Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
  • B29C70/021—Combinations of fibrous reinforcement and non-fibrous material
  • B29C70/025—Combinations of fibrous reinforcement and non-fibrous material with particular filler
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
  • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
  • B29C70/62—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres the filler being oriented during moulding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
  • B29K2105/16—Fillers
  • B29K2105/162—Nanoparticles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
  • B29K2105/16—Fillers
  • B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
  • B29K2105/167—Nanotubes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
  • B29K2995/0008—Magnetic or paramagnetic

Definitions

• the present invention relates to methods for making composite materials with non- spherical reinforcing particles embedded in a matrix as well as to composite materials obtained using the method and applications of such composite materials in particular for the reinforcement of fiber-reinforced laminates, adhesion between laminates, medical and dental applications, and structural materials in general for the automobile, aerospace, energy-related and construction industries. In general, it relates to composites with magnetically controlled orientational and spatial distribution of reinforcing particles.
• Composite materials with non-spherical reinforcing particles embedded in a matrix material are of high importance for many different applications, such as lightweight construction, etc.
• the non-spherical reinforcing particles are continuous or discontinuous fibres, rovings, platelets, whiskers, rods, tubes etc.
• One-dimensional particles like fibres, whiskers, rods and tubes have been extensively used to enhance the mechanical strength and stiffness of composites, in particular using polymeric matrices, but the reinforcement provided by each single particle is limited to one specific direction. This limitation has been partly overcome by stacking individual layers of different orientations of one-dimensional reinforcing particles into laminates or by using two- dimensional platelets that enable truly two-dimensional planar reinforcement.
• US 2005/0239948 discloses the alignment of carbon nanotubes using magnetic particles in order to make a composite material.
• Carbon nanotubes are provided with magnetic nanoparticles on their surface by means of attaching the magnetic nanoparticles via van der Waals forces between the carbon nanotubes and the nanoparticles.
• the attachment in this particular system is sufficient and can be effected by bringing the two materials into intimate contact with one another, for example in a fluid medium such as water.
• This reinforcing material is mixed with a polymer precursor material and subsequently the matrix is cross-linked.
• the process according to the invention involves the following steps: (1) possible surface modification of the reinforcing particles (e.g., platelets, rods, fibers, whiskers, ribbons, tubes) to enable a good adhesion between reinforcing particles and polymer matrix in the final composite, (2) adsorption of magnetic and/or superparamagnetic nanoparticles to the surface of reinforcing particles through van der Waals, electrostatic interactions and/or covalent bonds, (3) magnetic alignment of the reinforcing particles within a solution and/or polymer matrix, (4) setting of the matrix while the magnetic field is applied in order to fix the aligned structure, (5) possible further conditioning of the composite material (annealing, e.g.
• magnetic and/or superparamagnetic nano-particles are attached to the non- spherical reinforcing particles (this step may be preceded, accompanied or followed by a step of additional surface modification of the non-spherical reinforcing particles in order to make sure that in the final composite there is sufficient adhesion between the reinforcing particles and the surrounding matrix),
• the resulting reinforcing particles are introduced into a liquid matrix material and/or a liquid matrix-precursor material (or a matrix material which is at least sufficiently fluid to take up the reinforcing particles yet still allowing their orientation in the below sense), and
• the material of the matrix is solidified and/or polymerized and/or cross- linked.
• non-spherical reinforcing particles are preferably essentially non-magnetic.
• matrix material is preferentially essentially non-magnetic.
• the magnetic and/or super paramagnetic nanoparticles can distributed over the surface of the nonspherical reinforcing particles, they can on the other hand also essentially cover the surface of the nonspherical reinforcing particles as a single layer, and they may also essentially cover the surface of the nonspherical reinforcing particles in multilayer structures.
• a magnetic field is applied so as to align or locally concentrate the reinforcing particles in the matrix and this alignment is fixed in the matrix after the third step due to the solidification/polymerization/cross-linking of the matrix.
• This process is carried out with a weight ratio of the magnetic and/or superparamagnetic nano-particles to the non-spherical reinforcing particles lower than 0.25.
