DE102014006519A1 - Use of magnetic and / or magnetizable, polymeric micro- and / or nanocomposites for the production of complex, magnetic and / or magnetizable molded parts using additive manufacturers - Google Patents

Abstract

Use of magnetic and / or magnetizable, polymeric micro- and / or nanocomposites for producing complex, magnetic and / or magnetizable moldings using additive, in particular digitally controlled, additive, factories, methods for producing complex, magnetic and / or magnetizable moldings using additive, in particular digitally controlled, additive, factory and complex, magnetic and / or magnetizable moldings, which are composed of solid, magnetic and / or magnetizable, polymeric micro and / or nanocomposites.

Description

Field of the invention

The present invention relates to the use of magnetic and / or magnetizable, polymeric micro- and / or nanocomposites, in particular magnetizable, polymeric nanocomposites, for producing complex, magnetic and / or magnetizable moldings using additive, in particular digitally controlled, additive, factories.

Furthermore, the present invention relates to methods for producing complex, magnetic and / or magnetizable molded parts from magnetic and / or magnetizable, polymeric micro and / or nanocomposites, in particular magnetizable, polymeric nanocomposites, using additive, in particular digitally controlled, additive, factory.

Last but not least, the present invention relates to complex, magnetic and / or magnetizable molded parts, which are composed of at least one solid, magnetic and / or magnetizable, polymeric micro and / or nanocomposite, in particular a magnetizable, polymeric nanocomposite, constructed.

State of the art

Superparamagnetic nanoparticles which can be magnetized without hysteresis by an applied external magnetic field and demagnetized by switching off the external magnetic field, in particular based on hematite (Fe ₂ O ₃ ) and magnetite (Fe ₃ O ₄ ), have long been known. As is known, such superparamagnetic nanoparticles contain only a whitish district. On the other hand, microparticles may contain several white areas which are separated from each other by block walls. Such microparticles can be permanently magnetized by an applied external magnetic field (see the textbook of Ludovico Cadematiri and Geoffrey A. Ozin, Concepts of Nanochemistry, 6th Iron Oxide, pages 172-195, especially page 181, Figure 6.2 Iron Oxide Size, Wiley-VCH, 2009, ISBN 978-3-527-32597-9 ).

Methods for producing superparamagnetic and permanently magnetic nanoparticles have also been described many times. For example, reference is made to page 180 of the above textbook, which describes the preparation of iron oxide nanocrystals.

Magnetized and / or magnetizable micro- and / or nanoparticles of this type are widely used in engineering, chemistry, biology, physics and medicine.

From the German patent application DE 43 39 841 A1 For example, the production of needle-shaped, magnetically modified chromium dioxide having a needle length of 160 to 300 nm with improved temperature stability of permanent magnetization and narrow distribution of particle size is known. The chromium dioxide nanoparticles are prepared by reacting an aqueous chromium trioxide suspension, which has been mixed with an iron compound and a tellurium or antimony compound, with an organic reducing agent. The chromium dioxide nanoparticles are used, for example, in magnetic recording materials.

From the American patent US 7,691,285 B2 For example, the production of iron oxide nanoparticles in the presence of polymers such as dextran or polyethylenimine at high pressure is known. The resulting superparamagnetic nanoparticles can be used for a number of life science applications, for example in biotriming processes or as injectable contrast agents, carriers for radionuclides and as depots for active substances.

From the American patent US 8,557,215 B2 is a method for the production of magnetite nanoparticles by the joint explosion of two water-in-oil suspensions known below 2000 ° C.

From the American patent US 6,022,500 For example, the enzyme-catalyzed production of polymeric microspheres from monomers such as ethylphenol, naphthols or hydroxypyrenes in the presence of a surfactant compound is known. These microspheres can, among other things, be coated with ferrite crystals. The encapsulated ferrite crystals can be used in magnetic coatings, data storage, color imaging, magnetic chromatography and separation processes, magnetic cooling, ferrofluids, and magnetic resonance imaging. The ferrite crystals may further be used together with specific antibodies for the magnetic isolation, separation and purification of cells containing specific antigens and other biological materials.

From the German patent application DE 10 2006 037 702 A1 multifunctional magnetic composites are known for stem cell therapy and / or diagnostics. The magnetic colloids and active substances, for example in the form of growth factors, are encapsulated in polymer carriers to the surface of which stem cell and target cell receptor recognizing ligands are coupled. Preferably, the polymeric carriers are selected from the group of polysaccharides, polycyanoacrylates, polyacrylates, Polyamino acids, polyamino acid g-dextran, polylactides, polyglycolides, polyethylenimine, gelatin, hyaluronic acid, pullulans, dextran-g-polyethylene glycol alkyl ethers, agarose, pectins, dextran, silica gels, polyvinyl alcohol, polyether esters, heparin, dextran sulfate, chitosan, cellulose, polyacrolein, Polyesters, collagen, cellulose derivatives, poly-N-isopropylacrylamide, poly-N-substituted (meth) acrylamides, hydroxypropylcellulose, poly (epsilon-caprolactone), alginates, polyoxyethylene-polypropylene, linear copolymers, graft copolymers or block copolymers.

In addition, z. B. functionalized with proteins, superparamagnetic nanocomposites for the extraction of the alpha-enantiomers of D-glucose from a racemate serve (see, German Offenlegungsschrift DE 10 2012 001 318 A1 ).

The US patent application US 2012/0160828 A1 discloses magnetizable, polymeric nanocomposites of ferrite or chromium dioxide with a reversibly crosslinked polymer. When exposed to an electromagnetic field, these nanocomposites heat up, releasing bonds in the reversibly crosslinked polymer. This reduces the viscosity of the nanocomposites, which is why they can be used to cure cracks in polymers.

From the American patent US 7,815,820 B2 Magnetic and / or magnetizable, polymeric micro and / or nanocomposites are known, which serve the electromagnetic shielding. As the polymers, there may be used, inter alia, fluorosilicone, polyvinylidene fluoride, polyvinylidene fluoride-co-trifluorochloroethylene, polytrifluorochloroethylene-co-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene-chlorofluoroethylene copolymers, or polysiloxanes containing cyanoethyl groups. As ferromagnetic, ferrimagnetic or antiferromagnetic magnetic materials for the nanoparticles, BaFe ₁₂ O ₁₉ , (Bi, La, Tb) (Fe, Mn, DyPr) O ₃ , Ba ₃ CO ₂ Fe ₂₄ O ₄₁ , Y ₃ Fe ₅ O, among others, may be used ₁₂ , NiZnFe ₂ O ₄ , Cu _0.2 Mg _0.4 Zn _0.4 Fe ₂ O ₄ , Fe ₃ O ₄ (Cu, Ni, Zn) Fe ₂ O ₄ , TbMn ₂ O ₅ , PbNi _1/33 Nb _2/3 TiO ₃ -CuNiZn, BaTiO ₃ -NiZnFe ₂ O ₄ , BaTiO ₃ , SrTiO ₃ , (Ba, Sr) TiO ₃ , Pb (Zr, Ti) O ₃ , SrBi ₂ Ta ₂ O ₉ , PbNi _1/3 Nb _2/3 TiO ₃ -PbTio ₃ , PbMg _1/3 Nb _2/3 TiO ₃ -PbTiO ₃ , lanthanum-modified and lanthanum strontium-modified Pb (Zr, Ti) O ₃ , Pb (Zr _x Ti _1-x ) O ₃ , wherein x is greater than or equal to 1, PbHfO ₃ , PbZrO ₃ , Pb (Zr, Ti) O ₃ , PbLa (Zr, Sn, Ti) O ₃ , PbNb (ZrSnTi) O ₃ , Pb _1-x La _x (Zr _y Ti _1-y ) _{(1-x) / 4} O ₃ , wherein x is greater than or equal to 1 and y is greater than or equal to 1, NaNbO ₃ , (K, Na) (Nb, Ta) O ₃ , KNbO ₃ , BaZrO ₃ , Na _0.25 K _0.25 Bi _0.5 TiO ₃ , Ag (Ta, Nb) O ₃ or Na _0.5 B _6.5 TiO ₃ -K _0.5 Bi _0.5 TiO ₃ -BaTiO ₃ can be used.

Furthermore, z. B. superparamagnetic nanoparticles for the preparation of compact nanocomposite magnets, which is a matrix of at least one hard magnetic material such as SmCo ₃ , SmOo ₇ , Sm ₂ Co ₇ , Nd ₂ Fe ₁₄ B and FePt and dispersed therein nanoparticles of a soft magnetic material such alpha-Fe, iron-cobalt alloys containing Fe ₄ N, FeB and iron-nickel alloys can be used (see US patent application US 2012/0153212 A1).

In addition, magnetite nanoparticles may be part of complex quantum dots wherein the magnetite nanoparticles having a silica shell having at least one thiol group are linked through the thiol group to at least one CdSe / ZnS quantum dot. These magnetizable nanocomposites can be used for the destruction of cancer cells by RF magnetohyperthermia (see US patent application US 2011/0237862 A1).

From the international patent application WO 00/03403 are magnetic nanocomposites of the general formula (RE _{1 -yLay} ) Fe _100-vwxz Co _w M _z B _x known, wherein RE is a rare earth metal from the group cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, Erbium, thulium, ytterbium and lutetium and M is a metal from the group titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten and v = 5-15, w ≥ 5, x = 9-30, y = 0.05-0.5 and z = 0.1-5.

In the American patent US 8,591,759 B2 describe magnetizable polymeric nanocomposites containing nanoparticles based on iron, nickel, cobalt, gold, chromium, manganese and / or copper, in particular Fe ₃ O ₄ , CuFe ₂ O ₄ , NiFe ₂ O ₄ and MnFe ₂ O ₄ , include. The nanoparticles carry a shell of polystyrene or a derivative thereof, which is bonded to a biodegradable polymer. The polystyrene or the derivative thereof may contain a phosphonium ion-containing ionic liquid. The biodegradable polymer may be cellulose. The magnetizable nanocomposites can be used as biodegradable magnetic tapes on drywall, for magnetic shielding or for the separation of heavy metals from industrial waste.

From the Korean patent application KR 20130088602 A For example, magnetizable polymeric nanocomposites containing magnetizable nanoparticles coated with polyamide or polyacrylonitrile are known.

From the US patent application US 2013/0183249 A1 are stimulus sensitive, Magnetizable polymeric nanocomposites comprising magnetizable nanoparticles, an amphiphilic compound having a hydrophilic region having pyrene structures, a hydrophilic region, and a pharmaceutically active ingredient. The amphiphilic compound surrounds the pharmaceutically active ingredient, which in turn envelops the magnetizable nanoparticles and is bound to the hydrophobic region. The stimulable, magnetizable, polymeric nanocomposites are said to be stable in aqueous solution, have excellent magnetic properties, in which contact with a specific stimulant rapidly releases the pharmaceutically active ingredient and has target specific activity. They can therefore be used as a contrast agent or as a drug.

From the American patents US 8,459,976 B2 and US 8,173,060 B2 Nanocomposites with directional conductivity are known. The nanocomposites comprise a support of a ceramic or a polymer containing nanorods. The nanorods are aligned by means of an electric or magnetic field in an electrophoretic gel. Then the gel is removed and the nanorods are supported in the desired position. Thereafter, the supported, aligned nanorods are surrounded with the support.

