JP6370925B2 - Method for manufacturing a part made of a metal alloy having an amorphous phase - Google Patents

Description

  The present invention relates to a method of manufacturing a part made of at least partially amorphous metal alloy.

  Furthermore, the invention relates to parts made from metal alloys having an amorphous phase and the use of such parts.

  Amorphous metals and their alloys have been known for decades. The thin layers and their manufacture are disclosed, for example, in DE 352 018 A1 and a thin metallic glass is produced on the support by means of crench cooling (quenching) of the molten phase. Furthermore, for example, patent application EP2430205B1 describes a composite material made of an amorphous alloy, which requires a cooling rate of 102 K / s. The disadvantage of such known methods is that only thin layers or very small parts with a cross section of a few millimeters can be produced.

  Therefore, it is a problem to manufacture a large component having a complicated shape having an amorphous structure. The cooling rate required for large volumes of complex parts and semi-finished products is technically impossible. From WO 2008/039134 A1, a method for producing larger parts from amorphous metal powder is known. That is, the parts are constructed in layers by 3D printing technology, and the layer portions are melted by an electron beam.

  The drawback of this method is that it is very complex and expensive. Furthermore, such a method does not make the physical properties of the manufactured parts sufficiently uniform. If the cooling rate of the melt is too low, localized melting and recooling of the powder results in a limited over-crystallization and crystallization of the alloy. More precisely, due to the heat input and recooling during the local melting of the powder near the surface, a limited excess of crystallization temperature and crystallization of the alloy in the already solidified amorphous layer in the deep. Can occur. This creates an undesirable amount of crystalline phase in the part, resulting in a non-uniform distribution of the crystalline phase in the part.

The object of the present invention is therefore to overcome the drawbacks of the prior art. Specifically, it is to develop a method that can be carried out simply and inexpensively, and according to the method, the volume may be 0.1 cm ³ or larger, preferably 1 cm ³ or larger. It is possible to produce parts made of metal alloys with amorphous parts that can and can be produced in various and also complex shapes. The manufactured parts should also have very high uniformity with respect to physical properties and amorphous distribution. The object of the present invention is also to provide such a part. The above method should be simple to carry out and have good reproducibility. The manufactured parts should have a very high proportion of amorphous metal phase. Furthermore, the manufactured parts are preferably as dense as possible and have only a few holes. A further object is that the method can be carried out with as many different alloys as possible having an amorphous phase. Furthermore, it is preferred that the method can be carried out using equipment and tools that normally exist in the laboratory, as simple as possible.

The object of the present invention is achieved by a method for producing a part consisting of an at least partially amorphous metal alloy having the following steps:
A) providing a powder comprising a powder of at least partly amorphous metal alloy, comprising spherical powder particles, the powder particles having a diameter of less than 125 μm;
B) compressing the powder into the desired shape of the part to be manufactured;
C) During or after the compression, the powder is compressed and sintered by subjecting the powder to a temperature treatment at a temperature between the transition temperature of the amorphous phase of the metal alloy and the crystallization temperature. The step of sintering, wherein the part is sintered after the temperature treatment and the length of the temperature treatment is selected such that it has at least 85 percent amorphous parts.

  Preferably, the length of the temperature treatment is short, the powder is sintered after the temperature treatment, and at the longest, the part still has at least 85 percent amorphous parts after the temperature treatment. Selected.

Preferably, the powder consists of 100% powder particles having a diameter of less than 125 μm. Such particle size or particle size distribution is often referred to as D ₁₀₀ = 125 μm.

  In physics and chemistry, a substance in which atoms do not have an ordered structure but forms an irregular pattern, does not have long-range order, and has only short-range order is called an amorphous substance. A substance having a regular structure with respect to amorphous is called a crystal.

  Spherical particles need not be geometrically perfect spheres in the present invention, and may deviate from spheres. Preferred spherical powder particles have a rounded, at least approximately spherical shape and a ratio of the longest cross section to the shortest cross section of at most 2: 1. Therefore, in the present invention, a strict geometric or mathematical sphere by sphere geometry is not meant. The cross section means an extreme value dimension that runs through the powder particles. Particularly preferred spherical powder particles have a ratio of the longest cross section to the shortest cross section of at most 1.5: 1, or most particularly preferably spherical. In the present invention, the maximum cross section of the powder particle is adopted as the diameter.

