• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
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    • 专利摘要:

    公开号:AT510086A1
    申请号:T8162011
    申请日:2011-06-01
    公开日:2012-01-15
    发明作者:
    申请人:Helmholtz Zent B Mat & Energ；
    IPC主号:
    专利说明:

    «· * · - 15531 1
    description
    Process for producing metal foams and metal foam
    description
    The invention relates to a process for producing metal foams with stabilizing particles in the metal matrix, comprising at least the steps of producing a foamable starting material and foaming this starting material, wherein the stabilizing particles in the preparation of the foamable starting material in an in situ reaction of a reactive material and a Molten metal are generated, wherein the metal melt, the reactive material is added and mixed.
    Commonly known in the art are various methods for producing metal foams from the molten metal during which ceramic particles stabilizing the metal matrix, such as SiC, TiC, Al 2 O 3, MgO, TiB 2 or AIB 2 are incorporated. These incorporated micro- or nanoparticles affect such properties of the resulting metal foam such as viscosity, foam stability and good cuttability on their particle size and volume fraction. By way of example, the gas injection method and the casting method are mentioned here for the formation and incorporation of stabilizing SiC particles. Scripta Materialia 54 (2006) 1331-1334 reports a PM (powder metallurgy) process in which the wettability of, for example, A! 203 is to be improved by adding the reactive element Mg. This wettability is influenced by the reaction of Mg and Al at the metal-oxide interface to form MgAl204 (spinel). In this process, Al powder is mixed with TiH2 powder, then cold compressed. In order to increase the foam stability, Al-Mg powder and Al 2 O 3 particles are added and analyzed for different ratios of the mixture.
    In International Conference "ADVANCED METALLIC MATERIALS " 5-7 November, 2003, Smolenice, Slovakia, pp. 5-15, a metal foam is described in which a spinel layer (MgAl204) forms on the Al particles when the ratio Si / Mg is low. When more Si is present, no spinel layer is formed. The foamable starting material was based on AISi0.8Mg0.8 (in% by weight) + 10% by volume of Al 2 O 3 and was foamed by gas injection.
    It should be noted at this point that the composition of the alloys in% by weight is also stated below, the proportion of incorporated particles in% by volume, unless otherwise stated.
    The prior art, from which the invention proceeds, is described in DE 10 2006 031 213 B3. In this solution, stabilizing particles are produced in the preparation of the foamable precursor in an in situ reaction of molten reactive fluids and a molten metal, the molten metal containing the constituents of the nanometer to subpm diameter generating particles (such as e.g. TiC, TiB2 or AIB2 particles) is added at least as a fluoride salt, then mixed and heated above the melting temperature of the mixed components.
    While this method can produce Al metal foams with TiC or TiB2 or AIB2 particles having good foaming properties such as good viscosity / low brittleness and easier machinability, the use of fluorides still uses health and environmental hazardous materials. In addition, TiB2 particles do not have sufficient wetting properties for an effective ft * * k ft • I * * ♦ > · 1 «*« · · * «« «* * *« ft ft ft · | 3
    Reaction in the liquid phase in the preparation of the foamable starting material.
    The object of the invention is therefore to provide a method for the production of metal foams that no health and environmentally harmful ingredients needed and should be cheaper than the method according to the prior art and in which the particles generated in situ have at least as good stabilization properties as in the state of Mentioned technique for other particles.
    This object is achieved by a method of the type mentioned in that Si02 is added according to the invention as a reactive substance and are formed in the in situ reaction MgAI204 as stabilizing particles with a diameter in the nm to subpm range.
    In the method of the invention, which is simple and inexpensive, in situ sub-pm sized spinel particles (MgAl204) are produced which have surprisingly good stabilizing properties better than those produced by the prior art according to previously known and mentioned methods. The process also provides very fine and homogeneously formed particles.
