Large-volume metallic glass alloys containing nickel (Ni), cobalt (Co), molybdenum (Mo), and boron (B).

Abstract

The invention relates to nickel-based metallic glass alloys that can be produced in an amorphous structure, containing a high proportion of metals with high melting points and a high proportion of boron, and in which, when subjected to heat treatments above their crystallization temperatures, both a phase with high fracture toughness (nickel solid solution) and borides with high hardness values ​​can be precipitated.

Description

1 TARIFF Large volume containing nickel (Ni) - cobalt (Co) - molybdenum (Mo) - boron (B) METALLIC GLASS ALLOYS TECHNICAL AREA 5 The invention involves the production of a highly amorphous material with a very high melting point. metals that contain high levels of boron, and which are thermally resistant above their crystallization temperatures. When subjected to processing, it has a structure that possesses both high fracture toughness. both the phase (nickel solid solution) and borides with high hardness values It relates to nickel-based metallic glass alloys in which it can be precipitated. 10 PREVIOUS TECHNIQUE Metallic glass alloys possess highly unique physical and chemical properties. It is a group of materials. Due to its attractive properties, metallic glass has been used for the last 40 years. Extensive research is being conducted on alloys. As a result of this research, 15 many metallic glass alloys (such as Fe-based, Co-based, Ni-based, Cu-based, Zr-based) Furthermore, the crystallization behavior of metallic glass alloys has been improved in recent years. Studies conducted on metallic glass alloys and metal matrix composites It has also been shown that it can be used as a precursor in the production of metal matrix composites. traditionally, phases with high hardness such as carbide, boride, nitride and oxide or 20 phases of a metal matrix with high fracture toughness (nickel, cobalt, iron, copper, It is obtained by sintering together with (such as aluminum). Sintering processes are carried out at high temperatures. pressing (HP), hot isostatic pressing (HIP), spark plasma sintering (SPS), etc. This is done using various methods. These traditional methods for metal matrix composites... Instead, there are many advantages to producing metallic glasses by crystallization. 25 The most important of these advantages is the reduction in the critical casting thickness of the precursor metallic glass alloy. (the maximum cross-sectional thickness at which the alloy can be obtained in a completely glassy state) smaller composite parts with a certain cross-sectional thickness are produced by melting, casting, and subsequent heat treatment. It is possible to produce it in the desired geometry. This is achieved with traditional sintering methods. It is very important for obtaining parts with complex geometries that are difficult to produce. This is a significant advantage. Furthermore, the melting, casting, and heat treatment methods of composite parts... As a result of its production, pore formation will not occur in the structure. As is known... pores that may form when production is carried out by sintering, for example. 2 This is a factor that negatively affects the fracture toughness of the material. Furthermore, melting, found in the structure of composite materials produced through casting and heat treatment processes The distribution of the phases will be homogeneous. In sintering methods, the homogeneity of these phases is crucial. To ensure this, the components forming the composite undergo a high level of sintering before the sintering process. In mills of this type, mixing is required for extended periods (~24 hours). 5 Due to their complex shapes, some parts can also be produced using melting and casting methods. This can be difficult. In this case, the target product is first processed through simple melting and casting. It can be produced in one geometry and then shaped as desired by thermoplastic molding. can be brought in. Then, the shaped part is heat-treated to create a composite product. Available. 10 Composite materials obtained by crystallization of metallic glass alloys Heat treatment is necessary to achieve both high hardness and high fracture toughness. During this process, at least one of the phases formed (precipitated) in the structure must have high hardness, at least one of them must be It must also have high fracture toughness. In the literature, high amounts by heat treatment crystallization of metallic glass alloys containing boron and / or carbon, 15 composites containing boride and / or carbide type phases with high hardness in their structure There are studies showing that it can be produced. In general, Iron (Fe), Cobalt (Co) and large, iron-cobalt (Fe-Co) based deposits containing high levels of boron and / or carbon. at temperatures above the crystallization temperatures of bulk metallic glass alloys Composites produced by heat treatment have very high hardness values ​​(~1800 20 Hv) was obtained. The high hardness values ​​of these composites are achieved through heat treatment. (Fe,Cr)7C3, (Fe,Ni,Mo)23B6, (Fe,Cr)23(C,B)6, (Co,Fe)2B precipitated in the structure during the process. It originates from carbide and boride type phases such as (Co,Fe)23Ta2B6 and CoWB. Crystallization of bulk metallic glass alloys of Ni-Co-WB from composites Except for the composite produced in which both nickel solid solution and CoWB phase precipitate in its structure, 25 The presence of a phase capable of providing high fracture toughness has not been reported in any of them. Therefore, Ni-Co-WB is produced by crystallization of bulk metallic glass alloys. The fracture toughness values ​​of composites other than the composite produced are reported. It has not been done. A BRIEF DESCRIPTION OF THE INVENTION The invention relates to a nickel-based, bulk metallic product containing more than 12% (atomic) boron. It relates to glass alloys. The invention describes nickel with an amorphous structure. substantial large-volume metallic glass alloys above their crystallization temperatures 3 When subjected to heat treatment at these temperatures, their microstructures show both face-centered changes. In the resulting nickel solid solution with a cubic (FCC) structure, borides also precipitate. In the resulting nickel matrix composite, the nickel solid solution provides high fracture toughness, Precipitated borides also provide high hardness. Thus, improved toughness and rigidity are achieved. It can be transformed into a composite with the following properties 5 List of Figures Figure 1. X-ray of 0.3 mm section thickness samples of Ni-Co-Ta-B alloys. appearance of diffraction (XRD) patterns Figure 2. X-ray images of 0.3 mm section thickness samples of Ni-Co-Nb-B alloys. appearance of diffraction (XRD) patterns Figure 3. X-ray images of 0.3 mm section thickness samples of Ni-Co-VB alloys. appearance of diffraction (XRD) patterns Figure 4. X-ray images of 0.3 mm section thickness samples of Ni-Co-Mo-B alloys. The appearance of diffraction (XRD) patterns 15 Figure 5. Critical values ​​of some of the developed nickel-based bulk metallic glass alloys. X-ray diffraction (XRD) patterns of samples with a critical casting thickness (D). Figure 6. Results of DSC (heating) analysis of the alloys for which XRD analysis results are given. graphic view Figure 7. DSC analysis (cooling) results of the alloys for which XRD analysis results are given. graphic view Figure 8. Ni33Co30Mo16W2Nb4B15 metallic glass alloy subjected to 25 to 200 at 677 °C. X-rays of composite samples obtained as a result of heat treatments applied between minutes... appearance of ray diffraction (XRD) patterns Figure 9. Ni33Co30Mo16W2Nb4B15 metallic glass alloy subjected to 25 to 200 25 oxides at 677 °C. Composite samples obtained as a result of heat treatments applied between minutes. Graphical representation of the change in microhardness values ​​as a function of heat treatment time. Figure 10. XRD of a 2 mm cross-sectional thickness sample of Ni41Co22Mo22B15 alloy. the appearance of the pattern DETAILED DESCRIPTION OF THE INVENTION High quality composite materials obtained by crystallization of metallic glasses. In order for them to have fracture toughness, the composite structure must be modified during heat treatment. Formation of a phase or phases with a face-centered cubic (FCC) structure 4 It is necessary. As a result of heat treatment, a face-centered phase or For the formation of phases, a metallic glass alloy system based on copper or nickel is used. It is necessary. In the literature included in the known technique, a high percentage (>12% atomic) is required. a copper-based, bulk metallic glass alloy containing boron and / or carbon (completely amorphous) metallic 5 that can be obtained in the structure with a cross-sectional thickness greater than 0.3 mm (millimeters). (glasses) not reported. Containing high percentage (>12% atomic) boron and / or carbon. Only one nickel-based bulk metallic glass alloy system has been reported [TR 2019 04074 B, CN 113825855 B, US 12,098,451 B2]. This nickel-based alloy system The basic elements that make it up are nickel, cobalt, tungsten, and boron. This is the Ni-Co-WB compound. 10 As a result of crystallization through heat treatments, the structure has both high fracture toughness. both one phase (a nickel solid solution with a face-centered cubic (FCC) structure) and high Borides with high hardness (especially the CoWB phase) precipitate. The resulting composites... It has high hardness and fracture toughness values. However, this is a metallic glass. Because the alloy system contains a high percentage of tungsten, the alloys and the products obtained through heat treatment are 15. The densities of the composites obtained are approximately between 11-13 g / cm3. Density values ​​are higher than the densities of conventional metallic alloys (carbon steel) ~7.8 gr / cm3, stainless steels ~7.5-8 gr / cm3, nickel alloys ~7.8-9 gr / cm3, copper The density of alloys is higher (~8.7-8.9 g / cm3). These high density values ​​are associated with low 20 in applications where density is a key factor (requiring high strength / density) (for example, applications related to aviation, aerospace, and automotive) is an undesirable situation. In addition, Ni-Co-WB metallic glass alloys have a very high melting temperature. Because the alloys contain a high percentage of the tungsten element, which has a temperature of (3422 °C), they are suitable for vacuum applications. Production