Composite with multi-level structure for glass melting equipment and method for producing it

Abstract

FIELD: multilayer composite material.SUBSTANCE: multilayer composite material for contact with liquid glass melt and methods for producing it. Multilayer composite material which includes a supporting layer made of dispersion-hardened palladium or dispersion-hardened palladium alloys, or dispersion-hardened platinum, or dispersion-hardened platinum alloys, or dispersion-hardened platinum-rhodium alloy, with a grain size of 4-45 mcm, and a contact layer intended for contact with liquid glass melt and made of platinum or its alloys, with a grain size of 100-500 mcm. The specified method includes pressing in a press mold coils or bundles of wires with a diameter of 0.1-1.0 mm to obtain a single-layer blank of the supporting layer with a gas porosity of no more than 50% and pressing coils or bundles of wires with a diameter of 0.3-1.5 mm to obtain a single-layer blank of the contact layer with a gas porosity of no more than 50%. Then the resulting single-layer blanks are assembled into a package. The package is pressed into a briquette with a gas porosity of no more than 40%. The pressed briquette is forged or rolled using a hot method, and sheet metal is obtained by cold rolling in the form of the said multilayer composite material of the required final thickness. The multilayer composite material may contain an inner layer with a gas porosity of no more than 50% placed between the carrier layer and the contact layer.EFFECT: ensures an increase in the strength of the material of the layers of the multilayer composite material and the corrosion resistance of the layer in contact with liquid glass.21 cl, 5 dwg, 1 tbl

Description

[0001] Technical field

[0002] The invention relates to precious metal metallurgy, specifically to composite materials based on platinum group metals—palladium, platinum, rhodium, and platinum-rhodium alloys—strengthened with dispersed oxide particles. These materials can be used in the manufacture of glass melting equipment components operating in aggressive environments at high temperatures, including crucibles, stirrers, nozzles, feeders, and other components of glass melting and fiberglass production units.

[0003] A composite material is known for use at high temperatures in aggressive environments, particularly for the production of glass-melting vessels (SU549491, published March 5, 1977). The material consists of a base layer and two outer layers of platinum, with the base layer made of an alloy of palladium, rhodium, iridium / ruthenium, and platinum. The layer thicknesses are made in a ratio of 1:(3-20):1. The material is manufactured as follows: first, an ingot of the base layer alloy is obtained, then, after preliminary pressure treatment, it is clad on both sides with platinum using a cold rolling method using standard stacking technology.

[0004] A disadvantage of this material is the limited service life of parts made from it at high temperatures. Despite the high degree of affinity between the metals used (platinum and the base layer alloy), during high-temperature operation of crucibles with complex spatial shapes (e.g., with a spherical bottom) made from this composite material, a shift in the outer layers relative to the inner layers is observed. This is due to the weak adhesion between the layers caused by the cold rolling process, which achieves only limited diffusion bonding. Furthermore, the layers are made of homogeneous alloys with a cast structure and have a constant thickness across the entire surface of the workpiece. After crucible forming, the curved areas, especially the bottom area, become thinner.Thinner sections of the outer layers of homogeneous alloys with a cast structure have reduced resistance to tensile and compressive stresses, which promotes shear and leads to cracking. Cracks lead to loss of sealing in the feeder: if there is a crack in the feeder wall, liquid glass can leak onto the die bottom, and if there is a crack directly in the die bottom, it can cause molten glass to leak. As a result, the feeder fails. Damage to the outer layers in the crucible during optical glass melting leads to unwanted contact between the uncoated layer and the substance being processed, such as hot optical glass, where components of the exposed layer can enter, degrading the quality of the glass.

[0005] A known layered material (patent RU50149, published December 17, 2005) comprises sequentially arranged layers, at least one of which is made of a platinum-based material. The two outer layers are composed of iridium, while the inner layer, located between them and in continuous contact with them, is made of a platinum material. The thickness of the inner layer is at least 10 vol.% of the total thickness of the layered structure. The inner layer can be further strengthened by a dispersed oxide phase.

[0006] The disadvantages of this laminated material include insufficient heat resistance and the high chemical reactivity of iridium when in contact with optical glass. As a result of this interaction, iridium dissolves and causes coloration of the glass, which leads to a significant reduction in the service life of the product during high-temperature operation and a deterioration in the optical properties of the glass. This is due to iridium's high reactivity with optical glass components. Furthermore, using iridium for the outer layers significantly increases both the weight and cost of the finished product, especially when the thickness of the outer layers reaches the maximum possible value—90% of the total thickness of the laminated material.The significant difference in ductility and strength between cast iridium with a uniform structure and platinum reinforced with oxide additives leads to mutual layer displacement under thermal and cyclic mechanical loads, which are inevitable during the use of glass melting crucibles. This causes crucible failure and makes it impossible to fulfill its intended function. This defect (layer displacement) is particularly pronounced in areas with complex geometry, such as the spherical bottom of the crucible.

