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WO2013079655A2 - Procédé de fabrication d'un matériau composite, le matériau composite et l'utilisation du matériau composite pour fabriquer des produits déterminés - Google Patents

Procédé de fabrication d'un matériau composite, le matériau composite et l'utilisation du matériau composite pour fabriquer des produits déterminés Download PDF

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Publication number
WO2013079655A2
WO2013079655A2 PCT/EP2012/074077 EP2012074077W WO2013079655A2 WO 2013079655 A2 WO2013079655 A2 WO 2013079655A2 EP 2012074077 W EP2012074077 W EP 2012074077W WO 2013079655 A2 WO2013079655 A2 WO 2013079655A2
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WO
WIPO (PCT)
Prior art keywords
polymer
particles
ceramic
fraction
material fraction
Prior art date
Application number
PCT/EP2012/074077
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German (de)
English (en)
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WO2013079655A3 (fr
Inventor
Vitalij SALIKOV
Gerold Schneider
Stefan Heinrich
Michael Wolff
Sergiy ANTONYUK
Kristina BRANDT
Original Assignee
Technische Universität Hamburg-Harburg
Tutech Innovation Gmbh
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Application filed by Technische Universität Hamburg-Harburg, Tutech Innovation Gmbh filed Critical Technische Universität Hamburg-Harburg
Publication of WO2013079655A2 publication Critical patent/WO2013079655A2/fr
Publication of WO2013079655A3 publication Critical patent/WO2013079655A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/006—Pressing and sintering powders, granules or fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • B29B2009/163—Coating, i.e. applying a layer of liquid or solid material on the granule

Definitions

  • the present invention relates to a method for producing a composite material by means of fluidized bed technology, in particular spouted bed granulation, and hot pressing, wherein the composite material consists of at least a first material fraction and at least one polymer or biopolymer. Furthermore, the present invention relates to the composite materials produced by the above-mentioned method and to the use of these composite materials for the production of certain products.
  • Ceramic particles and the metal particles can be made of different ceramics and different ones
  • Metals exist and also have different particle size distributions, average particle sizes and particle shapes.
  • the properties of the composite are influenced by the proportions of material processed in the composite. For example, for many applications, a high proportion of ceramics is sought in composite materials, since, for example, the modulus of elasticity and hardness increase with increasing ceramic content. A certain proportion of metal particles also at least partially transmits the typical properties of metals, such as good plastic deformability, high strength and high breaking strength, to the composite material, so that when there is a mixture of ceramic and metal particles in the composite material, a property combination based thereon out forms.
  • the particles of material fractions, such as ceramic and / or metal, in the composite are bonded together using one or a mixture of polymers.
  • Structural ceramics as well as functional ceramics are used in the ceramic material fraction in the composite material.
  • structural ceramics The mechanical properties of the composite, such as strength, hardness, thermo-mechanical and chemical resistance, can be enhanced by using functional ceramics to influence other physical properties of the composite.
  • structural ceramics are Al2O3, Zr0 2 and an example of functional ceramics is lead zirconate titanate (PZT).
  • PZT lead zirconate titanate
  • lead-free piezoceramics and polymers such as potassium-sodium niobate (KNN) or ferromagnetic ceramics and metals are preferred.
  • the invention discloses a manufacturing route for achieving very high ceramic and / or metal levels in a ceramic-metal-polymer composite. This is achieved, as further explained below, by the combination of granulation, in which a material fraction is encased by another material fraction, and hot pressing of the granules produced in this way under high pressure.
  • the inventive method comprises the production of a composite material by fluidized bed technology, in particular spouted bed granulation and hot pressing, wherein the compressed composite material consists of at least a first material fraction and at least one polymer.