becomes difficult with melting methods other than arc melting, and in some cases even... This becomes impossible in certain situations. Therefore, the alloys must first be heated in a vacuum arc. 25 by melting (pre-alloying) and then suitable for the target application. by means of the method (mostly induction melting) it is remelted and the final product is in the desired form. (rods, strips, powder) need to be produced. In other words, in most cases, alloys Production processes must be two-stage. This situation affects the production process. This complicates, lengthens, and increases the cost. Therefore, high melting point 30 Instead of these types of alloys which have a high melting point, alloys with a lower melting point can be used. There is a need to develop new economical alloys that will make production a single-stage process. These needs are being felt. Advanced materials that meet these needs also serve both purposes. both ease of production and various economic savings during use. This will result in savings in production costs, product costs, fuel, and energy. Ni-Co-WB metallic glass alloys above their crystallization temperatures face-centered crystallization obtained by thermal processing at certain temperatures Composites consisting of nickel solid solution and borides with cubic (FCC) structure and 5 similar mechanical properties (high microhardness and high fracture toughness) and more making it possible to produce low-density composites, as well as more It is easy to manufacture because it consists of components with low melting points. (single-stage production) Ni-Co-WB metallic for the production of precursor metallic glass alloys. In glass alloy systems, other refractory elements (Ta, Nb, V or 10) can be used instead of tungsten. The use of Mo) may be possible. However, experimental work by the inventors is not recommended. Studies have shown that only the element molybdenum can be used in place of tungsten. It was found that tantalum, niobium, and vanadium replaced tungsten, respectively, in Figures 1, 2, 3, and 4. and alloys formed using molybdenum elements are die-cast into copper molds. X-ray diffraction (XRD) of samples produced with a section thickness of 0.3 mm using this method 15 The results of the analysis are given. Tantalum, niobium and vanadium were used instead of tungsten. Samples of alloys produced using these elements do not contain an amorphous structure. and appears to consist entirely of crystalline phases. These alloys are already completely Because they consist of crystalline phases, samples of alloys obtained by casting It is not possible to produce composites by crystallization through heat treatment. Another 20 Therefore, these alloys cannot be used as precursors for composite production. (Inventors) The results obtained show that only the element molybdenum can be used instead of tungsten. By using this method, large-volume metallic glass alloys with a completely amorphous structure can be obtained. It has been shown that these alloys, which have a completely amorphous structure, can be treated with heat. Suitable for use as a precursor for composite production. 25 In the description of the nickel-based bulk metallic glass alloy that is the subject of the invention The nominal composition description used is given below: NiaCobMocBdM1eM2fM3gM4h M1: Fe (iron), Cu (copper), Cr (chromium), Mn (manganese), Al (aluminum) and Sn 30 at least one of the elements (tin) 6 M2: Ti (titanium), Zr (zirconium), Er (erbium), Sm (samarium), Nd (neodymium), Y (yttrium), La (lanthanum) and Hf (hafnium) one of them M3: Made from W (tungsten), Ta (tantalum), Nb (niobium) and V (vanadium) elements at least one of them 5 M4: Contains at least the elements C (carbon), Si (silicon), P (phosphorus), and Be (beryllium). It indicates one of them. The amounts of components (a, b, c, d, e, f, g, h) are specified as a percentage based on atomic levels. Here, a: 10-65, b: 2-40, c: 5-40, d: 12.1-35, e: 0-40, f: 0-15, g: 0-20, h: 0-20 10 a+b+e+f: ranges between 20-75. c+g: varies between 5-40. d+h: varies between 12.1 and 35. Some of the bulk metallic glass alloys of Ni-Co-Mo-B that are the subject of the invention compositions, critical casting thicknesses and thermal properties (glass transition temperature, Examples of crystallization temperature and liquidus temperature are given in Table 1. Additionally... The density of some of the bulky metallic glass alloys of Ni-Co-Mo-B, which are the subject of the invention with their values ​​as previously stated in patent document number TR2019 / 04074 belonging to the inventors 20 The announced invention concerns the density of large-volume metallic glass alloys, Ni-Co-WB. The values ​​are given in Table 2. The obtained data are for Ni- with the same Ni, Co and B content. When comparing bulk metallic glass alloys Co-Mo-B and Ni-Co-WB, Ni-Co-Mo- The densities of large-volume metallic glass alloys are significantly higher. This indicates that it is low. 25 The new alloys described in this invention are produced by the arc melting method, and the casting process... This was achieved using the suction casting method inside an arc melting furnace. Critical casting thicknesses of alloys, with varying cross-sectional thicknesses and high purity. This was determined using copper (electrolytic copper) casting molds. The produced samples... Structural analyses were performed using X-ray diffraction (XRD). XRD analysis 30 According to the results, the largest cross-section in which an alloy can be obtained in a completely amorphous structure That thickness has been considered the critical casting thickness for that alloy. Glass transitions of nickel-based bulk metallic glass alloys given in Table 1 temperature (Tg) and crystallization temperature (Tx) values ​​were obtained using differential thermal calorimetry. 