[0007] The closest in technical essence to the claimed invention is a composite material for the manufacture of crucibles, described in patent US4525433A (published on June 25, 1985). This material consists of two outer layers and one inner base layer. The outer layers are made of dispersion-hardened platinum group metals or their platinum-containing alloys. The inner layer is made of palladium, dispersion-hardened palladium, a palladium alloy, or a dispersion-hardened palladium alloy. The technology for producing the material includes the following stages: a plate intended for the inner layer is cleaned with sandpaper until a smooth satin surface is obtained, washed with soap and water, and then dried. For the outer layers, ingots are made from the appropriate melts; The surfaces of the ingots that will be in contact with the inner layer are similarly cleaned with sandpaper, washed and dried.The inner layer is then placed between the prepared surfaces of the outer layers, and the entire assembly is joined under uniform pressure to form a blank. The exposed edges of the blank are sealed using argon arc welding. The blank is then placed in a nitrogen-purged furnace and held at 1600°F (871°C) for 15 minutes. The heated blank is removed from the furnace, hot-rolled, and then quenched in cold water. If necessary, additional cold rolling is performed until the required composite thickness is achieved.

[0008] A disadvantage of this material, adopted as a prototype, is the insufficient service life of parts made from it when used at high temperatures. This disadvantage is due to both the molding technology used and the composite's design. Low temperatures and short thermal soak times result in weak interdiffusion between the layers, resulting in a diffusion layer that is too thin to provide reliable long-term adhesion. Subsequent rolling of the blank further reduces the thickness of this layer. During crucible operation, such a diffusion layer is unable to withstand combined thermal and mechanical loads, especially in the spherical bottom area, causing mutual layer shear, uneven wall thickness, and inhomogeneity of the part's internal surface.Furthermore, each layer of the composite is made of a dispersion-hardened metal or alloy produced by spraying molten droplets onto a cooled target. According to the invention description, the grain size in this material exceeds 160 µm and is largely determined (inherited) by the size of the initial sprayed droplets, which also exceed 160 µm. With such droplet sizes, in the short time from sputtering to deposition on the target, oxidation of the zirconium contained in the alloy occurs predominantly on the droplet surface, while its interior remains virtually unoxidized. This results in a low overall oxidation rate and an uneven distribution of zirconium oxide—the main dispersion hardener—concentrated primarily at the boundaries of the fused droplets.As a result, the material's heat resistance is insufficient: the dispersed phase ineffectively prevents grain growth and offers weak resistance to dislocation movement at high temperatures, which promotes crack formation. Taken together, these factors lead to premature failure of the crucible during glass melting.

[0009] Thus, the existing level of technology does not provide an effective, technologically advanced and economically feasible solution for the production of highly loaded components designed for long-term operation at high temperatures made of precious metals and combining low weight, high corrosion resistance and creep resistance under prolonged contact with molten glass.

[0010] Disclosure of invention

[0011] The objective of the invention is to create a composite with a multi-level structure, in which the multi-layer structure determines the macro-level of strengthening, and the grain structure of the layers and the presence of a strengthening dispersed phase determine the micro and / or nano-level of strengthening, for the production of glass melting equipment units (crucibles, stirrers, nozzles, pipes and other elements of glass production units), ensuring long-term and efficient operation at high temperatures.

[0012] The technical result consists in increasing the strength of the layer material and the corrosion resistance of the layer in contact with liquid glass.

[0013] The technical result is achieved through a multilayer composite material designed for contact with liquid glass melt, including:

[0014] - a supporting layer designed to maintain the crucible shape and prevent the formation of hot cracks at high operating temperatures, made of dispersion-hardened palladium or dispersion-hardened palladium alloys, or dispersion-hardened platinum, or dispersion-hardened platinum alloys, in particular platinum-rhodium alloys, with an average grain size of 4-45 μm. Dispersion strengthening is achieved by fixing the grain boundaries with uniformly distributed dispersed zirconium oxide particles;

[0015] - a contact layer designed for contact with liquid optical glass melt to prevent it from being stained by the material of the crucible, stirrer and other units, made of platinum or its alloys and having an equiaxed homogeneous structure with a grain size of 100-500 μm, which ensures high corrosion resistance during interaction with optical glass, since an increase in grain size reduces the dissolution of platinum in glass, reduces material loss, helps maintain the continuity of the layer for a longer period and reduces the likelihood of glass staining due to the accumulation of platinum in it.