  • the method according to the invention comprises the following steps: producing a fluidized particle layer consisting of the at least first material fraction and a fluid stream, injecting a solution of at least one solvent and the at least one polymer or a melt of the at least one polymer into the fluidized bed, granulating the at least first Material fraction in combination with the at least one polymer to a granulate and pressing the granules under heat, wherein the granules is heated in a temperature range above a glass transition temperature and below a decomposition temperature of the at least one polymer, to form a composite material.
  • Spouted bed apparatuses and thus generally spouted bed technology are known in the art. They are described, for example, in DE 100 04 939 C1 and WO 2010/028710 A2.
  • first a fluidization of a first material fraction takes place. This is understood as meaning the displacement of a material fraction consisting of solid particles by an upward fluid flow into a liquid-like state. This fluid flow is realized for example by an air or more generally a gas flow.
  • the fluidization takes place, in particular in the fluidization of small particles ( ⁇ 50 ⁇ ), preferably in a jet bed system, but in principle is any structure with which a fluidization of the particular desired particle fraction can be achieved and an injection can take place.
  • the particles of the first material fraction are suspended by the fluid flow, or they make a circulating movement in the apparatus, forming a vortex or spouted bed state.
  • the particles of the first material fraction are present at least in the spray zone of the nozzle separated from each other, so that they are accessible from the outside around.
  • the solution of the at least one solvent for the at least one polymer or the melt of the at least one polymer is sprayed into the fluidized bed.
  • At least one further material fraction into the process of granulation in addition to the first material fraction.
  • This at least one further material fraction is preferably suspended in the polymer solution or polymer melt or first suspended in the solvent with subsequent dissolution of the polymer in the suspension, and then sprayed into the fluidized bed and / or in combination with the first material fraction by the fluid flow in the fluidized bed swirled. It is preferred that the material fractions used have different mean particle sizes, in order to increase in this way the degree of filling of the compressed composite material.
  • this granulate is processed under pressure and / or temperature, preferably compressed with heat.
  • this granulate is processed under pressure and / or temperature, preferably compressed with heat.
  • heat is supplied in a temperature range below a decomposition temperature of the at least one polymer.
  • the pressing temperature is preferably used in a range between a glass transition temperature of a polymer and a decomposition temperature of a polymer, preferably in the range of a typical processing temperature depending on the polymers involved.
  • At least one second material fraction and optionally also a third and / or further material fractions are preferably used in addition to the first material fraction for the production of the composite material.
  • each type of ceramics, metals, metal alloys, pre-structured particles for example ceramic-metal, ceramic-polymer, metal-polymer, ceramic-metal-polymer
  • pre-structured particles for example ceramic-metal, ceramic-polymer, metal-polymer, ceramic-metal-polymer
  • polymers for example, thermoplastics, thermosets and epoxy resins are used.
  • the particles may be spherical, non-spherical, angular, platelike, oblong, acicular, or regularly shaped (eg, square).
  • the first material fraction consists, for example, of ceramic particles of a first mean grain size or of metal particles of a first average grain size or of a mixture of such ceramic and metal particles.
  • the second material fraction preferably consists of ceramic particles of a second average particle size or of metal particles of a second average particle size or of a mixture of such ceramic and metal particles.
  • the production method according to the invention is preferably suitable for the production of a ceramic-ceramic-polymer composite, a ceramic-metal-polymer composite, a metal-metal-polymer composite, a ceramic Polymer or a metal-polymer composite.
  • a polymer-polymer composite material in which, for example, one material fraction consists of an epoxy resin and the other material fraction consists of a thermoplastic.
  • ceramic and / or metal-polymer composites are produced by fluidized bed granulation and hot pressing. These are used in the manufacture of certain products.
  • both the materials and their volume fractions in the composite material can be adjusted in a targeted manner. For example, for many applications it is preferred to achieve a high ceramic content in the range of 50-90 vol.% And a polymer content in the range of about 1-50 vol.% In the compressed composite.
  • a first and a second material fraction of ceramic particles processed using spouted bed technology are examples of spouted bed technology.