7 This was determined using a device called a Diagnostic and Statistical Survey (DSC). The heating rate used during the analysis was 20 °C / min. Table Liquidus temperature (Tl) of nickel-based bulk metallic glass alloys given in 1. The values ​​were also determined by DSC analysis. For this purpose, the samples were first put into a DSC device. It was heated to a temperature of 1500 °C and completely melted. Then, the completely melted Tl values ​​were determined while the samples were cooled at a cooling rate of 20 °C / min. 5 Composition (% atomic) Critical (mm) Tg (°C) Tx (°C) TL (°C) Ni25Co30Mo30B15 0.5 583 640 1321 Ni33Co26Mo26B15 0.3 563 609 1275 Ni41Co22Mo22B15 0.3 508 571 1254 Ni33Co30Mo22B15 0.3 539 577 1289 Ni33Co30Mo20W2B15 0.3 538 585 1283 Ni33Co30Mo18W4B15 0.3 560 590 1272 Ni33Co30Mo16W6B15 0.3 563 601 1287 Ni33Co30Mo16W4Nb2B15 0.3 560 601 1352 Ni33Co30Mo16W2Nb4B15 0.5 556 609 1270 Ni33Co28Fe2Mo16W2Nb4B15 0.3 559 602 1202 Ni35Co30Mo16W2Nb4B13 0.3 551 596 1275 Table 1. Critical values ​​of some of the developed nickel-based bulk metallic glass alloys. Casting thicknesses (Dcritical), glass transition (Tg), crystallization (Tx) and liquidus (Tl) temperatures Intensity (gr / cm3) Ni-Co-Mo-B Ni-Co-WB Ni25Co30Mo30B15 Ni33Co26Mo26B15 Ni25Co30W30B15 Ni33Co26W26B15 9,281 9,192 13,081 12,434 Table 2. Densities of bulk metallic glass alloys of Ni-Co-Mo-B and Ni-Co-WB. values. Some of the nickel-based bulk metallic glass alloys given in Table 1 The XRD analysis results of samples with critical casting thickness (Dcritical) are shown in Figure 5. The XRD analysis results of the alloys given in Figure 5 and the DSC analysis results of the alloys given in Figure 5 are shown. This is shown in Figures 6 and 7. Figure 6 shows the DSC analysis obtained with a heating rate of 20 °C / min. The results show the glass transition (Tg) and crystallization (Tx) temperatures of each alloy. This is shown in Figure 7, where a cooling rate of 20 °C / min is applied after complete melting. The liquidus (Tl) temperatures of each alloy were obtained in the DSC analysis results. shown. 20 8 The nickel-based bulk metallic glass alloys shown in Table 1 are part of the invention. The values ​​in the table are given as examples without limiting the scope of protection. Examples of how the composition of a 100% alloy can be formed when collected. This reveals that the invention consists of nickel-based, bulky metallic glass alloys. Its basic components are the elements nickel (Ni), cobalt (Co), molybdenum (Mo), and boron (B). These 5 The four elements must be present simultaneously in all alloys in the proportions specified above (%a, b, c and ). d) must be present. In addition to these four main elements (Ni, Co, Mo and B), M1, The elements named M2, M3 and M4 are present in the specified proportions (% e, f, g respectively). and h) inclusion of alloys improved by incorporating them into the alloy composition into the formulation It is not mandatory. 10 Alloys are melted by vacuum arc melting in a protective gas environment. They are manufactured. Alloy parts that are completely melted are electrolytic copper. It is produced by vacuum suction casting using molds and rapid cooling. However, different production methods involving a protective gas atmosphere are used in the production of these alloys. casting methods (induction melting route, injection casting, bending casting, 15 Thick section parts can also be produced using methods such as die casting. In addition, the developed nickel-based metallic glass alloys are also available in powder form. It can be produced. For production in powder form, various atomization methods (gas) are used. (such as atomization, water atomization, ultrasonic powder atomization) First, it is produced in the form of thin strips using the melt spinning method, and then the strips are processed in 20... The grinding method can also be used. These metallic glass alloy powders are produced. then various sintering methods (hot pressing (HP), hot isostatic pressing) Sintered by methods such as (HIP), spark plasma sintering (SPS), resulting in a completely amorphous structure. It is possible to obtain products with the desired dimensions and geometry. In addition, The metallic glass alloy powders produced are used in additive manufacturing, which is developing today. 25 methods (selective laser sintering (SLS), selective laser melting (SLM), electron beam fully amorphous in structure (such as melting (EBM), direct metal deposition (DMD)). It is also possible to obtain products with the desired dimensions and geometry. In addition, the manufactured products... Various coating methods using metallic glass powders (high-speed oxygen-fueled) (HVOF), plasma coating, cold spraying, laser coating, etc.) with weak materials 30 applied to it with a completely amorphous structure, high hardness and wear resistance. It is possible to obtain coatings. 