[0016] In particular embodiments of the invention:

[0017] - dispersion strengthening is performed by dispersed particles of zirconium oxide;

[0018] - the material is provided with at least one inner layer, which is placed between the carrier layer and the contact layer and is made of palladium or its alloys, or of dispersion-hardened palladium or dispersion-hardened palladium alloys;

[0019] - the internal interacting surfaces of the said carrier layer and contact layer are made flat;

[0020] - the internal interacting surfaces of the said carrier layer, contact layer and inner layer or inner layers are made flat;

[0021] - the internal interacting surfaces of the said bearing layer and contact layer are made with relief serrated surfaces;

[0022] - the internal interacting surfaces of the said carrier layer, contact layer and inner layer or inner layers are made with relief serrated surfaces;

[0023] - the specified internal interacting surfaces are made serrated with an amplitude of 0.5-10 mm with a pitch of 1-40 mm;

[0024] - the internal interacting surfaces of the said bearing layer and contact layer are made involute or sinusoidal;

[0025] - the internal interacting surfaces of the said carrier layer, contact layer and inner layer or inner layers are made involute or sinusoidal;

[0026] - the mentioned internal interacting surfaces are made involute or sinusoidal with an amplitude of 0.5-10 mm with a step of 1-40 mm.

[0027] The technical result is also achieved by a method for producing a multilayer composite material intended for contact with liquid glass melt, including:

[0028] - pressing in a press mold of coils or bundles of wires with a diameter of 0.1-1.0 mm, made of dispersion-hardened palladium or dispersion-hardened palladium alloys, or dispersion-hardened platinum, or dispersion-hardened platinum alloys, or dispersion-hardened platinum-rhodium alloy to obtain a single-layer blank of the supporting layer with a gas porosity of no more than 50%;

[0029] - pressing coils or bundles of wires with a diameter of 0.3-1.5 mm from platinum or its alloys to obtain a single-layer blank of a contact layer intended for contact with liquid molten glass, with a gas porosity of no more than 50%;

[0030] - assembly of the obtained single-layer blanks into a package;

[0031] - pressing the package into a briquette with a gas porosity of no more than 40%;

[0032] - forging or hot rolling of pressed briquette;

[0033] - obtaining by cold rolling sheet metal in the form of a multilayer composite of the required final thickness, in which the supporting layer has a grain size of 4-45 μm and the contact layer for contact with liquid glass melt has a grain size of 100-500 μm.

[0034] In particular embodiments of the method:

[0035] - pressed briquettes from a single-layer blank of the supporting layer and a single-layer blank of the contact layer are forged to obtain a forging with a gas porosity of no more than 1.0%;

[0036] - hot rolling of pressed briquettes from a single-layer blank of the supporting layer and a single-layer blank of the contact layer is carried out with a degree of compression of at least 5% in one pass on a hot rolling mill;

[0037] - the contacting surfaces of the single-layer blank of the carrier layer and the single-layer blank of the contact layer are formed with relief by means of relief punches in a press mold;

[0038] - the contact surfaces of the single-layer blank of the carrier layer and the single-layer blank of the contact layer are formed with a jagged relief;

[0039] - the contacting surfaces of the single-layer workpiece of the carrier layer and the single-layer workpiece of the contact layer are formed with an involute or sinusoidal relief.

[0040] The technical result is also achieved by a method for producing a multilayer composite material intended for contact with liquid glass melt, including:

[0041] - pressing in a press mold of coils or bundles of wires with a diameter of 0.1-1.0 mm, made of dispersion-hardened palladium or dispersion-hardened palladium alloys, or dispersion-hardened platinum, or dispersion-hardened platinum alloys, or dispersion-hardened platinum-rhodium alloy to obtain a single-layer blank of the supporting layer with a gas porosity of no more than 50%,

[0042] - pressing coils or bundles of wires with a diameter of 0.3-1.5 mm from platinum or its alloys to obtain a single-layer blank of a contact layer intended for contact with liquid molten glass, with a gas porosity of no more than 50%,

[0043] - pressing of coils or bundles of wires with a diameter of 0.1-1.0 mm made of palladium or its alloys, or of dispersion-hardened palladium or dispersion-hardened palladium alloys to obtain a single-layer blank of the inner layer, with a gas porosity of not more than 50%,

[0044] - subsequent assembly of the obtained single-layer blanks into a package in such a way that an inner layer is placed between the contact and carrier layers,

[0045] - pressing the package into a briquette with a gas porosity of no more than 40%,

[0046] - forging or hot rolling of pressed briquette,

[0047] - obtaining by cold rolling sheet metal in the form of a multilayer composite of the required final thickness, in which the supporting layer has a grain size of 4-45 μm and the contact layer for contact with liquid glass melt has a grain size of 100-500 μm.

[0048] In particular embodiments of the method:

[0049] - the contacting surfaces of the single-layer blank of the carrier layer, the single-layer blank of the contact layer and the single-layer blank of the inner layer are formed with relief by means of relief punches in a press mold.