  • the ceramic particles of the second material fraction are preferably at least a factor of 2, more preferably at least a factor of 10 smaller than the ceramic particles of the first material fraction. These particle sizes open up the possibility that the small ceramic particles with the help of the at least one polymer as an agent on the surface of the large ceramic particles deposit, so that granules of large and small ceramic particles formed by the polymer. Spraying the polymer solution or the polymer melt - in which at least one material fraction is suspended - into the fluidized bed of a spouted bed apparatus ensures that the at least one polymer is deposited dropwise or in a relatively thin layer and evenly on the ceramic and / or metal particles.
  • a possible process variant is also to suspend a polymer in a liquid instead of dissolving it, and optionally to suspend a material fraction in this polymer suspension.
  • the polymer suspension then becomes fluid during hot pressing and performs a similar function to the polymer solution described above.
  • a polymer solution refers to at least one polymer dissolved in a solvent.
  • a polymer suspension refers to at least one polymer suspended in a liquid. Both in the polymer solution and in the polymer suspension, at least one material fraction can be suspended in order to subsequently be able to produce a granulate in the spouted bed apparatus.
  • the term polymer solution stands by way of example for a polymer solution and a polymer suspension.
  • the material composition can be varied. In this case, preferably the pressing pressure is chosen to be sufficiently large.
  • ceramic filling levels of less than 64 vol.% In the composite material can also be achieved, which is of interest for certain applications, such as, for example, filter materials.
  • a desired porosity is set specifically, which forms the starting point or the practical basis for the later use of the composite material.
  • a ceramic degree of filling ⁇ 64% by volume can be realized by a correspondingly low selected pressing pressure. At very high pressures, the filling level does not increase with increasing pressure. However, with a sufficient reduction of the pressing pressure, the degree of filling decreases with the pressing pressure, and the more so, the smaller the pressing pressure is selected. The lowest possible resulting degree of filling is given by the bulk density of the agglomerates of the first material fraction.
  • the porosity of the composite material can also be adjusted by using a grain size for the suspended material fraction in the polymer solution, which is slightly smaller than the grain size of the first material fraction, eg Keram ik, is.
  • I preferably gives a particle size ratio of first to second material fraction of ⁇ 10.
  • Figure 1 is a schematic representation of a preferred embodiment of a
  • Figure 2 is a schematic representation of a preferred Ausumngsform of
  • FIG. 3 shows a flow chart of a preferred embodiment of the fluffing method for a composite material.
  • the present invention discloses the production of a composite material using spouted technology and hot pressing.
  • one or more Material fractions A, B, C, D, preferably ceramic and / or metal, and at least one polymer P as starting materials in a known jet layer system produced a granulate G.
  • this granulate G both the proportions of the material fraction or material fractions used and the polymer content can be adjusted.
  • the granules G are hot-pressed to the composite material.
  • the hot-pressing temperature does not exceed a decomposition temperature Tz of the polymer used, so that the polymer content is retained in the granules G and the resulting composite material.
  • a high proportion of ceramic and / or metal is used the granulated with the at least one polymer P particles of one or more material fractions A, B, C, D achieved, so that in the later composite material after eliminating the gap volume by pressing a high degree of filling of the introduced material fractions A, B, C, D. preferably over 70 vol.% Can be reached.
  • the thickness of the polymer layer forming on the particles of the material fraction (s) can be influenced and therefore the polymer content in the later composite material can be selectively adjusted.
  • a composite material whose properties can be determined by the degree of filling of the material and polymer fraction. Accordingly, the polymer content of the composite material produced by jet technology can be controlled by varying the amount of polymer supplied.
  • the layer thickness of the polymer layer on the particles of the at least first material fraction can preferably be adjusted within wide limits by means of the production method according to the invention.
  • the layer thickness takes values in a range of a few nanometers, while no second material fraction, a high dilution of the polymer solution, - 0 -
  • Polymer melt or polymer suspension and a good wetting behavior of the polymer solution, polymer melt or polymer suspension on the first material fraction is present, and up to several hundred micrometers or even millimeters.