The US patent application US 2013/0334455 A1 discloses magnetizable, polymeric nanocomposites which comprise superparamagnetic nanoparticles, such as magnetite or CoFe ₂ O ₄ , which are distributed in a dielectric polymer. Uniform distribution is achieved using surface-active compounds such as oleylamine or oleic acid.

From the American patent US 8,426,489 B1 For example, a dental filling material is known that contains magnetizable nanoparticles and carbon nanotubes in a curable starting material for a biocompatible polymer.

From the American patent US 8,389,626 B2 Polycarbonate nanocomposites, including polycarbonate-polysiloxane nanocomposites are known, the metallic nanoparticles based on cobalt, rhodium, iridium, copper, silver, gold, platinum, palladium, iron, nickel, manganese, samarium, neodymium, praseodymium, gadolinium , Titanium, Zirconium, Silicon, Indium, Scandium, Yttrium, Lanthanum, Cerium, Promethium, Europium, Erbium, Holmium, Erbium, Thulium, Ytterbium and Lutetium. The polycarbonate nanocomposites are prepared by mixing together a diol, an activated carbonate, a starting material for the metal, and a solvent, and polymerizing the resulting mixture to form the metal nanoparticles in situ. The polycarbonate nanocomposites can still polymeric and low molecular weight stabilizers, fillers such as metal oxide nanoparticles and additives such as heat stabilizers, antioxidants, UV stabilizers, plasticizers, catalysts, optical effects, catalysts, quenchers, mold release agents, flame retardants, blowing agents, impact modifiers, processing aids and other polymers and Contain oligomers. The polycarbonate nanocomposites can be formed into articles using standard and known processing techniques. Molded articles can be made by compression molding, blow molding, injection molding and other molding methods. They are also suitable as plastic containers, food packaging, glazes or glazes, plates, protective materials against projectiles such as protective vests, IR-reflective coatings, optical data carriers, biological labels, electroluminescent displays and for antibacterial and antiviral applications as well as biodetection applications. Cobalt nanoparticles containing polycarbonate nanocomposites can be used for magnetic recording, medical sensors, packaging materials for electronics, IR-reflective coatings, scratch-resistant coatings, coatings for tools and for barrier layers.

From the American patent US 8,075,794 B2 are also known magnetizable, polymeric nanocomposites. They are made by mixing expanded crystalline graphite with magnetizable nanoparticles such as iron nanoparticles and dispersing the platelet-shaped magnetizable graphite nanoparticles in a polymer. The platelet-shaped, magnetizable graphite nanoparticles can be aligned by an applied, external magnetic field. Thermosets such as epoxy resins, polyurethane resins, polyurea resins, polysiloxanes and alkyd resins or thermoplastics such as polyamides, proteins, polyesters, polyethers, polyurethanes, polysiloxanes, phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, cellulose, polysulfides , Polyacetals, polyethylene oxides, polycaprolactams, polylactones, polylactides, polyimides, polypropylenes, nylons, polycarbonates and polyolefins.

From the international patent application WO 2010/115043 A1 are known magnetizable, polymeric nanocomposites containing magnetizable nanoparticles based on iron, hematite, magnetite or CoFe ₂ O ₄ . The magnetizable nanoparticles are surrounded by a polymeric shell obtained by photopolymerization of monomers such as methylmethacrylate, benzylmethacrylate, dimethylaminomethacrylate, hexylmethacrylate, isobutylmethacrylate, vinylmethacrylate, 3- (trimethoxysilyl) propyl methacrylate or trimethylolpropane triacrylate, which are located on the surface of the magnetizable nanoparticles produced. The magnetizable nanoparticles surrounded by the polymeric shell are dispersed in at least one of the aforementioned monomers, after which the monomer or monomer mixture is polymerized with electromagnetic radiation or thermally polymerized.

From the American patents US 6,995,234 B2 and US 7,786,188 B2 Dendrimers based on anionic polyamidoamines (PAMAM) or polypropylamines (POPAM) containing immobilized silver, cadmium, iron, nickel and manganese sulfide nanoparticles are known.

From the Korean patent application KR 20070097596 are magnetizable, polymeric nanocomposites based on lactide-glycolide copolymers known. The nanocomposites may contain pharmaceutically active ingredients.

From the international patent application WO 2009 / 002569A2 For example, magnetizable polymeric nanocomposites are known that form ferromagnetic thin film structures with giant magnetoresistance. The ferromagnetic thin-film structures are prepared by polymerizing monomers on the activated surface of magnetizable nanoparticles (Surface-Initiated Polymerization, SIP) and drying the resulting magnetizable, polymeric nanocomposites and then charring them.

From the Slovenian patent application SL 22539 A are magnetizable, polymeric nanocomposites based on a PMMA matrix known. The nanocomposites can be produced by precipitation polymerization.

From the American patent US 8,277,581 B2 For example, platelet-shaped soft magnetic nickel-iron-zinc nanoparticles having a thickness of ≦ 1 μm and an aspect ratio ≥ 2 are known. They can be used like Permalloy ^® (Nickel-Iron-Micro- and / or Nanoparticles) or Sendust for the production of composites and coatings for magnetic shielding.

In the article Composite Electromagnetic Wave Absorber Made of Permalloy or Sendust and Effect of Particle Size on Absorption Characteristics by K. Sakai et al. in PIERS (Progress in Electromagnetics Research Symposium) Online, Vol. 4, No. 8, pp. 846-853, 2008 , describes the production of molded parts (tori and cuboid) from polystyrene-permalloy and polystyrene Sendust microcomposites. For this purpose, the microparticles are suspended in a solution of polystyrene in acetone. Subsequently, the acetone is distilled off. The resulting mixture is melted and shaped under pressure into pellets, which are then used to make the moldings.

From the American patent US 6,923,923 B2 discloses a method for producing micrometer-scale, electrically conductive metal structures, in which an ink containing metal nanoparticles such as silver-palladium nanoparticles, applied to a substrate, after which forms the applied ink with a PDMS stamp into structures. The resulting structures are heated to a temperature near the melting point of the metallic nanoparticles, thereby forming the electrically conductive metal structures.

Magnetic polymer nanocomposites containing superparamagnetic metal oxide nanoparticles such as maghemite in a matrix based on a functional group-containing polymer such as poly (4-vinylpyridine) are known from the US patent application US 2012/0141602 A1.

The use of the known, magnetizable, polymeric nanocomposites for the production of complex, magnetizable moldings by means of additive, ie accumulation of, constructing factories, in particular digitally controlled, additive, constructive manufacturers, in particular 3D printers, will not be described.

US 2004/022561 A1 discloses a process for producing three-dimensional models by the digitally controlled fused deposition modeling (FDM) of thermoplastic polyphenylene sulfone-polycarbonate polymer blends. The polymer blends may contain clay nanocomposites.

The use of magnetic and / or magnetizable polymeric nanocomposites in this process is not described.

Object of the present invention

The present invention was based on the object to find a new use for magnetic and / or magnetizable, polymeric micro and / or nanocomposites.

In particular, the invention was based on the object to find new methods for the production of complex, magnetic and / or magnetizable moldings from magnetic and / or magnetizable, polymeric micro and / or nanocomposites, which allow complex, three-dimensional moldings quickly, in easy way to produce precise and excellent reproducible.

Not least, the invention was the object of the invention to provide complex, magnetic and / or magnetizable moldings based on magnetic and / or magnetizable, polymeric micro and / or nanocomposites, which are advantageous in engineering, chemistry, physics, the Biology and medicine can be applied in a variety of ways.

Inventive solution

Accordingly, the novel use of magnetic and / or magnetizable, polymeric micro- and / or nanocomposites for the production of complex, magnetic and / or magnetizable moldings has been found by means of additive, in particular digitally controlled, additive manufacturers, hereinafter referred to as "inventive use" ,

• (1) die Ausgangsprodukte mindestens eines magnetischen und/oder magnetisierbaren, polymeren Mikro- und/oder Nanocomposits separat oder als Gemisch mindestens zweier Ausgangsprodukte als formlose Fluide mindestens einem additiven Fabrikator zudosiert werden und
• (2) mithilfe des mindestens einen additiven Fabrikators unter gleichzeitiger Verfestigung der Ausgangsprodukte zu dem mindestens einen magnetischen und/oder magnetisierbaren, polymeren Mikro- und/oder Nanocomposit schichtweise angehäuft werden, bis mindestens ein vorgegebenes Formteil aufgebaut ist;

oder alternativ

• (3) die Ausgangsprodukte mindestens eines magnetischen und/oder magnetisierbaren, polymeren Mikro- und/oder Nanocomposits miteinander vermischt werden, so dass mindestens ein festes, formneutrales, magnetisches und/oder magnetisierbares, polymeres Mikro- und/oder Nanocomposit resultiert,
• (4) das mindestens eine feste, formneutrale, magnetische und/oder magnetisierbare, polymere Mikro- und/oder Nanocomposit in einen formlosen, fluiden Zustand überführt und in diesem Zustand mindestens einem additiven Fabrikator zudosiert wird und
• (5) mithilfe des mindestens einen additiven Fabrikators unter gleichzeitiger Verfestigung des fluiden, magnetischen und/oder magnetisierbaren, polymeren Mikro- und/oder Nanocomposits schichtweise angehäuft wird, bis mindestens ein vorgegebenes Formteil aufgebaut ist;

oder alternativ

• (6) die Ausgangsprodukte mindestens eines magnetischen und/oder magnetisierbaren, polymeren Mikro- und/oder Nanocomposits miteinander vermischt werden, so dass mindestens ein festes, formneutrales, magnetisches und/oder magnetisierbares, polymeres Mikro- und/oder Nanocomposit resultiert,
• (7) das mindestens eine feste, formneutrale, magnetische und/oder magnetisierbare, polymere Mikro- und/oder Nanocomposit in Pulverform einem additiven Fabrikator zudosiert wird und
• (8) mithilfe des mindestens einen additiven Fabrikators schichtweise angehäuft wird, bis mindestens ein vorgegebenes Formteil resultiert.

In addition, the new process for the production of complex, magnetic and / or magnetizable moldings has been found using additive, especially digitally controlled, additive, factories in which

• (1) the starting products of at least one magnetic and / or magnetizable, polymeric micro- and / or nanocomposite are added separately or as a mixture of at least two starting materials as formless fluids to at least one additive factory and
• (2) by means of the at least one additive Fabrikators while simultaneously solidifying the starting materials to the at least one magnetic and / or magnetizable, polymeric micro- and / or nanocomposite are accumulated in layers until at least one predetermined molding is constructed;

or alternatively

• (3) the starting products of at least one magnetic and / or magnetizable, polymeric micro- and / or nanocomposite are mixed together so that at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite results,
• (4) the at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite is converted into a formless, fluid state and is added in this state to at least one additive factory and
• (5) is accumulated in layers by means of the at least one additive factory while solidifying the fluid, magnetic and / or magnetizable, polymeric micro and / or nanocomposite until at least one predetermined molding is built up;

or alternatively

• (6) the starting products of at least one magnetic and / or magnetizable, polymeric micro- and / or nanocomposite are mixed together so that at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite results,
• (7) the at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite in powder form is metered into an additive factory and
• (8) is accumulated in layers by means of the at least one additive factory until at least one predetermined shaped part results.