The spherical shape of the powder particles has the following advantages:
The spherical particles form a flowable powder, which is particularly preferred during stratification with a powder tank and a doctor blade (Rakel);
Increase the bulk density of the powder;
The powder particles have similar curved surfaces and soften by temperature treatment under the same conditions (temperature, time, and the same thermal energy input)-or at least soften under conditions close to the same conditions. Thereby, they combine with adjacent powder particles and sinter particularly well in a short time, at known time points and at known time intervals. A further advantage of a large bulk density is that the shrinkage of the parts during sintering is small. Thereby, processing close to the final shape is possible.

  According to a preferred embodiment of the invention, the part can be considered sintered if it has a density of at least 97% of the theoretical density of the complete amorphous metal alloy.

  Sintering or sintering is understood in the context of the present invention as a process in which the powder particles soften at the surface, bond together and remain bonded after cooling. In this way, an integrated object or an integrated part is manufactured from the powder.

  The transition temperature of the amorphous phase is often referred to as the glass transition temperature or transition point or glass transition point, and it is clarified that these are terms synonymous with the transition temperature.

  Preferably, the powder is filled into a mold or mold and then the powder in the mold or mold is compacted or compacted using a mold.

  In the present invention, heating and cooling until reaching the transition temperature should be as fast as possible. This is because, even at temperatures below the transition temperature, crystallization occurs in the crystal seeds that inevitably exist before softening of the powder particles leading to powder sintering has not yet occurred. In the present invention, plastic deformation of the powder particles should be achieved, which results in compression of the powder and thus accelerated sintering of the powder. Temperature overshoot beyond the desired set point temperature or final temperature should be minimized.

  The powder particle size of the powder and the powder particle size distribution of the powder can be achieved by the production process and the screening of the raw material powder. Accordingly, the powder provided in the present invention is prepared by sieving the raw powder before being provided or used in the method of the present invention. This is because the raw material powder already has the desired characteristics after the preparation step. Furthermore, sieving ensures that the number of powder particles produced by sintering many powder particles (so-called satellite formation) and contained in the raw powder and having a shape greatly deviating from the spherical shape, or It can also be minimized.

According to the invention, it is also proposed as a preferred configuration of the method that the temperature treatment is carried out under vacuum, preferably compressing the powder by temperature treatment under a vacuum of at least 10 ⁻³ mbar.

  This can prevent the powder surface from reacting very strongly with the surrounding gas. That is, the metal oxide and other reaction products act as a nucleating agent for the crystalline phase that has a negative impact on the purity of the amorphous phase in the part being produced.

  In addition or alternatively, for the same reasons, in the present invention, the temperature treatment can also be carried out under protective gas, preferably at least 99.99% pure, particularly preferably at least 99.999. It can be carried out in particular under a noble gas such as argon with a purity of%. Preferably, in such an embodiment, most of the residual gas can be removed by repeatedly degassing and purging the atmosphere in which compression and temperature treatment or only temperature treatment is performed with a rare gas, particularly argon.

  Alternatively, in the present invention, the temperature treatment can be performed under a reducing gas, particularly a forming gas, in order to keep harmful metal oxides to a minimum.

  A further measure to reduce the amount of metal oxide in the part can be taken during the temperature treatment of the powder and / or during the production of the powder by using an oxygen getter.

  Furthermore, in the present invention, the powder can be compressed by hot isostatic pressing or hot pressing.

  The combination of compression and temperature treatment results in a more dense part. Furthermore, since the bonding is strengthened by the plastic deformation between the powder particles and the sintering is promoted, the temperature treatment time can be shortened and the proportion of the crystal phase of the part is reduced.

  According to a further further embodiment of the invention, the temperature treatment time is selected such that said part has at least 90 percent, preferably more than 95 percent, particularly preferably more than 98 percent amorphous parts. it can.

  The greater the proportion of amorphous phase in the part, the closer it is to the desired physical properties of the part that is completely amorphous.

  In a preferred configuration of the invention, a powder comprising an amorphous metal alloy having at least 50 weight percent zirconium or an at least partially amorphous metal alloy can be used.

  Zirconium-containing amorphous metal alloys are particularly suitable for carrying out the method of the invention. This is because many of these alloys have a large difference between the transition temperature and the crystallization temperature, which makes the method easier to implement.

In a highly preferred configuration of the invention, the powder comprising an amorphous metal alloy or at least partially amorphous metal alloy is
a) 58 to 77 weight percent zirconium,
b) 0 to 3 weight percent hafnium,
c) 20 to 30 weight percent copper,
d) 2 to 6 weight percent aluminum, and e) 1 to 3 weight percent niobium.