  • the polymer solution, polymer melt or polymer suspension is preferably diluted, so that the resulting layer thickness is essentially determined by the interface properties between wetting liquid and particle surface.
  • For a thick layer increase the concentration of the polymer in the solution, the melt or the suspension and increase the total amount of polymer solution or polymer melt or polymer suspension to be sprayed. In this way, the layer thickness of the polymer used can be easily adjusted within these wide limits and thus adapted to the gap volume between the particles of the at least one material fraction.
  • a composite material with, for example, a high proportion of ceramic is sought, whose mechanical properties, such as modulus of elasticity and hardness, also increase with increasing ceramic content.
  • mechanical properties such as modulus of elasticity and hardness
  • dense a packing of ceramic particles in the compressed composite material is sought, which just contains just enough polymer that the remaining gap volume between the ceramic particles is preferably completely filled by the polymer portion of the composite material.
  • a proportion of polymer in the composite which exceeds the void volume between the particles of the material fractions of the composite reduces the degree of filling of the material fraction or material fractions, such as ceramic, in the composite, while a polymer fraction below the available void volume in the composite restricts the residual porosity in the composite Episode has. Since a polymer fraction above or below the gap volume available in the composite material between the particles of the material fraction / material fractions can have a negative effect on mechanical / functional properties of the composite material, it is preferable to optimally adapt the polymer fraction to the void volume available in the composite material Particles of the desired material fraction or material fractions. This optimum adaptation of the polymer content leads to improved mechanical properties.
  • the amount of polymer can be precisely adjusted to exactly fill the void volume of the processed material fractions after pressing.
  • the polymer content does not cause a reduction in the degree of filling, and nevertheless a pore-free structure is formed, so that the formation of cracking centers is made more difficult.
  • the proportion of polymer is adjusted by the amount or concentration of polymer solution / polymer melt in which a material fraction may otherwise be suspended.
  • the preferred composite material is composed of at least a first material fraction A and a polymer fraction.
  • the first material fraction A consists of ceramic or polymer or metal particles or particles of a pre-structured composite material.
  • the particles of the first material fraction A preferably have a first mean grain size and a first grain size distribution.
  • the particles of the first material fraction A form the so-called bed material 10, which is fluidized in the fluidized bed or jet bed apparatus (SI).
  • the fluid stream 20 By means of a heater, the fluid stream 20, preferably the air, is heated to assist a drying process within the fluidized bed 30.
  • the targeted heating of the fluid stream 20 is adjusted as a function of a vapor pressure of a solvent to be evaporated of a polymer solution (see below).
  • the temperature range of the fluid flow 20, preferably 10-100 ° C. is to be set such that at least partial to complete evaporation of the solvent of the polymer solution results in a coating of the particles of the bed material 10.
  • the bed material 10 is preferably the first material fraction A mixed with one or more further material fractions B (Sil).
  • a ceramic-ceramic or ceramic-metal or metal / ceramic-prestructured particle mixture is formed, which is fluidized as bed material 10 in the spouted bed apparatus in the fluidized bed 30.
  • a solution of at least one solvent for at least one polymer and the at least one polymer or polymer melt are injected into the fluidized bed 30 of bed material 10 in the spouted bed apparatus (SVI).
  • SVI spouted bed apparatus
  • the at least one polymer P is dissolved in a corresponding solvent L. It is further preferred to dissolve a plurality of polymers in corresponding more or only one solvent L. It is also preferred to make a polymer melt from a plurality of polymers (SIE).
  • SIE polymers
  • a further material fraction C is added to the polymer solution or polymer melt (SIV). This results in a polymer solution / polymer melt in which a second fraction of material is suspended.
  • SIV polymer solution or polymer melt
  • the addition of further material fractions depends on the properties to be achieved in the later composite material.