In the following, the new process for the production of complex, magnetic and / or magnetizable molded parts by means of additive factories is referred to as "inventive process".

Not least, the new complex, magnetic and / or magnetizable molded parts were found, which are composed of at least one solid, magnetic and / or magnetizable, polymeric micro and / or nanocomposite and which are referred to below as "molded parts according to the invention".

Advantages of the invention

In view of the prior art, it was surprising and unforeseeable for the skilled person that the object underlying the present invention could be achieved by means of the use according to the invention, the method according to the invention and the moldings according to the invention.

In particular, it was surprising that due to the use according to the invention by means of the method according to the invention even highly complex, magnetic and / or magnetizable moldings could be produced very quickly, in a simple manner, in large series very well reproducible and precisely in the finest details.

Even the finest details of the molded parts according to the invention, in particular of the highly complex molded parts according to the invention, correspond exactly to the given dimensions and geometries, in particular the digital ones. Therefore, the moldings according to the invention in large series and the particular application in the art, chemistry, physics, biology and medicine could be made particularly well adapted.

Detailed description of the invention

The present invention is directed to the use of magnetic and / or magnetizable, polymeric micro- and / or nanocomposites for producing complex, magnetic and / or magnetizable moldings using additive manufacturers, in particular digitally controlled, additive manufacturers.

In the context of the present invention, "complex shaped parts" are to be understood to mean shaped parts which, due to their three-dimensional geometry, stand out from shapeless objects such as gases, liquids or powders and from shape-neutral objects such as ribbons or plates.

The magnetic and / or magnetizable, polymeric micro- and / or nanocomposites to be used according to the invention contain at least one type of magnetic and / or magnetizable micro- and / or nanoparticles. These may be paramagnetic, in particular superparamagnetic, ferromagnetic, antiferromagnetic or ferrimagnetic micro- and / or nanoparticles. In particular, superparamagnetic nanoparticles are used.

In the context of the present invention, microparticles are understood to be particles which have a particle size in the range from 1 to <1000 μm.

In the context of the present invention, nanoparticles are understood as meaning particles which have a particle size in the range of <1000 nm.

• – Eisen, Kobalt, Nickel sowie Legierungen des Eisens mit mindestens einem Metall, das aus der Gruppe, bestehend aus Ruthenium, Osmium, Kobalt, Rhodium, Iridium, Nickel, Palladium, Platin, Kupfer, Silber, Gold, Zink, Cadmium Scandium, Yttrium, Lanthan, Cer, Praseodym, Neodym, Samarium, Europium, Gadolinium Terbiumoxid, Dysprosium, Holmium, Erbium, Thulium, Ytterbium, Lutetium, Titan, Zirkonium, Hafnium, Vanadium, Niob, Tantal, Chrom, Molybän, Wolfram, Mangan, Rhenium, Aluminium, Gallium, Indium, Thallium, Germanium, Zinn, Blei, Antimon und Wismut, ausgewählt ist; Beispiele geeigneter Metallegierungen sind weichmagnetische Metallegierungen wie Permalloy^® auf der Basis von Nickel und Eisen, Nickel-Eisen-Zink-Legierungen oder Sendust auf der Basis von Aluminium, Silizium und Eisen; RE_1-yLay)Fe_100-v-w-zCo_wM_zB_x, worin RE für ein Seltenerdmetall aus der Gruppe Cer, Praseodym, Neodym, Samarium, Europium, Gadolinium, Terbiumoxid, Terbiumoxid, Dysprosium, Holmium, Erbium, Thulium, Ytterbium und Lutetium und M für ein Metall aus der Gruppe Titan, Zirkonium, Hafnium, Vanadium, Niob, Tantal, Chrom, Molybän und Wolfram stehen und v = 5–15, w ≥ 5, x = 9–30, y = 0,05–0,5 und z = 0,1–5; die vorstehend genannten Metalle und Metallegierungen können noch mindestens ein weiteres Metall und/oder Nichtmetall, das oder die aus der Gruppe, bestehend aus Lithium, Natrium, Kalium, Rubidium, Cäsium, Beryllium, Magnesium, Calcium, Strontium, Barium, Bor, Kohlenstoff, Silizium, Stickstoff, Phosphor, Arsen, Sauerstoff, Schwefel, Selen, Tellur, Fluor, Chlor, Brom und Jod, ausgewählt ist oder sind, in nichtstöchiometrischen Mengen enthalten. Ein besonders gut geeignetes Material dieser Art ist NdFeB; sowie
• – Metalloxide, Granate, Spinelle und Ferrite; Beispiele besonders gut geeigneter Materialien dieser Art sind Fe₃O₄, CoFe₂O₄, NiFe₂O₄, MnFe₂O₄, SrFe₂O₄, BaFe₂O₄, CuFe₂O₄, Y₃Fe₅O₁₂, CrO₂, MnO, Mn₃O₄, Mn₂O, FeO, Fe₂O₃, NiO, Cr₂O₃, CoO, Co₃O₄, BaFe₁₂O₁₉, (Bi,La,Tb)(Fe,Mn,DyPr)O₃, Ba₃Co₂Fe₂₄O₄₁, Y₃Fe₅O₁₂, NiZnFe₂O₄, Cu_0,2Mg_0,4Zn_0,4Fe₂O₄, Fe₃O₄(Cu,Ni,Zn)Fe₂O₄, TbMn₂O₅, PbNi_1/33Nb_2/3TiO₃-CuNiZn, BaTiO₃-NiZnFe₂O₄, dotiertes BaTiO₃, dotiertes SrTiO₃, (Ba,Sr)TiO₃, Pb(Zr,Ti)O₃, SrBi₂Ta₂O₉, PbNi_1/3Nb_2/3TiO₃-PbTio₃, PbMg_1/3Nb_2/3TiO₃-PbTiO₃, Lanthan-modifiziertes und Lanthan-Strontium-modifiziertes Pb(Zr,Ti)O₃, Pb(Zr_xTi_1-x)O₃, worin x größer als oder gleich 1, PbHfO₃, PbZrO₃, Pb(Zr,Ti)O₃, PbLa(Zr,Sn,Ti)O₃, PbNb(ZrSnTi)O₃, Pb_1-xLa_x(Zr_yTi_1-y)_(1-x)/4O₃, worin x größer als oder gleich 1 und y größer als oder gleich 1, LuMnO₃, NaNbO₃, (K,Na)(Nb,Ta)O₃, KNbO₃, BaZrO₃, Na_0,25K_0,25Bi_0,5TiO₃, Ag(Ta,Nb)O₃ oder Na_0,5Bi_0,5TiO₃-K_0,5Bi_0,5TiO₃-BaTiO₃.

Examples of suitable materials for producing such magnetic and / or magnetizable micro and / or nanoparticles are

• - Iron, cobalt, nickel and alloys of iron with at least one metal selected from the group consisting of ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium scandium, yttrium , Lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium terbium oxide, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, Aluminum, gallium, indium, thallium, germanium, tin, lead, antimony and bismuth; Examples of suitable metal alloys are soft magnetic metal alloys such as Permalloy ^® based on nickel and iron, nickel-iron-zinc alloy or Sendust based on aluminum, silicon and iron; RE _1-yLay ) Fe _100-vwz Co _w M _z B _x , where RE is a rare earth metal from the group cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium oxide, terbium oxide, dysprosium, holmium, erbium, thulium, ytterbium and Lutetium and M represent a metal from the group titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten and v = 5-15, w ≥ 5, x = 9-30, y = 0.05- 0.5 and z = 0.1-5; the aforementioned metals and metal alloys may further comprise at least one other metal and / or nonmetal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, carbon, Silicon, nitrogen, phosphorus, arsenic, oxygen, sulfur, selenium, tellurium, fluorine, chlorine, bromine and iodine, is or are included in non-stoichiometric amounts. A particularly suitable material of this type is NdFeB; such as
• - metal oxides, garnets, spinels and ferrites; Examples of particularly suitable materials of this type are Fe ₃ O ₄ , CoFe ₂ O ₄ , NiFe ₂ O ₄ , MnFe ₂ O ₄ , SrFe ₂ O ₄ , BaFe ₂ O ₄ , CuFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CrO ₂ , MnO, Mn ₃ O ₄ , Mn ₂ O, FeO, Fe ₂ O ₃ , NiO, Cr ₂ O ₃ , CoO, Co ₃ O ₄ , BaFe ₁₂ O ₁₉ , (Bi, La, Tb) (Fe, Mn, DyPr) O ₃ , Ba ₃ Co ₂ Fe ₂₄ O ₄₁ , Y ₃ Fe ₅ O ₁₂ , NiZnFe ₂ O ₄ , Cu _0.2 Mg _0.4 Zn _0.4 Fe ₂ O ₄ , Fe ₃ O ₄ ( Cu, Ni, Zn) Fe ₂ O ₄ , TbMn ₂ O ₅ , PbNi _1/33 Nb _2/3 TiO ₃ -CuNiZn, BaTiO ₃ -NiZnFe ₂ O ₄ , doped BaTiO ₃ , doped SrTiO ₃ , (Ba, Sr) TiO ₃ , Pb (Zr, Ti) O ₃ , SrBi ₂ Ta ₂ O ₉ , PbNi _1/3 Nb _2/3 TiO ₃ -PbTio ₃ , PbMg _1/3 Nb _2/3 TiO ₃ -PbTiO ₃ , lanthanum-modified and lanthanum-strontium-modified Pb (Zr, Ti) O _3, Pb (Zr _x Ti _1-x) O _3, where x is greater than or equal to 1, PbHfO _3, PbZrO _3, Pb (Zr, Ti) O _3, PbLa (Zr, Sn, Ti) O ₃ , PbNb (ZrSnTi) O ₃ , Pb _1-x La _x (Zr _y Ti _1-y ) _{(1-x) / 4} O ₃ , wherein x is greater than or equal to 1 and y is greater than or equal to 1, LuMnO ₃ , NaNbO ₃ , (K, Na) (Nb, Ta) O ₃ , KNbO ₃ , BaZrO ₃ , Na _0.25 K _0.25 Bi _0.5 TiO ₃ , Ag (Ta, Nb) O ₃ or Na _0.5 Bi _0.5 TiO ₃ -K _0.5 Bi _0.5 TiO ₃ -BaTiO ₃ .

The magnetic and / or magnetizable micro- and / or nanoparticles can have a wide variety of morphologies and geometric shapes, so that they are outstanding for the other constituents of the solid, magnetic and / or magnetizable, polymeric micro- and / or nanocomposites to be used according to the invention and their respective Purpose can be adjusted.

Thus, they can be compact and have at least one cavity and / or a core-shell structure, wherein the core and the shell can be constructed of different materials. They may also have different geometric shapes such as spheres, ellipsoids, cubes, cuboids, pyramids, cones, cylinders, rhombuses, dodecahedra, truncated dodecahedra, icosahedra, truncated icosahedra, dumbbells, tori, platelets or needles with circular, oval, elliptical, square, triangular , quadrangular, pentagonal, hexagonal, heptagonal, octagonal or star-shaped (three-, four-, five- or multi-zigzag) outline. If necessary, existing edges and corners can be rounded. It is also possible for two or more micro- and / or nanoparticles of different morphology and / or geometric form to be assembled together. For example, spherical micro- and / or nanoparticles may have pointed outgrowths in the form of cones. Or two or three cylindrical micro- and / or nanoparticles can assemble to form a T-shaped or Y-shaped particle. Furthermore, their surface can have depressions, so that the micro- and / or nanoparticles have a strawberry, raspberry or blackberry-shaped morphology. Last but not least, the dumbbells, tori, needles or plates can be bent in at least one direction of the room.