• the weight ratio here is defined as (mass of magnetic and/or superparamagnetic nano-particles)/(mass of non-spherical reinforcing particles).
• Figure 10 schematically illustrates a two-dimensional reinforcing particle (upper part) and a one-dimensional reinforcing particle (lower part) and the corresponding designation of the dimensions as used in this description.
• the magnetic and/or superparamagnetic nano-particles are generally to be understood as being spherical or nonspherical particles with average diameters in the range of 1 -200 nm
• it is possible to work with comparably low magnetic and/or superparamagnetic nano-particle loading i.e. with a low weight ratio of the magnetic and/or superparamagnetic nano- particles to the non-spherical reinforcing particles of below 0.25.
• Magnetic orientation allows for essentially unlimited tailoring of the spatial distribution of the reinforcing particles in the matrix and correspondingly allows for essentially unlimited tailoring of the reinforcing properties.
• it is possible to orient the reinforcing particles in the matrix e.g.
• a magnetic field of less than 5000 Gauss, preferably less than 500 Gauss can be applied as opposed to a minimum field necessary in the range of 5000 Gauss in state-of-the-art.
• a magnetic field of less than 5000 Gauss preferably less than 500 Gauss can be applied as opposed to a minimum field necessary in the range of 5000 Gauss in state-of-the-art.
• the non-spherical reinforcing particles have an average length (1) in one dimension of at least 0.5 ⁇ .
• a minimum average length of the longest axis of the reinforcing particle can also be below this value, so for example above 10 nm.
• the non-spherical reinforcing particles are selected from the group of one-dimensional reinforcing particles, so preferably from the group of fibres, rods, tubes or whiskers or combinations thereof with an average diameter (d) in the range of 1 nm-1 mm, preferably in the range of 1 ⁇ -100 ⁇ , with the proviso that the length (1) is at least twice, preferably at least five times as large as the diameter (d).
• the shape of the cross-section of these one-dimensional reinforcing particles can be circular, but also different cross-sectional shapes are possible such as rectangular, square, cocoon, oval shapes etc. It is also possible for some applications to go for aggregates of such particles.
• the non-spherical reinforcing particles are two-dimensional reinforcing particles, preferably selected from the group of platelets, ribbons or combinations thereof with a thickness (t) in the range of 1 nm-10 ⁇ , preferably in the range of 50 nm-1000 nm and preferably with a width (w) in the range of 10 nm - 100 ⁇ , with the proviso that the length (1) is at least twice, preferably at least five times larger than the thickness (t) and with the proviso that the width (w) is larger than the thickness (t), preferably at least twice as large as the thickness (t).
• the cross-sectional area in a direction to the length can be rectangular but it can also be oval or ellipsoid, the above values for the thickness and the width corresponding to the main axes of such shapes.
• the numerical values given correspond to average values.
• a combination of one-dimensional and two- dimensional reinforcing particles is used.
• different types of one- dimensional reinforcing particles can be used in one composite material as well as different types of two-dimensional reinforcing particles in order to tailor the reinforcing particles, but also combinations of one-dimensional and two-dimensional reinforcing particles.
• the weight ratio of the magnetic and/or superparamagnetic nano-particles to the non-spherical reinforcing particles is in the range of 0.00001-0.10, preferably in the range of 0.0001-0.05. In particular with these low magnetic and/or superparamagnetic nano-particle loadings still very high orientational order can be generated.
• a magnetic field in the range of 1-5000 Gauss preferably in the range of 5-2000 Gauss, more preferably in a range below 1000 Gauss, most preferably in the range of 5-500 Gauss is applied, wherein the necessary strength of the magnetic fields for proper alignment depends on factors such as viscosity of the matrix, setting time of the matrix, magnetic properties and size of the nano-particles, size of the reinforcing particles etc.
• Such a magnetic field has to be applied for a timespan sufficient to align the reinforcing particles in the matrix.
• the magnetic and/or superparamagnetic nano-particles are attached to the non-spherical reinforcing particles by van der Waals, electrostatic and/or covalent attachment, preferably the attachment is electrostatic and/or covalent, as this allows a much more firm attachment and a much more efficient alignment with high magnetic fields and/or under more difficult matrix conditions.