  The remainder until reaching 100 weight percent is zirconium. The alloy may contain general impurities. This zirconium-containing amorphous metal alloy is particularly suitable for carrying out the method of the invention.

  The spherical amorphous metal alloy powder is preferably melted by atomization, preferably by atomization in a noble gas, in particular argon, particularly preferably with a purity of 99.99%, 99.999% or more. It may be produced by melt atomization in a high purity noble gas. In the present invention, when the metal alloy has an amorphous phase portion of at least 85 volume percent, the amorphous metal alloy is also referred to.

  The production of the powder is, of course, performed before the powder is provided. By melt atomization, spherical powder particles are easily produced at low cost. By using a rare gas, particularly argon or high-purity argon, during the melt atomization, harmful impurities such as metal oxides in the powder are reduced as much as possible.

  According to a further embodiment of the invention, the powder may contain less than 1 weight percent of particles with a diameter of less than 5 μm, or the powder contains less than 1 weight percent of particles with a diameter of less than 5 μm. In addition, sieving or wind simpling processing may be performed.

  In the present invention, preferably, powder particles having a diameter of less than 5 μm are removed by wind sorting, or more precisely, powder particle portions having a diameter of less than 5 μm are reduced by wind sorting.

  The reduction of powder particle parts with a diameter of less than 5 μm allows the powder surface to be more reactive to oxidation by the gas surrounding the powder particle or other harmful chemical reactions with such gas (sum of all powder particle surfaces). ) Is limited. Furthermore, limiting the particle size of the powder ensures that the softening of the powder particles occurs under similar conditions (with respect to temperature and time and thus the energy input generated). This is because compaction of the powder is achieved by compression because of the similar curvature and volume of the surface of the powder particles. A small amount of fine powder particles (less than 5 μm) has no adverse effect. This is because such powder particles can penetrate between larger particles, thus increasing the density of the unsintered powder. However, too much fine powder particles are preferably removed because they adversely affect the flowability of the powder. That is, fine (small) powder particles tend to aggregate with larger particles.

In one preferred embodiment of the method of the present invention, the temperature treatment of the powder is performed at a temperature (T) between the transition temperature and the maximum temperature, the maximum temperature being relative to the transition temperature (T _T ). 30% above the temperature difference between the transition temperature (T _T ) and the crystallization temperature (T _K ) of the amorphous phase of the metal alloy, preferably the maximum temperature is relative to the transition temperature (T _T ) 20% or 10% above the temperature difference between the transition temperature (T _T ) and the crystallization temperature (T _K ) of the amorphous phase.

If the temperature treatment is carried out strictly at or above the transition temperature, the formation and growth of the crystalline phase is relatively slight and the purity of the amorphous phase in the part (amorphous) The phase ratio) is high. Expressed by the equation, the temperature T at which the powder is subjected to the temperature treatment should satisfy the following conditions with respect to the transition temperature T _T and the crystallization temperature T _{K of the} amorphous phase of the metal alloy:
T _T <T <T _T + (30/100) * (T _K −T _T ), or preferably T _T <T <T _T + (20/100) * (T _K −T _T ), or in particular Preferably T _T <T <T _T + (10/100) * (T _K −T _T ).

  If the temperature treatment is performed in the temperature range specified by the above mathematical formula, the formation of the crystal phase in the part is reduced and the sintering is performed.

  In a particularly advantageous configuration of the method according to the invention, the temperature treatment time is selected according to the geometry of the part to be produced, in particular the thickness, and preferably according to the maximum relevant diameter of the part to be produced. Selected.

  The geometrical shape or thickness of the manufactured part is such that heat conduction is performed in the powder to be molded and the part to be molded, respectively. Consider heating up. Thereby, the powder is also sintered inside the component.

  The maximum associated diameter of the part can be determined geometrically by the largest sphere that can be geometrically accommodated within the part. In determining the maximum associated diameter, grooves or gaps in the object can be ignored. They contribute nothing or little to the heat input by the surrounding gas and / or other heat source (eg less than 5% in total).

  Preferably, the length of the temperature treatment ranges from 3 seconds per millimeter of the part thickness or wall thickness or the maximum associated diameter of the manufactured part to 900 seconds per millimeter of the manufactured part thickness or maximum associated diameter. The temperature treatment length is preferably from 5 seconds per millimeter of the part thickness or wall thickness or the maximum relevant diameter of the part to be produced, to the thickness of the part to be produced. Or a time range of up to 600 seconds per millimeter of maximum associated diameter.