The diameter of the magnetic and / or magnetizable micro- and / or nanoparticles can vary very widely and can therefore be perfectly adapted to the other constituents of the solid, magnetic and / or magnetizable polymeric nanocomposites to be used according to the invention and their respective intended use.

In the context of the present invention, the diameter of magnetic and / or magnetizable microparticles and / or nanoparticles which have no spherical shape is equal to the longest path taken by the respective microparticles and / or nanoparticles.

The diameter is preferably 1 to <1000 nm, preferably 1.5 to 750 nm, particularly preferably 2 to 500 nm, very particularly preferably 2.5 to 100 nm and in particular 3 to 50 nm.

Likewise, the average particle size of the magnetic and / or magnetizable nanoparticles measured using transmission electron microscopy (TEM), scanning electron microscopy (SEM), scanning transmission electron microscopy (RTEM), atomic force microscopy (AFM) or scanning tunneling microscopy (TRM) can vary very widely and can be perfectly adapted to the other components of the invention used, solid, magnetic and / or magnetizable, polymeric nanocomposites and their respective application.

The mean particle size is preferably 1 to <1000 nm, preferably 1.5 to 750 nm, particularly preferably 2 to 500 nm, very particularly preferably 2.5 to 100 nm and in particular 3 to 50 nm.

The diameter of the magnetic and / or magnetizable microparticles can likewise vary very widely and can therefore be adapted excellently to the other constituents of the solid, magnetic and / or magnetizable polymeric microcomposites to be used according to the invention and their respective intended use.

In the context of the present invention, the diameter of magnetic and / or magnetizable microparticles which have no spherical shape is equal to the longest path taken by the respective microparticles.

The diameter is preferably from 1 to <1000 μm, preferably from 1.5 to 750 μm, more preferably from 2 to 500 μm, very particularly preferably from 2.5 to 100 μm and in particular from 3 to 50 μm.

Similarly, transmission electron microscopy (TEM), scanning electron microscopy (SEM), scanning transmission electron microscopy (RTEM), atomic force microscopy (AFM), scanning tunneling microscopy (TRM) or laser light scattering may vary very widely and excellently vary the other components of magnetic particle size to be used according to the invention, solid, magnetic and / or magnetizable polymers with microparticles and their respective intended use.

The mean particle size is preferably 1 to <1000 nm, preferably 1.5 to 750 nm, particularly preferably 2 to 500 nm, very particularly preferably 2.5 to 100 nm and in particular 3 to 50 nm.

The magnetic and / or magnetizable micro- and / or nanoparticles can have a monomodal, bimodal or polymodal particle size distribution. Preferably, the particle size distribution is monomodal.

The monomodal particle size distribution can be comparatively wide. This means that the proportion of particularly fine and particularly coarse micro- and / or nanoparticles in a sample is relatively high. The monomodal particle size distribution is preferably comparatively narrow with a small proportion of particularly fine and particularly coarse microparticles and / or nanoparticles in a sample, since this ensures the most uniform possible property profile of the sample.

The magnetic and / or magnetizable micro- and / or nanoparticles can be attached to diamagnetic, non-magnetisable micro- and / or nanoparticles, but preferably nanoparticles. The magnetic and / or magnetizable micro- and / or nanoparticles and the diamagnetic micro- and / or nanoparticles can by Covalent and / or ionic bonds, hydrogen bonds, electrostatic attraction and / or van der Waalskräfte be bound to each other.

• – Oxide aus der Gruppe, bestehend aus Scandiumoxid, Yttriumoxid, Titandioxid, Zirconiumdioxid, Yttrium-stabilisiertes Zirconiumdioxid, Hafniumdioxid, Vanadiumoxid, Nioboxid, Tantaloxid, Manganoxid, Eisenoxid, Chromoxid, Molybdänoxid, Wolframoxid, Zinkoxid, Oxide der Lanthanide, bevorzugt Lanthanoxid und Ceroxid, insbesondere Ceroxid, Oxide der Actinide, Magnesiumoxid, Calciumoxid, Strontiumoxid, Bariumoxid, Aluminiumoxid, znikdosiertes Aluminiumoxid, Galliumoxid, Indiumoxid, Siliziumdioxid, Germaniumoxid, Zinnoxid, Antimonoxid, Bismutoxid, Zeolithe, Spinelle, Mischoxide aus mindestens zwei der genannten Oxide wie Antimon-Zinn-Oxid, Iridium-Zinn-Oxid, Bariumtitanat, Bleititanat oder Bleizirkonattitanat;
• – Phosphate wie Hydroxylapatit oder Calciumsphosphat;
• – Polyoxymetallate (POM);
• – Sulfide, Selenide und Telluride aus der Gruppe, bestehend aus Arsen-, Antimon-, Wismut-, Cadmium-, Zink-, Eisen-, Silber-, Blei- und Kupfersulfid, Cadmiumselenid, Zinnselenid, Zinkselenid, Cadmiumtellurid und Bleitellurid;
• – Nitride wie Bornitrid, Siliziumnitrid, Aluminiumnitrid, Galliumnitrid und Titannitrid;
• – Phosphide, Arsenide und Antimonide aus der Gruppe, bestehend aus Aluminiumphosphid Galliumphosphid, Indiumphosphid, Aluminiumarsenid, Galliumarsenid, Indiumarsenid, Aluminiumantimonid, Galliumantimonid, Indiumantimonid;
• – Zintl-Phasen wie Na₄Sn₉, Na₄Pb₉, Na₂Pb₁₀, Na₃[Cu@Sn₉], Na₇[Ge₉CuGe₉] oder Na₁₂[Sn₂@Cu₁₂Sn²⁰];
• – Kohlenstoff wie Fullerene, Graphen, Graphit, Diamant und funktionalisierte und nicht funktionalisierte Kohlenstoff-Nanoröhrchen;
• – metallorganische Gerüstverbindungen (MOFs);
• – Carbide wie Borcarbid, Siliziumcarbid, Wolframcarbid, Titancarbid oder Cadmiumcarbid;
• – Boride wie Zirkonborid; sowie
• – Silicide wie Molybdänsilicid.

Examples of suitable materials from which the diamagnetic micro- and / or nanoparticles can be constructed are in particular

• Oxides from the group consisting of scandium oxide, yttrium oxide, titanium dioxide, zirconium dioxide, yttrium-stabilized zirconium dioxide, hafnium dioxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, iron oxide, chromium oxide, molybdenum oxide, tungsten oxide, zinc oxide, oxides of lanthanides, preferably lanthanum oxide and cerium oxide, in particular cerium oxide, oxides of actinides, magnesium oxide, calcium oxide, strontium oxide, barium oxide, aluminum oxide, zinc-doped aluminum oxide, gallium oxide, indium oxide, silicon dioxide, germanium oxide, tin oxide, antimony oxide, bismuth oxide, zeolites, spinels, mixed oxides of at least two of the abovementioned oxides such as antimony-tin oxide. Oxide, iridium-tin oxide, barium titanate, lead titanate or lead zirconate titanate;
• - phosphates such as hydroxyapatite or calcium phosphate;
• - polyoxymetalates (POM);
• - sulfides, selenides and tellurides from the group consisting of arsenic, antimony, bismuth, cadmium, zinc, iron, silver, lead and copper sulfide, cadmium selenide, tin selenide, zinc selenide, cadmium telluride and lead telluride;
• Nitrides such as boron nitride, silicon nitride, aluminum nitride, gallium nitride and titanium nitride;
• Phosphides, arsenides and antimonides selected from the group consisting of aluminum phosphide gallium phosphide, indium phosphide, aluminum arsenide, gallium arsenide, indium arsenide, aluminum antimonide, gallium antimonide, indium antimonide;
• Zintl phases such as Na ₄ Sn ₉ , Na ₄ Pb ₉ , Na ₂ Pb ₁₀ , Na ₃ [Cu @ Sn ₉ ], Na ₇ [Ge ₉ CuGe ₉ ] or Na ₁₂ [Sn ₂ @ Cu ₁₂ Sn ²⁰ ];
• - Carbon such as fullerenes, graphene, graphite, diamond and functionalized and non-functionalized carbon nanotubes;
• - organometallic frameworks (MOFs);
• Carbides, such as boron carbide, silicon carbide, tungsten carbide, titanium carbide or cadmium carbide;
• - borides such as zirconium boride; such as
• Silicides such as molybdenum silicide.

The magnetic and / or magnetizable micro- and / or nanoparticles can be present "naked". That is, their surface is not surrounded by a shell and / or is not functionalized.

The magnetic and / or magnetizable micro- and / or nanoparticles are preferably surrounded by a shell and / or carry at least one functional group. The material of the shells may carry the functional groups or else the functional groups may be present directly on the surface of the magnetizable nanoparticles.

The material of the shell and / or the functional groups are selected so that the magnetic and / or magnetizable micro- and / or nanoparticles are particularly rapidly and homogeneously in the polymeric matrix of the solid, magnetic and / or magnetizable, polymeric micro- and / or or modulate or mask the physical and / or chemical properties of the magnetic and / or magnetizable micro- and / or nanoparticles in a certain desired manner.

The sheaths and / or the functional groups can be bound to the surface of the magnetic and / or magnetizable micro- and / or nanoparticles via covalent and / or ionic bonds and / or electrostatic and / or van der Waals forces.

The bond between the surface of the magnetic and / or magnetizable micro- and / or nanoparticles and the shell and / or the functional groups may be permanent or reversible, d. H. be solvable again.

The shells may be constructed of organic, inorganic and organometallic, polymeric, oligomeric and low molecular weight materials or combinations of at least two of these materials.

The following are examples of suitable functional groups and materials for the shells of the magnetic and / or magnetizable micro- and / or nanoparticles. The person skilled in the art can select the functional groups and materials which are particularly suitable for the particular case on the basis of the property profiles known to him.

Common and known functional groups:

• Fluorine, chlorine, bromine and iodine atoms; Hydroxyl, thiol, ether, thioether, amino, peroxide, aldehyde, acetal, carboxyl, peroxycarboxyl, ester, amide, hydrazide and urethane groups; Imide, hydrazone and hydroxime, amide and hydroxamic acid groups; Groups derived from formamidine, formamidoxime, formamidrazone, formhydrazidine, formhydrazidoxime, formamidrazone, formoxamidine, formhydroxamoxime and formoxamidrazone; Nitrile, isocyanate, thiocyanate, isothiocyanate, isonitrile, lactide, lactone, lactam, oxime, nitroso, nitro, azo, azoxy, hydrazine, hydrazone, azine, carbodiimide , Azide, azane, sulfen, sulfenamide, sulfonamide, Thioaldehyde, thioketone, thioacetal, thiocarboxylic acid, sulfonium, sulfur halide, sulfoxide, sulfone, sulfimine, sulfoximine, sultone, sultam, sulfone, silane, siloxane, phosphine, phosphine oxide, Phosphonium, phosphoric, phosphorous, phosphonic, phosphatic, phosphinate and phosphonate groups.