• the non-spherical reinforcing particles are bonded and/or attached to the surrounding matrix material, preferably by a subsequent fourth annealing step with heat treatment and/or irradiation treatment and/or pressure treatment.
• These treatments can be made possible and effective by the above-mentioned treatment of the reinforcing particles prior to the embedding in the matrix in order to provide for this adhesion.
• the reinforcing particles are provided with a coating or a surface treatment prior to, during or after step 1 of the above process, this coating or surface modification for example having corresponding functional chemical groups, can be covalently linked to the matrix or linked to the matrix via hydrogen bonds or the like.
• heat treatment temperatures well below the melting temperature are chosen, typically at least 10°C, preferably at least 25°C below the melting temperature.
• the non-spherical reinforcing particles can be platelets, fibres, whiskers, rods, tubes, ribbons, wherein preferably such structures are made of or based on metallic, ceramic, polymeric or composite materials, preferably selected from alumina platelets, gibbsite platelets, clay platelets, talc platelets, mica platelets, glass platelets, silicon carbide platelets, aluminum boride platelets, graphite platelets, aluminum platelets, copper platelets, glass fibres, polymer fibres, carbon fibers, silicon carbide whiskers and silicon nitride whiskers.
• metallic, ceramic, polymeric or composite materials preferably selected from alumina platelets, gibbsite platelets, clay platelets, talc platelets, mica platelets, glass platelets, silicon carbide platelets, aluminum boride platelets, graphite platelets, aluminum platelets, copper platelets, glass fibres, polymer fibres, carbon fibers, silicon carbide whiskers and silicon nitride whiskers.
• the magnetic and/or superparamagnetic nano-particles can be attached to the non-spherical reinforcing particles by electrostatic attachment.
• This is possible according to a preferred embodiment by immersing the magnetic and/or superparamagnetic nano-particles and the non-spherical reinforcing particles in a fluid, preferably in water, under conditions such that the non-spherical reinforcing particles and the magnetic and/or superparamagnetic nano-particles have opposite charge, wherein the charges are strong enough such that the energy of electrostatic attraction is larger than thermal energy when the particles are close to each other, typically tens of nanometers apart.
• the opposite charge is generated by adapting the pH of the solution to a value above the isoelectric point of one element and below the isoelectric point of the other element (an element being the magnetic and/or superparamagnetic particle or the reinforcing particle, respectively).
• the non-spherical reinforcing particles are coated with a material allowing for the generation of charged non-spherical reinforcing particles if immersed in water.
• magnetic and/or superparamagnetic nanoparticles can be coated with a material allowing for the generation of charged magnetic and/or superparamagnetic nanoparticles if immersed in water.
• the non-spherical reinforcing particles can be coated with a material allowing for bonding and/or attachment of the non-spherical reinforcing particles during the third step and/or during a subsequent annealing step.
• the liquid matrix material and/or the liquid matrix-precursor material is a cross-linkable and/or non-cross-linkable polymeric material, a polymer precursor material or a ceramic (precursor) material.
• polyurethanes Preferably it is selected from the group of polyurethanes, polyethylenes, polypropylenes, polyamides, polyesters, epoxies, polyimides, poly(ether ether ketone), poly(tetra fluorethylene), poly(ethylene terephthalate), poly(vinyl alcohol), as well as natural compounds such us chitosan, agarose, gellan gum, gelatine, collagen, natural rubber, starch and alginate .
• matrix materials are metals and ceramics. The addition and alignment of reinforcing particles in steels, metal alloys or ceramics (e.g. tungsten carbide) leads to harder cutting tools for example.
• the magnetic and/or superparamagnetic nano-particles can, as mentioned above, selectively be removed from the matrix. Indeed removal of the magnetic and/or superparamagnetic nano-particles can be desirable for reasons such as colour induced by the magnetic and/or superparamagnetic nano-particles, but also for chemical and/or physical reasons. Unexpectedly removal of the magnetic and/or superparamagnetic nano-particles out of the solidified matrix with the oriented reinforcing particles embedded therein is possible without imparting or even destroying the orientation of the reinforcing particles.