9 Alloys with a critical casting thickness value less than 0.3 mm are also available in powder form. These alloys can be produced in powder form using atomization methods (gas). atomization, water atomization and ultrasonic powder atomization, etc.) with or before by melt spinning method to produce in thin strips and then the thin strips They can be produced by grinding. The glass formation capabilities of the alloys are 5. Powders produced from certain alloys vary depending on their composition. It may not be completely amorphous in structure, and the powders may contain some amorphous phase along with a certain amount of amorphous phase in their structure. A nickel solid solution and some boride phases may also be present. This produced material is completely... an amorphous structure or, in addition to the amorphous phase, some nickel solid solution and borides Metallic glass powders containing a specific structure can be sintered using various methods (HP, HIP, SPS 10). (such as) by sintering, resulting in a completely or largely amorphous structure (with some of its structure (containing nickel solid solution and boride), large volumes with the desired geometry and size. It is possible to obtain parts. In addition, this completely amorphous structure that is produced... or a structure containing a certain amount of nickel solid solution and borides in addition to the amorphous phase Today's developing additive manufacturing methods with metallic glass powders 15 (Such as SLS, SLM, EBM, DMD) with the desired completely or largely amorphous structure. It is also possible to obtain products with specific dimensions and geometry. Moreover, this is entirely... an amorphous structure or, in addition to the amorphous phase, some nickel solid solution and borides Various coating methods are used using metallic glass powders with a structure containing (high (such as rapid oxygen-fueled combustion (HVOF), cold spraying, laser coating) with weak materials 20 with a completely or largely amorphous structure, high hardness and wear resistance. It is possible to obtain coatings with high durability. The Ni-based alloys mentioned in our invention can be melted in a single stage, with low... High strength with a relationship between density, high hardness and high fracture toughness. The need for developing alloys is met by 25 known alloys in terms of their compositions. It is an invention that cannot be derived from technology. The invention consists of a large-volume nickel-based metallic material. The basic components of glass alloys are nickel (Ni), cobalt (Co), molybdenum (Mo), and boron (B). These are the elements. These four elements are present simultaneously in all alloys as mentioned above. The nickel-based bulk metallic product, which is the subject of the invention, is found in the following proportions (%a, b, c and d). Glass alloys have been developed. In addition to these four main elements (Ni, Co, Mo and B), M1, 30 The elements named M2, M3 and M4 are present in the specified proportions (% e, f, g respectively). and h) thermal properties of alloys improved by incorporating alloys into the alloy composition (Tg and Tx) and critical casting thicknesses (Dcritical) are being increased to even higher levels. The invention refers to nickel-based bulk metallic glass alloys that can be produced using nickel in known techniques. The biggest difference that distinguishes it from bulky metallic glass alloys is that it has both a high percentage It contains both molybdenum (5-40% atomic) and a high percentage of boron (12.1-35% atomic). Because the resulting composite material has both high hardness and high toughness. In order for it to have this, at least one of the phases formed (precipitated) in the structure during heat treatment must be present. One of them must have high hardness and at least one must have high toughness. 5 Thus, high volume ratios of borides with high hardness (especially CoMoB) are possible. It is allowed to settle. The alloy elements that make up the invention are Nickel (Ni), Cobalt (Co), and Molybdenum (Mo). and Boron (B) is always present in all alloys. Because the nickel-based large alloys that have been developed The structure of composite materials obtained by heat treatment of bulky metallic glasses will be 10 for the precipitation of a nickel solid solution with high toughness in the composition of all alloys The presence of the nickel element is required. It precipitates as a result of heat treatment, forming a composite. borides (especially the CoMoB phase) that will ensure high hardness For this to occur, the elements that form this phase (Co, Mo, and B) must be present in the composition of the alloys. These elements must be present. The proportions of these elements in alloys must be within the specified ranges (%a, 15). b, c and d) are included. The elements are grouped as M1, M2, M3 and M4. Improving both the glass-forming capabilities and thermal stability of alloys It has been used for this purpose. For example, containing only the elements Ni, Co, Mo and B. The critical casting thickness of Ni33Co30Mo22B15 alloy is 0.3 mm, while 4% niobium (Nb) (M3) and critical casting 20 of Ni33Co30Mo16Nb4W2B15 alloy with 2% tungsten (W) (M3) additive. Its thickness is 0.5 mm. Tg and Tx of Ni33Co30Mo22B15 metallic glass alloy. The temperatures were determined to be 539°C and 577°C respectively. 