[0050] - the contact surfaces of the single-layer blank of the carrier layer, the single-layer blank of the contact layer and the single-layer blank of the inner layer are formed with a jagged relief.

[0051] - the contacting surfaces of the single-layer blank of the supporting layer, the single-layer blank of the contact layer and the single-layer blank of the inner layer are formed with an involute or sinusoidal relief.

[0052] The layer arrangement allows for a composite with a multi-layer structure and the required corrosion and heat resistance. High corrosion resistance is ensured by the contact layer, which has a uniform coarse-grained structure with a grain size of 100-500 μm when interacting with optical glass. Increasing the grain size reduces platinum dissolution in the glass, minimizes material loss, helps maintain the layer's integrity for a longer period, and reduces the risk of glass staining due to platinum accumulation. High heat resistance is achieved through a supporting, reinforced layer with a grain size of 4-45 μm, which limits crucible deformation and reduces the risk of hot cracking during operation at high temperatures.

[0053] The adhesion of the layers, which in certain cases is ensured by the relief profile of the mating surfaces of the layers, as well as the optimal thickness of each layer, increases the strength of the resulting multilayer material at the macro level.

[0054] The composite material's layer structure ensures their strengthening at the micro- and / or nanoscale. The use of metals and their alloys with dispersed hardeners for the layers helps limit the movement of structural defects (dislocations) in the crystal lattice that can lead to hot cracks at high temperatures and pressures, thereby increasing the heat resistance of the layers. Producing layers with controlled grain size parameters reduces the risk of dislocations in these layers, which in turn eliminates layer-by-layer flow within each layer, which can lead to layer displacement relative to one another. The increased mechanical strength of the layers, combined with the elimination of the risk of layer shear within individual layers, ensures the absence of cracks in the composite material as a whole, ensuring high long-term strength of the product made from this material under both static and cyclic loads.

[0055] The features of the manufacturing method for a composite with a multi-level structure ensure the production of the declared material with the required properties of corrosion resistance and heat resistance:

[0056] - the initial single-layer blank for the supporting layer is made from coils or bundles of wires made of dispersion-hardened palladium or dispersion-hardened palladium alloys, or dispersion-hardened platinum, or dispersion-hardened platinum alloys, in particular platinum-rhodium alloys with a diameter of 0.1-1.0 mm with an already limited average grain size, the boundaries of which are stabilized by dispersed particles (as is known, wire has a small grain size compared to ingots, sheet metal). Before pressing, the coils or bundles are laid with different orientations of individual wires, which makes it possible to set the grain size required for the supporting layer already at the initial stage, and pressed to a blank with a gas porosity of no more than 50%;

[0057] - the initial single-layer blank for the inner layer is made from coils or bundles of wires made of palladium or its alloys, or from dispersion-hardened palladium or dispersion-hardened palladium alloys with a diameter of 0.1-1.0 mm. Before pressing, the coils or bundles are laid with individual wires in different orientations, which allows the grain size required for the supporting layer to be set at the initial stage, and then pressed to a blank with a gas porosity of no more than 50%.

[0058] - the initial single-layer blank for the contact layer is made from coils or bundles of wires made of platinum or its alloys with a larger diameter of 0.3-1.5 mm, pressed in a press mold to obtain single-layer blanks with a gas porosity of no more than 50% of an equiaxed homogeneous structure with a larger grain size, compared to the supporting and / or inner layer;

[0059] - pressed single-layer blanks are assembled and pressed into a briquette with a gas porosity of no more than 40%, and if the mating surfaces are embossed, then the assembly of single-layer blanks into a package is carried out with a congruent combination of the reliefs of the mating surfaces;

[0060] - pressed briquettes of two or more layers are sent either to a forging operation predominantly along the direction of the layer stack arrangement, or are sent to a hot rolling operation with high compression along the direction of the layer stack arrangement, which leads to homogenization and uniformity of the structure, preventing the growth of grains of the carrier and / or inner layer, and obtaining a composite multilayer material of the required thickness with a gas porosity of no more than 1.0%;

[0061] - multilayer blanks after deep hot deformation of forging or rolling are sent to cold rolling of sheet blanks to the final thickness.

[0062] Since single-layer blanks consist of materials that differ in chemical composition, degree of hardening, and microstructure determined by the diameter of the starting wire, the parameters and modes of all stages, from pressing a stack of single-layer blanks into a briquette, subsequent pressing or forging of the briquette to obtaining the final material, and ending with heat treatment, are selected taking these initial characteristics into account. In addition to strengthening individual layers, in particular by blocking dislocations within each layer to prevent crack initiation, certain embodiments of the invention further eliminate relative shear between layers after diffusion bonding. This is achieved by forming congruent reliefs on the mating surfaces of adjacent layers.Furthermore, this surface topography, combined with the specified plastic deformation regimes, increases the actual contact area between the layers by more than 30% compared to the area of ​​a perfectly flat contact. This significantly increases the bond strength between the layers and facilitates the formation of a composite material with high heat resistance. The inner layer also acts as an additional barrier, preventing the propagation of through transverse cracks—from the outer surface of one outer layer to the outer surface of the opposite outer layer. This crack inhibition or absorption is due to differences in the plastic properties of adjacent layers at their contact interface.