• Removal of the magnetic and/or superparamagnetic nano-particles can for example be effected by treating the composite material with an acidic fluid, wherein preferably the acidic fluid has a pH-value below 3, preferably below 1 , and wherein the treatment takes place at a temperature preferably 10-30°C below the melting point of the matrix, more preferably below 30°C.
• the treatment takes place for a timespan of less than 48 hours, preferably of less than 10 minutes.
• the acidic fluid removal of the magnetic and/or superparamagnetic nanoparticles is an aqueous solution of nitric acid, sulphuric acid or phosphoric acid, preferably with a pH in the range of 0-3.
• the proposed method allows tailoring of the actual reinforcing properties by means of tailoring the distribution of the reinforcing particles in the matrix.
• This can be effected in that prior to and/or during the third step a magnetic field is applied so as to lead to an inhomogeneous distribution of the reinforcing particles.
• This inhomogeneous distribution can be a variable concentration of the reinforcing particles as a function of the location in the matrix. It can also be a variable orientational distribution of the reinforcing particles as a function of the location in the matrix. It can also be a combination of the two, namely a combination of variable concentration and variable orientational distribution in the material.
• the present invention relates to a composite material with non-spherical reinforcing particles embedded in a matrix, obtainable and/or obtained using a method as outlined above.
• the non-spherical reinforcing particles are magnetically aligned in the matrix material of the composite material, wherein preferably there is an inhomogeneous distribution (in the sense of concentration or in the sense of orientation as a function of location in the matrix) of the non-spherical reinforcing materials in the matrix.
• the composite material takes the shape of a coating or a film, and the non-spherical reinforcing particles are on average arranged in the matrix with the long axis essentially perpendicular to the plane of the coating and/or film (or at least at an angle larger than 45° with respect to the plane).
• the composite material is essentially free from magnetic and/or superparamagnetic nano- particles. This is possible by the above-mentioned additional step of subsequent removal of the magnetic and/or superparamagnetic nano-particles from the matrix.
• the present invention relates to the use of a composite material according to the description given above as construction material and/or an adhesive layer and/or a surface coating or surface film and/or as an intermediate layer in a laminate and/or a scratch- resistant lamina and/or a dental restoration and/or an artificial scaffold for tissue regeneration, preferably with an orientational distribution of the non-spherical reinforcing particles e.g. in a plane perpendicular to the plane of the layer, preferably for applications such as automobile construction, aerospatial construction, biomedical implants, dental restorations, strengthened glues and adhesives, cutting tools.
• Typical materials to be used in accordance with the invention are as follows:
• This method for 3D reinforcement of matrices through magnetically controlled spatial and orientational distribution of reinforcing elements is general and can be applied to a variety of reinforcing particles and matrix materials as well as different types of magnetic and/or superparamagnetic nanoparticles.
• the following materials can be used:
• non-spherical reinforcing particles including, but not limited to, the following: alumina platelets, glass fibers, clay particles, carbon fibers, Kevlar fibers, polyethylene fibers, cellulose fibers.
• the main requirement is that the particles exhibit anisotropy in shape in at least one axis.
• they can be rods, platelets, fibers, whiskers, tubes, ribbons, ellipsoids, etc.
• the method applies generally to magnetic and/or superparamagnetic nanoparticles including, but not limited to, the following: iron oxide (such as Fe 3 0 4 , Fe 2 0 3 ), cobalt, nickel, and derived alloys. These magnetic and/or superparamagnetic nanoparticles must be responsive to an applied magnetic field. Also, the magnetic and/or superparamagnetic nanoparticles are generally in the size range of 1-200 nm in diameter,
• the method applies generally to a variety of matrices including, but not limited to, the following: thermoplastic and thermoset polymers, ceramics and metals.
• iron oxide nanoparticles are adsorbed onto aluminum oxide platelets. Subsequently, these platelets are added to a thermoplastic polymer, such as polyurethane.
• a thermoplastic polymer such as polyurethane.
• glass fibers can be pretreated with cobalt nanoparticles and then added to a thermoset polymer, such as a commercial epoxy.