    In embodiments of the invention, it is provided that SiO 2 is added to the melt mixture as a fine powder having a grain fineness of < 100 pm, preferably < 50 μιτι, is added, i. as a quartz powder, or as a fine powder with a high internal porosity > 20% and a grain fineness of < 200 pm (microsilica). The proportion of SiO 2 added to the molten metal is 2.5% by weight to 7.5% by weight, the addition being possible in amounts of 0.5% by weight. The addition of SiO 2 can be carried out in such a way that SiO 2 is added to the molten metal with stirring, heated to above 1023 K and kept at this temperature for one hour to 5 hours. 4
    Other embodiments provide to use as molten metal an aluminum-magnesium melt, wherein the magnesium in a proportion of the melt of 0.5 to 5 wt.% Is added.
    As molten metal, however, it is also possible to use an aluminum-silicon-magnesium melt or an aluminum-silicon melt, which, in addition to the SiO 2 particles, also contains Mg.
    A molten metal which is particularly suitable with regard to foamability and viscosity is formed from 2.6% by weight of magnesium, 5% by weight of SiO 2 and aluminum. With this composition of the melt, MgAl204 is formed in a large proportion in the foamable starting material, while MgO, Al203 and some transition phases are formed only in small proportions, which is a prerequisite for good foamability.
    The foaming of the starting material can take place in different ways, on the one hand characterized in that the melt after in situ generation of the stabilizing particles for foaming the starting material powdered metal hydride, in particular TiH2, ZrH2l CaH2 or MgH2, or even powdered carbonate, such as Ca2C03, from 1 to 3% by weight as foaming middle! added, then cooled the melt and then the melt is foamed. The actual foaming can be carried out with the prior art by known means (eg the mold-grip method or the Alporas-method). The foaming of the starting material can also be done by gas injection at 973 K.
    It has been found that the MgAl204 particles formed in situ are capable of stabilizing the metal matrix during foam formation. The MgAl204 particles have a size between 60 nm and 3 pm. They have good wettability with aluminum. It has been found, in particular, that fine-grained quartz powder can be used in situ for the in-situ "* * * * * * * * # φ *"% * * * ♦ * "a" * * * "" * * * * ♦ "* * · | | * ·· * · * »« 4 «4 * * * · * bi» | 5
    Formation of MgAl204 particles by addition into the molten metal is suitable. Another important parameter is the proportion of Mg in the molten metal, whereby the influence of a relatively large proportion on the formation of undesirable phases as well as the greater reaction time in the formation of Al 2 O 3 must be considered as counteracting effects.
    The invention also includes a metal foam containing stabilizing particles in a metal matrix, wherein the stabilizing particles of MgAI204 formed and contained between 1 to 4 vol.% In the metal matrix, have a size between 60 nm and 3 μιτι and the metal foam formed therefrom of uniformly arranged polygonal foam pores having an average diameter of 1 to 5 mm, producible by a process comprising the following steps: producing the stabilizing particles in an in situ reaction of a reactive material and a molten metal, the molten metal SiO 2 for producing MgAl 2 O 4 are added as particles with a diameter in the nm to subpm range, then mixed and heated above the melting temperature of the components of the molten metal, then the melt of metal and stabilizing particles is cooled and finally foamed.
    The metal matrix is formed in particular from aluminum and magnesium and the melt preferably comprises 2.6% by weight of magnesium, 5% by weight of SiO 2 particles and aluminum.
    The invention will now be explained in more detail in exemplary embodiments with reference to FIGS. To show:
    FIG. 1: SEM image of the composition of the foamable starting material formed during Example 4 with octahedral MgAl204 crystals; FIG. ► * ί «t * · 'f fr 4 f« • * * * * 4 | * fr * * * * 4 I »4t 44» · I * I | 6
    Fig. 2: EDX spectrum of the MgAl204 crystal formed during Example 4;
    FIG. 3: EDX spectrum of the Al-Mg-O transition phases formed during Example 4; FIG.
    4 shows X-ray diffraction images of the foamable starting material according to Example 1 and according to Example 4;
    5: photographs of the foamed starting material with stabilizing MgAl204 particles;
    FIG. 6: X-ray tomographic images of a foamable starting material in transverse and longitudinal section after 5 minutes of foaming and after 8 minutes of foaming.
    Embodiment 1
    In this first embodiment, a foamable starting material in the composition Al-MgAl204 is prepared by mixing quartz powder into an Al-5 wt.% Mg melt at 1023 K for 5 hours. The resulting mixture still has some SiO 2 particles in the Al matrix, suggesting an incomplete reaction.
