% of silicon, 0.20% of carbon, 0.30% of chromium, 1.20% of nickel, 0.45% of molybdenum, 0.10% of vanadium, 0.01% of yttrium, 0.010% of phosphorus, 0.008% of sulfur and the balance of iron.
The preparation method of the alloy steel casting comprises the following steps: preparing materials according to the components and content of the alloy steel, smelting the alloy by adopting a non-oxidation smelting process, adding the prepared ceramic alloy powder into the molten steel when the temperature of the alloy steel reaches 1500 ℃, and mixing for 15 minutes under the stirring condition; degassing, removing impurities and refining the melt, injecting the melt obtained by refining into a preheated mold cavity from a feed inlet, naturally cooling to 360 ℃ after the mold cavity is full, opening the mold to obtain a molded casting, and further performing heat treatment; the heat treatment is divided into two steps: the first step is as follows: the quenching and tempering treatment is that the temperature of the formed casting is raised to 920 ℃ at the speed of 8 ℃/min, and after the temperature is preserved for 40 min, the formed casting is cooled for 3 h by oil quenching; the second step is as follows: after the first step of treatment, the casting is sent into a furnace, the temperature is raised to 710 ℃ at the speed of 7.0 ℃/minute, the temperature is kept for 1.5 hours, and the casting is cooled to room temperature by air.
In the preparation method of the alloy steel casting, the addition amount of the ceramic alloy powder is 0.07 percent of the mass of the molten steel.
In the preparation method of the alloy steel casting, the preheating temperature of a die cavity is 340 ℃ in advance.
Example 2
A method for improving the thermal fatigue resistance of an alloy steel casting is characterized in that in the preparation of the alloy steel casting, the thermal fatigue resistance of the alloy steel casting is improved by adding prepared ceramic alloy powder and mixing.
The preparation method of the ceramic alloy powder comprises the following steps: weighing 31 g of kaolin powder and silicon carbide according to the mass ratio of 3.5:1, putting the kaolin powder and the silicon carbide into a mortar, adding 22 ml of abietyl alcohol solution, mixing and continuously grinding for 2.5 hours, putting the ground material into a vibration mill, adding 14 g of boron oxide and 7.5 g of alumina powder, mixing for 2.5 hours, adding 55 ml of polyvinyl alcohol aqueous solution with the mass concentration of 19% into the obtained mixed powder, continuously mixing for 45 minutes in a high-speed mixer at the mixing speed of 3800 rpm, putting the mixed material into a drying oven at 205 ℃ for drying for 4.5 hours, heating to 410 ℃, preserving heat for 3.5 hours, removing overflow liquid, putting the rest of the material into a tubular furnace for sintering, heating to 1880 ℃ at the speed of 13 ℃/minute under the protection of argon gas, preserving heat for 75 minutes, naturally cooling to room temperature along with the furnace, putting the material into an oven at 115 ℃ for drying for 3.5 hours, grinding to obtain powder with the particle size of 1-10 microns, namely ceramic alloy powder; the ceramic alloy powder prepared by the method has small density, large specific surface area and strong affinity with iron element, forms uniformly dispersed lamellar nucleation, inhibits the growth of crystal grains, promotes balanced solidification, obviously reduces heat sensitivity, has the functions of refining the crystal grains and strengthening, and has important influence on the heat stability of alloy steel castings.
The mass ratio of the rosin to the ethanol solvent in the rosin alcohol solution is 1.8: 5.5;
the alloy steel comprises the following elements in percentage by mass: 0.32% of silicon, 0.21% of carbon, 0.32% of chromium, 1.25% of nickel, 0.50% of molybdenum, 0.11% of vanadium, 0.015% of yttrium, 0.013% of phosphorus, 0.009% of sulfur and the balance iron.
The preparation method of the alloy steel casting comprises the following steps: batching according to the components and content of the alloy steel, smelting the alloy by adopting a non-oxidation smelting process, adding the prepared ceramic alloy powder into the molten steel when the temperature of the alloy steel reaches 1530 ℃, and mixing for 18 minutes under the stirring condition; degassing, removing impurities and refining the melt, injecting the melt obtained by refining into a preheated mold cavity from a feed inlet, naturally cooling to 370 ℃ after the mold cavity is full, opening the mold to obtain a molded casting, and further performing heat treatment; the heat treatment is divided into two steps: the first step is as follows: the quenching and tempering treatment is that the temperature of the formed casting is raised to 925 ℃ at the speed of 9 ℃/min, the temperature is preserved for 42 min, and then the formed casting is cooled for 3.5 h by oil quenching; the second step is as follows: after the first step of treatment, the casting is sent into a furnace, the temperature is raised to 715 ℃ at the speed of 7.3 ℃/minute, the temperature is kept for 1.8 hours, and the casting is cooled to room temperature by air.