• the surface chemistry of the reinforcing particles is preferably tailored in order to obtain a strong adhesion between reinforcing particles and the polymer matrix and to therefore effectively attain a high level of reinforcement in the final composite. This can be accomplished by coating the reinforcing particles with short molecules, ions and/or polymers that can provide strong adhesion between reinforcing particles and polymer matrix through van der Waals forces, electrostatic forces or even covalent bonds.
• surface modification procedures are a few examples of possible surface modification procedures:
• silane molecules containing an amine functional group can be used to coat the surface of metal oxide reinforcing particles (e.g. A1 2 0 3 , Si0 2 , Ti0 2 , Zr0 2 , etc) and afterwards establish a covalent bond with another functional group of the polymer matrix (e.g. epoxy, isocyanate, carboxylic acid, etc.).
• metal oxide reinforcing particles e.g. A1 2 0 3 , Si0 2 , Ti0 2 , Zr0 2 , etc
• another functional group of the polymer matrix e.g. epoxy, isocyanate, carboxylic acid, etc.
• nitro-dopamine or dopamine can adsorb onto the surface of the reinforcing particles via strong ligand exchange reactions and also provide an amine functional group to establish covalent bonds with functional groups of the polymer matrix (e.g. epoxy, isocyanate, carboxylic acid, etc.).
• functional groups of the polymer matrix e.g. epoxy, isocyanate, carboxylic acid, etc.
• Noncovalent interfacial bonding via small molecules Short-chain molecules adsorbed on the reinforcement surface can be used to mimic intermolecular forces found in the polymer matrix itself (e.g. van der Waals and hydrogen bonding forces), so as to provide a good stress-transfer from the polymer matrix to the reinforcing particles while allowing for extensive plastic deformation of the matrix when the shear strength of the polymer is achieved.
• reinforcing particles modified with small amine- containing molecules like APTES, nitrodopamine or dopamine can be incorporated in amine-based matrices to provide good adhesion between reinforcement and polymer matrix without any chemical reaction between surface and matrix functional groups.
• Grafting preformed polymers (“graft to” approach): using the “grafting to” approach, macromolecules like for example poly(vinyl pyrrolidone) (molecular weight in the range 40.000 - 1.300.000 g/mol) can be electrostatically adsorbed on the surface of the reinforcing particles to afterwards obtain strong interfacial adhesion via physical entanglements between the adsorbed macromolecules and the polymer matrix. High molecular weight molecules can also be covalently attached to reinforcing particles using for example PEGylation reactions.
• macromolecules like for example poly(vinyl pyrrolidone) (molecular weight in the range 40.000 - 1.300.000 g/mol) can be electrostatically adsorbed on the surface of the reinforcing particles to afterwards obtain strong interfacial adhesion via physical entanglements between the adsorbed macromolecules and the polymer matrix.
• High molecular weight molecules can also be covalently attached to reinforcing particles using for example PEGy
• polyethylene glycol with different molecular weights can react with tetrachlorosilane, which can be further covalently adsorbed onto the reinforcing particles through the remaining hydrolyzable groups, providing a polymer chain covalently attached to the surface.
• This polymeric chain also provides physical entanglements with the polymer matrix, contributing to the stress transfer at the interface reinforcement-matrix.
• polymerization from surface-adsorbed small molecules (“graft from” approach): polymer chains can be covalently attached on the particle surface using the "grafting from” approach where polymer chains are induced to grow from the reinforcement surface. Examples of this procedure include the adsorption of a polymerization reaction catalyst and/or initiator on the particle surface to afterwards carry out a polymerization reaction in the presence of those modified particles.
• a polymerization reaction catalyst and/or initiator on the particle surface to afterwards carry out a polymerization reaction in the presence of those modified particles.
• tin octoate can be used as catalyst, and toluene diisocyanate and polytetrahydrofuran as monomers for the "in situ" polymerization.
• catechol or pyrogallol-based molecules with an amine functional group e.g.
• nitrodopamine, dopamine can be used to coat the surface of oxide particles through ligand exchange reactions and to establish covalent bonds to the polymer matrix by reacting the amine group with carboxylic acid groups from the matrix polymer, using the well-established carbodiimide chemistry for carboxylic acid activation.