  By studying the shape, thickness or wall thickness of the part and / or the maximum associated diameter of the part, the length of the temperature treatment is such that sufficient sintering of the powder takes place and at the same time the formation of crystalline phases in the part. It is chosen to be as small as possible or ideally to minimize the formation of crystalline phases. For a specific part and use, it is sufficient that only the peripheral part of the part is completely sintered, and unsintered powder may still be present inside the part. However, it is preferred that the part is completely (and internally) sintered.

  The basic problem of the present invention is also solved by a part consisting of a compacted and sintered spherical amorphous metal alloy powder having at least 85 percent amorphous parts.

  The part may be manufactured using the method of the present invention. Such a method of the present invention is as described above.

  The basic problem of the present invention is also solved by the use of such parts as gears, friction wheels, wear resistant parts, housings, watch housings, transmission parts or semi-finished products.

  The present invention produces larger and / or more complex parts from amorphous metal alloy powders by using spherical powder particles of an appropriate size and temperature treatment at an appropriate temperature for an appropriate short time. The part is based on the surprising finding that the majority (at least 85 volume percent) consists of the amorphous phase and thus has the favorable physical properties of the amorphous metal alloy. Accordingly, the present invention describes for the first time a method by which a part can be produced by sintering powder from an amorphous metal alloy or a metal alloy comprising at least 85% amorphous phase. In, most of the amorphous phase remains maintained. Preferably, during the sintering of the powder, the temperature treatment depends on the size of the part to be manufactured in order to maintain as much amorphous phase as possible, or to keep as little crystalline phase part in the metal alloy as possible. The length of is adjusted. For the same purpose, it is preferred that the temperature treatment is carried out under protective gas or under vacuum to minimize as much as possible other reaction products with metal oxides or air formed in the powder and thus in the part. Such metal oxides and other reaction products in particular act as crystallization nuclei, thus reducing the amount of amorphous phase in the part.

  In the method of the present invention, particularly good results can be obtained when an amorphous metal powder for the production of the part is produced by melt atomization and the powder is X-ray amorphous. In that case, the powder particles are preferably less than 125 μm. In melt atomization, the molten droplets of the resulting alloy are cooled rapidly by the process gas stream (argon), thus contributing to the presence of an amorphous powder fraction. According to a further variant of the invention, from this powder most of the fine dust (particles smaller than 5 μm) and coarse particles larger than 125 μm are separated and removed, for example, by powder sieving and / or wind sorting. Such powder fraction is an optimal raw material (conditioning powder) for producing complex amorphous parts by compression and temperature treatment, and the pressure and temperature steps performed sequentially or in combination are It gives very good results regarding the amorphous behavior of the part. By using the powder thus prepared, a part having a particularly large amount of the amorphous metal phase can be obtained. At the same time, the parts thus obtained and produced from such powders have a high degree of sintered powder particles and a low porosity, preferably less than 5%. The above limitation of particle size prevents situations where such particles having a larger cross section than the resulting layer can then be removed by a doctor blade, i.e. the layer is incomplete.

  What is important here is that in the above method, the amorphous powder is not heated to or beyond the crystallization temperature. Otherwise, crystallization occurs and the amorphous properties of the alloy are lost. On the other hand, it is necessary to heat the material to at least the transition temperature, ie the temperature at which the amorphous phase of the metal alloy changes from a plastic region to a rigid state during cooling. In this temperature region, the powder particles are bonded without crystallizing. The transition temperature is often called the glass transition temperature.

  However, it is almost impossible technically to make impurities completely free, especially oxygen free, and there is no point in terms of cost, so it is impossible to avoid fine crystalline inclusions. A small amount of oxygen in the double-digit ppm range causes the formation of the corresponding oxide of the oxygen affinity component of the alloy. These then exist as small crystallization nuclei and may become granular small oxide inclusions, which can be detected at 1000X magnification in the microscopic image or as a peak in the X-ray diffraction test. Can do. Similar effects may be caused by other impurities in the feedstock or additional elements such as nitrogen.

  The length of the temperature treatment depends mainly on the volume of the part and as a rule should not be too long. This is because each small crystal nucleus still becomes a seed crystal, and the crystal may grow, and an undesirable crystal phase spreads in the part. Tests with zircon-based alloys have shown that temperature treatment in the temperature range according to the invention with a length of up to 400 seconds per 1 mm section of the part gives particularly good results. At 50 Kelvin below the transition temperature, undesirable crystal growth already occurs in part, so the heating phase should also occur as fast as possible.