    Embodiment 2
    An Al-1 wt.% Mg melt produced at 1023 K is mixed into coarse-grained quartz powder and stirred for one hour. An increase in the reaction time to 3 or 5 hours has no effect on the microstructure, which is probably due to the lower Mg content compared to Example 1 and the coarse-grained quartz particles that do not support a reaction.
    Embodiment 3
    In turn, a melt produced at 1023 K, now with a larger proportion of Mg, namely an Al-5 wt.% Mg melt, is mixed with coarse-grained quartz powder with stirring. The reaction time is also here at 3 and 5 hours. It has been found that the microstructures contain large areas of Mg-Al-O transition phases with parallelepiped morphology, moreover, this composition has a high viscosity, which is due to the larger proportion of Mg, which tends to form MgO and thus the higher viscosity reasons.
    Embodiment 4
    It can be seen from the preceding three embodiments that the Mg content, the size of the SiO 2 particles and the process steps in the production of the foamable starting material influence its microstructure.
    In the fourth embodiment, the Mg content is now reduced to about half compared to the previous embodiment. Thus, the fine-grained SiO 2 powder (diameter of the grains 44 pm) pretreated at 923 K in two hours is mixed with an Al-2.6 wt.% Mg melt at 1023 K and subjected to a reaction time of 5 hours. As a result, a large amount of very fine MgAl 2 O 4 particles in the AISi 2 matrix and only negligibly viable Al-Mg-O transition phases could be found; the mixture no longer had any unreacted SiO 2 particles and no other phases such as MgO or Al 2 O 3 were detected , In Figure 1, the octahedral morphology of the MgAl 2 O 4 particles - shown at different scales - in the Al-Si-Mg matrix can be well recognized. For the samples prepared in Example 4, EDX spectra were recorded. Here, Fig. 2 confirms the composition of the stabilizing particles formed in situ that these are MgAl 2 O 4 particles since the At.% Ratio of Al / Mg here is approximately equal to 2. Fig. 3. shows the EDX spectrum of the transition phases Al-Mg-0 with Al / Mg = 13.72. In summary, the following table presents the EDX results of the analysis of the stabilizing spinel particles MgA1204 and the transition phases Al-Mg-O.
    Element MgAl204 (At.%) Al-Mg-O (At.%) O 61.99 55.53 43.26 Mg 12.06 9.33 3.76 Al 24.46 34.55 51.61 Al / Mg 2.02 3.70 13.72 X-ray diffraction images of the foamable starting materials prepared in Example 1 and 4 are shown in FIG. 4. While only one MgAl 2 O 4 phase was detected in the Al-Mg-Si matrix for the sample prepared according to Embodiment 4, MgO and SiO 2 are also present in the sample prepared according to Embodiment 1.
    The foaming process is carried out at a temperature of 1018 K by means of the FORMGRIP process (Foaming of Reinforced Metals by Gas Release in Precursors, in which a metal oxide sheaths the TiH2 powder until it enters the melt). In photographs in Fig. 5, the results for the foamable starting materials AISi2 / MgAl204 / 3.38p (a), for AISi2 / MgAl204 / 2.53p and AISi2 / MgAl204 / 1.7p (where p is the proportion of the particles in the metal foam in Vol.% Means) - each produced according to Embodiment 4 - for three different particle volumes (decreasing from left to right) with two different foaming, namely 100 s and 150 s, shown. 9
    6 shows 2D and 3D X-ray tomographic images in cross section (left) and in longitudinal section (right) for a foamable starting material produced according to exemplary embodiment 4 after foaming for 5 minutes (top) and after foaming for 8 minutes (bottom). The foaming process was carried out in a closed steel mold with 40 mm diameter and 50 mm height. After a foaming time of 5 min regular pores have formed and an approximately uniform distribution of the pores can be seen, the gas fraction is ~ 0.74. At the 8-minute foaming time, the gas fraction is ~ 0.8. Recognizable in the associated longitudinal section are defects in the non-foamed areas and in the cell structure.