• reinforcing particles can be functionalized with perfluorophenylazide, which afterwards reacts with for example polystyrene, poly(2-ethyl- 2-oxazoline), poly(4-vinylpirydine), polyimide through photopolymerization processes, e.
• Bare surfaces containing polar groups for certain matrix polymers good adhesion between the reinforcing particles and the matrix can also be achieved by a thermal treatment of the final composite, which induces crystallization of polar segments of the polymer on the surface of the reinforcement.
• the magnetic and/or superparamagnetic nanoparticles can be adsorbed to the reinforcing particles through electrostatics, van der Waals or through covalent bonds,
• Electrostatic adsorption it is important that the electrostatic surface charge of the fibers and the nanoparticles are opposite, (one is negatively charged and one is positively charged). Opposite charges can be achieved by either selecting reinforcing particles and nanoparticles with an opposite natural surface charge at a given pH or by altering, through chemical treatment or coatings, the surface charge of one or both of these elements. Both cationic and anionic magnetic and/or superparamagnetic nanoparticles are commercially available, such as the respective EMG-605 and EMG-705 ferrofluids from the company Ferrotec.
• One example is to suspend 50 nm commercial iron oxide nanoparticles, such as from Nanostructured and Amorphous Materials Inc., in water with a pH of 4 to give them a naturally positive charge.
• the fibers Upon adding glass fibers to this solution, such as those commercially available from Fibre Glast Development Corporation, the fibers will exhibit a natural negative surface charge. Through electrostatics, the magnetic and/or superparamagnetic nanoparticles will then adsorb to the fibers under these conditions, as shown in Figure 1.
• Another example is to use treated iron oxide nanoparticles coated with surfactants that provide an anionic surface charge, such as that available to purchase from commercial sources, such as the EMG-705 solution from Ferrotec. These nanoparticles will electrostatically adsorb at neutral pH to aluminum oxide platelets, such as those commercially available from Antaria (grade Al-Pearl), which are naturally cationic at pH of 7. See Figure 2.
• ionic surfactants and/or polymeric molecules can be adsorbed in a layer-by-layer fashion in order to provide strong adsorption of the magnetic and/or superparamagnetic nanoparticles on the surface of the reinforcing particles.
• Reinforcing carbon nanotubes for instance can be first coated with the anionic polymer poly(sodium 4- styrene sulfonate), followed by the electrostatic adsorption of the cationic polymer poly(dimethyldiallylammonium chloride) and finally the adsorption of negatively charged magnetic and/or superparamagnetic nanoparticles as those commercially available from Ferrotec.
• the magnetic and/or superparamagnetic nanoparticles can also be attached to the surface of the reinforcing particles through covalent bonds.
• reinforcing particles and magnetic and/or superparamagnetic nanoparticles must be surface modified with appropriate organic functional groups.
• Covalent bonds can be formed either by direct reaction between those functional groups or by using a cross linking agent, as schematically exemplified in Figure 3.
• metal oxide reinforcing particles e.g. glass fibers and alumina platelets
• silane coupling agents Figure 4a
• Cathecol- and pyrogallol-based molecules can also be used to provide organic functional groups on metal oxide surfaces.
• dopamine and nitrodopamine supplied by Aldrich and Surface Solutions Gmbh respectively, can attach strongly to alumina surfaces providing free amine groups ( Figure 4b), which can be further used for coupling magnetic and/or superparamagnetic nanoparticles through covalent bonds.
• One example is to use an amine silane to modify both the glass fiber and the magnetic and/or superparamagnetic nanoparticle surface.
• a diisocyanate can be used as a crosslinker, coupling the magnetic and/or superparamagnetic nanoparticle to the glass fiber surface ( Figure 5a).
• Another example is to use an amine and an epoxy silane to modify the glass fiber and the magnetic and/or superparamagnetic nanoparticles respectively.
• a covalent bond can be formed linking the magnetic and/or superparamagnetic nanoparticle onto the glass fiber surface ( Figure 5b).
• a cathecol-based molecule can also be used to provide amine groups.
• carbodiimide chemistry can be used to covalently bind amine groups from one surface to carboxylic acids groups from the other surface.