In the preparation method of the alloy steel casting, the addition amount of the ceramic alloy powder is 0.08 percent of the mass of the molten steel.
In the preparation method of the alloy steel casting, the preheating temperature of the die cavity is 345 ℃ in advance.
Example 3
A method for improving the thermal fatigue resistance of an alloy steel casting is characterized in that in the preparation of the alloy steel casting, the thermal fatigue resistance of the alloy steel casting is improved by adding prepared ceramic alloy powder and mixing.
The preparation method of the ceramic alloy powder comprises the following steps: weighing 32 g of kaolinite powder and silicon carbide according to the mass ratio of 4:1, placing the kaolinite powder and the silicon carbide into a mortar, adding 25 ml of abietic alcohol solution, mixing and continuously grinding for 3 hours, placing the ground material into a vibration mill, adding 15 g of boron oxide and 8 g of alumina powder, mixing for 3 hours, adding 60 ml of polyvinyl alcohol aqueous solution with the mass concentration of 20% into the obtained mixed powder, continuously mixing for 50 minutes in a high-speed mixing mill at the mixing speed of 4000 rpm, placing the mixed material into a drying box at the temperature of 210 ℃ for drying for 5 hours, then heating to 420 ℃, keeping the temperature for 4 hours, removing overflow liquid, placing the rest material into a tubular furnace for sintering, heating to 1900 ℃ at the speed of 14 ℃/minute under the protection of argon, keeping the temperature for 80 minutes, naturally cooling to room temperature along with the furnace, placing into an oven at the temperature of 120 ℃ for drying for 4 hours, grinding to obtain powder with the particle size of 1-10 microns, namely ceramic alloy powder; the ceramic alloy powder prepared by the method has small density, large specific surface area and strong affinity with iron element, forms uniformly dispersed lamellar nucleation, inhibits the growth of crystal grains, promotes balanced solidification, obviously reduces heat sensitivity, has the functions of refining the crystal grains and strengthening, and has important influence on the heat stability of alloy steel castings.
The mass ratio of the rosin to the ethanol solvent in the rosin alcohol solution is 1.9: 6;
the alloy steel comprises the following elements in percentage by mass: 0.34% of silicon, 0.23% of carbon, 0.35% of chromium, 1.30% of nickel, 0.55% of molybdenum, 0.12% of vanadium, 0.02% of yttrium, 0.015% of phosphorus, 0.010% of sulfur and the balance of iron.
The preparation method of the alloy steel casting comprises the following steps: the preparation method comprises the following steps of (1) preparing materials according to the components and content of alloy steel, carrying out alloy smelting by adopting a non-oxidation smelting process, adding prepared ceramic alloy powder into molten steel when the temperature of the alloy steel reaches 1550 ℃, and mixing for 20 minutes under the stirring condition; degassing, removing impurities and refining the melt, injecting the melt obtained by refining into a preheated mold cavity from a feed inlet, naturally cooling to 380 ℃ after the mold cavity is full, opening the mold to obtain a molded casting, and further performing heat treatment; the heat treatment is divided into two steps: the first step is as follows: the quenching and tempering treatment is that the temperature of the formed casting is raised to 930 ℃ at the speed of 10 ℃/min, the temperature is kept for 45 min, and then the formed casting is cooled for 4 h by oil quenching; the second step is as follows: after the first step of treatment, the casting is sent into a furnace, the temperature is raised to 720 ℃ at the speed of 7.5 ℃/minute, the temperature is kept for 2.0 hours, and the casting is cooled to the room temperature by air.
In the preparation method of the alloy steel casting, the addition amount of the ceramic alloy powder is 0.10 percent of the mass of the molten steel.
In the preparation method of the alloy steel casting, the preheating temperature of a die cavity is 350 ℃ in advance.
According to the method disclosed by the embodiment 1-3, the thermal fatigue resistance of the alloy steel casting is improved, the crack propagation speed is reduced, the number of cold and hot cycles at the temperature of 0-650 ℃ is 5000, and the maximum value of the propagation speed of the main crack is only 0.05 micron/time.