[0063] Thus, the proposed group of inventions enables the creation of a composite with a multilayer structure characterized by high interlayer adhesion strength, crack resistance, and heat resistance. This ensures the geometric stability of components made from this material, maintaining their functionality during long-term operation under intense cyclic thermal and mechanical loads, and high corrosion resistance. As a result, irreversible platinum loss caused by its dissolution in optical glass is reduced, while simultaneously improving the quality of the glass itself by reducing the concentration of dissolved platinum within it.

[0064] Brief description of drawings

[0065] The invention is illustrated by images:

[0066] Fig. 1 - schematic three-dimensional image of a composite with a multi-level structure of 2 layers (the internal interacting surfaces of the outer and inner layers are made flat).

[0067] Fig. 2 - schematic three-dimensional image of a composite with a multi-level structure of 3 layers (the internal interacting surfaces of the outer and inner layers are made flat);

[0068] Fig. 3 - schematic three-dimensional image of a composite with a multi-level structure of 2 layers (the surfaces of the mating layers are made with relief serrated surfaces with the formation of a diffusion layer of constant thickness);

[0069] Fig. 4 - schematic three-dimensional image of a composite with a multi-level structure of 3 layers (the surfaces of the mating layers are made jagged with the formation of a diffusion layer of constant thickness);

[0070] Fig. 5 - schematic three-dimensional image of a composite with a multi-level structure of 2 layers (the surfaces of the mating layers are made wavy / sinusoidal).

[0071] Layer 1 - supporting layer made of dispersion-strengthened material with a fine-grained structure of 4-45 μm, layer 2 - in contact with the glass melt, having a coarse-grained structure of 100-500 μm, layer 3 - inner layer, enclosed between layer 1 and layer 2, with different composition and structure depending on the purpose.

[0072] The multi-layer composite design options shown in the figures are preferred, but not limited to. Depending on the required performance characteristics, the materials used (diameter and chemical composition of the extruded wire), and the intended application, other multi-layer composite design options may be implemented.

[0073] Implementation of the invention

[0074] The composite with a multilevel structure comprises at least two layers: one supporting layer 1 that is not in contact with the liquid glass melt, and one layer 2 intended for contact with the liquid glass melt (after forming a crucible from such material), as shown in Fig. 1. The supporting layer is made of dispersion-strengthened palladium or dispersion-strengthened palladium alloys, or dispersion-strengthened platinum or dispersion-strengthened platinum alloys, in particular platinum-rhodium alloys, and has a fine-grained structure with an average grain size of 4-45 μm. Layer 2, in contact with the liquid glass melt, is made of platinum and its alloys with a coarse-grained structure with an average grain size of 100-500 μm. Dispersion strengthening is achieved by fixing grain boundaries with uniformly distributed dispersed zirconium oxide particles.

[0075] A composite with a multilevel structure may contain more than two layers: two outer layers 1 and 2, differing in structure and composition (see the description above for Fig. 1) and at least one inner layer 3, enclosed between the outer layers and made of palladium or its alloy, or of dispersion-strengthened palladium or dispersion-strengthened palladium alloys, differing in the composition of the main components and reinforcing particles of zirconium oxide from the supporting layer 1 (Figs. 3, 4, 5). The number of inner layers and their chemical composition may vary depending on the performance parameters of the final material. All inner layers are made with an average grain size from 4 to 500 μm.

[0076] The contacting surfaces of the outer 1, 2 and inner layers 3 may be made flat (Fig. 1, 2) or congruently relief (Fig. 3-5). The relief of the layer connection may be of any kind, in particular jagged with sinusoidal, wavy, involute, etc., both the same for all surfaces of the layers, and different (when one pair of mating surfaces has a sinusoidal relief, and the second pair - an involute relief). In this case, the relief of different pairs of mating surfaces may be made with a shift relative to the relief of the other (other) pairs of mating surfaces with the formation of an inner layer (inner layers) of variable thickness throughout the material.

[0077] The internal interacting surfaces are made toothed with sinusoidal, wave-shaped and involute, having a tooth height (amplitude) of 0.5-10 mm and a distance between teeth (pitch / period) of 1-40 mm.