• Magnetic and/or superparamagnetic nanoparticles can also be adsorbed on the surface of reinforcing particles through van der Waals interactions.
• negatively charged magnetic nanoparticles Ferotec
• negatively charged alumina platelets Antaria
• a salt e.g. NaCl
• concentrations higher than the critical coagulation concentration e.g. 0.3 M
• the field needs to provide a torque on the particle that overcomes competing forces, such as gravity, thermal motion or steric hinderance.
• competing forces such as gravity, thermal motion or steric hinderance.
• moderate magnetic fields in the range of 1 - 5000 Gauss are strong enough to orient fibers and platelets.
• Such magnetic fields can either be applied with solenoids or with permanent magnets. Stronger magnetic fields, such as those produced with NMR MRI machines, are not required but can also be employed.
• thermoplastic polymer such as polyurethane
• This field can be applied with commercially available permanent magnets, such as those from the company Supermagnete.
• Setting of the matrix can occur through (1) simple evaporation of the solvent from a polymer solution at high temperatures and/or low pressures, (2) crosslinking and/or polymerization reactions within the polymer matrix triggered by temperature or light, (3) solidification of a polymer melt upon cooling.
• an additional conditioning step is sometimes advantageous.
• a strong adhesion between reinforcing alumina platelets and a thermoplastic polyurethane matrix is achieved by heat-treating the final composite at 120-130°C for 3 hours.
• the formation of strong interfaces in polyurethane films containing about 20%vol of vertically aligned alumina platelets is clearly indicated by a 3-fold and 9-fold increase of the out-of-plane stiffness of the film, as compared to the out-of-plane stiffness of films reinforced with horizontal platelets and films without platelets, respectively.
• light and/or heat can also be used to promote strong interfacial adhesion.
• Common chemicals are known to dissolve magnetic and/or superparamagnetic nanoparticles into solution. These chemicals can be used as a post treatment on the composite matrix to remove the magnetic and/or superparamagnetic particles after the matrix is set. It is required that the chemical dissolves the magnetic and/or superparamagnetic nanoparticles at an increased rate as compared with degrading the matrix or reinforcing particles.
• 15 M phosphoric acid can be used to dissolve iron oxide from polyurethane films reinforced with alumina platelets as shown in Figure 9.
• Treatment in phosphoric acid for 1 hour dissolves all magnetic and/or superparamagnetic particles without degrading the material or compromising the alignment of the platelets.
• Fig. 1 shows (a) Glass microrods (roughly 50 ⁇ in length by 10 ⁇ in diameter) with electrostatically adsorbed iron oxide nanoparticles. (b) 50 nm iron oxide nanoparticles under higher magnification.
• Fig. 2 shows (a) Aluminum oxide platelets (roughly 7.5 ⁇ in diameter and 200 nm in thickness) which have electrostatically adsorbed iron oxide nanoparticles. (b) Under higher magnification the 12 nm iron oxide nanoparticles.
• Fig. 3 shows strategies for covalent binding magnetic nanoparticles to Fibers
• a cross linker can be used to covalently couple a fiber and a magnetic nanoparticle which contain the same functional group.
• Fig. 4 shows organic molecules which can be used to provide covalent bond between fibers and magnetic nanoparticles.
• Fig. 5 Examples of covalent binding using silanes.
• Fig. 6 Illustrative examples of possible configurations of magnetized platelets are depicted.
• no applied field allows the magnetized platelet to orient in a standard configuration, parallel to the film.
• a uniform vertical field is applied which orients the platelets perpendicular to the film.
• a magnetic field is applied locally around a hole in the matrix. The field orients local platelets.
• the local field applies a gradient that spatially clusters platelets locally around the affected area.
• Platelet reinforcement with adsorbed magnetic nanoparticles are oriented perpendicular to the matrix surface in an applied magnetic field. Shown here are aluminum oxide platelets with adsorbed iron oxide nanoparticle in polyurethane.
• no applied field allows the platelets to orient in a standard gravity-driven configuration, parallel to the film.
• a uniform vertical field is applied which orients the magnetized platelets perpendicular to the film while not affecting the non-magnetized platelets.