Usual and Known Functional Additives for Plastics:

Examples of suitable additives are thermally and / or active-radiation-curable reactive diluents, low-boiling organic solvents and high-boiling organic solvents ("long solvents"), water, UV absorbers, light stabilizers, free-radical scavengers, thermolabile radical initiators, photoinitiators and co-initiators, crosslinking agents, as used in one-component systems, catalysts for thermal crosslinking, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting and dispersing agents and surfactants, adhesion promoters, leveling agents, film-forming auxiliaries, sag control agents (SCA), rheology control additives (thickeners), Flame retardants, siccatives, drying agents, anti-skinning agents, corrosion inhibitors, waxes, matting agents, reinforcing fibers or precursors of organically modified ceramic materials.

Examples of suitable thermally curable reactive diluents are positionally isomeric diethyloctanediols or hydroxyl-containing hyperbranched compounds or dendrimers, as described, for example, in German patent applications DE 198 05 421 A1 . DE 198 09 643 A1 or DE 198 40 405 A1 to be discribed.

Examples of suitable actinic radiation curable reactive diluents are those in Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 described under the keyword »reactive diluents«. In the context of the present invention, actinic radiation is understood as meaning corpuscular radiation such as electron radiation, alpha radiation, beta radiation and proton radiation, as well as electromagnetic radiation such as infrared, visible light, UV radiation, X-radiation and gamma radiation. In particular, UV radiation is used.

Examples of suitable low-boiling organic solvents and high-boiling organic solvents ("long solvents") are ketones such as methyl ethyl ketone, methyl isoamyl ketone or methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate, ethyl ethoxypropionate, methoxypropyl acetate or butyl glycol acetate ethers such as dibutyl ether or ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol , Butylene glycol or Dibutylenglykoldimethyl-, diethyl or -dibutylether, N-methylpyrrolidone or xylenes or mixtures of aromatic and / or aliphatic hydrocarbons such as Solventnaphtha ^® , gasoline 135/180, Dipentene or Solvesso ^® .

Examples of suitable thermolabile radical initiators are organic peroxides, organic azo compounds or C-C-cleaving initiators such as dialkyl peroxides, peroxycarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers.

Examples of suitable catalysts for the crosslinking are dibutyltin dilaurate, dibutyltin dioleate, lithium decanoate, zinc octoate or bismuth salts, such as bismuth lactate or dimethylolpropionate.

Examples of suitable photoinitiators and coinitiators are in Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446 , described.

Examples of suitable additional crosslinking agents, as used in so-called one-component systems, are amino resins, as described, for example, in US Pat Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 29 , "Amino resins," the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff. , the book "Paints, Coatings and Solvents", secondly revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff. , the patents US 4,710,542 A1 or EP-B-0 245 700 A1 as well as in the article of Singh and coworkers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry" in Advanced Organic Coatings Science and Technology Series, 1991, Vol. 13, pp. 193 to 207 , carboxyl-containing compounds or resins, as described for example in the patent DE 196 52 813 A1 described epoxy-containing compounds or resins, as described for example in the patents EP 0 299 420 A1 . DE 22 14 650 B1 . DE 27 49 576 B1 . US 4,091,048 A or US 3,781,379 A be blocked polyisocyanates, as described for example in the patents US 4,444,954 A . DE 196 17 086 A1 . DE 196 31 269 A1 . EP 0 004 571 A1 or EP 0 582 051 A1 and / or tris (alkoxycarbonylamino) triazines, as described in the patents US 4,939,213 A . US 5,084,541 A . US 5,288,865 A or EP 0 604 922 A1 to be discribed.

Examples of suitable deaerators are diazadicycloundecane or benzoin.

Examples of suitable emulsifiers, wetting and dispersing agents or surfactants are the customary and known anionic, cationic, nonionic and zwitterionic wetting agents, as described, for example, in US Pat Römpp Online, April 2014, Georg Thieme Verlag, »Wetting Agents« will be described in detail.

An example of a suitable coupling agent is tricyclodecanedimethanol.

Examples of suitable film-forming auxiliaries are cellulose derivatives such as cellulose acetobutyrate (CAB).

Examples of suitable transparent fillers are those based on silica, alumina or zirconia; In addition, it is still on the Römpp Lexikon Lacke and printing inks, Georg Thieme publishing house, Stuttgart, 1998, pages 250 to 252 , referenced.

Examples of suitable Sag control agents are ureas, modified ureas and / or silicas, as described for example in the literature EP 0 192 304 A1 . DE 23 59 923 A1 . DE 18 05 693 A1 . WO 94/22968 . DE 27 51 761 C1 . WO 97/12945 or "paint + varnish", 11/1992, pages 829 ff., Are described.

Examples of suitable rheology-controlling additives are those from the patents WO 94/22968 . EP 0 276 501 A1 . EP 0 249 201 A1 or WO 97/12945 known; crosslinked polymeric microparticles, as described for example in the EP 0 008 127 A1 are disclosed; inorganic phyllosilicates such as aluminum-magnesium silicates, sodium magnesium and sodium magnesium fluorine lithium phyllosilicates of the montmorillonite type; Silicas such as aerosils; or synthetic polymers having ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates.

An example of a suitable matting agent is magnesium stearate.

Examples of suitable reinforcing fibers are basalt fibers, boron fibers, glass fibers, ceramic fibers, silica fibers, metallic reinforcing fibers such as steel fibers, aramid fibers, Kevlar fibers, polyester fibers, nylon fibers, Teflon fibers, polyethylene fibers, polypropylene fibers, PMMA fibers, lignin fibers and cellulose fibers.

Examples of suitable precursors for organically modified ceramic materials are hydrolyzable organometallic compounds, in particular of silicon and aluminum.

Further examples of the additives listed above, as well as examples of suitable UV absorbers, radical scavengers, leveling agents, flame retardants, siccatives, drying agents, skin preventatives, corrosion inhibitors and waxes (B) are described in the textbook "Paint Additives" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998 , described in detail.

Further examples of additives are dyes, colored pigments, white pigments, fluorescent pigments and phosphorescent pigments (phosphors).

Carbohydrates:

• Glyceraldehyde, erythrose, threose, ribose, arabinose, xylose, lyxose, fructose, allose, altrose, glucose, mannose, idose, galactose talose, rhamnose, amino sugars such as neuraminic acid, muramic acid, glucosamine, mannosamine, aldonic acids, ketoaldonic acids, aldaric acids, pyranoses, sucrose , Lactose, raffinose, panose and homopolysaccharides and heteropolysaccharides and proteoglycans, wherein the polysaccharide portion outweighs the protein portion, such as starch, dextran, cyclodextrin, arabinogalactan, celluloses, modified celluloses, lignocelluloses, chitin, chitosan and glycosaminoglycans.

Monoalcohols:

• Methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, amyl alcohol isoamyl alcohol, cyclopentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and their stereoisomers.

polyols:

• Glycerol, trimethylolpropane, pentaerythritol, alditols, cyclitols, dimers and oligomers of glycerin, trimethylolpropane, pentaerythritol, alditols and cyclitols; preferably tetritols, pentitols, hexitols, heptitols and octitols; preferably arabinitol, ribitol, xylitol, erythritol, threitol, galactitol, mannitol, glucitol, allitol, altritol, iditol, maltitol, isomaltitol, lactitol, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, Deca-, undeca- and dodecaglycerol, -trimethylolpropane, -erythritol, -threitol and -pentaerythritol, 1,2,3,4-tetrahydroxycyclohexanes, 1,2,3,4,5-pentahydroxycyclohexanes, myo-, scyllo-, muco- , chiro-, neo-, allo-, epi- and cis-inositol.

polyhydroxycarboxylic:

• Glycerol, citric, tartaric, threonine, erythron, xylon, ascorbic, glucone, galacturon, iduron, mannuron, glucuron, guluron, glycuron, glucar, uluson, diketogulone, and lactobionic.

Polyhydroxyphenols and -benzenecarboxylic acids:

• Pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-trishydroxybenzene, phloroglucinol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dihydroxybenzoic and 2,4,6-, 2,4,5-, 2,3,4- and 3,4,5-trihydroxybenzoic acid (bile acid).

Amine:

• Ammonia, ammonium, mono-, di- and trialkyl-, -aryl-, cycloalkyl-, -alkylaryl-, -alkylcycloakyl-, -cycloalkylaryl- and -alkylcycloalkylarylamines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, tert. Butylamine, benzylamine, cyclohexylamine, dodecylamine, cocoamine, tallowamine, adamantylamine, aniline, ethylenediamine, propylenediamine, butylenediamine, piperidine, piperazine, pyrazolidine, pyrazine, quinuclidine and morpholine.

thiols:

• Mercaptopropionic acid, dimercaptosuccinic acid (DMSA), dithiothreitol (DTT) and octadecanethiol.

Click Chemistry:

• Compounds for click reactions such as the copper-catalyzed cycloaddition of azides and alkynes, Diels-Alder reactions, reactions of z. B. folic acid with alkyne groups and dipolar cycloadditions with z. For example, poly (tert-butyl acrylate).

fatty acids:

• Lauric, myristic, oleic, palmitic, linoleic, stearic, arachinic and behenic acid.

Polymers and oligomers with functional groups:

• Poly (trimethylammoniumethylacrlylat), polyacrylamide, poly (D, L-lactide-co-ethylene glycol), Pluronic ^®, Tetronic ^®, Polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), poly (alkyl cyanoacrylate), poly (lactic acid), poly (epsilon- caprolactone), polyethylene glycol (PEG), poly (oxyethylene-co-propene) bisphosphonate, poly (acrylic acid), poly (methacrylic acid), hyaluronic acid, alginic acid, pectic acid, poly (ethyleneimine), poly (vinylpyridine), polyisobutene, poly (styrenesulfonic acid) , Poly (glycidyl methacrylate), poly (methacryloyloxyethyltrimethylammonium chloride) (MATAC), poly (L-lysine) and poly (3- (trimethoxysilyl) propylmethacrylate-r-PEG-methylethermethacrylate), proteins such as treptavidin, trypsin, albumin, immunoglobulin, oligo-, and Polynucleotides such as DNA and RNA, peptides such as Arginylglycylasparginsäure (RGD), AGKGTPSLETTP peptide (A54), HSYHSHSLLRMF peptide (C10) and glutathione, enzymes such as glucose oxidase, dendrimers such as polypropyleneimine Tetrahexacontaamin dendrimer generation 5 (PPI G5), poly (amidoamine ) (PA MAM) and guanidine dendrimers, phosphonic acid and dithiopyridine functionalized polystyrenes, functionalized polyethylene glycols (PEG: degree of polymerization 4-10, especially 5) such as PEG (5) -nitroDOPA, -nitrodopamine, -mimosine, -hydroxydopamine, -hydroxypyridine, -hydroxypyrone and carboxyl.