[0078] The method for producing a composite with a multi-level structure includes:

[0079] - manufacturing of an initial single-layer blank for a supporting layer with a gas porosity of no more than 50% by pressing under a pressure of at least 100 MPa coils or bundles of wires made of dispersion-hardened palladium, dispersion-hardened palladium alloys, dispersion-hardened platinum or dispersion-hardened platinum alloys, in particular platinum-rhodium alloys with a diameter of 0.1-1.0 mm, laid with different orientations of individual wires;

[0080] - production of an initial single-layer blank for the inner layer with a gas porosity of no more than 50% by pressing under a pressure of at least 100 MPa coils or bundles of wires made of palladium or its alloys, or of dispersion-hardened palladium or dispersion-hardened palladium alloys with a diameter of 0.1-1.0 mm, laid with different orientations of individual wires;

[0081] - production of an initial single-layer blank for a contact layer with a gas porosity of no more than 50% by pressing under a pressure of at least 100 MPa coils or bundles of wires made of platinum or its alloys, with a diameter of 0.3-1.5 mm, laid with different orientations of individual wires;

[0082] - assembly of a package of pressed single-layer blanks, and in the case of the mating surfaces being made relief, the assembly is carried out with congruent alignment of the reliefs on the contacting surfaces;

[0083] - pressing the assembled package under a pressure of at least 100 MPa until a briquette with a gas porosity of no more than 40% is obtained;

[0084] - obtaining forgings with a gas porosity of no more than 1.0% by forging pressed briquettes at a high temperature of at least 0.6 times the melting temperature of the material, mainly along the direction of the layers in the package, or obtaining hot-rolled blanks with a gas porosity of no more than 1.0% by hot rolling at a temperature of at least 0.6 times the melting temperature and with a high degree of compression - at least 5% in one pass on a hot-rolling mill - along the direction of the layers in the package;

[0085] - obtaining sheet metal of the required final thickness by means of cold rolling.

[0086] The formation of the relief of the contacting surfaces of the workpieces is carried out on a press in a press mold using punches with a relief surface until the required relief contour is obtained with a tooth height (amplitude) of 0.5-10 mm and a distance between teeth (pitch / period) of 1-40 mm (see Fig. 3-5).

[0087] The claimed invention is illustrated by examples provided in the table, which present various embodiments of a composite with a multi-level structure that achieve the claimed technical result. A 30-liter crucible, manufactured from the specified composite embodiments in accordance with the invention, was used as a test sample. All composite materials were produced using the described method: first, briquettes with a gas porosity of 40% were formed, which were then forged (samples Nos. 7-12) or hot rolled (samples Nos. 1-6) until the required overall thickness of the composite material was achieved.From the obtained composite sheets with a multi-level structure, crucibles with a capacity of 30 liters were manufactured using standard technology in such a way that the contact layer, made of platinum or its alloys and intended for interaction with the liquid glass melt, was oriented inside the crucible cavity, while the supporting and / or inner layer did not have contact with the melt and were located on the outside.

[0088] A qualitative assessment of crucible materials from various multilayer material samples was performed in the laboratory. Laboratory tests were conducted to determine the materials' 100-hour long-term strength at 1200°C. Under production conditions, the percentage of platinum loss was estimated as the decrease in platinum content in the crucible after use relative to the initial platinum content. The thickness S of layers 1, 2, and 3 was determined by microscopic analysis of a crucible sample section as the arithmetic mean between the thickness opposite the protrusion and opposite the depression. The grain size of the layers was determined by obtaining a metallographic section of the composite material samples and then measuring the grain size.

[0089] Table

[0090] Sample number Profile of the reliefs of the mating surfaces Total thickness of composite, mm Characteristics of layers 100-hour long-term strength at 1200C, MPa % loss of platinum after operation. Glass contact layer A tooth height, mm Relief pitch F, mm Inner layer A tooth height, mm Relief pitch F, mm Bearing layer Compound, % S, mm Grain size, µm Compound, % S, mm Compound, % S, mm Grain size, µm 1 flat (Fig. 1) 2 Pl 99.9 1 100-300 - - - - - PdDS 1 4-30 4,0-4,5 0,8 2 flat (Fig. 1) 2 Pl 99.9 1 250-500 - - - - - PlPd 75-25 1 25-45 3,8-4,1 0,6 3 flat (Fig. 1) 4 Pl 99.9 0,5 100-200 - - - - - PlDS 3,5 10-25 25,0-28,0 0,85 4 flat (Fig. 2) 4 Pl 99.9 1 200-450 - - Pd 99.9 1 - - PlPd 50-50DS 2 15-30 5,5-6,0 0,6 5 flat (Fig. 2) 4 PlRd 95-5 0,5 250-500 - - PlPd 75-25 3 - - PlRd 90-10DS 0,5 5-20 9,7-10,2 0,9 6 flat (Fig. 2) 4 Pl 99.9 1 300-500 - - PdDS 2 - - PlRd 90-10DS 1 5-20 15,6-16,2 1 7 serrated (Fig. 3) 21,5 Pl 99.9 11 100-250 10 40 - - - PdDS 10,5 4-30 7,4-7,8 0,75 8 serrated (Fig. 4) 3 Pl 99.9 0,7 100-250 0,5 1 PlPd 50-50DS 1,3 0,5 1 PlRd 90-10DS 1 15-30 20,8-21,2 0,75 9 serrated (Fig. 5) 4,3 Pl 99.9 1,2 100-250 1 4 PdPl 75-25DS 1,9 0,7 3 PlRd 90-10DS 1,2 4-20 18,9-19,2 0,75 10 The prototype is flat (Fig. 1) 2 Pl 99.9 1 50-90 - - - - - Pd 99.9 1 50-120 2,9-3,2 1,2 11 The prototype is flat (Fig. 1) 4 Pl 99.9 2 50-90 - - - - - PlRd 90-10 2 50-100 6,5-7,1 1,1 12 The prototype is flat (Fig. 2) 4 Pl 99.9 1 50-90 - - Pd 99.9 2 - - PlRd 90-10 1 50-100 4,5-4,9 1,3