  • ceramic, metal and / or polymer particles and particles of composite materials are used alone or in combination.
  • the particles of the second C and of the further material fractions 1) have a second middle
  • the particles of the bed material 10 and the particles of the second C and further material fractions D have a size ratio in the range 4-10: 1, preferably 6-10: 1 and even more preferably from about 10-100: 1. It is also preferred to choose an even larger size ratio of about 100: 1 to about 100,000: 1.
  • the particle sizes of the bed material 10 preferably in the range of 10-30 ⁇ and the particle sizes of the second C and other material fractions D preferably in the range of 0.2-5 ⁇ .
  • step SVI the polymer solution / polymer melt in which at least one second material fraction is suspended is injected into the fluidized bed 30 of bed material 10.
  • the injection is preferably carried out via a two-material nozzle.
  • the spraying rate during injection depends on the selected construction of the jet bed apparatus and a vapor pressure of the solvent L used for the polymer P. According to a preferred embodiment of the present production process, the spray rate is about 10 g / min.
  • the polymer solution / polymer melt or the suspension is distributed in the form of small droplets in the fluidized bed 30. These droplets deposit on the particles of the bed material 10 so that the particles of the second C and further material fractionally D serve as coating particles for the particles of the bed material 10.
  • the at least one polymer in the polymer solution serves as adhesion promoter between particles of the bed material 10 and coating particles n as soon as the solvent L has evaporated from the droplets of the polymer solution.
  • polymer melt or polymer suspension is injected into the fluidized bed 30, more or less coating particles and polymer deposit on the particles of the bed material 10.
  • This process is illustrated schematically at the lower right edge of FIG.
  • the proportions to be used of the introduced into the spout apparatus materials hang as follows from each other.
  • the optimum amount of bed material 10 which is fluidized in the fluidized bed is dictated by the geometry of the spouted bed equipment used. According to a preferred embodiment, this amount is about 200-400 g of ceramic particles.
  • metal particles such as, for example, silver or copper, can be supplied to the fluidized bed 30 via the above-mentioned suspension.
  • the optimum ratio of large to small particles, ie particles of the bed material 10 and the coating particles of the suspension is about 60:40 vol.%. This results in the amount of small particles in the suspension.
  • the effective amount of the bed material 10 is somewhat lower than the amount of bed material 10 introduced into the spouted apparatus. The reason is that certain losses of bed material 10 may occur during the manufacturing process. These losses occur, for example, due to the adhesion of the particles of the bed material 10 to the walls of the spouted bed apparatus and to the discharge of smaller particles of the bed material 10 via the fluid flow 20 from the fluidized bed 30.
  • the amount of dissolved polymer P in the polymer solution is determined by the fact that the void volume between the compressed particles in the composite material remaining after a hot pressing process (see below) is preferably completely filled with the polymer P or a plurality of polymers.
  • the amount of solvent for the polymer P is again determined from the amount of polymer P to be dissolved.
  • the amount of solvent is also preferably chosen such that a sufficiently low viscosity of the polymer solution or of the suspension of polymer solution and second / further material fraction (s) C: D is guaranteed.
  • the pH of the suspension of polymer solution and second / further material for action (s) C; D is adjusted by addition of any acid or base such that it deviates from the isoelectric point of the ceramic particles preferably used in the second material fraction C in order to stabilize the suspension and to avoid agglomeration of the ceramic particles in the suspension.
  • the adjustment of the pH value is important, especially for small particle sizes, ie particles large ⁇ 5 ⁇ m, since the agglomerate tion occurs increasingly.
  • the distribution or dispersion of the particles of the second material fraction C or further material fraction D in the suspension is carried out in an ultrasonic bath according to an embodiment of the present production method. Of course, other known methods are equally applicable for this purpose, which serve for distributing particles in a suspension.
  • the material fractions A, B, C present in the fluidized bed 30 are granulated , D by means of the / the polymers (SV1I).