Drug:

• Cytostatics such as cyclophosphamide, trofosfamide, ifosfamide, chlorambucil, melphalan, carmustine, lomustine, semustine, busulfan, cisplatin, carboplatin, methotrexate,% fluorouracil: cytarbine, mercapturin, thioguanine, vinblastine, vincristine, etoposide, dactinomycin, daunarubicin, doxorubicin, bleomycin, Mitomycin, mitoxantrone, diethylstilbestrol, drostanolone, testolactone, tamoxifen, aminogluthedimide, buserelin, goserelin, leuprorelin, triptorelin, hydroxyurea and procarbacin.

complexing agents:

• Complexones such as nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA), phosphonic acids such as [(2-aminoethyl) hydroxymethylene] - and [(5-aminopentyl) hyroxymethylene] diphosphonic acid and crown ethers.

Metal Complexes:

Usual and known coordination, sandwich and chelate complexes of the abovementioned metals and their cations with organic and inorganic anions, in particular fluoride, chloride, bromide, iodide, ammonia, amines, phosphines, thiols, sulfides, cyanide, cyanate, isocyanate, thiocyanate, Isothiocyanate, boranes, carbon monoxide, aromatics or heteroaromatics.

In particular, wetting agents or surfactants are used as additives, as this prevents aggregation and / or agglomeration of the micro- and / or nanoparticles and a homogeneous distribution is achieved in the polymer matrix.

The above-listed functional groups and materials for the shell of the magnetic and / or magnetizable micro- and / or nanoparticles are only examples and not finally enumerated. The enumeration is therefore intended to illustrate the variety of possibilities, and the expert can readily specify other possibilities due to his general expertise.

In the solid, magnetic and / or magnetizable, polymeric micro- and / or nanocomposites to be used according to the invention, the micro- and / or nanoparticles described above are preferably distributed homogeneously in a polymeric matrix.

The polymeric matrix may be constructed of conventional and known thermoplastic or thermoset polymers.

Suitable thermoplastic polymers are customary and known linear and / or branched and / or block-like, comb-like and / or random polyaddition resins, polycondensation resins and / or (co) polymers of ethylenically unsaturated monomers.

Examples of suitable (co) polymers are (meth) acrylate (co) polymers and / or polystyrene, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinylamides, polyacrylonitriles, polyethylenes, polypropylenes, polybutylenes, polyisoprenes and / or copolymers thereof.

Examples of suitable polyaddition resins or polycondensation resins are polyesters, alkyds, polylactones, polycarbonates, polyethers, proteins, epoxy resin-amine adducts, polyurethanes, alkyd resins polysiloxanes, phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, cellulose, polysulfides , Polyacetals, polyethylene oxides, polycaprolactams, polylactones, polylactides, polyimides, and / or polyureas.

As is known, the thermosets are prepared from polyfunctional, low molecular weight and / or oligomeric compounds by (co) polymerization initiated thermally and / or with actinic radiation. Suitable functional low molecular weight and / or oligomeric compounds are the reactive diluents, catalysts and initiators listed above.

Again, the list of thermoplastics and thermosets listed above is not exhaustive, but in particular to illustrate the variety of possibilities. Other suitable materials for the polymeric matrix can be readily selected by those skilled in the art, based on their general knowledge.

Once the polymeric matrix has been formed from thermoplastics, the magnetizable nanoparticles are incorporated into the thermoplastics by conventional and well-known methods of producing polymer blends.

If the polymeric matrix is composed of thermosetting plastics, the magnetizable nanoparticles are incorporated into the starting materials of the thermosets by means of customary and known mixing methods, after which the resulting mixtures are polymerized and crosslinked as a result.

For mixing the materials, it is possible to use the customary and known mixing units, such as high-speed stirrers, Ultraturrax, inline dissolvers, homogenizing nozzles, static mixers, microfluidizers, extruders or kneaders.

Preferably, mixing units are used, which are constructed of non-magnetic materials. As a result, the unwanted accumulation of magnetic and / or magnetizable micro- and / or nanoparticles is prevented on the components of the mixing units and ensures a homogeneous mixing.

The content of the magnetic and / or magnetizable, polymeric micro- and / or nanocomposites to be used according to the invention on magnetic and / or magnetizable micro- and / or nanoparticles can vary extremely widely and can therefore be adapted to the requirements of the individual case in a particularly advantageous manner. The content is preferably from 0.1 to 99.9% by weight, preferably from 0.5 to 90% by weight, in each case based on the total amount of a magnetic and / or magnetizable, polymeric micro- and / or nanocomposite to be used according to the invention. %, more preferably 1 to 80 wt .-% and in particular 2 to 70 wt .-%.

According to the invention, the magnetic and / or magnetizable, polymeric micro- and / or nanocomposites for producing complex, magnetic and / or magnetizable moldings by means of additive, d. H. accumulating, building factory, especially digitally controlled, additive manufacturers, manufactured.

Preferably, the additive Fabrikatoren are also constructed of non-magnetic materials in order to avoid the above-described disturbing effects from the outset.

Preferably, 3D printers are used as digitally controlled additive manufacturers, the geometry of the complex, magnetic and / or magnetizable moldings being predetermined by CAD / CAM programs.

Preferably, 3D printers designed for selective laser melting, selective electron beam melting, selective laser sintering, stereolithography, digital light processing, polyjet modeling, cold gas spraying or melt layers are used.

The choice of the construction technique depends in particular on the physicochemical properties of the solid, magnetic and / or magnetizable, polymeric micro- and / or nanocomposites or their precursors to be used according to the invention.

Thus, in a first preferred variant of the process according to the invention, the starting materials of at least one magnetic and / or magnetizable, polymeric micro- and / or nanocomposite are added separately or as a mixture of at least two starting materials as formless fluids to at least one additive, in particular digitally controlled, additive, factory using the at least one additive, in particular digitally controlled, additive, factory with simultaneous solidification of the starting products to the at least one magnetic and / or magnetizable, polymeric micro and / or nanocomposite in particular digitally piled in layers accumulated until at least one predetermined, in particular digitally predetermined, Molded part is constructed. This variant of the method according to the invention is particularly suitable for the production of complex, magnetic and / or magnetizable molded parts based on thermosets.

In a second preferred variant, the starting materials of at least one magnetic and / or magnetizable, polymeric micro- and / or nanocomposite are mixed together so that at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite results. Thereafter, the at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite is converted into an informal, fluid state and metered in this state at least one additive, especially digitally controlled, additive, factory and using the at least one additive, in particular digitally controlled, additive, factory with simultaneous solidification of the fluid, magnetic and / or magnetizable, polymeric micro and / or Nanocomposits especially digitally controlled in layers accumulated until at least one predetermined, in particular digitally predetermined, molded part is constructed.

In a third preferred variant of the process according to the invention, the starting materials of at least one magnetic and / or magnetizable, polymeric micro- and / or nanocomposite are mixed together so that at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite results. Subsequently, the at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite in powder form is added to an additive, in particular digitally controlled, additive, factory and digitally using the at least one additive, in particular digitally controlled, additive, factory accumulated controlled until at least a predetermined, in particular digitally predetermined, molded part results.

In the method according to the invention, however, there is also the possibility that a molded part according to the invention is constructed in such a way that it has alternating magnetic and / or magnetizable regions and nonmagnetic and / or nonmagnetizable regions. This can be achieved by interrupting the supply of the magnetic and / or magnetizable, polymeric micro- and / or nanocomposites to be used according to the invention and instead of a layer of a non-magnetic and / or non-magnetizable thermoplastic polymer or the starting materials for one magnetic and / or non-magnetisable thermosets are applied, after which again a layer of the invention to be used, magnetic and / or magnetizable, polymeric micro and / or nanocomposite is applied. This process can be repeated several times.

In the method according to the invention, it is furthermore possible that a molded part according to the invention is constructed in such a way that its core has one type of magnetic and / or magnetizable micro- and / or nanoparticles and its surface at least one other type of magnetic and / or magnetizable micro and / or nanoparticles. In this case, it is of particular advantage that the structure of this layer or layers on the surface can be specifically influenced by magnetic fields. In this way, for example, a molded part according to the invention can be constructed whose core contains a type of naked magnetic and / or magnetizable micro- and / or nanoparticles, whereas the layer has modified, magnetic and / or magnetizable micro- and / or nanoparticles on the surface.

In the context of the present invention, "informal" means that the material in question has no fixed shape but adapts to the shapes of a container. Formless materials are therefore liquid or gaseous.

In the context of the present invention, "shape-neutral" means that the material in question is band-shaped or wire-shaped.

In particular, if magnetic micro- and / or nanoparticles are used for the production and processing of micro- and / or nanocomposites, the structure of the molded parts according to the invention is carried out in at least one, in particular one, inhomogeneous or homogeneous, in particular homogeneous, magnetic field. This ensures that the moldings according to the invention obtain the desired orientation of the magnetization. This is particularly important if in the manufacture and processing of the micro- and / or nanocomposites so high temperatures are used that the magnetic microparticles are demagnetized.

The required magnetic fields can be provided by means of customary and known permanent magnets and / or electromagnets. For example, homogeneous magnetic fields can be produced using Helmholtz coils.

With the aid of the method according to the invention, even highly complex moldings according to the invention can be produced quickly and easily in a very reproducible manner in large series, with the moldings according to the invention precisely matching the digitally predefined prototypes even in the finest details.

The molded parts according to the invention can therefore with particular advantage in all fields of science and technology, especially in the fields of information processing, Fluidiksysteme, construction, spatial planning, traffic planning, infrastructure planning, engineering and construction, architecture, environmental technology and sustainability, water management, energy technology, clean room technology, lab-on-chip technology, drive technology, automotive technology, technology relating to rail vehicles and watercraft, in particular marine engineering, aerospace engineering, medical technology, manufacturing technology, production engineering, 3D printing, chemistry, materials science, physics, biology, biochemistry, biotechnology, pharmacy, toxicology, food technology and nutritional supplement technology, especially with regard to nanotechnology and especially with respect to Wed. micro and / or nanomaterials, micro and / or nanoelectromechanical systems, micro and nano sensors, micro and nanoactuators, micro and / or nanopositioning systems, micro and / or nanophotonics, micro and / or nano instruments, micro and / or or nanomachines, micro and / or nanorobots, micro and / or nanofluidics and lab-on-chips, and methods for their production and their use. In particular, their magnetic properties and / or their magnetizability can be exploited in many and advantageous ways.

In particular, due to the use according to the invention and the method according to the invention, even complex, flexible, magnetic and / or magnetizable molded parts according to the invention that pulsate in electromagnetic alternating fields and are colored due to plasmon resonances are available.

Furthermore, the complex moldings according to the invention can replace the materials commonly used in electromagnetic and mechanical devices, which in individual cases leads to significant weight savings and thus also to energy savings. By way of example, the following uses for the complex molded parts according to the invention are listed:

In chemical engineering:

• - printed catalyst moldings such as catalyst networks for reactors;
• - printed absorber and adsorber moldings;
• - Printed packing for distillation columns.

In electromechanics:

• - Actuating magnets for reed contacts, z. B. spoke magnet for bicycle tacho sensor;
• - damping (eddy current brake) z. B. at roller coasters and in the electricity meter;
• - Transducer with permanent magnetic adjustment (historically detached from triac control);
• - Electric motors, z. B. self-excited DC motors, rotor small synchronous motors;
• - field generation in moving coil meters;
• - field magnets of loudspeakers and dynamic microphones and head and earphones, permanent magnet synchronous motor, rotor of electronically commutated motors;
• - runners of smaller generators, z. B. bicycle dynamo;
• - Linear swivel motor for reading head arm of a computer hard disk; or
• - Permanent magnet generator, z. B. in modern wind turbines.