[0091] Notes:

[0092] - the prefix “DS” denotes dispersion-stabilized (dispersion-hardened) alloy;

[0093] - the contact layer of platinum sample No. 3 was pressed from wire with a diameter of 0.3-0.5;

[0094] - the contact layer of platinum of samples No. 1, 7, 8, 9 was pressed from wire with a diameter of 0.55-0.1.0;

[0095] - contact layer made of platinum or PlRd 95-5 samples No. 2, 4, 5, 6 was pressed from wire with a diameter of 1.05-1.5;

[0096] - the supporting and / or inner layers of samples No. 1-6 were pressed from wire with a diameter of 0.6-1.0;

[0097] - the supporting and / or internal parts of samples No. 7-9 were pressed from wire with a diameter of 0.1-0.5;

[0098] - Sample No. 10 is a prototype in relation to samples No. 1, 2;

[0099] - Sample No. 11 is a prototype in relation to samples No. 3, 7;

[0100] - Sample No. 12 is a prototype in relation to samples No. 4, 5, 6, 8, 9.

[0101] The results of experimental and laboratory studies indicate that multilayer materials with a flat layer connection, a fine-grained structure of the contact layer and a cast homogeneous structure of the supporting layer (samples No. 10-12) have low strength and demonstrate an increased level of platinum loss after crucible operation.

[0102] The highest 100-hour long-term strength at 1200°C, as well as the lowest platinum loss, were demonstrated by samples Nos. 3, 5, 6, 8, and 9. These samples were made from composites with a multilayer structure and contained dispersion-hardened PlDS or PlRd90-10DS alloys in the supporting layer. Moreover, the particularly fine and dense contact relief between the layers (observed in samples Nos. 7-9) contributes to strengthening the bond and, consequently, increasing the overall strength of the composite.

[0103] Samples made from materials corresponding to the claimed invention (No. 1-9) are distinguished by improved performance characteristics: a reduced percentage of platinum loss during use, as well as increased shear and long-term strength at high temperatures and thermomechanical loads.

[0104] Thus, the proposed group of inventions enables the production of a composite with a multilayer structure, intended for the manufacture of glass melting equipment components such as crucibles, stirrers, nozzles, pipes, and other glass melting unit parts. This ensures long-term and efficient operation of the products at high temperatures by increasing the strength of the multilayer material, improving interlayer adhesion, preventing crack formation, and reducing platinum operating losses.

Claims

1. A multilayer composite material intended for contact with liquid molten glass, comprising a carrier layer made of dispersion-hardened palladium or dispersion-hardened palladium alloys, or dispersion-hardened platinum, or dispersion-hardened platinum alloys, or dispersion-hardened platinum-rhodium alloy, with a grain size of 4-45 μm, and a contact layer intended for contact with liquid molten glass and made of platinum or its alloys, with a grain size of 100-500 μm.

2. A multilayer composite material according to paragraph 1, characterized in that the dispersion strengthening is performed by dispersed particles of zirconium oxide.

3. A multilayer composite material according to claim 1, characterized in that it is provided with at least one inner layer, which is placed between the carrier layer and the contact layer and is made of palladium or its alloys, or of dispersion-hardened palladium, or dispersion-hardened palladium alloys.

4. A multilayer composite material according to claim 1, characterized in that the internal interacting surfaces of the said carrier layer and contact layer are made flat.

5. A multilayer composite material according to paragraph 3, characterized in that the internal interacting surfaces of the said carrier layer, contact layer and inner layer or inner layers are made flat.

6. A multilayer composite material according to claim 1, characterized in that the internal interacting surfaces of the said supporting layer and contact layer are made with relief serrated surfaces.

7. A multilayer composite material according to paragraph 3, characterized in that the internal interacting surfaces of the said supporting layer, contact layer and inner layer or inner layers are made with relief serrated surfaces.