フローチャートにおいて、Ｔは処理温度、Ｔ_Ｔは非晶質金属合金の転移温度及びＴ_Ｋは、金属合金の非晶質相の結晶化温度を示す。 Hereinafter, further embodiments of the present invention will be described with reference to flowcharts schematically shown, but the present invention is not limited thereto.

In the flowchart, T represents a processing temperature, T _T represents a transition temperature of the amorphous metal alloy, and T _K represents a crystallization temperature of the amorphous phase of the metal alloy.

Amorphous metal powder is produced from a metal alloy whose composition is suitable for the formation of an amorphous phase or which already consists of an amorphous phase. Powder fractionation is then carried out, and too small and too large powder particles (Pulver-Teilchen) or powder particles (Pulverpartiquel) are removed, in particular by sieving and wind sorting. The powder can be compressed into a desired shape with or without temperature input. When the powder is compression molded without temperature input, it is subsequently referred to as sintering in the present invention or is subjected to a temperature treatment that causes sintering. The temperature treatment during or after compression is performed for a maximum of 900 seconds per 1 mm of the cross section of the component at a temperature higher than the transition temperature T _{T of the} amorphous phase of the metal alloy used and lower than the crystallization temperature T _K. Is called.

  In the following examples, the method of the present invention is specifically described, and the results obtained thereby are evaluated.

Example 1:
70.5 weight percent zirconium (Haines & Maassen Metalhandsgesellschaft mbH Bonn, Zr-201-Zirkon Crystalbar), 0.2 weight percent hafnium (Alpha Aesar GmbH & Co KG Karlsruhe, Hafnum 99, Hafnum. 23.9 weight percent copper (Alpha Aesar GmbH & Co KG Karlsruhe, Copper plate, Oxygen free, High Conductivity (OFCH), item number 45210), 3.6 weight percent aluminum (Alpha Aesar GmbH H & Co Kul An alloy consisting of Ium Ingot 99.999%, Item No. 10571) and 1.8 weight percent niobium (Alpha Aesar GmbH & Co KG Karlsruhe, Niob Folie 99.97%, Item No.00238) was introduced into an induction melting plant (VSG, Inductiv beheizte). It was melted under 800 mbar of argon (Argon 6.0, Linde AG, Prague) in Vakuum-, Schmelz-und Giessanage, Nuermont, Freiburg) and poured into a water-cooled copper mold. From the alloy thus obtained, for example, using a method as known in WO 99/30858 A1, a melt is melted with argon in a Nanoval melt atomizer (Nanoval GmbH & Co. KG, Berlin). Nebulization produced a fine powder.

  When separating fines by wind separation using Condux-Feinstichter CFS (Netsch-Feinhahltechnik GmbH, Germany), less than 0.1% of the particles are less than 5 μm in size, ie at least 99.9% have a diameter or size of 5 μm or greater. Also, all powder particles larger than 125 μm are removed using a 125 μm mesh analytical sieve (Retsch GmbH, Hahn, Germany, product no. 60.131.000125). When the powder thus obtained is examined by X-ray diffraction, it has more than 95% amorphous parts.

The powder fraction obtained in this manner is subjected to a compressor (32 mm, P0764, sensitive Chromatography-Handel Berlin, Berlin-type) in a Laborpresse 54MP250D (Msscientific Chromatography-Handel GmbH, Berlin) every 5.0 grams. Compress with a pressure of 15 tons. The compact is then compressed for 120 seconds at 410 ° C. at a pressure of about 10 ⁻⁵ mbar in a vacuum sinter (Gero Hochtemperatur-Vakuumtemperofen LHTW 100-200 / 22, Neuhausen). Thereafter, the compressed product is subjected to a final pressure of 90 MPa at a temperature of 400 ° C. under high-purity argon (Argon 6.0, Linde AG, Prague) by hot isostatic pressing at 200 MPa. Compress.

  The 15 parts thus produced were analyzed for the proportion of amorphous surface in the tissue using metallographic microscope images. As a result, it was shown that 92% of the surface was amorphous on average.