  • the resulting granulate G is subsequently pressed, preferably hot-pressed while supplying heat without reaching the glass transition temperature of the polymer (s), which is illustrated schematically in FIG.
  • the pressing process preferably takes place in a pressure range of 100 MPa to 1 GPa and preferably at a pressing temperature of (TG + 10 ° C) to (T G + 100 ° C). Pressure and temperature, as explained below, can also be chosen differently within very wide limits as required.
  • the term "hot pressing” is to be understood as meaning that, in order to achieve optimum processing of the polymer (s) during pressing, an amount of heat is added or removed, the polymer (s) are therefore warm or cold relative to a room temperature of, say, 20 ° C be pressed.
  • the hot pressing of ceramic-polymer composites into composites with high packing densities is preferably carried out at a pressure and temperature sufficient to press the granules into the densest possible random packing structure.
  • a further increase in the pressing pressure then causes only an elastic deformation of the ceramic particles.
  • the pressure should be chosen so large that the particles of the injected (second or further) material fraction, which re-shift the swirled first material fraction, are pressed into the void volume of the larger particle fraction of material relative to the particle size during the pressing process.
  • Preferred pressing pressures for an example process described are between 50 MPa and 1 GPa.
  • the pressing pressure is limited by possible damage in the material, which results from an excessive elastic deformation of the ceramic particles and subsequent relief in the material. Down there is no limit.
  • a significantly higher compression pressure may be useful, which is determined by the (possibly desired) plastic deformability of the metal particles.
  • the pressing pressure In order to achieve lower fill levels or a higher polymer content, it is also preferred to choose the pressing pressure much lower, for example, only a few 10 MPa or even smaller. In general, the pressing pressure is to be matched to the desired properties of the composite material.
  • the respective suitable compression pressure in a wide range, namely of approximately 0 Pa - thus a highly porous composite produced only by heat during hot pressing - to several GPa - thus a highly filled composite material with possible plastic deformation of contained metal particles.
  • the appropriate pressing pressure also depends on the pressing temperature used.
  • the pressing process preferably takes place with the supply of heat to the granulate G to be compacted.
  • a temperature T is reached which is preferably above a glass transition temperature TG or melting temperature T s and below a decomposition temperature Tz of the polymer (s) P used in the granulate G.
  • a temperature range above a glass transition temperature TQ of the polymer P used is set in the granulate G. If a polymer is used which is composed of several components (eg thermosets), then the lower limit may be given by the glass transition temperature and / or melting point of the individual components.
  • the appropriate compression pressure depends on the viscosity of the polymer P in the granulate G under pressure, on the particle nature of the material fractions in the granulate G, such as, for example, size, shape and size distribution. depends on the desired properties of the compressed composite material.
  • the following description of an exemplary batch process illustrates how the amounts of the individual material fractions and hence also the layer thickness of the polymer layer result from the respective requirements for the composite material.
  • the layer thickness of the polymer layer is calculated as follows from the desired composition of the composite material and the resulting volume fractions of the individual material fractions. For example, if a composite material with 80 vol% ceramic and 20 vol% polymer is desired, then dissolve just as much polymer in the solvent that the polymer content is 20 vol%. This is preferably realized in a batch process as follows.
  • particle size ratio under point 1) which leads to the desired packing density, represents a lower limit, but could also be chosen to be higher to some extent. If a larger particle size ratio is chosen, but the amount of polymer is not adjusted appropriately, then the presence of the preferably incompressible polymer prevents densification to higher packing densities.
  • the polymer coating on the particles of at least the first material fraction can also consist of a plurality of polymer layers applied one behind the other.
  • different polymer solutions / polymer melts / polymer suspensions with in each case other polymers and / or particles suspended therein are preferably sprayed or sprayed into the jet bed apparatus one after the other or simultaneously. In this way, preferably three or more different particle sizes are combined.
  • Suitable polymer P is any plastic and also any biopolymer which can be dissolved in a corresponding solvent L or suspended in a liquid or whose melt has a sufficiently low viscosity for injection.