    权利要求:
    Claims (16)
    [1]
    1. A process for the preparation of metal foams with stabilizing particles in the metal matrix, comprising at least the process steps producing a foamable starting material and foaming this starting material, wherein the stabilizing particles in the preparation of the foamable starting material in an in situ reaction of a reactive substance and a molten metal are produced, wherein the reactive material is added to the molten metal and mixed, characterized in that as a reactive substance SiO 2 is added and formed in the in situ reaction MgAI204 as stabilizing particles with a diameter in the nm to subpm range.
    [2]
    2. The method according to claim 1, characterized in that SiO 2 is used as a fine powder having a particle size of < 100 μm, preferably < 50 pm, is added.
    [3]
    3. Process according to claim 1, characterized in that SiO 2 is present as a fine powder with a high internal porosity > 20% and a grain fineness of < 200 pm is added.
    [4]
    4. The method according to claim 1, characterized in that SiO 2 is added in a proportion of 2.5 wt.% To 7.5 wt.% Based on the molten metal. Η
    [5]
    5. The method according to claim 4, characterized in that SiO 2 is added in rates of 0.5 wt.%.
    [6]
    6. The method according to claim 1, characterized in that S1O2 is added while stirring in the molten metal, heated to above 1023 K and maintained at this temperature for one hour to 5 hours.
    [7]
    7. The method according to claim 1, characterized in that an aluminum-magnesium melt is used as the molten metal.
    [8]
    8. The method according to claim 7, characterized in that magnesium is used in a proportion of 0.5 to 5 wt.% In the molten metal.
    [9]
    9. The method according to claim 1, characterized in that a molten aluminum-silicon-magnesium melt is used as the molten metal.
    [10]
    10. The method according to claim 1 or claim 7, characterized in that an aluminum-silicon melt is used as the molten metal, which is added in addition to the SiO 2 particles and Mg.
    [11]
    11. The method according to at least one of the preceding claims, characterized in that the foamable starting material from 2.6 wt.% Magnesium, 5 wt.% SiO 2 particles and aluminum is formed. ≪ * < * "" * * "", * · · · ♦ * * «* *« · «*« 12
    [12]
    12. The method according to claim 1, characterized in that the melt after in situ generation of the stabilizing particles for foaming the starting material powdered metal hydride or powdered carbonate of 1 to 3 wt.% Added as foaming agent, then the melt is cooled and foamed.
    [13]
    13. The method according to claim 12, characterized in that is used as the metal hydride T1H2, ZrH2, CaH2 or MgH2.
    [14]
    14. The method according to claim 1, characterized in that the foamable starting material is foamed by external gas injection at 973 K.
    [15]
    Metal foam containing stabilizing particles in a metal matrix, wherein the stabilizing particles are formed of MgAl 2 O 4 and contained between 1 to 4% by volume in the metal matrix, have a size between 60 nm and 3 pm, and the metal foam formed therefrom is uniformly arranged Polygonal foam pores having an average diameter of 1 to 5 mm, producible by a method comprising the following steps: producing the stabilizing particles in an in situ reaction of a reactive material and a molten metal, wherein the molten metal SiO 2 for producing MgAI204 as particles with a diameter in the subpm to nm range, then mixed and heated above the melting temperature of the components of the molten metal, then the melt of metal and stabilizing particles is cooled and finally foamed. 13 »1t BL *
    [16]
    16. Metal foam according to claim 15, characterized in that the metal matrix is formed from aluminum and magnesium and silicon.

    Λ ·! '56 Mariahilfer GOrt ii 3S / 1 7 '· ύ > 'Di * i1 C-pa.x: (+4.1 1) 892 8s 333
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    引用文献:
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    DE19801941A1|1997-08-30|1999-03-04|Honsel Ag|Alloy and method of making articles from this alloy|
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    DE10325819B4|2003-06-07|2005-06-23|Friedrich-Alexander-Universität Erlangen-Nürnberg|Process for producing a metal foam body|
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    法律状态:
    2017-02-15| MM01| Lapse because of not paying annual fees|Effective date: 20160601 |
    优先权:
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    DE201010024669|DE102010024669B3|2010-06-18|2010-06-18|Producing metal foam with stabilizing particles in metal matrix, comprises producing foamable starting material, foaming the starting material, and generating stabilizing particles in in-situ reaction of reactive substance and molten metal|
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