Example 2:
70.5 weight percent zirconium (Haines & Maassen Metalhandsgesellschaft mbH Bonn, Zr-201-Zirkon Crystalbar), 0.2 weight percent hafnium (Alpha Aesar GmbH & Co KG Karlsruhe, Hafnum 99, Hafnum. 23.9 weight percent copper (Alpha Aesar GmbH & Co KG Karlsruhe, Copper plate, Oxygen free, High Conductivity (OFCH), Item No. 45210), 3.6 weight percent aluminum (Alpha Aesar GmbH, Co., Ltd.) an alloy consisting of Nium Ingot 99.999%, Item No. 10571) and 1.8 weight percent niobium (Alpha Aesar GmbH & Co KG Karlsruhe, Niob Folie 99.97%, Item No. 00288) was introduced into an induction melting plant (VSG, inductive beheitze). It was melted under 800 mbar of argon (Argon 6.0, Linde AG, Prague) in Vakuum-, Schmelz-und Giessanlage, Nuermont, Freiburg and poured into a water-cooled copper mold. From the alloy thus obtained, for example, using a method as known in WO 99/30858 A1, a melt is melted with argon in a Nanoval melt atomizer (Nanoval GmbH & Co. KG, Berlin). Nebulization produced a fine powder.

  When separating fines by separation with wind sorting using Condux-Feinstichter CFS (Netsch-Feinhahltechnik GmbH, Germany), less than 0.1% of the particles are less than 5 μm in size. Also, all powder particles larger than 125 μm were removed using a 125 μm mesh analytical sieve (Retsch GmbH, Hahn, Germany, product no. 60.131.000125). When the powder thus obtained is examined by X-ray diffraction, it has more than 95% amorphous parts.

  The powder fraction thus obtained was sintered every 15.0 grams at a temperature of 400 ° C. for 3 minutes by hot pressing using a pressure of 200 megapascals (200 MPa).

  The 15 parts thus produced were analyzed for the proportion of amorphous surface in the tissue using metallographic microscope images. As a result, it was shown that 85% of the surface was amorphous on average.

Example 3:
70.6 weight percent zirconium (Haines & Maassen Metalhandsgesellschaft mbH Bonn, Zr-201-Zirkon Crystalbar, 23.9 weight percent copper (Alpha Aesar GmbH H & Co KG Karlsruhe, CopperOpel H ) 3.7 weight percent aluminum (Alpha Aesar GmbH & Co KG Karlsruhe, Aluminum Ingot 99.999%, product no. 10571) and 1.8 weight percent niobium (Alpha Aesar GmbH & Co KG Karlsruhe, Niob Folie 99.97%). No. 28368) is melted under 800 mbar of argon (Argon 6.0, Linde AG, Prague) in an induction melting plant (VSG, inductive beheizte Vakuum-, Schmelz-und Giessurage, Nuermont, Freiburg). It was poured into a water-cooled copper mold. From the alloy thus obtained, for example, using a method as known in WO 99/30858 A1, a melt is melted with argon in a Nanoval melt atomizer (Nanoval GmbH & Co. KG, Berlin). Nebulization produced a fine powder.

  When separating fines by separation with wind sorting using Condux-Feinstichter CFS (Netsch-Feinhahltechnik GmbH, Germany), less than 0.1% of the particles are less than 5 μm in size. Also, all powder particles larger than 125 μm were removed using sieving with a 125 μm mesh analytical sieve (Retsch GmbH, Hahn, Germany, product no. 60.131.000125). When the powder thus obtained is examined by X-ray diffraction, it has more than 95% amorphous parts.

  The powder fraction thus obtained was compressed every 15.0 grams under a pressure of 200 megapascal (200 MPa) and sintered at a temperature of 400 ° C. for 3 minutes.

  The 15 parts thus produced were analyzed for the proportion of amorphous surface in the tissue using metallographic microscope images. As a result, it was shown that 87% of the surface was amorphous on average.

Example 4:
70.6 weight percent zirconium (Haines & Maassen Metalhandsgesellschaft mbH Bonn, Zr-201-Zirkon Crystalbar, 23.9 weight percent copper (Alpha Aesar GmbH H & Co KG Karlsruhe, CopperOpel H ) 3.7 weight percent aluminum (Alpha Aesar GmbH & Co KG Karlsruhe, Aluminum Ingot 99.999%, product no. 10571) and 1.8 weight percent niobium (Alpha Aesar GmbH & Co KG Karlsruhe, Niob Folie 99.97%). No. 28388) is melted under 800 mbar of argon (Argon 6.0, Linde AG, Prague) in an induction melting plant (VSG, inductive beheizte Vakuum-, Schmelz-und Giessurage, Nuermont, Freiburg). It was poured into a water-cooled copper mold. From the alloy thus obtained, for example, using a method as known in WO 99/30858 A1, a melt is melted with argon in a Nanoval melt atomizer (Nanoval GmbH & Co. KG, Berlin). Nebulization produced a fine powder.