8. A multilayer composite material according to paragraph 6 or 7, characterized in that said internal interacting surfaces are made jagged with an amplitude of 0.5-10 mm with a pitch of 1-40 mm.

9. A multilayer composite material according to claim 1, characterized in that the internal interacting surfaces of the said supporting layer and contact layer are made involute or sinusoidal.

10. A multilayer composite material according to paragraph 3, characterized in that the internal interacting surfaces of the said supporting layer, contact layer and inner layer or inner layers are made involute or sinusoidal.

11. A multilayer composite material according to paragraph 9 or 10, characterized in that the said internal interacting surfaces are made involute or sinusoidal with an amplitude of 0.5-10 mm with a step of 1-40 mm.

12. A method for producing a multilayer composite material intended for contact with molten glass, comprising pressing in a mold coils or bundles of wires with a diameter of 0.1-1.0 mm made of dispersion-hardened palladium or dispersion-hardened palladium alloys, or dispersion-hardened platinum, or dispersion-hardened platinum alloys, or dispersion-hardened platinum-rhodium alloy, to obtain a single-layer blank of the supporting layer with a gas porosity of no more than 50% and pressing coils or bundles of wires with a diameter of 0.3-1.5 mm made of platinum or its alloys to obtain a single-layer blank of the contact layer intended for contact with molten glass, with a gas porosity of no more than 50%, subsequent assembly of the obtained single-layer blanks into a package and pressing the package into a briquette with a gas porosity of no more than 40%,forging or hot rolling the pressed briquette and then producing by cold rolling a sheet metal product in the form of a multilayer composite material of the required final thickness, in which the supporting layer has a grain size of 4-45 μm, and the contact layer for contact with the liquid glass melt has a grain size of 100-500 μm, 13. The method according to paragraph 12, characterized in that pressed briquettes from a single-layer blank of the supporting layer and a single-layer blank of the contact layer are forged to obtain a forging with a gas porosity of no more than 1.0%.

14. The method according to paragraph 12, characterized in that hot rolling of pressed briquettes is carried out from a single-layer blank of the supporting layer and a single-layer blank of the contact layer with a degree of compression of at least 5% in one pass on a hot rolling mill.

15. The method according to paragraph 12, characterized in that the contacting surfaces of the single-layer blank of the carrier layer and the single-layer blank of the contact layer are formed with a relief by means of relief punches in a press mold.

16. The method according to paragraph 15, characterized in that the contacting surfaces of the single-layer blank of the supporting layer and the single-layer blank of the contact layer are formed with a jagged relief.

17. The method according to paragraph 15, characterized in that the contacting surfaces of the single-layer blank of the supporting layer and the single-layer blank of the contact layer are formed with an involute or sinusoidal relief.

18. A method for producing a multilayer composite material intended for contact with molten glass, comprising pressing in a mold coils or bundles of wires with a diameter of 0.1-1.0 mm, made of dispersion-hardened palladium or dispersion-hardened palladium alloys, or dispersion-hardened platinum, or dispersion-hardened platinum alloys, or dispersion-hardened platinum-rhodium alloy, to obtain a single-layer blank of the supporting layer with a gas porosity of no more than 50%, pressing coils or bundles of wires with a diameter of 0.3-1.5 mm from platinum or its alloys to obtain a single-layer blank of the contact layer intended for contact with molten glass, with a gas porosity of no more than 50%, pressing coils or bundles of wires with a diameter of 0.1-1.0 mm from palladium or its alloys, or from dispersion-hardened palladium,or dispersion-strengthened palladium alloys to obtain a single-layer blank of the inner layer with a gas porosity of no more than 50%, the subsequent assembly of the obtained single-layer blanks into a package in such a way that an inner layer is placed between the contact and supporting layers, pressing the package into a briquette with a gas porosity of no more than 40%, forging or hot-rolling the pressed briquette, obtaining by cold rolling sheet metal in the form of a multilayer composite material of the required final thickness, in which the supporting layer has a grain size of 4-45 μm, and the contact layer for contact with the liquid glass melt has a grain size of 100-500 μm.

19. The method according to claim 18, characterized in that the contacting surfaces of the single-layer blank of the carrier layer, the single-layer blank of the contact layer and the single-layer blank of the inner layer are formed with a relief by means of relief punches in a press mold.

20. The method according to paragraph 19, characterized in that the contacting surfaces of the single-layer blank of the supporting layer, the single-layer blank of the contact layer and the single-layer blank of the inner layer are formed with a jagged relief.

21. The method according to paragraph 19, characterized in that the contacting surfaces of the single-layer blank of the supporting layer, the single-layer blank of the contact layer and the single-layer blank of the inner layer are formed with an involute or sinusoidal relief.

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