  • the polymers P polyvinyl alcohol (PVA) and polyvinyl butyral (PVB) were used, which dissolve in water or ethanol.
  • PVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • Biopolymers in this context refer to polymers which consist of biogenic raw materials (renewable raw materials) and / or which are biodegradable. Examples of these are proteins, for which collagen is an example, or peptides, RNA and DNA. Such biopolymers are often referred to as biological macromolecules.
  • the polymers and biopolymers are summarized under the name polymers for ease of explanation.
  • material fraction A; B; C; D are all solid substances whose properties are of interest for the composite to be produced and which are present in a suitable average particle size or grain size or can be processed to achieve this average particle size.
  • ceramics A1 2 0 3 , Ti0 2 , Si0 2 , Zr0 2 , BaTiC, PZT, KNN, BNT, ZnO, mullite, Fe 2 0 3 , Hydroxilapatitit, Caiciumsphosphat, Biogläser be mentioned.
  • metals and metal alloys mention may be made of Cu, Ag, Al, Au, Fe, Si, Cu x Zn y , Ni x Fe y Ti x Al y .
  • the particles of the material fraction A; B; C can have a spherical or non-spherical shape, such as, for example, edged, platelet-shaped, rod-shaped.
  • a spherical or non-spherical shape such as, for example, edged, platelet-shaped, rod-shaped.
  • platelet-shaped a-Al 2 O 3 ceramic particles in the particle size range d 50 32-38 ⁇ m and irregularly shaped a-Al 2 O 3 ceramic particles in the particle size range -25 ⁇ used as bedding material 10
  • the polymer used is preferably partially hydrolyzed polyvinyl alcohol with deionized water as solvent and polyvinyl butyral with ethanol as solvent.
  • a first material fraction A consisting of ceramic particles of a monomodal particle size distribution in combination with a injected polymer P without further material fraction a composite material with a Keramikikan- part up to about 64 vol .-% in the pressed state produced.
  • a second material fraction C of smaller ceramic particles is mixed with the polymer solution / polymer melt in comparison with the particles of the first material fraction A.
  • the ceramic particles of the second material fraction C are preferably smaller by at least a factor of 10 or more than the particles of the first material fraction A. If an amount of the second material fraction C of approximately 60-65% by volume is mixed.
  • the ceramic particles of material fraction A of the polymer solution after completion of the manufacturing process described above, preferably a compressed composite material with a 70-90% volume fraction of ceramic obtained.
  • the ceramic proportion which arises is dependent on the size ratio of the particle classes, the mass ratio of the at least two particle fractions and the particle shape of the material fractions involved, given a sufficiently high pressing pressure and preferably randomly homogeneous mixing of the particle size classes.
  • the influence of each of these factors can be found in literature data.
  • maximum ceramic content of about 87 voI .-%
  • the influence of the particle shape as a deviating from the spherical shape particle shape both to a lower and to a - with a special arrangement of the particles - Can lead to higher ceramic content.
  • platelet-shaped particles under certain circumstances, for example, results in a higher volume fraction.
  • the production route described above is transferable to the metal / polymer material system. Due to the slightly different material properties of metal compared to ceramic, the production parameters, for example, to the interface behavior metal / polymer, the behavior of the changed behavior of the metal particles as bed material 10 in the fluidized bed 30 and the sedimentation behavior of the metal particles in suspended form in the polymer solution. As a result of the manufacturing process to yield composite materials with a degree of filling of up to 99.9 vol% 'of ceramic and / or metal, which is partly attributable to the plastic deformability of the metal particles.
  • a preferred application is Silver as a metal in a ceramic composite as a denture, because silver kills bacteria when used as a dental filling material or dental implant. Another example of a preferred metal is copper. d) A porous ceramic-metal-polymer composite
  • the production method of the invention described above can also be used to produce a porous, yet solid filter material.