6% was added to the alloy. Ni33Co30Mo16W6B15 metallic glass obtained as a result of tungsten (W) (M3) addition The Tg and Tx temperatures of the alloy were measured as 563°C and 601°C, respectively. tungsten As a result of this addition, the thermal stability of the alloy has been increased. With the increase in thermal stability, 25 the alloy remains amorphous or composite without undergoing structural change at higher temperatures. It is made available for use in the structure. The nickel-based bulk metallic glass alloys that are the subject of this invention have both high percentages It contains nickel and molybdenum, as well as a high percentage of boron. The nickel that is the subject of our invention... Crystallization of large-volume metallic glass alloys based on the principles given in Table 1 is 30 By subjecting them to heat treatment at temperatures above their specified temperatures, both high fracture rates are achieved. It has a face-centered cubic (FCC) structure that provides its toughness, and contains a certain amount of cobalt. and nickel solid solution containing molybdenum as well as borides which provide high hardness (especially CoMoB) is precipitating. Large-volume nickel-based metallic compounds are used as precursors. 11 The crystallization temperatures of glass alloys depend on the composition of the alloys. Because it varies, the required heat treatment temperatures are different for each metallic glass alloy. They are different. For example, face-centric cubic (FCC) provides high fracture toughness. a nickel solid solution with a structure containing some cobalt and molybdenum and Precipitation of borides providing high hardness in Ni33Co30Mo22B15 alloy at 577 °C 5 and needs to be heat treated at temperatures above that, Ni25Co30Mo30B15 The alloy must be heat-treated at temperatures of 640 °C and above. Without limiting the scope of protection of our invention, for example, The crystallization temperature of the Ni33Co30Mo16W2Nb4B15 metallic glass alloy is 607 °C. Samples of Ni33Co30Mo16W2Nb4B15 alloy with a completely amorphous structure were subjected to 677 °C 10 subjected to heat treatment at a temperature for periods ranging from 25 to 200 minutes. The XRD patterns of the resulting composite samples are given in Figure 8. A sample of the alloy with a completely amorphous structure was subjected to heat treatment for 25 minutes. When held, the nickel solid exhibits a certain amount of face-centered cubic (FCC) structure. The solution is precipitating. Additionally, there is some amorphous phase in the structure. Heat treatment 15 When the duration is increased to 50 minutes, the amount of nickel solid solution precipitated in the structure increases. It is increasing. However, some amorphous phase is still present in the structure. 75 min. the amount of nickel solid solution precipitated in the structure as a result of the heat treatment carried out during the process It is increasing. In addition, a very small amount of CoMoB phase is also precipitating. Besides this The structure also contains a small amount of amorphous phase. Heat treatment time is 20 to 100 minutes. When removed, in addition to the nickel solid solution that precipitated in the structure, a significant amount The CoMoB phase is observed to have precipitated. Additionally, a very small amount of Ni3Mo is present in the structure. It has been determined that the phase precipitates. Heat treatments performed for longer than 100 minutes. As a result, the amounts of phases formed (precipitated) in the composite structure do not change. It has been determined. 25 In short, the low-volume nickel-based metallic glass alloys that are the subject of this invention the structure as a result of being subjected to heat treatment at high temperatures and for short heat treatment times Only nickel solid solution crystals with a FCC structure precipitate. As a result, the structure consists of an amorphous phase and a solid nickel solution. Heat treatment temperature. and / or when the heat treatment time is increased, in addition to the nickel solid solution, the CoMoB phase 30 It also precipitates. As a result, the structure consists of nickel solid solution and CoMoB phase. It consists of. Samples of Ni33Co30Mo16W2Nb4B15 alloy having a completely amorphous structure Heat treated at a temperature of 677 °C for durations ranging from 25 to 200 minutes. 12 The microhardness values ​​of the samples obtained as a result of the heat treatment depend on the heat treatment time. The variation in hardness is given in Figure 9. The Vickers hardness values ​​of the composite samples are shown. The microhardness was determined by applying a load of 500 g (4.9 N) for 15 seconds on a microhardness tester. Microhardness measurement results were obtained from 10 different regions for each composite sample. It is the arithmetic mean of the measurements. 