  When separating fines by separation with wind sorting using Condux-Feinstichter CFS (Netsch-Feinhahltechnik GmbH, Germany), less than 0.1% of the particles are less than 5 μm in size. Also, all powder particles larger than 125 μm were removed using a 125 μm mesh analytical sieve (Retsch GmbH, Hahn, Germany, product no. 60.131.000125). When the powder thus obtained is examined by X-ray diffraction, it has more than 95% amorphous parts.

  50 grams of the powder fraction obtained in this way was transferred into a compressor (32 mm, P0764, massimetric Chromatography-Handel Berlin, 25 g) in a Laborpresse 54MP250D (Msscientific Chromatography-Handel GmbH, Berlin) And sintered under a high purity argon (Argon 6.0, Linde AG, Prague) at a temperature of 410 ° C. for 5 minutes.

  The parts thus produced were analyzed for the proportion of the amorphous surface in the tissue using metallographic microscope images. As a result, it was shown that 90% of the surface was amorphous on average.

In the table below, the measurement results for Examples 1 to 4 are shown in relation to the reference measurement values.

Test and measuring method 1) Measuring method of particle size of metal alloy powder:
The particle size of the inorganic powders was measured by laser light scattering (Laserligtst) using a Sympatec Helos BR / R3 (Sympatec GmbH) equipped with a RODOS / M dry dispersion system (Sympatec GmbH) with a vibration supply device (VIBRI). . At least 10 g of sample was added dry and dispersed at 1 bar primary pressure and the measurement started. An optical density of 1.9% to 2.1% was used as the starting standard. The measurement time was 10 seconds. Evaluation was performed according to the MIE theory, and d50 was used as a measure of particle size.

2) Test method for density measurement:
For the measurement of density, it is accurately measured using a digital outer micrometer (Buegelmesscherubube) (PR1367, Mitutoyo Messgeraete Leonberg GmbH, Leonberg) by creating a geometrically accurate cube by polishing the surface. be able to. First, the volume is determined mathematically. Next, the exact weight is determined with an analytical balance (XPE-analytical balance manufactured by Mettler-Toledo GmbH). The density is obtained from the relationship between the measured weight and the calculated volume.

  The theoretical density of the amorphous alloy corresponds to the density at the melting point.

3) Test method for measuring the amorphous surface ratio in a part:
For the above purpose, according to DIN EN ISO 1463, 15 metallized structures are produced. At that time, SiC-Folie 1200 (Struers GmbH, Willich), then 6 μm, 3 μm and 1 μm diamond polishing means (Struers GmbH, Willich), then chemical mechanical oxide polishing suspension OP-S (Struers GmbH, Polishing is performed by a polishing process using Willich). The ground surface thus produced is analyzed for the crystal surface ratio in the microscope image at a magnification of 1000 times under an optical microscope (Leica DM 4000M, Leica DM 6000M). For this purpose, the software, Leica Phase Expert, was used to evaluate the area percentage of the crystalline part relative to the total area of the image, with the dark area being crystallized and the bright part being amorphous. . An amorphous matrix is defined as the reference phase and expressed as a percentage of the total measured area. Ten different sample surfaces were measured and averaged.

4) Test method for measuring transition temperature:
For the above purpose, a Rh-Maeanderheizer, integrated control thermocouple S-type, DSC404F1A72 sample transport system and a high temperature tubular oven with a crucible with an Al ₂ O ₃ lid, Calorimeter with an OTS-system with three getter rings to remove trace amounts of oxygen during the measurement and an automatically operated vacuum system with a two-stage rotary pump, Netzsch DSC 404 F1 Pegasus (Erich NETZSCH GmbH & Co. Holding KG )It was used. All measurements were performed under protective gas (Argon 6.0, Linde AG) at a flow rate of 50 ml / min. The evaluation was performed using software, Proteus 6.1. For the measurement of TT, the tangent method (“glass transition”) was used in the range between 380 ° C. and 420 ° C. (start, midpoint, inflection point, end). For measurement of TK, “Complex Peak” evaluation in the temperature range of 450-500 ° C. is used (area, peak, start, end, width, height), and for Tm, in the temperature range of 875-930 ° C. A “Complex Peak” rating was used (area, peak, start, end, width, height). For measurement, a 25 mg +/− 0.5 mg sample was weighed into a crucible and measured at the following heating rate and temperature range.
20-375 ° C .: heating rate 20 K / min
375-500 ° C .: Heating rate 1 K / min
500-850 ° C .: heating rate 20 K / min
Higher than 850 ° C: heating rate 10K / min

  For the determination of the amorphous part of the part, the crystallization enthalpy was determined using the “Complex Peak” method. In that case, a 100% amorphous sample (obtained by melt spinning) having a crystallization enthalpy of −47.0 J / g was used as a reference.