  • a volume fraction of the first material fraction A in the composite material can be reduced to a smaller value by reducing the compression pressure during hot pressing of about 64% by volume, so that a compressed preferred composite material having the following composition is obtained:
  • Ceramic content X 40-50 vol.% Consisting of the first material fraction A
  • the coated particles of the first material fraction A of the bed material 10 are preferably selectively agglomerated during the spouting process.
  • the manufacturing process must be modified so that agglomeration occurs increasingly.
  • the temperature in the swirling layer may be reduced and / or the droplet size of the injected suspension may be increased (for example, by reducing the nozzle air flow).
  • two material fractions A; C consisting of ceramic or metal particles with different mean grain size and therefore used with two different ball packages, so that a ceramic or metallic or mixed ceramic-metallic filling degree in the range of 50-90 vol%, preferably 65-90 vol% is achieved.
  • platelet-shaped ceramic particles of a first material fraction A with plastically deformable metal particles of a second material fraction C in the above-described fluffing method so that a volume fraction of the sum of both material fractions A and C in the range of 50-100% by volume, preferably 70-95% by volume.
  • Possible products or product groups which can be produced by the described method are: dentures and bone substitutes with precisely adapted properties, machine parts (for example gears, seals), artificial stone, kitchen worktops, tiles, dishes, filters, magnetic plastic, high-voltage electrical insulator Dielectric strength, adjustable di- and piezoelectric ceramic-polymer composites, silencers, adjustable ferromagnetic ceramic-metal Polymer composites, multiferroic ceramic-metal-polymer composites. Any products with increased wear resistance. Continuous transitions in plastic to ceramic-polymer-metal composites, which make the plastic harder and more wear-resistant in certain places (eg shaft bushings). The use of biopolymers results in biodegradable environmentally friendly materials.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un matériau composite au moyen de la technologie des solides fluidisés, en particulier par granulation dans une installation à lit fluidisé et compression à chaud, le matériau composite étant constitué d'au moins une première fraction de matière A et d'au moins un polymère ou biopolymère et le procédé présentant les étapes suivantes: production d'une couche de particules fluidisée constituée d'au moins une première fraction de matière et d'un courant de fluide ; injection d'une solution d'au moins un solvant et dudit polymère (biopolymère) ou dudit polymère fondu dans la couche fluidisée ; granulation de ladite première fraction de matière A en combinaison avec ledit polymère en granules ; et pressage des granules sous apport de chaleur, les granules étant chauffés dans une plage de température supérieure à la température ambiante et inférieure à la température de décomposition dudit polymère.
PCT/EP2012/074077 2011-12-01 2012-11-30 Procédé de fabrication d'un matériau composite, le matériau composite et l'utilisation du matériau composite pour fabriquer des produits déterminés WO2013079655A2 (fr)

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DE102011119939.3 2011-12-01
DE201110119939 DE102011119939A1 (de) 2011-12-01 2011-12-01 Verfahren zur Herstellung eines Verbundwerkstoffs, der Verbundwerkstoff und die Verwendung des Verbundwerkstoffs zur Herstellung bestimmter Produkte

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WO2010028710A2 (fr) 2008-09-11 2010-03-18 Glatt Ingenieurtechnik Gmbh Procédé et dispositif de traitement de matière à grain fin en lit jaillissant

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DE10322062A1 (de) 2003-05-15 2004-12-02 Glatt Ingenieurtechnik Gmbh Verfahren und Vorrichtung zum Aufbringen von Flüssigkeiten in eine Feststoffströmung eines Strahlschichtapparates
DE102006011391A1 (de) 2006-03-09 2007-09-20 Glatt Gmbh Anlagen mit beschichteten Sprühdüsen
WO2010028710A2 (fr) 2008-09-11 2010-03-18 Glatt Ingenieurtechnik Gmbh Procédé et dispositif de traitement de matière à grain fin en lit jaillissant

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