In electronics:

• - field magnets for circulators in the microwave technology;
• - Field magnets of magnetrons, z. B. 2 magnetic rings in the microwave oven;
• - correction magnets on picture tubes;
• - Field magnet in coil-like components, which exploit the resulting asymmetric saturation of a ferrite core (transducing effect); or
• - Particle accelerator technology: Deflection and focusing magnets in ring accelerators as well as in undulators and wigglers for generating synchrotron radiation.

In mechanics:

• - Holding magnets, magnetic feet;
• - magnetic bearings;
• - rotating magnetic waves;
• - magnetic valves;
• - magnetic closures on furniture doors, women's handbags, pseudo-piercings;
• - Through walls acting through clutches, z. B. magnetic stirrer for stirring liquids in laboratory vessels;
• - Click systems for molded parts instead of mechanical connections
• - magnetic tapes;
• - magical strips;
• - magnetic implants;
• - magnetic holders; or
• - Magnetic clasps for jewelry.

In magnet technology:

• - In coils with ferromagnetic cores:
• - actuation solenoids of relays and contactors;
• - Door opener magnet, magnets in buzzers and door gongs;
• - Magnetic couplings (in vacuum pumps or air conditioning compressors in motor vehicles) and brakes (with return spring in lawnmowers and on cranes);
• - pull magnets, push magnets;
• - Solenoids (magnetic cranes in steelworks);
• - Magnetic rail brake on rail vehicles;
• - Magnets to set switches of rail vehicles;
• - AC magnets in diaphragm pumps or dosing pumps (air pump for aquariums, additives or fuels) and vibratory conveyors;
• - Excitation field generation in electric motors (as in the vacuum cleaner) and generators (automotive alternator, power plant);
• - separators for substance separation "ferromagnetic" / "non-ferromagnetic" (magnetic separator for sorting waste);
• Deflection magnets in particle accelerator particle accelerators;
• - Ablenkspulen- and Fokussiermagnete (electron microscope, electron beam welding, picture tubes);
• - nitrogen-cooled pulse magnets for high-field investigations; The best example is provided by the European record holder for high magnetic fields, the Institut Hochfeld-Magnetlabor Dresden;
• - Electromagnetically operated injection injectors in diesel engines with the injection method common rail; or
• - Magnetic filter and electro-magnetic filter for the removal of finely divided ferromagnetic solids (finely divided iron oxides) from the circulation condensates of power plants and the circulating waters of district heating networks.
• - In coils without ferromagnetic core material:
• - field generation for traveling wave tubes;
• - field generation for induction furnaces;
• - Actuation coils for reed contacts;
• - Superconducting magnets in nuclear magnetic resonance tomographs and for research, such as nuclear fusion reactors based on fusion by means of magnetic inclusion;
• - uncooled magnetic coils for high field investigations;
• - Forming, welding, joining and cutting of metals; or
• - Bittermagnet (named after its developer at the National Magnet Laboratory of the MIT Francis Bitter), consisting of a stack of about 250 conductor and insulator plates, by water cooling fields up to 20 Tesla in continuous operation, up to 100 Tesla in pulse mode achievable.

In other uses:

• - geeks;
• - toys;
• - joke articles;
• - furniture like folding chairs;
• - Robotica;
• - Magenta gloves or shoes;
• - dishes and glasses;
• - clothing and textile; or
• - Sextoys.

The invention will now be described by way of example with reference to FIGS 1 to 4 explained in more detail.

Both 1 to 4 they are schematic, non-limiting representations intended to illustrate their principles of construction and operation. The in the 1 to 4 therefore, does not necessarily correspond to the proportions used in practice.

It shows in simplified, not to scale representation:

1 the top view of a cross section through the inventive magnetic test arrangement 1 ;

2 the top view of a cross section through the magnet 2 along the section line CD;

3 the top view of a longitudinal section through the inventive magnetic test arrangement 1 along the section line EF;

4 the top view of a cross section through the erfindungsgeäße magnetic experimental arrangement 1 along the section line GH.

In the 1 to 4 the reference signs have the following meaning:

LIST OF REFERENCE NUMBERS

1

magnetic test arrangement

2

cylindrical permanent magnet made of a hard magnetic, polymeric microcomposite

3.1, 3.2, 3.3

Soft magnetic shields made of a soft magnetic, polymeric microcomposite

4.1, 4.2, 4.3, 4.4

disk-shaped, displaceable, soft-magnetic shields made of a soft-magnetic, polymeric microcomposite

5.1

cross-shaped shaped part with a circular cross section of the beams and arms with a superparamagnetic, polymeric nanocomposite layer 7.1

5.2, 5.3, 5.4

Moldings made of superparamagnetic, polymeric nanocomposites

5.2.1, 5.3.1, 5.4.1

Circular cross-section fittings with superparamagnetic polymeric nanocomposite layers

6

diamagnetic carrier

7.1, 7.2, 7.3, 7.4

diamagnetic, polymeric nanocomposite layer

A

open position of sliding magnetic shields 4.1 - 4.4

B

closed position of the displaceable magnetic shields 4.1 - 4.4

CD

Cutting line through the permanent magnet 2 and its magnetic shield 3.1

E-F

Cutting line through the magnetic test arrangement 1

G-H

Cutting line through the magnetic test arrangement 1

N

North pole of the permanent magnet 2

S

South pole of the permanent magnet 2

R

Guide groove for the disk-shaped, displaceable, soft-magnetic shields made of a soft-magnetic polymeric microcomposite 4.1 . 4.2 . 4.3 . 4.4

V

Well in the carrier 6 for receiving the components of the magnetic test arrangement 1

example 1

Production of a Molecular Model of Fullerene with Superparamagnetic Properties from a Superparamagnetic Polymeric Nanocomposite Granules Using an Additive Factory

Iron oxide nanoparticles of a mean particle size d ₅₀ of 10 nm measured by scanning transmission electron microscopy (STEM) were determined according to the textbook of Ludovico Cademartiri and Geoffre A. Ozin, Concepts of Nanochemistry, WILEYVCH, 2012, at page 180 and prepared in hexane using a long alkyl group anionic surfactant (sodium dodecyl sulfate, weight ratio iron oxide nanoparticles: surfactant = 100: 1). The dispersion was continuously metered into a twin-shaft vented extruder composed of non-magnetizable components and mixed with a polystyrene melt containing 0.5% by weight of a silicone release agent based on the total amount of the melt, to give a polymeric nanocomposite Melt with a content of homogeneously distributed iron oxide nanoparticles of 10 wt .-%, based on the total amount of the polymer nanocomposite melt resulted. The hexane was continuously distilled from the melt during the extrusion, and the polymeric nanocomposite melt was continuously discharged as a strand, cooled and granulated. Scanning transmission micrographs on sections showed the homogeneous distribution of the iron oxide nanoparticles in the polystyrene matrix. The polymeric nanocomposite granules were stored until further use.

For 3D printing, the polymeric nanocomposite granules, as described, for example, in US Pat. Appl. US 2004/0222561 A1, were metered as a melt into the printhead of a digitally controlled 3D printer constructed from non-magnetizable components and thus as a fullerene molecular model Inner diameter of 10 cm on a planar pad of polyethersulfone (Ultrason ^® from BASF SE), which, based on the total amount of the carrier, 0.5 wt .-% of a silicone release agent, layered. The finished molecular model could easily be detached from the planar surface and corresponded fully to the digital template. The molecular model was aesthetically pleasing and had no grooves, cracks, or injection molding remnants.

Due to its superparamagnetic properties, it could be moved and / or suspended using magnetic fields. It was perfect for science education.

Example 2

Production of hard magnetic, polymeric nanocomposite moldings using an additive factory

A powdery mixture of 50 parts by weight of commercial hematite nanoparticles having an average particle size of 92 nm (IoLiTec, Heilbronn), 2 parts by weight of a nonionic surfactant (triblock copolymer: polyethylene glycol block polypropylene glycol block polyethylene glycol having a number average molecular weight Mn of 2900 daltons) and 48 parts by weight of polyoxymethylene (POM, number average molecular weight Mn: 60,000 daltons) were intimately mixed on a fluid mixer and homogenized on a twin-screw extruder as a melt, discharged and granulated. Scanning transmission micrographs on sections demonstrated the homogeneous distribution of the iron oxide nanoparticles in the polyoxymethylene matrix. The resulting polymeric nanocomposite granules were stored under nitrogen until further use.

For 3D printing, the polymeric nanocomposite granules, as described, for example, in US Patent Application US 2004/0222561 A1, were metered as a melt into the print head of a digitally controlled 3D printer constructed from non-magnetizable materials and thus in the homogeneous magnetic field of a Helmholtz coil centrosymmetric, gear-shaped shaped parts of a diameter (tooth outer edge to opposite tooth outer edge) of 10 cm and a uniform thickness of 2 cm on a planar diamagnetic pad constructed according to Example 1. The moldings each had 20 teeth and a centrally located 1 cm wide vertical bore. The solidification and cooling of the applied polymeric nanocomposite granulate melt took place within the homogeneous magnetic field of a Helmholtz coil, so that the resulting gear-shaped shaped parts had magnetic fields perpendicular to their horizontal surfaces lying opposite each other. The resulting polymeric nanocomposite gears were very easily detached from the substrate and used as permanent magnets.

Example 3

Production of the magnetic test arrangement 1 with the help of additive manufacturers

For the preparation of the magnetic test arrangement 1 First of all, the corresponding magnetic and / or magnetizable components were manufactured using additive manufacturers.

Production Example 3.1

The production of a soft magnetic, polymeric microcomposite granules

A powdery mixture of 50 parts by weight of commercially available Permalloy ^® microparticles of a mean particle size of 10 microns and an aspect ratio of> 3, 2 parts by weight of a nonionic surfactant (triblock copolymer: polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol having a number average molecular weight Mn of 2900 Dalton ) and 48 parts by weight of polyoxymethylene (POM, number average molecular weight Mn: 60,000 daltons) were intimately mixed on a fluid mixer and homogenized on a twin-screw extruder as a melt, discharged and granulated. Scanning transmission microscope pictures of sections demonstrated the homogeneous distribution of the permalloy ^® microparticles in the Polyoxymethylenmatrix. The resulting nanocomposite granules were stored under nitrogen until further use.

Production Example 3.2

Production of a Magnetically Shielded Permanent Magnet 2 . 3.1 according to FIGS. 1 to 4 made of a hard-magnetic, polymeric microcomposite granulate

The soft-magnetic, polymeric microcomposite granules of the preparation example 3.1 was added as a melt to the first printhead of a digitally controlled 3D printer constructed from non-magnetizable components and thus in the homogeneous magnetic field of a Helmholtz coil initially a circular disc of 7 cm diameter and 1 cm thickness on a planar, diamagnetic pad according to example 1 built.

Subsequently, the hard magnetic polymer nanocomposite granules of Example 2 was added as a melt to the second printhead of the digitally controlled 3D printer constructed of non-magnetizable components and thus in the homogeneous magnetic field of the Helmholtz coil the cylindrical permanent magnet 2 of a diameter of 5 cm and a length of 10 cm built on the previously produced circular disc.