• a magnetic field is applied locally around a hole in the matrix. The field orients locally the magnetized platelets.
• the local field applies a gradient that spatially clusters the magnetized platelets locally around the affected area while leaving the non-magnetic platelets essentially unaffected.
• Reinforcing particles with adsorbed magnetic nanoparticles in a polymer matrix subjected to a solvent that dissolves the magnetic nanoparticles.
• a solvent that dissolves the magnetic nanoparticles.
• the film was submerged in the phosphoric acid solution to dissolve the iron oxide and left the platelets in their original state as seen in the SEM (top left) and in the photographs before (top right) and after treatment (bottom), schematic representation of the reinforcing particles, wherein in the upper part a two-dimensional reinforcing particle is shown, namely in the form of platelets/ribbons and the corresponding dimensions are indicated, and in the lower part a one-dimensional reinforcing particle is given and the dimensions of a fibre/rod/tube/whisker are indicated.
• Example 1 Out-of-plane reinforced thermoplastic polymer films produced with alumina platelets, iron oxide nanoparticles and polyurethane as reinforcing particles, magnetic particles and thermoplastic matrix polymer, respectively.
• thermoplastic polyurethane (PU, Estallon C64) in dimethylformamide (DMF) solution is made and stirred for 30 hours at 60 DC.
• the magnetized platelets are then added at a concentration of 2% Vol to the PU.
• the solution is thoroughly stirred for 2 hours and sonicated for 5 minutes to ensure homogeneity.
• the solution is then air-degassed in a desiccator for 1 hour.
• the solution is then film casted onto a glass substrate.
• a 400 Gauss magnetic field is applied perpendicular to the film and the glass is kept at 60°C on a hotplate.
• the magnetic field will orient the magnetized aluminum oxide platelets perpendicular to the film as the DMF evaporates. Evaporation of DMF leads to an elastic polyurethane film that fixes the oriented structure.
• the polyurethane film Upon complete solvent evaporation, the polyurethane film will contain 20% Vol of perpendicularly oriented platelets such as is shown in Figure 7.
• thermoset polymer film produced with alumina platelets, iron oxide nanoparticles and epoxy resin as reinforcing particles, magnetic particles and thermoset matrix polymer, respectively.
• the magnetized platelets are then added to the resin system at a concentration of 10 Vol.
• the mixture is thoroughly stirred for 120 minutes and sonicated for 5 minutes to ensure homogeneity.
• the solution is then air-degassed in a desiccator for 60 minutes.
• the solution is then film casted onto a Teflon mold.
• a 400 Gauss magnetic field is applied perpendicular to the film and the glass is kept at 60°C on a hotplate.
• the magnetic field will orient the magnetized alumina platelets perpendicular to the film.
• Such aligned structure is finally set through cross-linking reactions in the resin system, which are accelerated at the hotplate temperature of 80°C.
• Crosslinking occurs between molecules in the bulk matrix as well as between matrix molecules and the functional groups present in the alumina platelets (e.g. amine and/or epoxy groups).
• thermoset polymer film produced with glass fibers, iron oxide nanoparticles and epoxy resin as reinforcing particles, magnetic particles and thermoset matrix polymer, respectively.
• the magnetized fibers are then added to the resin system at a concentration of 10 %Vol.
• the mixture is thoroughly stirred for 120 minutes and sonicated for 5 minutes to ensure homogeneity.
• the solution is then dessicated for 60 minutes.
• the solution is then film casted onto a Teflon mold.
• a 400 Gauss magnetic field is applied perpendicular to the film and the glass is kept at 60°C on a hotplate.
• the magnetic field will orient the magnetized glass fibers perpendicular to the film.
• Such aligned structure is finally set through cross-linking reactions in the resin system, which are accelerated at the hotplate temperature of 80°C.
• Crosslinking occurs between molecules in the bulk matrix as well as between matrix molecules and the functional groups present in the glass fibers (e.g. amine and/or epoxy groups).
• the crosslinked film can then be submersed in a solution of 15M phosphoric acid for 1 hour to dissolve the iron oxide from the glass fibers.

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