5 of the completely amorphous sample of the alloy. Its hardness has been determined as 1026 Hv. The alloy has a completely amorphous structure. The composite obtained by subjecting the sample to heat treatment for 25 minutes. The microhardness value was measured as 1219 Hv. Increasing the heat treatment time. As a result, it was determined that the microhardness values ​​of the obtained composites increased. 75 Phases precipitated in the structure as a result of heat treatment for min. (nickel solid solution and CoMoB) 10 Thanks to this, a composite material with a microhardness value of 1260 HV has been obtained. An example of a composite material related to the invention is given as follows: Obtained by heat treatment of Ni33Co30Mo16W2Nb4B15 metallic glass alloy. The microhardness values ​​of these composite materials depend on the heat treatment temperature and the heat treatment process. Depending on the time, the volume of nickel solid solution and CoMoB phases precipitated in the structure is 15 It varies depending on the ratios and average particle sizes. The subject of the invention The fracture toughness of composites also depends on the heat treatment time and heat treatment temperature. volume ratios of nickel solid solution and CoMoB phases precipitated in the structure and average It varies depending on the particle size. Atomization methods (gas atomization, water atomization and ultrasonic powder 20 (such as atomization) or by first producing it in the form of thin strips using the melt spinning method then a completely amorphous structure is obtained by grinding thin strips. produced by sintering or additive manufacturing of metallic glass alloy powders. parts with a completely amorphous structure, metallic glass alloy used in production 25 as a result of being subjected to heat treatment at temperatures above the crystallization temperature. nickel solid solution with FCC structure and borides (especially CoMoB phase) It precipitates. As a result, the produced part is obtained in a composite structure. It is also an amorphous structure obtained using metallic glass powders. coatings above the crystallization temperature of the alloy used in the coating A nickel solid solution with a YMC structure is obtained by subjecting it to heat treatment at temperatures of 30°C. Borides (especially the CoMoB phase) precipitate. As a result, high hardness and A composite coating with fracture toughness is obtained. Atomization methods (gas atomization, water atomization and ultrasonic powder) (such as atomization) or by first producing it in the form of thin strips using the melt spinning method 13 obtained by grinding thin strips, which is completely amorphous. metallic that does not have a crystalline structure but contains some crystalline phase (nickel solid solution and borides). Partially amorphous glass alloy powders are produced by sintering or additive manufacturing. parts with this structure, crystallization of metallic glass alloy used in production As a result of being subjected to heat treatment at temperatures above this temperature, 5 is formed in the structure. In addition to the phases already present, nickel solid solutions and borides with FCC structure. (Especially the CoMoB phase) precipitates. As a result, the produced part becomes a composite. This is achieved in the structure. Furthermore, it is obtained using these metallic glass powders. coatings with a partially amorphous structure, crystallization of the alloy used in the coating As a result of being subjected to heat treatment at temperatures above this temperature, 10% of the structure is formed. In addition to the phases already present, nickel solid solutions and borides with FCC structure. (especially the CoMoB phase) is precipitating. As a result, high hardness and fracture resistance are observed. A composite coating with high toughness is obtained. Some alloys with a critical casting thickness value less than 0.3 mm Atomization methods (gas atomization, water atomization and ultrasonic powder 15 (such as atomization) or by first producing it in the form of thin strips using the melt spinning method The structure of the powders produced by then grinding the thin strips is completely different. It can consist of crystalline phases (nickel solid solution and borides). This produced fully crystalline structure... Alloy powders consisting of phases are processed using various sintering methods (such as HP, HIP, SPS). 20 formed by sintering from completely crystalline phases (nickel solid solution and borides) To obtain large-volume parts with the desired geometry and dimensions using composite structures. It is possible. Because this approach does not involve a heat treatment process, it saves energy in some applications. It may be preferred in terms of efficiency. In addition, this fully crystalline material that is produced... Alloy powders consisting of phases are used in additive manufacturing, which is developing today. Using methods (such as SLS, SLM, EBM, DMD) to create composite structures of desired dimensions and 25 It is also possible to obtain products with specific geometry. Furthermore, this is entirely crystalline. Alloy powders consisting of phases are coated using various methods (high-speed oxygen-fuel (HVOF), high-performance coating on weak materials (such as cold spraying, laser coating) fully crystalline phases (nickel solid