  The ratio of the crystallization enthalpy of the part to the reference crystallization enthalpy gives the ratio of the amorphous phase.

5) Measurement of elemental composition by emission spectral analysis (ICP):
An emission spectrometer, Varian Vista-MPX (Varian Inc.) was used. Two metal calibration samples were prepared and measured from a standard solution having a known metal content (eg, 1000 mg / I) in aqua regia medium (3: 1 concentrated hydrochloric acid and concentrated nitric acid).

The ICP-instrument parameters were as follows:
Output: 1.25kW
Plasma gas: 15.0 l / min (argon)
Auxiliary gas: 1.50 l / min (argon)
Nebulizer gas pressure: 220 kPa (argon)
Iteration: 20s
Equilibration time: 45s
Observation height (Beobachungshohe): 10 mm
Sample aspiration: 45s
Cleaning time: 10s
Pump speed: 20Upm
Number of iterations: 3

  About measurement of sample: As described above, 3 ml of nitric acid and 9 ml of hydrochloric acid were added to 0.10 g +/− 0.02 g of sample, and in microwave (Anton Paar apparatus: Multiwave 3000) at 800-1200 W for 60 min. Process within. The treated sample is transferred to a 100 ml flask with 50% by volume hydrochloric acid and measured.

  The features of the invention disclosed in the above description and in the claims, flowcharts and embodiments can be used individually and in any combination for the implementation of the invention in various embodiments of the invention.

Claims (11)

A method for producing a part comprising at least a partially amorphous metal alloy having the following steps:
Providing a powder comprising a powder of at least partly amorphous metal alloy, comprising spherical powder particles, the powder particles having a diameter of less than 125 μm; the powder having a diameter of less than 5 μm Sieving the powder or subjecting it to wind sorting so that it contains less than 1 weight percent of particles or less than 1 weight percent of particles with a diameter of less than 5 μm; Forming the desired shape of the part; by temperature treating the powder at a temperature between the transition temperature of the amorphous phase of the metal alloy and the crystallization temperature during or after the compression, the powder was pressed and a step of sintering, the part is sintered after temperature treatment, the length of temperature treatment so as to have an amorphous portion of at least 85 percent are selected, pre Amorphous portion of the component is determined as the ratio of the crystallization enthalpy of the component relative crystallization enthalpy of 100% amorphous sample, the crystallization enthalpy is measured by differential scanning calorimetry, process. The method according to claim 1, wherein the temperature treatment is performed under vacuum.   The method according to claim 1 or 2, wherein the powder is compressed by hot isostatic pressing or hot pressing. The method of claim 1, wherein the temperature treatment time is selected so that the part has at least 90 percent amorphous portions .   5. A method according to claim 1, wherein a powder consisting of an amorphous metal alloy with at least 50 weight percent zirconium is used. A powder made of an amorphous metal alloy
a) 58 to 77 weight percent zirconium,
b) 0 to 3 weight percent hafnium,
c) 20 to 30 weight percent copper,
d) 2 to 6 weight percent aluminum, and e) 1 to 3 weight percent niobium,
Composed of,
The method according to claim 1. The method according to claim 1, wherein the spherical amorphous metal alloy powder is produced by melt atomization . The temperature treatment of the powder is performed at a temperature (T) between a transition temperature and a maximum temperature, and the maximum temperature is a transition temperature (T _T ) of the amorphous phase of the metal alloy with respect to the transition temperature (T _T). ) And the crystallization temperature (T _K ), which is 30% above the temperature difference. The method according to claim 1 , wherein the temperature treatment time is selected according to the geometry of the part to be produced. The length of temperature treatment, from 3 seconds per millimeter thickness or maximum associated diameter of the part to be produced, the time range of up to 900 seconds per millimeter thickness or maximum associated diameter of the part to be produced, wherein Item 10. The method according to item 1 of item 1-9 . The method according to claim 1 , wherein the powder particles are plastically deformed by the temperature treatment.