Simultaneously with the structure of the cylindrical permanent magnet 2 was the soft magnetic, polymeric microcomposite granules of the preparation example 3.1 as melt further dosed to the second print head of the 3D printer and thus at the same time the tubular portion of the magnetic shield 3.1 an outer diameter of 7 cm, an inner diameter of 5 cm and a length of 10 cm on the first generated circular disc constructed.

After cooling of the molding in the homogeneous magnetic field of the Helmholtz coil resulted in the permanent magnet 2 with the soft magnetic shield 3.1 , which could be easily detached from the planar, diamagnetic pad. The magnetic field of the permanent magnet 2 was oriented along its longitudinal axis, so that the base and top surface of the Norpol N and the south pole S formed.

Production Example 3.3

Production of soft magnetic shields 4.1 - 4.4 according to FIGS. 4 made of a soft magnetic, polymeric microcomposite granules

The disc-shaped, soft magnetic shields 4.1 . 4.2 . 4.3 and 4.4 were using the first printhead of the above-described 3D printer from the microgranules of the manufacturing example 3.1 built on a planar, diamagnetic pad according to Example 1 in the homogeneous magnetic field of a Helmholtz coil.

The disk-shaped, soft-magnetic shielding 4.1 with a circular outline had a diameter of 7 cm and a thickness of 1 cm.

The disc-shaped, soft magnetic shields 4.2 . 4.3 and 4.4 with square outline had edge lengths of 5 cm.

Production Example 3.4

Preparation of superparamagnetic, polymeric nanocomposite moldings 5.2 . 5.3 and 5.4 according to FIGS. 1 and 3 from a superparamagnetic, polymeric nanocomposite granulate

The superparamagnetic, polymeric nanocomposite granules of Example 1 were melted and added as a melt to the print head of a digitally controlled 3D printer constructed from non-magnetizable components and thus to the differently shaped, superparamagnetic, polymeric nanocomposite moldings 5.2 (Cube with an edge length of 4 cm), 5.3 (Circular cylinder with a diameter of 5 cm and a height of 6 cm) and 5.4 (hexagonal cylinder with an edge length of 2 cm and a height of 5 cm) according to the 1 and 3 formed on a planar, diamagnetic pad according to Example 1. After their construction, the moldings could be easily detached from the pad and stored for further use.

Production Example 3.5

Preparation of Shielded Superparamagnetic Polymer Nanocomposite Connectors 5.2.1 . 5.3.1 and 5.4.1 according to FIGS. 1 and 4

The superparamagnetic, polymeric nanocomposite granules of example 1 were melted and added as a melt to the first print head of a digitally controlled 3D printer constructed from non-magnetizable components.

At the same time, the melt of the soft magnetic polymeric microcomposite granules of the preparation example became 3.1 dosed to the second print head of the 3D printer.

In addition, at the same time, the melt of a diamagnetic, polymeric nanocomposite granules, in each case based on the granules, 55 wt .-% polyoxymethylene (POM, number average molecular weight Mn: 60,000 daltons) and 45 wt .-% Aerosil ^{® added to} the third printhead of the 3D printer.

The shielded, superparamagnetic, polymeric nanocomposite connectors 5.2.1 . 5.3.1 and 5.4.1 were successively built on a planar, diamagnetic pad according to Example 1.

The connection part 5.2.1 The shape of a 5 cm long circular cylinder with a planar, base and top surface of a diameter of 3 cm, which were aligned parallel to each other. The circular cylinder had a 2 cm diameter superparamagnetic polymer nanocomposite core and, over its entire length, the diamagnetic polymeric nanocomposite layer surrounding it concentrically 7.2 a uniform thickness of 0.5 cm. The diamagnetic polymeric nanocomposite layer 7.2 was in turn concentric over its entire length with a soft magnetic, polymeric microcomposite layer 3.2 surrounded by a uniform thickness of 0.5 cm. The base and the top surface remained free. The three layers stuck together perfectly.

The connection part 5.3.1 with the superparamagnetic, polymeric nanocomposite layer, the soft magnetic, polymeric microcomposite layer 3.3 and the diamagnetic polymeric nanocomposite layer 7.3 was constructed in the same way and had substantially the same dimensions as the connecting part 5.2.1 on, except that the top surface was concave, so that they are in the magnetic experimental setup 1 flush with the superparamagnetic polymeric nanocomposite molding 5.3 joined.

The connection part 5.4 .1 with the superparamagnetic polymeric nanocomposite layer, the soft magnetic, polymeric microcomposite layer 3.4 and the diamagnetic polymeric nanocomposite layer 7.4 was also constructed in the same way and had substantially the same dimensions as the connecting parts 5.2.1 and 5.3.1 on, except that the top surface was V-shaped, so that they are in the magnetic experimental setup 1 flush with an edge of the superparamagnetic, polymeric nanocomposite molding 5.4 joined and this included.

Production Example 3.6

Production of the cruciform molding 5.1 with a circular cross-section of the bars and arms with a superparamagnetic, polymeric nanocomposite layer 7.1 according to FIGS. 1, 3 and 4

The superparamagnetic, polymeric nanocomposite granules of example 1 were melted and added as a melt to the first print head of a digitally controlled 3D printer constructed from non-magnetizable components.

At the same time, the melt of the soft magnetic, polymeric microcomposite granules of the preparation example was 3.1 dosed to the second print head of the 3D printer.

In addition, at the same time, the melt of a diamagnetic, polymeric nanocomposite granules, based in each case on the granules, 55 wt .-% polyoxymethylene (POM, number average molecular weight Mn 60,000 daltons) and 45 wt .-% Aerosil ^® the third print head of the 3D printer added.

The cruciform molding 5.1 was on a diamagnetic pad according to Example 1 built up. It had the same layer structure as the connecting parts 5.2.1 . 5.3.1 and 5.4.1 on. The two open ends of the beam were coated and circular and arranged parallel to each other. Likewise, the respective open end of the two arms was coated and circular executed, with the two open ends were arranged parallel to each other.

The beam of the molding 5.1 was 20 cm long. The crossing point with the arms was 10 cm from the ends of the beam. The arms were each 5 cm long.

The cruciform molding 5.1 was easily detached from the base. His three layers clung brilliantly to each other.

Production Example 3.6

Assembly of the magnetic test arrangement 1 1 from the components of the manufacturing examples described above 3.2 - 3.5

For the assembly was a correspondingly sized, diamagnetic carrier 6 provided. In its upper horizontal surface, it had suitably shaped recesses V, in which the components of the manufacturing examples 3.3 - 3.5 in the in the 1 and 3 were placed as shown.

What the soft magnetic shields of the manufacturing example 3.3 they were inserted into matching diamagnetic frames. The diamagnetic frames each had a device for connecting to a respective mechanical actuator. By means of the mechanical actuators, the soft magnetic shields could 4.1 - 4.4 are moved independently of each other in the guide grooves R between the open position A and the closed position B back and forth.

The hard magnetic permanent magnet 2 was outside the carrier 6 opposite one of the two ends of the beam of the cross-shaped superparamagnetic molding 5.1 placed.

Was the soft magnetic shield 4.1 brought into the open position A, was in the cross-shaped superparamagnetic molding 5.1 induces a magnetic field. When the soft magnetic shield was returned to the closed position B, the magnetic field in the cross superparamagnetic molded article broke 5.1 together again. In this way, the molded part could be magnetized and demagnetized without hysteresis.

In the same way, the superparamagnetic molded parts could 5.2 . 5.3 and or 5.4 by opening and closing their associated soft magnetic shields 4.2 . 4.3 and or 4.4 hysteresis free magnetized and demagnetized.

Using the magnetic experimental setup 1 It was therefore possible to investigate the influence of the material composition and the spatial geometry of superparamagnetic moldings on their superparamagnetic behavior.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Claims (12)

Use of magnetic and / or magnetizable, polymeric micro- and / or nanocomposites for the production of complex, magnetic and / or magnetizable molded parts using additive manufacturers. Use according to claim 1, characterized in that the magnetic and / or magnetizable, polymeric micro- and / or nanocomposites at least one type of magnetic and / or magnetizable micro and / or nanoparticles, which are dispersed in a polymeric matrix containing. Use according to claim 2, characterized in that the polymeric matrix is composed of at least one thermoplastic or thermosetting polymers. Use according to one of claims 1 to 3, characterized in that 3D printers are used as additive manufacturers. Use according to claim 4, characterized in that the 3D printers are designed for selective laser melting, selective electron beam melting, selective laser sintering, stereolithography, digital light processing, polyjet modeling, cold gas spraying or melt layers. Process for the production of complex, magnetizable moldings using additive manufacturers, in which (1) the starting products of at least one magnetic and / or magnetizable, polymeric micro- and / or nanocomposite are added separately or as a mixture of at least two starting materials as formless fluids to at least one additive factory and (2) by means of the at least one additive Fabrikators while simultaneously solidifying the starting materials to the at least one magnetic and / or magnetizable, polymeric micro- and / or nanocomposite are accumulated in layers until at least one predetermined molding is constructed; or alternatively (3) the starting products of at least one magnetic and / or magnetizable, polymeric micro- and / or nanocomposite are mixed together so that at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite results, (4) the at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite is converted into a formless, fluid state and is added in this state to at least one additive factory and (5) is accumulated in layers by means of the at least one additive factory while solidifying the fluid, magnetic and / or magnetizable, polymeric micro and / or nanocomposite until at least one predetermined molding is built up; or alternatively (6) the starting products of at least one magnetic and / or magnetizable, polymeric micro- and / or nanocomposite are mixed together so that at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite results, (7) the at least one solid, shape-neutral, magnetic and / or magnetizable, polymeric micro- and / or nanocomposite in powder form is metered into an additive factory and (8) is accumulated in layers by means of the at least one additive factory until at least one predetermined shaped part results. A method according to claim 6, characterized in that the additive manufacturers are 3D printers. A method according to claim 7, characterized in that the 3D printers are designed for selective laser melting, selective electron beam melting, selective laser sintering, stereolithography, digital light processing, polyjet modeling, cold gas spraying or melt layers. Method according to one of claims 6 to 8, characterized in that the starting materials of the solid, magnetic and / or magnetizable, polymeric micro and / or nanocomposites - at least one type of magnetic and / or magnetizable micro and / or nanoparticles and - at least one contain thermoplastic polymer and / or at least one thermally and / or with actinic radiation polymerizable monomer as starting material for at least one thermosetting and / or thermoplastic polymer. A method according to claim 9, characterized in that the starting materials of the solid, magnetic and / or magnetizable, polymeric micro and / or nanocomposites diamagnetic micro and / or nanoparticles, functional groups, additives for plastics, carbohydrates, monoalcohols, polyols, polyhydroxycarboxylic acids, Polyhydroxyphenols and -benzenecarboxylic acids, amines, thiols, compounds for click reactions, fatty acids, polymers and oligomers with functional Groups, drugs, complexing agents and / or metal complexes. Method according to one of claims 6 to 10, characterized in that the structure of the complex, magnetic and / or magnetizable moldings is carried out in at least one inhomogeneous or a homogeneous magnetic field. Complex, magnetic and / or magnetizable moldings, which are composed of at least one solid, magnetic and / or magnetizable, polymeric micro and / or nanocomposite.

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