The invention effectively solves the problem of poor thermal fatigue resistance of the alloy steel casting caused by element inclusion, has the characteristics of low cost, low energy consumption and good economy, greatly prolongs the service life of the alloy steel casting, can realize the practical significance of enhancing the service performance of the alloy steel casting and improving the market competitiveness, has higher value for the research of alloy thermal fatigue performance, obviously promotes the rapid development and the sustainable development of resources of the modern alloy casting industry, and is a technical scheme which is extremely worthy of popularization and use.
Claims (7)
1. A method for improving the thermal fatigue resistance of an alloy steel casting is characterized in that in the preparation of the alloy steel casting, the thermal fatigue resistance of the alloy steel casting is improved by adding prepared ceramic alloy powder and mixing;
the preparation method of the ceramic alloy powder comprises the following steps:
(1) weighing 30-32 g of kaolin powder and silicon carbide according to the mass ratio of 3-4:1, putting the kaolin powder and the silicon carbide into a mortar, adding 20-25 ml of rosin alcohol solution, mixing and continuously grinding for 2-3 hours, putting the ground material into a vibration mill, adding 13-15 g of boron oxide and 7-8 g of alumina powder, mixing for 2-3 hours, adding 50-60 ml of polyvinyl alcohol aqueous solution into the obtained mixed powder, and continuously mixing for 40-50 minutes in a high-speed mixing roll at the mixing speed of 3500 + 4000 rpm;
(2) drying the mixed material in a drying oven at 210 ℃ under 200-plus-one temperature for 4-5 hours, heating to 420 ℃ under 400-plus-one temperature, preserving heat for 3-4 hours, removing overflow liquid, sintering the residual material in a tube furnace, heating to 1900 ℃ under 1850-plus-one temperature at the speed of 12-14 ℃/min under the protection of argon, preserving heat for 70-80 minutes, naturally cooling to room temperature along with the furnace, drying in an oven at 120 ℃ under 110-plus-one temperature for 3-4 hours, and grinding into powder, namely the ceramic alloy powder;
the preparation method of the alloy steel casting comprises the following steps: the preparation method comprises the following steps of (1) preparing materials according to the components and content of alloy steel, smelting the alloy, adding the prepared ceramic alloy powder into molten steel when the temperature of the alloy steel reaches 1500-; degassing, removing impurities and refining the melt, injecting the melt obtained by refining into a preheated mold cavity from a feeding port, naturally cooling to the temperature of 360-380 ℃ after the mold cavity is filled, opening the mold to obtain a molded casting, and further performing heat treatment.
2. The method for improving the thermal fatigue resistance of alloy steel castings according to claim 1, wherein the mass ratio of the rosin to the ethanol solvent in the rosin alcohol solution in step (1) is 1.7-1.9: 5-6.
3. The method for improving the thermal fatigue resistance of alloy steel castings according to claim 1, wherein the mass concentration of the aqueous solution of polyvinyl alcohol in the step (1) is 18-20%.
4. The method for improving the thermal fatigue resistance of alloy steel castings according to claim 1, wherein the alloy steel comprises the following elements by mass percent: 0.30-0.34 percent of silicon, 0.20-0.23 percent of carbon, 0.30-0.35 percent of chromium, 1.20-1.30 percent of nickel, 0.45-0.55 percent of molybdenum, 0.10-0.12 percent of vanadium, 0.01-0.02 percent of yttrium, 0.010-0.015 percent of phosphorus, 0.008-0.010 percent of sulfur and the balance of iron.
5. The method for improving the thermal fatigue resistance of the alloy steel casting as claimed in claim 1, wherein in the preparation method of the alloy steel casting, the addition amount of the ceramic alloy powder is 0.07-0.10% of the mass of molten steel.
6. The method for improving the thermal fatigue resistance of the alloy steel casting as claimed in claim 1, wherein in the preparation method of the alloy steel casting, the preheating temperature of the die cavity is 340-350 ℃.
7. The method for improving the thermal fatigue resistance of alloy steel castings according to claim 1, wherein the grain size of the ceramal powder is in the range of 1-10 microns.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2607632A (en) * | 2021-06-10 | 2022-12-14 | Armadillo Metal Coatings Ltd | Modified cast metal object |
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2019
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2607632A (en) * | 2021-06-10 | 2022-12-14 | Armadillo Metal Coatings Ltd | Modified cast metal object |
| WO2022258783A1 (en) * | 2021-06-10 | 2022-12-15 | Armadillo Metal Coatings Ltd | Modified cast metal object |
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