solution and) with hardness and wear resistance It is possible to obtain composite coatings consisting of borides. This approach involves a thermal 30°C. Because it does not involve a processing step, it is preferred in some applications for energy efficiency reasons. that is the reason. Thicknesses of the alloys covered by the invention that exceed the critical casting thicknesses casting methods of the parts (induction melting route and injection casting, 14 It is possible to produce composite structures using methods such as bending casting, die casting, etc. The structure of a part with a cross-sectional thickness greater than the critical casting thickness of the alloy, Depending on the section thickness, it consists of partly amorphous and partly crystalline phases (nickel only). (solid solution or nickel solid solution and borides) can be formed as well as completely crystalline. from phases (nickel solid solution only or nickel solid solution and borides) 5 Crystallization can occur if the part contains a partially amorphous structure. the final result is achieved by heat treatment at a temperature above the specified temperature for a suitable period of time. Composite structures can be obtained. The manufactured part consists entirely of crystalline phases. In this case, no heat treatment is required. The first approach involves a partial heat treatment process, and the second involves any heat treatment. Because it does not involve a processing step, it is preferred in some applications for energy efficiency reasons. That could be the reason. Without limiting the scope of protection of our invention, for example, Ni41Co22Mo22B15 The critical casting thickness of the metallic glass alloy is 0.3 mm. Ni41Co22Mo22B15 alloy. The sample, produced with a cross-sectional thickness of 2 mm using the absorption casting method in a copper mold, is 15. The XRD pattern is given in Figure 10. The sample consists only of nickel solid solution and The presence of the CoMoB phase is observed. The resulting sample was already present after casting. Because it has a composite structure, it does not require any heat treatment. There isn't any. The nickel-based bulk metallic glass alloys that are the subject of our invention exhibit crystallization at 20°C. as a result of being subjected to heat treatment at temperatures above their specified temperatures, its structure... both a phase with high fracture toughness (nickel solid solution) and high nickel-based solutions in which borides with high hardness (primarily the CoMoB phase) can be formed. They are bulky metallic glass alloys. The CoMoB phase has an orthorhombic structure in space. The group Pnma and lattice parameters are a=5.803 Å (Angstrom), b= 3.253 Å and c=6.677 Å. It is Å.

Claims

REQUESTS 1. Large-volume nickel-based metallic glass containing a high percentage of refractory metals and boron. It is an alloy and its characteristic is that it has the formula NiaCobMocBdM1eM2fM3gM4h, which is 5. It is characteristic.

2. The material referred to in Claim 1 is M1, and its properties are; Fe, Cu, Cr, Mn, Al and Sn. It is characterized by having at least one of its elements.

3. The M2 mentioned in Claim 1 has the following properties: Ti, Zr, Er, Sm, Nd, Y, La and Hf. It is characterized by having at least one of its elements.

4. M3, mentioned in Claim 1, is characterized by containing at least one of the elements Ta, Nb, Mo, and V. It is characterized by being one of them. 15 5. The M4 mentioned in Claim 1 is characterized by having at least one element each of C, Si, P, and Be. It is characterized by being one of them.

6. Nickel-based 20 containing high proportion of refractory metal and boron, as mentioned in Claim 1. It is a large-volume metallic glass alloy, and its characteristic is based on atomic percentage; - The amount of component a is between 10 and 65, - The amount of component b is between 2 and 40, - The amount of component c is between 5 and 40, - The amount of component d is between 12.1 and 35.25 - The amount of component e ranges from 0 to 40, - The amount of component f is between 0 and 15, -g component amount between 0 and 20, -h is characterized by the component amount being between 0 and 20.

7. The alloy mentioned in Claim 1 is characterized by its ability to be formed into a composite structure through heat treatment. It is characterized by its acquisition. 16 8. The alloy referred to in Claim 1, whose characteristic is that it is above the critical casting thickness. a composite structure with a cross-sectional thickness, high stiffness and wear resistance It is characterized by its winning.

9. The alloy referred to in Claim 1, whose characteristic is; 5 above the critical casting thickness. a composite with a cross-sectional thickness, high stiffness and wear resistance It is characterized by having a coating on the structure.

10. The quantities of the components mentioned in Claim 6 are characterized by: - The sum of the amounts of components a+b+e+f is between 20 and 75% on an atomic basis, 10 - The total amount of c+g components is 5 to 40% on an atomic basis. - The sum of the d+h component amounts is between 12.1% and 35% on an atomic basis. It is characterized by its being. 20 30

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